

㹇 㒊
┠

ḟ

1

ᕳ㢌ゝ  ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ Ụཎṇ༤ ················································· 12ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࣭ࢼࣀࢸࢡࣀࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒
஦ᴗྜྠ࣮࣡ࢡࢩࣙࢵࣉ ························ 23ィ⟬ᶵࢩࢫࢸ࣒
3.1 ィ⟬ᶵࢩࢫࢸ࣒ࡢ඲యീ······································································· 33.2 ࣮࢟ࣗᵓᡂ························································································· 53.3 ࣮࢟ࣗಀᩘ························································································· 64 ୍⯡ሗ࿌
4.1 ࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛࡢ㛤Ⓨ࣭බ㛤 ························································ 75 2020 ᖺᗘィ⟬ᶵ✌ാ≧ἣ࠾ࡼࡧ฼⏝⪅ᩘ
5.1

฼⏝⏦ㄳࣉࣟࢪ࢙ࢡࢺ࠾ࡼࡧ฼⏝⪅ᩘ ····················································11

5.2㟁ຊ౑⏝࠾ࡼࡧィ⟬ᶵ✌ാ≧ἣ·····························································11

5.3ィ⟬ᶵ฼⏝≧ἣ················································································· 12

5.4ࢡࣛࢫู CPU ౑⏝᫬㛫 ······································································ 13

5.5ࢡࣛࢫูࢪࣙࣈฎ⌮௳ᩘ····································································· 13

5.6 ࢪࣙࣈࡢᐇ⾜≧ἣ·············································································· 14
6 ㈨ᩱ
6.1 ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮㐠Ⴀጤဨ···························································· 166.2 ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮⫋ဨ·································································· 176.3 ฼⏝⪅ᩘ࡜ CPU ᫬㛫ࡢ᥎⛣ ································································ 187 ◊✲᪋タࡢ⌧≧࡜ᑗ᮶ィ⏬ (ศᏊ◊࣏࣮ࣜࢺ 2020 ࡼࡾ㌿㍕) ··························· 21ᕳ㢌ゝィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮Ụཎṇ༤⮬↛⛉Ꮫ◊✲ᶵᵓィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡛ࡣࠊࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮ࢩࢫࢸ࣒ࢆ඲ᅜࡢ
◊✲⪅ࡢ᪉ࠎ࡟ඹྠ฼⏝ࢆ㏻ࡌ࡚ࡈ฼⏝࠸ࡓࡔ࠸࡚࠾ࡾࡲࡍࠋ฼⏝⪅ᩘࡣࡇࡇᩘᖺቑ࠼࡚ࡁ
࡚࠾ࡾࠊ ᖺᗘࡣඹ⏝஦ᴗᯟࢆྵࡵ࡚ࢢ࣮ࣝࣉᩘࡣ ࠊ฼⏝⪅ᩘࡣ  ྡ࡟࡞ࡾࡲࡋ
ࡓࠋ฼⏝⪅ࡢ᪉ࠎࡢ◊✲ศ㔝ࡶᗈࡀࡗ࡚ࡁ࡚࠾ࡾࠊศᏊ⛉Ꮫࠊ≀ᛶ⛉Ꮫࠊ⏕≀⛉Ꮫࡔࡅ࡛࡞
ࡃࠊ᭷ᶵ໬Ꮫࡸ㘒య໬Ꮫࡢᐇ㦂◊✲࡟ࡶά⏝ࡉࢀ࡚ࡁ࡚࠸ࡲࡍࠋᖜᗈ࠸ศ㔝ࡢィ⟬ࡢࢽ࣮ࢬ࡟ᑐᛂࡍ࡭ࡃࠊ࢔ࣉࣜࢣ࣮ࢩࣙࣥࣛ࢖ࣈࣛࣜࡢ඘ᐇࢆᚰ᥃ࡅ࡚࠾ࡾࠊ⌧ᅾࠊࢯࣇࢺ㸰㸴௳ࠊ࢖ࣥࢱ࣮ࣇ࢙࣮ࢫ㸳௳ࢆⓏ㘓ࡋ࡚࠸ࡲࡍࠋࡇࢀࡽࡢࣁ࣮ࢻࡸࢯࣇࢺࡀࠊ࣮ࣘࢨ࣮ࡢⓙᵝࡢ◊✲࡟ά⏝ࡋ࡚࠸ࡓࡔࡅࡿࡼ࠺࡟ࠊ฼౽ᛶࢆ㔜どࡋࡓ㐠⏝ࢆᚰ᥃ࡅ࡚࠸ࡃᡤᏑ࡛ࡍࠋ
⌧ᅾࡢࢡࣛࢫࢱ࣮₇⟬ࢧ࣮ࣂ࣮ࡣࠊ ᖺᗘ࡟᭦᪂ࡉࢀ࡚࠾ࡾࠊ*38 ࢆྵࡵࡓ⥲₇⟬ᛶ⬟ࡣ 3)ORSV ࡛ࡍࠋࡋ࠿ࡋࠊᑟධ࠿ࡽ㸲ᖺࡀ⤒㐣ࡋ࡚࠾ࡾࠊ⦾ᛁᮇ࡟ࡣࢪࣙࣈᚅࡕࡍࡿࡇ
࡜ࡶቑ࠼࡚ࡁ࡚࠸ࡲࡍࠋ ᖺ  ᭶࡟ࡣ᪂ࡋ࠸ィ⟬ᶵࡀᑟධࡉࢀࡿணᐃ࡛ࡍࡀࠊࡶ࠺ࡋࡤ
ࡽࡃ⌧ᅾࡢࢧ࣮ࣂ࣮ࢆ᭷ຠ࡟ά⏝࠸ࡓࡔࡅࡿࡼ࠺ࠊ࠾㢪࠸ࡋࡓ࠸࡜ᛮ࠸ࡲࡍࠋࢪࣙࣈࢡࣛࢫ
ࡶ࠸ࡃࡘ࠿ࡈࡊ࠸ࡲࡍࡢ࡛ࠊ࣮ࣘࢨ࣮ࡢⓙᵝࡢィ⟬ࡢෆᐜ࡟ྜࢃࡏࡓ฼⏝ࢆࡋ࡚࠸ࡓࡔࡅ
ࡿ࡜ຠ⋡ⓗ࡟ィ⟬ࡀᐇ⾜ࡉࢀࡿ࡜ᛮ࠸ࡲࡍࠋ࠾Ẽ࡙ࡁࡢⅬࡸࡈ㉁ၥࡀࡈࡊ࠸ࡲࡋࡓࡽࠊᙜࢭ
ࣥࢱ࣮ࡲ࡛ࡈ㐃⤡࠸ࡓࡔࡅࡲࡍ࡜ᖾ࠸࡛ࡍࠋ
ᙜࢭࣥࢱ࣮࡛ࡣࠊⱝᡭ◊✲⪅ࡢ⫱ᡂࠊ◊✲⪅㛫ࡢ᝟ሗ஺᥮ࡸ஺ὶࡶ㔜どࡋ࡚࠸ࡲࡍࠋ
ᖺᗘࡣࠊࢥࣟࢼ⚝ࡢࡓࡵ඲࡚࢜ࣥࣛ࢖ࣥ㛤ദ࡜࡞ࡾࡲࡋࡓࠋ ᖺ  ᭶  ᪥࡟ࠕศᏊࢩ࣑
࣮ࣗࣞࢩࣙࣥࢫࢡ࣮ࣝࠖࢆࠊ ᖺ  ᭶ 㹼 ᪥࡟ࠕ㔞Ꮚ໬Ꮫࢫࢡ࣮ࣝࠖࢆ㛤ദࡋࠊࡑࢀࡒࢀ  ྡࠊ ྡࡢཧຍࢆ࠸ࡓࡔ࠸࡚࠾ࡾࡲࡍࠋィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࣮࣡ࢡࢩࣙࢵࣉࡣࠊ
 ᖺ  ᭶ 㹼 ᪥࡟ࢼࣀࢸࢡࣀࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗ࡜ࡢྜྠ࡛ࠕࢹ࣮ࢱ⛉Ꮫ࡟ᇶ࡙ࡃ⌮ㄽ࣭ィ⟬⛉Ꮫ࡜ᐇ㦂⛉Ꮫࡢ༠ാࢆ┠ᣦࡋ࡚ࠖࢆࢸ࣮࣐࡜ࡋ࡚㛤ദࡋࡲࡋࡓࠋࢼࣀࣉ
ࣛࢵࢺ஦ᴗ࡟࠾ࡅࡿࢹ࣮ࢱ๰ฟ࡟ࡘ࠸࡚ᐇ㦂ࡢඛ⏕᪉࠿ࡽࠊࢹ࣮ࢱ⛉Ꮫࡢ᭱㏆ࡢᒎ㛤࡟ࡘ࠸࡚ᙜヱศ㔝࡛ά㌍ࡉࢀ࡚࠸ࡿ⌮ㄽィ⟬⛉Ꮫศ㔝ࡢⱝᡭࡢඛ⏕᪉࠿ࡽࡈㅮ₇ࢆ࠸ࡓࡔࡁࡲ
ࡋࡓࠋࡇࡢྜྠ࣮࣡ࢡࢩࣙࢵࣉ࡟ࡶ  ྡࡢཧຍࢆ࠸ࡓࡔࡁࡲࡋࡓࠋ
᭱㏆ࠊᙜࢭࣥࢱ࣮࡛ࡣ㐠Ⴀయไ࡟ࡶኚ໬ࡀࡈࡊ࠸ࡲࡋࡓࠋዟᮧஂኈ෸ᩍᤵࡣࠊ ᖺᗘࡼࡾ᪂ࡓ࡟タ❧ࡉࢀࡓ ([&(//6 ࡀᮏົ࡜࡞ࡾࡲࡋࡓࡀࠊᘬࡁ⥆ࡁᙜࢭࣥࢱ࣮࡟ࡶే௵࡜ࡋ
࡚ࡈ༠ຊ࠸ࡓࡔ࠸࡚࠸ࡲࡍࠋ ᖺ  ᭶࡟ࡣࠊᒸᓮᆂ୍෸ᩍᤵࡀ╔௵ࡉࢀࡲࡋࡓࠋ᪂ࡋ࠸
యไ࡛㐠Ⴀ࡟ຊࢆ࠸ࢀ࡚ࡲ࠸ࡾࡲࡍࠋ
ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡛ࡣࠊ௒ᚋࡶ኱つᶍ㧗㏿ィ⟬⎔ቃࡸࢯࣇࢺ࢚࢘࢔ࢆᥦ౪ࡍࡿ࡜࡜
ࡶ࡟ࠊேᮦ⫱ᡂࡸ◊✲஺ὶࢆ㏻ࡌ࡚⌮ㄽศᏊ⛉ᏛࡢⓎᒎࡢ୍⩼ࢆᢸ࠺ࡇ࡜ࡀ࡛ࡁࢀࡤ࡜⪃࠼࡚࠾ࡾࡲࡍࠋ௒ᚋ࡜ࡶⓙᵝࡢ࠿࠸ࡈᣦᑟࠊࡈᨭ᥼ࢆ㈷ࡾࡲࡍࡼ࠺ࡼࢁࡋࡃ࠾㢪࠸࠸ࡓࡋ

ࡲࡍࠋ
- 1 -

ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࣭ࢼࣀࢸࢡࣀࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗྜྠ࣮࣡ࢡࢩࣙࢵࣉ
ࢸ࣮࣐㸸ࠕࢹ࣮ࢱ⛉Ꮫ࡟ᇶ࡙ࡃ⌮ㄽ࣭ィ⟬⛉Ꮫ࡜ᐇ㦂⛉Ꮫࡢ༠ാࢆ┠ᣦࡋ࡚ࠖ
᪥᫬㸸 ᖺ  ᭶  ᪥㸦ⅆ㸧 ᫬  ศ㹼 ᪥㸦Ỉ㸧 ᫬఍ ሙ㸸Zoom ࡟ࡼࡿ࢜ࣥࣛ࢖ࣥ㓄ಙཧຍ⪅㸸 ྡ
࣏ࢫࢱ࣮Ⓨ⾲㸸 ௳ ᖺᗘࡢࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣡ࢡࢩࣙࢵࣉ࡛ࡣࠊศᏊ⛉Ꮫ◊✲ᡤ࡛ᐇ᪋ࡋ࡚࠸ࡿィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢඹྠ฼⏝࠾ࡼࡧࢼࣀࢸࢡࣀࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗࡀ༠ຊࡋࠊศᏊ⛉Ꮫศ㔝࡟࠾ࡅࡿࢹ࣮ࢱࡢά⏝ࡸ࣐ࢸࣜ࢔ࣝࢬ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡘ࠸࡚㆟ㄽࡋࡓࠋࡲࡓࢹ࣮ࢱ⛉ᏛࡸᶵᲔᏛ⩦࡟ᇶ࡙ࡃᇶ♏໬Ꮫࡸ≀㉁࣭ᮦᩱ⛉Ꮫࡢ᭱๓⥺࡛◊✲ࢆᐇ᪋ࡋ࡚࠸ࡿ◊✲⪅ࡀ㞟ࡲࡾࠊ◊✲஺ὶ࡜ពぢ஺᥮ࢆࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊᑗ᮶ࡢ≀㉁⛉Ꮫ࣭ᮦᩱ⛉Ꮫ◊✲ࡢᒎᮃࠊࡲࡓᮏศ㔝࡟࠾ࡅࡿィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡜ࢼࣀࢸࢡࣀࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗࡢᙺ๭࡟ࡘ࠸࡚ࡶ㆟ㄽࡀ࡞ࡉࢀࡓࠋ࢜ࣥࣛ࢖ࣥ࡟࡚ྜィ  ௳ࡢ࣏ࢫࢱ࣮Ⓨ⾲ࡀ࠶ࡾࠊཧຍ⪅ࡣྜィ  ྡ࡛࠶ࡗࡓࠋ


ㅮ₇⪅࣭ᶓᒣ฼ᙪ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧ࠕᩥ⛉┬ࢼࣀࢸࢡࣀࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒ࡢ⌧≧࡜ḟᮇ࣐ࢸࣜ࢔ࣝ '; ࣉࣛࢵࢺ
ࣇ࢛࣮࣒࡬ࡢᮇᚅࠖ
࣭ྂᕝ ㈉㸦᪂₲኱Ꮫ㸧ࠕᶵ⬟ᛶ≀㉁ࡢ㟁Ꮚࢫࣆࣥඹ㬆◊✲ࡢ⌧≧ࠖ࣭㧗ぢ ๛㸦ி㒔኱Ꮫ㸧ࠕ☢໬ィ ᢏ⾡࡟ࡼࡿᶵ⬟ᛶᮦᩱࡢ⌮ゎ࣐ࢸࣜ࢔ࣝ '; ࡟ᇶ࡙࠸ࡓᮦᩱ᥈⣴࡟ྥࡅ࡚ࠖ
࣭㔠Ꮚᘯᫀ㸦᫂἞኱Ꮫ㸧ࠕࢣࣔ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࣭࣐ࢸࣜ࢔ࣝࢬ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟࠾ࡅࡿ┤᥋ⓗࣔࢹࣝ㏫ゎᯒ࡜ࡑࡢᛂ⏝౛ࠖ
࣭⿇ᒣ៞ኴ㑻㸦1,06㸧ࠕ࣐ࢸࣜ࢔ࣝࢬ࣭࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿ⵳㟁ụ⏝㟁ゎᾮᮦᩱ᥈⣴ࠖ࣭᳃ ᐶᩄ㸦୰ኸ኱Ꮫ㸧ࠕ㟁Ꮚ≧ែ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿ࢖࢜ࣥᾮయࡢ࢞ࢫศ㞳྾཰≉ᛶ᭱㐺໬ࠖ࣭⏿୰⨾✑㸦៞᠕⩏ሿ኱Ꮫ㸧ࠕ཯ᛂ⤒㊰ࡢࢹ࣮ࢱ࣮࣋ࢫ࡜ᶵᲔᏛ⩦ࢆ⏝࠸ࡿゐ፹࣭Ⓨගᮦᩱࡢ⌮ゎ࣭ศᏊタィࠖ࣭༡㇂ⱥ⨾㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧ࠕ㟁Ꮚࣇ࢛ࣀࣥ┦஫స⏝ࡢ⢭ᐦィ⟬࡜ࡑࡢᛂ⏝ࠖ࣭ᑠᯘṇே㸦໭ᾏ㐨኱Ꮫ㸧ࠕ㔞Ꮚ໬Ꮫィ⟬࡜ࢹ࣮ࢱ⛉Ꮫࡢే⏝࡟ࡼࡿゐ፹࣭⾲㠃྾╔⣔ࡢゎᯒ࡜ண ࠖ࣭⏣௦ᇶ៞㸦ᮾὒ኱Ꮫ㸧ࠕගᏛάᛶࢆᣢࡘ᭷ᶵᑠศᏊࡢ GHQRYR タィࠖ࣭⸨Ἴ⨾㉳Ⓩ㸦᪩✄⏣኱Ꮫ㸧ࠕ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘࡢ㛤Ⓨࠊ཯ᛂண ࠊ཯ᛂ᮲௳᭱㐺໬࡟ᑐࡍࡿ㔞Ꮚ໬Ꮫィ⟬࡜ᶵᲔᏛ⩦ࡢᛂ⏝ࠖ- 2 -3. ィ⟬ᶵࢩࢫࢸ࣒
3.1. ィ⟬ᶵࢩࢫࢸ࣒ࡢ඲యീ

- 3 -ࡇࢀࡲ࡛㉸㧗㏿ศᏊࢩ࣑࣮ࣗࣞࢱࢩࢫࢸ࣒࡜㧗ᛶ⬟ศᏊࢩ࣑࣮ࣗࣞࢱࢩࢫࢸ࣒ࡢ஧⣔⤫ࡔࡗࡓࢩࢫࢸ࣒
ࢆ⤫ྜࡋ࡚ࠊ᪂ࡓ࡞㧗ᛶ⬟ศᏊࢩ࣑࣮ࣗࣞࢱࢩࢫࢸ࣒࡜ࡋ࡚ 2017 ᖺ 10 ᭶࡟㐠⏝ࢆ㛤ጞࡋࡲࡋࡓࠋ₇⟬ࢧ࣮ࣂ࡜ࡋ࡚ NEC 〇ࢩ࣮ࣜࢬ㸦LX 406Rh-2ࠊLX 110Rh-1ࠊLX 108Th-4G ࡢ 3 ᶵ✀㸧ࠊࣇࣟࣥࢺ࢚ࣥࢻࢧ࣮ࣂ࡜
ࡋ࡚ NEC 〇 LX 406Rh-2ࠊእ㒊☢Ẽࢹ࢕ࢫࢡ⿦⨨࡜ࡋ࡚ DDN 〇 SFA14KXE ࡜ࡑࡢ୪ิࣇ࢓࢖ࣝࢩࢫࢸ࣒ࡢ
DDN ExaScaler (Lustre)ࠊ࢖ࣥࢱ࣮ࢥࢿࢡࢺࡢ Intel Omni Path (100Gbps)ࡀᑟධࡉࢀ࡚࠸ࡲࡍࠋ
P100 ࢆᦚ㍕ࡋࡓ GPU ࢔ࣉࣜࢣ࣮ࢩࣙࣥ㛤Ⓨ⏝ࡢࣇࣟࣥࢺ࢚ࣥࢻࢧ࣮ࣂ࣮ࡣࠊィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡛⥔ᣢ⟶⌮ࡋ࡚࠸ࡲࡍࠋ

NEC LX ࢩ࣮ࣜࢬࡢ⟂య- 4 -3.2. ࣮࢟ࣗᵓᡂ
ไ㝈᫬㛫ࡣ⤒㐣᫬㛫࡛ไ㝈ࡉࢀࡲࡍࠋ㛩ᩓᮇ࡟ࡣࢢ࣮ࣝࣉไ㝈ࢆ⦆࿴ࡍࡿࡇ࡜ࡀ࠶ࡾࡲࡍࠋy ඲฼⏝⪅ࡀ฼⏝ྍ⬟࡞࣮࢟ࣗ
ࢩࢫࢸ࣒

cclx

࣮࢟ࣗྡ
₇⟬
(jobtype ྡ) ࣀ࣮ࢻ࣓࣮ࣔࣜ

1 ࢪࣙࣈࡢไ㝈PN(large)ccnf

18.8GB/ࢥ࢔1ࠥ10 ࣀ࣮ࢻ
㸦40ࠥ400 ࢥ࢔㸧

PN(small)ccnn
ccnf

4.4GB/ࢥ࢔

1㹼32 ࣀ࣮ࢻ
㸦40ࠥ1280 ࢥ࢔㸧PN(core)

cccc
ccca

4.8GB/ࢥ࢔

1ࠥ36 ࢥ࢔

300 ୓Ⅼ௨ୖ
100 ୓Ⅼ௨ୖ
30 ୓Ⅼ௨ୖ
10 ୓Ⅼ௨ୖ
10 ୓Ⅼᮍ‶4000/72
2560/48
1600/30
960/16320/12ࢢ࣮ࣝࣉࢧࣈ࣑ࢵࢺไ㝈
๭ᙜⅬᩘ

ࢪࣙࣈᩘ

300 ୓Ⅼ௨ୖ
100 ୓Ⅼ௨ୖ
30 ୓Ⅼ௨ୖ
10 ୓Ⅼ௨ୖ
10 ୓Ⅼᮍ‶

4000
2560
1600
960
320

1ࠥ48GPU1ࠥ12 ࢥ࢔/GPU

PN(gpu,gpup)
ccca

7.3GB/ࢥ࢔
1㹼8GPU1㹼3 ࢥ࢔/GPU

PN(gpuv)¾

ࢢ࣮ࣝࣉᐇ⾜ไ㝈
ࢥ࢔ᩘ/
๭ᙜⅬᩘ
GPU ᩘ

ࢪࣙࣈࡢ᭱኱᫬㛫ࡣࠊᐃᮇ࣓ࣥࢸࢼࣥࢫࡲ࡛࡛ࡍࠋࡓࡔࡋࠊ1 㐌㛫ࢆ㉺࠼ࡿࢪࣙࣈࡀᐇ⾜࡛ࡁࡿ₇⟬ࣀ࣮ࢻࡣ඲యࡢ༙ᩘ࡛ࡍࠋ

¾

526 ࣀ࣮ࢻ୪ิࡲ࡛ࡢࢪࣙࣈࡣࠊྠ୍ OmniPath ࢢ࣮ࣝࣉෆ࡟᥋⥆ࡉࢀࡓ₇⟬ࣀ࣮ࢻ࡛ᐇ⾜ࡉࢀࡲࡍࠋ

¾

5 ࣀ࣮ࢻ௨ୖࡢࢪࣙࣈࢆᐇ⾜ྍ⬟࡞ ccnn ࣀ࣮ࢻᩘࡣ 526 ࡛ࡍࠋ¾

ࢪࣙࣈࡢ᭱኱᫬㛫ࡀ 1 ᪥௨ୗࡢࢪࣙࣈࢱ࢖ࣉ small ࡢࢪࣙࣈࡣࠊ₇⟬ࣀ࣮ࢻ ccnf ࡛ᐇ⾜ࡉࢀࡿሙྜࡀ࠶
ࡾࡲࡍࠋ

¾

ࢪࣙࣈࡢ᭱኱᫬㛫ࡀ 1 ᪥௨ୗ࡛せồࢥ࢔ᩘࡀ 4-18 ࡢࢪࣙࣈࢱ࢖ࣉ core ࡢࢪࣙࣈࡣࠊ₇⟬ࣀ࣮ࢻ ccca ࡛ᐇ⾜ࡉࢀࡿሙྜࡀ࠶ࡾࡲࡍࠋ

¾

ࢪࣙࣈࢱ࢖ࣉ core, gpu, gpup, gpuv ࡢࢪࣙࣈࡣ௚ࡢࢪࣙࣈ࡜ࣀ࣮ࢻࢆඹ᭷ࡋࡲࡍࠋ

¾

₇⟬ࣀ࣮ࢻ ccca ࡟ࡣ GPU ࡜ࡋ࡚ P100 ࢆᦚ㍕ࡋ࡚࠸ࡿࡶࡢ࡜ࠊV100 ࢆᦚ㍕ࡋ࡚࠸ࡿࡶࡢ࡜ࡀ࠶ࡾࡲࡍࠋ
P100 ࢆ฼⏝ࡍࡿሙྜ࡟ࡣ gpup ࢆࠊV100 ࢆ฼⏝ࡍࡿሙྜ࡟ࡣ gpuv ࢆᣦᐃࡍࡿᚲせࡀ࠶ࡾࡲࡍࠋgpu ࢆᣦᐃࡋࡓሙྜ࡟ࡣ P100 ࠿ V100 ࡢ࡝ࡕࡽ࠿ࢆ฼⏝ࡍࡿࡇ࡜࡟࡞ࡾࡲࡍࠋ

¾

ࢢ࣮ࣝࣉไ㝈ࢆุ᩿ࡍࡿⅬᩘ࡟ࡣ㏣ຍⅬᩘࢆྵࡳࡲࡏࢇࠋ

y ู㏵⏦ㄳࡀᚲせ࡞࣮࢟ࣗ
ࢩࢫࢸ࣒

࣮࢟ࣗྡ

ไ㝈᫬㛫

࣓࣮ࣔࣜ

cclx

ᑓ᭷฼⏝

7 ᪥㛫༢఩

4.4GB/ࢥ࢔

¾

1 ࢪࣙࣈ࠶ࡓࡾࡢࢥ࢔ᩘᛂ┦ㄯไ㝈᫬㛫ࡣࠊ⤒㐣᫬㛫࡛ไ㝈ࡉࢀࡲࡍࠋ

- 5 -ࢢ࣮ࣝࣉไ㝈
チྍࡉࢀࡓࢥ࢔ᩘ

3.3. ࣮࢟ࣗಀᩘ
ᐇ㝿ࡢ฼⏝ᩱ㔠ࡣ↓ᩱ࡛ࡍࠋࣉࣟࢪ࢙ࢡࢺㄢ㢟ࡈ࡜࡟ CPU Ⅼᩘࡀ๭ࡾᙜ࡚ࡽࢀࡲࡍࠋCPU ࢆ౑࠺ࡇ࡜࡟
ࡼࡗ࡚๭ᙜⅬᩘࡀῶࡾࡲࡍࠋྛࢢ࣮ࣝࣉࡣ๭ࡾᙜ࡚ࡽࢀࡓ๭ᙜⅬᩘࢆ㉺࠼࡚ィ⟬ᶵࢆ฼⏝ࡍࡿࡇ࡜ࡣ࡛ࡁ
ࡲࡏࢇࠋ
ᾘ㈝Ⅼᩘࡣࢩࢫࢸ࣒ẖ࡟タᐃࡉࢀ࡚࠸ࡿ CPU ࣮࢟ࣗಀᩘ࡜ GPU ࣮࢟ࣗಀᩘ࡟ࡼࡾồࡵࡽࢀࡲࡍࠋ
ࢩࢫࢸ࣒
cclx
(jobtype=large)
cclx(jobtype=small)
cclx(jobtype=core)cclx(jobtype=gpu, gpup)
cclx(jobtype=gpuv)

CPU ࣮࢟ࣗಀᩘ

GPU ࣮࢟ࣗಀᩘ

42 / (Ⅼ/(ࣀ࣮ࢻ*᫬㛫))-28 / (Ⅼ/(ࣀ࣮ࢻ*᫬㛫))-

1.0 / (Ⅼ/(ࢥ࢔*᫬㛫))
1.0 / (Ⅼ/(ࢥ࢔*᫬㛫))

10 / (Ⅼ/(GPU*᫬㛫))

1.0 / (Ⅼ/(ࢥ࢔*᫬㛫))

15 / (Ⅼ/(GPU*᫬㛫))¾

఍ヰฎ⌮ࡢ ccfep, ccgpuv ࡣ CPU ᫬㛫࡛ CPU Ⅼᩘࡀᾘ㈝ࡉࢀࡲࡍࠋ(ccgpuv ࡣ 2019/7 ࡟✌ാ㛤ጞ)¾

఍ヰฎ⌮ࡢ ccgpu1, ccgpu2, ccgpup ࡛ࡣ CPU Ⅼᩘࡀᾘ㈝ࡉࢀࡲࡏࢇࠋ(ccgpu1, ccgpu2 ࡣ 2019/10 ࡟බ㛤೵Ṇࠊ௦ࢃࡾ࡟ ccgpup ࢆබ㛤)¾

௚ࡢࢩࢫࢸ࣒ࡣࠊ⤒㐣᫬㛫࡛ CPU Ⅼᩘࡀᾘ㈝ࡉࢀࡲࡍࠋ

- 6 -4. ୍⯡ሗ࿌
4.1. ࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛࡢ㛤Ⓨ࣭බ㛤ࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛ㛤Ⓨࡣࠊ᪂つࣉࣟࢢ࣒ࣛࡢ㛤Ⓨࡶࡋࡃࡣ᪤Ꮡࣉࣟࢢ࣒ࣛࡢᨵⰋ࣭Ⓨᒎ࡜࠸࠺࠿ࡓࡕ࡛
⾜ࢃࢀࡓࣉࣟࢢ࣒ࣛ㛤Ⓨ⏦ㄳ࡟ᇶ࡙࠸࡚ࠊCPU ᫬㛫ࠊࣇ࢓࢖ࣝᐜ㔞࡞࡝ࡢィ⟬㈨※ࢆᥦ౪ࡍࡿ௦ࢃࡾ࡟ࠊࣛ
࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛࡢࡦ࡜ࡘ࡜ࡋ࡚ࢯࣇࢺ࢙࢘࢔ࢆࢭࣥࢱ࣮࡛ᐇ⾜ྍ⬟࡞ᙧᘧ࡛Ⓩ㘓ࡋࠊ୍⯡࣮ࣘࢨ࣮࡟ྥࡅ
࡚බ㛤ࡍࡿࡶࡢ࡛ࡍࠋࡑࡢ௚࡟ࠊ࣓࣮࣮࣭࢝࣋ࣥࢲ࣮࡟ࢯࣇࢺ࢙࢘࢔ࡢ࢖ࣥࢫࢺ࣮ࣝసᴗࢆ౫㢗ࡋࡓࡾࠊࢭࣥ
ࢱ࣮⫋ဨࡀ࢖ࣥࢫࢺ࣮ࣝసᴗࢆᐇ᪋ࡋࡓࡾࡋࡓࡶࡢࡶࠊࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛ࡜ࡋ࡚බ㛤ࡋ࡚࠸ࡲࡍࠋྡ๓㻌㻌
ABINITAMBER㻌
AutoDock
CP2K
CRYSTALDIRACGAMESS㻌
Gaussian㻌
GENESISGROMACS㻌
GRRM㻌
LAMMPS
Molpro㻌NAMD㻌NBO/NBOView
NTChemNWChem
OpenMolcas
ORCA
PSI4
Quantum
ESPRESSO㻌
Reaction Plus
SIESTA㻌SMASH
TURBOMOLE㻌
GaussView㻌
Luscus
Molden㻌
VMD㻌ෆᐜ㻌㻌
A package for material science within density functional theory, using a plane wave basis set
and pseudopotentials.
A package of molecular simulation programs.㻌
Suite of automated docking tools.
A quantum chemistry and solid state physics software package.
General-purpose programs for the study of crystalline solids.
Computes molecular properties using relativistic quantum chemical methods (named after P. A.
M. Dirac).
General atomic and molecular electronic structure system.㻌
Ab initio molecular orbital calculations.㻌
Molecular dynamics and modeling software for bimolecular systems such as proteins, lipids,
glycans, and their complexes.
Fast, Free and Flexible MD㻌
Automated Exploration of Reaction Pathways.㻌
Large-scale Atomic/Molecular Massively Parallel Simulator.
A complete system of ab initio programs.㻌
A scalable molecular dynamics program.㻌
Discovery tool for chemical insights from complex wave functions.
A comprehensive new software of ab initio quantum chemistry made in AICS from scratch.
Computational chemistry tools that are scalable both in their ability to treat large scientificcomputational chemistry problems
Quantum chemistry software
An ab initio quantum chemistry program package
An open-source suite of ab initio quantum chemistry programs designed for efficient, highaccuracy simulations of a variety of molecular properties.
An integrated suite of Open-Source computer codes for electronic-structure calculations andmaterials modeling at the nanoscale.㻌
Program to obtain the transition state and reaction path along the user’s expected reaction
mechanism.
Efficient electronic structure calculations and ab initio molecular dynamics simulations ofmolecules and solids㻌
Scalable Molecular Analysis Solver for High performance computing systems
One of the fastest programs for standard quantum chemical applications.㻌
A viewer for Gaussian㻌A portable GUI for Molcas and other chemical software
A visualization program of molecular and structure.㻌
Molecular graphics viewer㻌- 7 -䝟䝑䜿䞊䝆䝥䝻䜾䝷䝮ྡ㻌㻌㻭㻮㻵㻺㻵㼀㻌
㻭㼙㼎㼑㼞㻌

㻯㻼㻞㻷㻌㻯㻾㼅㻿㼀㻭㻸㻌
㻰㻵㻾㻭㻯㻌
㻳㻭㻹㻱㻿㻿㻌

㻳㼍㼡㼟㼟㼕㼍㼚㻌㻳㻱㻺㻱㻿㻵㻿㻌

㻳㻾㻻㻹㻭㻯㻿㻌

䝞䞊䝆䝵䞁㻌㻌
㻤㻚㻤㻚㻟㻌
㻞㻜㻌
㻞㻜㻌
㻝㻤㻌
㻝㻤㻌
㻝㻤㻌
㻝㻤㻌
㻝㻢㻌
㻝㻢㻌
㻝㻠㻌
㻝㻞㻌
㻣㻚㻝㻚㻜㻌
㻢㻚㻝㻚㻜㻌
㻝㻣㻌
㻝㻠㻌
㻝㻤㻚㻜㻌
㻞㻜㻞㻜㻌
㻞㻜㻝㻥㻌
㻞㻜㻝㻤㻌
㻞㻜㻝㻤㻌
㻞㻜㻝㻣㻌
㻞㻜㻝㻣㻌
㻝㻢㻌
㻝㻢㻌
㻝㻢㻌
㻜㻥㻌
㻜㻥㻌
㻜㻥㻌
㻜㻥㻌
㻝㻚㻢㻚㻜㻌
㻝㻚㻠㻚㻜㻌
㻝㻚㻟㻚㻜㻌
㻝㻚㻝㻚㻢㻌
㻝㻚㻝㻚㻡㻌
㻞㻜㻞㻜㻚㻢㻌
㻞㻜㻞㻜㻚㻠㻌
㻞㻜㻞㻜㻚㻞㻌
㻞㻜㻝㻥㻚㻢㻌
㻞㻜㻝㻥㻚㻠㻌
㻞㻜㻝㻥㻚㻞㻌
㻞㻜㻝㻤㻚㻤㻌
㻞㻜㻝㻤㻚㻣㻌
㻞㻜㻝㻤㻚㻢㻌
㻞㻜㻝㻤㻚㻟㻌
㻞㻜㻝㻤㻚㻝㻌
㻞㻜㻝㻢㻚㻢㻌
㻞㻜㻝㻢㻚㻡㻌
㻞㻜㻝㻢㻚㻠㻌
㻞㻜㻝㻢㻚㻟㻌
㻞㻜㻝㻢㻚㻝㻌
㻡㻚㻝㻚㻡㻌
㻡㻚㻝㻚㻠㻌

䝸䝡䝆䝵䞁㻌㻌
㻌㼡㼜㼐㼍㼠㼑㻌㻥㻌㼡㼜㼐㼍㼠㼑㻌㻜㻌㼎㼡㼓㼒㼕㼤㻌㻝㻢㻌㼎㼡㼓㼒㼕㼤㻌㻝㻞㻌㼎㼡㼓㼒㼕㼤㻌㻝㻝㻌㼎㼡㼓㼒㼕㼤㻌㻝㻌㼎㼡㼓㼒㼕㼤㻌㻝㻡㻌㼎㼡㼓㼒㼕㼤㻌㻝㻜㻌㼎㼡㼓㼒㼕㼤㻌㻝㻝㻌㼎㼡㼓㼒㼕㼤㻌㻞㻝㻌㻌㻌㻝㻚㻜㻚㻞㻌
㻝㻚㻜㻚㻠㻌
㻌㻶㼡㼚㻟㻜㻌
㻿㼑㼜㻟㻜㻌
㻿㼑㼜㻟㻜㻌
㻲㼑㼎㻝㻠㻌
㻺㼛㼢㻝㻝㻌
㻭㼜㼞㻞㻜㻌
㻯㻚㻜㻝㻌
㻮㻚㻜㻝㻌
㻭㻚㻜㻟㻌
㻱㻚㻜㻝㻌
㻰㻚㻜㻝㻌
㻯㻚㻜㻝㻌
㻮㻚㻜㻝㻌
㻌
㻌
㻌㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌㻌
㻌
㻌
㻌㻌

ᑟධ᪥㻌㻌
䖂㻌㻔㻞㻜㻝㻤㻛㻣㻛㻝㻜㻕㻌䕿㻌 㻔㻞㻜㻞㻝㻛㻞㻛㻞㻠㻕䖪㻌䕿㻌 㻔㻞㻜㻞㻜㻛㻢㻛㻥㻕䖪㻌䖂㻌㻔㻞㻜㻝㻥㻛㻥㻛㻝㻜㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻞㻛㻝㻠㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻞㻛㻝㻠㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻢㻛㻠㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻣㻛㻞㻡㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻣㻛㻝㻜㻛㻜㻝㻕䖪㻌䕿㻌㻔㻞㻜㻝㻡㻛㻣㻛㻞㻝㻕㻌䕿㻌㻔㻞㻜㻝㻟㻛㻝㻞㻛㻝㻜㻕㻌䖂㻌㻔㻞㻜㻞㻜㻛㻞㻛㻞㻣㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻝㻝㻛㻞㻞㻕䖪㻌䕿㻌 㻔㻞㻜㻞㻜㻛㻝㻛㻞㻣㻕㻌䕿㻌 㻔㻞㻜㻝㻢㻛㻡㻛㻝㻝㻕㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻡㻛㻝㻠㻕㻌䕿㻌㻔㻞㻜㻞㻜㻛㻤㻛㻝㻥㻕㻌䖂㻌㻔㻞㻜㻝㻥㻛㻝㻞㻛㻝㻟㻕㻌䕿㻌㻔㻞㻜㻝㻤㻛㻝㻝㻛㻥㻕㻌䕿㻌㻔㻞㻜㻝㻤㻛㻟㻛㻝㻥㻕㻌䕿㻌㻔㻞㻜㻝㻣㻛㻝㻞㻛㻝㻡㻕㻌䕿㻌㻔㻞㻜㻝㻣㻛㻝㻜㻛㻝㻕㻌䕿㻌㻔㻞㻜㻝㻥㻛㻤㻛㻞㻕㻌䖂㻌㻔㻞㻜㻝㻤㻛㻟㻛㻝㻞㻕䖪㻌䕿㻌㻔㻞㻜㻝㻣㻛㻞㻛㻝㻟㻕㻌䖂㻌㻔㻞㻜㻝㻡㻛㻝㻞㻛㻞㻠㻕㻌䕿㻌㻔㻞㻜㻝㻟㻛㻣㻛㻞㻡㻕㻌䕿㻌㻔㻞㻜㻝㻞㻛㻞㻛㻝㻕㻌䕿㻌㻔㻞㻜㻝㻞㻛㻞㻛㻣㻕㻌䕿㻌 㻔㻞㻜㻞㻜㻛㻝㻞㻛㻞㻤㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻝㻝㻛㻞㻝㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻥㻛㻠㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻣㻛㻝㻞㻛㻝㻟㻕䖪㻌䕿㻌 㻌㻔㻞㻜㻝㻣㻛㻤㻛㻠㻕㻌䕿㻌 㻔㻞㻜㻞㻝㻛㻟㻛㻤㻕䖪㻌䕿㻌 㻔㻞㻜㻞㻜㻛㻝㻜㻛㻝㻞㻕䖪㻌䕿㻌 㻔㻞㻜㻞㻜㻛㻡㻛㻝㻟㻕䖪㻌䖂㻌㻔㻞㻜㻞㻜㻛㻟㻛㻡㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻝㻜㻛㻤㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻠㻛㻝㻤㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻝㻜㻛㻤㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻣㻛㻝㻥㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻟㻛㻞㻣㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻥㻛㻠㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻠㻛㻝㻣㻕㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻞㻛㻞㻞㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻠㻛㻝㻣㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻣㻛㻝㻜㻛㻜㻝㻕䖪㻌䕿㻌㻔㻞㻜㻝㻣㻛㻟㻛㻝㻢㻕䖪㻌䕿㻌㻔㻞㻜㻝㻣㻛㻞㻛㻞㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻠㻛㻝㻣㻕䖪㻌䕿㻌㻔㻞㻜㻝㻤㻛㻝㻛㻝㻥㻕䖪㻌- 8 -㻳㻾㻾㻹㻌

㻸㻭㻹㻹㻼㻿㻌

㻹㼛㼘㼜㼞㼛㻌

㻺㻭㻹㻰㻌
㻺㻮㻻㻌

㻺㼀㻯㼔㼑㼙㻌
㻺㼃㻯㼔㼑㼙㻌
㻻㼜㼑㼚㻹㼛㼘㼏㼍㼟㻌
㻻㻾㻯㻭㻌
㻼㻿㻵㻠㻌
㻽㼡㼍㼚㼠㼡㼙㻌㻱㻿㻼㻾㻱㻿㻿㻻㻌㻾㼑㼍㼏㼠㼕㼛㼚㻼㼘㼡㼟㻌㻿㻵㻱㻿㼀㻭㻌
㻿㻹㻭㻿㻴㻌
㼀㼁㻾㻮㻻㻹㻻㻸㻱㻌ྡ๓㻌㻌㻳㼍㼡㼟㼟㼂㼕㼑㼣㻌㻸㼡㼟㼏㼡㼟㻌
㻹㼛㼘㼐㼑㼚㻌
㻺㻮㻻㼂㼕㼑㼣㻞㻌㼂㻹㻰㻌㻠㻚㻡㻚㻡㻌㻝㻣㻌㻝㻠㻌㻝㻝㻌㻞㻥㻻㼏㼠㻞㻜㻌
㻣㻭㼡㼓㻝㻥㻌
㻞㻞㻭㼡㼓㻝㻤㻌
㻝㻢㻹㼍㼞㻝㻤㻌
㻞㻜㻞㻜㻚㻝㻚㻞㻌㻞㻜㻝㻥㻚㻞㻚㻟㻌㻞㻜㻝㻥㻚㻝㻚㻞㻌㻞㻜㻝㻤㻚㻞㻌
㻞㻜㻝㻡㻚㻝㻌
㻞㻜㻝㻡㻚㻝㻌
㻞㻜㻝㻡㻚㻝㻌
㻞㻜㻝㻞㻚㻝㻌
㻞㻚㻝㻟㻌
㻞㻚㻝㻝㻌
㻣㻚㻜㻌
㻣㻚㻜㻌
㻢㻚㻜㻌
㻢㻚㻜㻌
㻞㻜㻝㻟㻚㻡㻚㻜㻌㻢㻚㻤㻌㻞㻜㻚㻝㻜㻌
㻔㻞㻜㻝㻥㻛㻢㻛㻠㻕㻌㻠㻚㻞㻚㻝㻌
㻝㻚㻝㻌
㻢㻚㻣㻌
㻢㻚㻡㻌
㻢㻚㻟㻌
㻢㻚㻝㻌
㻡㻚㻠㻌
㻡㻚㻝㻚㻞㻌
㻝㻚㻜㻌㻠㻚㻜㻚㻞㻌
㻟㻚㻝㻌㻞㻚㻞㻚㻜㻌
㻣㻚㻡㻌㻣㻚㻠㻚㻝㻌㻣㻚㻠㻌㻣㻚㻟㻌㻣㻚㻞㻚㻝㻌
㻣㻚㻞㻌䝞䞊䝆䝵䞁㻌㻌
㻢㻚㻝㻚㻝㻌
㻢㻚㻜㻚㻝㻢㻌
㻡㻚㻜㻚㻥㻌
㻜㻚㻤㻚㻢㻌
㻡㻚㻣㻌㻞㻌㻝㻚㻥㻚㻟㻌

㻌
㻌
㻌㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻌
㻟㻟㻌
㻞㻣㻌
㻝㻥㻌
㻟㻣㻌
㻌㻌
㻣㻌
㻞㻌
㻝㻤㻌
㻌㻝㻢㻌
㻌
㻌
㻌
㻌㻌
㻌
㻌
㻌㻌
㻌㻌
㻌
㻌㻌
㻌
㻌
㻌
㻌
㻌㻌
㻌

䝸
㻌 䝡䝆䝵䞁㻌㻌㻌㻌㻌㻌㻌㻌䕿㻌㻔㻞㻜㻝㻞㻛㻢㻛㻝㻞㻕䖪㻌䕿㻌㻔㻞㻜㻞㻝㻛㻝㻛㻞㻣㻕㻌䖂㻌㻔㻞㻜㻝㻡㻛㻣㻛㻞㻥㻕㻌䕿㻌㻔㻞㻜㻝㻞㻛㻥㻛㻞㻢㻕㻌䕿㻌 㻔㻞㻜㻞㻝㻛㻟㻛㻡㻕䖪㻌䖂㻌㻔㻞㻜㻝㻥㻛㻝㻝㻛㻝㻠㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻝㻝㻛㻢㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻡㻛㻝㻜㻕䖪㻌䕿㻌 㻔㻞㻜㻞㻜㻛㻝㻜㻛㻞㻜㻕㻌䖂㻌㻔㻞㻜㻝㻥㻛㻝㻞㻛㻝㻜㻕㻌䕿㻌 㻔㻞㻜㻝㻥㻛㻠㻛㻝㻢㻕㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻝㻞㻛㻞㻜㻕㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻢㻛㻝㻞㻕㻌䕿㻌㻔㻞㻜㻝㻣㻛㻝㻞㻛㻝㻠㻕㻌䕿㻌㻔㻞㻜㻝㻣㻛㻝㻜㻛㻝㻕㻌䕿㻌㻔㻞㻜㻝㻢㻛㻠㻛㻝㻥㻕㻌䖂㻌㻔㻞㻜㻝㻤㻛㻝㻞㻛㻣㻕䖪㻌䕿㻌 㻔㻞㻜㻝㻣㻛㻝㻜㻛㻝㻕䖪㻌䕿㻌㻔㻞㻜㻞㻜㻛㻝㻛㻢㻕㻌䖂㻌 㻔㻞㻜㻝㻥㻛㻝㻛㻞㻟㻕㻌䖂㻌 㻔㻞㻜㻝㻤㻛㻟㻛㻝㻢㻕㻌䕿㻌㻔㻞㻜㻝㻤㻛㻞㻛㻢㻕㻌䖂㻌㻔㻞㻜㻝㻡㻛㻠㻛㻞㻜㻕㻌䖂㻌㻔㻞㻜㻝㻤㻛㻝㻛㻞㻞㻕㻌䕿㻌㻔㻞㻜㻞㻜㻛㻝㻞㻛㻣㻕㻌䖂㻌㻔㻞㻜㻝㻥㻛㻢㻛㻣㻕㻌䕿㻌㻔㻞㻜㻞㻜㻛㻝㻛㻤㻕㻌䖂㻌㻔㻞㻜㻝㻤㻛㻝㻛㻝㻞㻕㻌䕿㻌㻔㻞㻜㻞㻝㻛㻝㻛㻡㻕㻌䖪㻌䕿㻌㻔㻞㻜㻞㻜㻛㻣㻛㻥㻕㻌䖂㻌㻔㻞㻜㻝㻤㻛㻝㻞㻛㻝㻣㻕㻌䕿㻌㻔㻞㻜㻝㻣㻛㻥㻛㻝㻠㻕㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻝㻞㻛㻝㻣㻕㻌䕿㻌 㻔㻞㻜㻝㻡㻛㻠㻛㻤㻕㻌䖂㻌㻔㻞㻜㻝㻤㻛㻝㻛㻞㻞㻕㻌䖂㻌㻔㻞㻜㻝㻥㻛㻟㻛㻝㻠㻕㻌䕿㻌 㻔㻞㻜㻝㻞㻛㻤㻛㻝㻢㻕㻌䕿㻌㻔㻞㻜㻝㻣㻛㻡㻛㻝㻢㻕㻌䕿㻌㻔㻞㻜㻞㻜㻛㻣㻛㻟㻜㻕㻌䖂㻌㻔㻞㻜㻞㻜㻛㻟㻛㻞㻕㻌䕿㻌㻔㻞㻜㻝㻥㻛㻤㻛㻞㻜㻕㻌䕿㻌 㻔㻞㻜㻝㻤㻛㻣㻛㻞㻟㻕㻌䕿㻌㻔㻞㻜㻝㻣㻛㻝㻞㻛㻝㻞㻕㻌䕿㻌㻔㻞㻜㻝㻣㻛㻤㻛㻠㻕㻌ᑟධ᪥㻌㻌䕿㻌㻔㻞㻜㻝㻥㻛㻝㻜㻛㻞㻥㻕㻌䖂㻌㻔㻞㻜㻝㻣㻛㻞㻛㻞㻕㻌䖂㻌㻔㻞㻜㻝㻟㻛㻟㻛㻝㻟㻕㻌䖂㻌㻔㻞㻜㻝㻥㻛㻢㻛㻝㻜㻕㻌䖂㻌㻔㻞㻜㻝㻢㻛㻝㻝㻛㻞㻞㻕㻌䖂㻌㻔㻞㻜㻝㻤㻛㻞㻛㻢㻕㻌䖂㻌㻔㻞㻜㻝㻤㻛㻞㻛㻝㻥㻕㻌- 9 -‫۔‬: ࢖ࣥࢫࢺ࣮ࣝ῭ࡳࠋg16 ࡢࡼ࠺࡞ูྡࡀタᐃࡉࢀ࡚࠸ࡿࠋ
‫ۑ‬: ࢖ࣥࢫࢺ࣮ࣝ῭ࡳࠋg16a03 ࡢࡼ࠺࡟ᣦᐃࡍࡿᚲせࡀ࠶ࡿࠋ‫ۼ‬: GPU ∧ࡀ⏝ពࡉࢀ࡚࠸ࡿࠋ

- 10 -

㻡㻚䚷㻞㻜㻞㻜ᖺᗘ㻌ィ⟬ᶵ✌ാ≧ἣ䛚䜘䜃฼⏝⪅ᩘ㻡㻚㻝䚷฼⏝⏦ㄳ䝥䝻䝆䜵䜽䝖䛚䜘䜃฼⏝⪅ᩘ

฼⏝ศ㔝

CPUⅬᩘ

฼⏝༊ศ

ࣉࣟࢪ࢙ࢡࢺᩘ

࣮ࣘࢨᩘ

᪋タ฼⏝

243

1,018

309,788,728

272,600,993

200,874,522

ᡤෆ

14

53

53,199,400

53,139,400

28,603,281

᪋タ฼⏝

0

0

0

0

0

ᡤෆ

2

3

700,000

700,000

87,070᪋タ฼⏝

1

3

1,408,000

1,393,920

660,582ᡤෆ1

1

300,000

300,000

2,808

ィ⟬≀㉁⛉Ꮫࢫࣃࢥࣥඹ⏝஦ᴗ฼⏝ᯟ10

65

28,750,000

28,750,000

14,592,328

ྜࠉࠉィ

271

1,143

394,146,128

356,884,313

244,820,591

ศᏊ⛉Ꮫ

⏕⌮Ꮫ

ᇶ♏⏕≀Ꮫ

๭ࠉࠉᙜ

⏦ࠉࠉㄳ

ᐇࠉࠉ⦼

㻡㻚㻞䚷㟁ຊ౑⏝䛚䜘䜃ィ⟬ᶵ✌ാ≧ἣ㟁ຊ㔞 N:Kᖺ᭶ࢩࢫࢸ࣒✌ാ᫬㛫Type-NN

Type-NF

Type-CC

Type-CA

2020ᖺ4᭶

419,001

664

100

664

100

663

100

661

100

5᭶

459,243

734

100

734

100

734

100

734

100

6᭶

473,878

710

100

710

100

710

100

710

100

7᭶

505,357

734

100

734

100

734

100

734

100

8᭶

509,510

734

100

734

100

734

100

734

100

9᭶

478,687

710

100

710

100

710

100

710

100

10᭶

455,451

699

100

699

100

699

100

699

100

11᭶

475,843

720

100

720

100

720

100

720

100

12᭶

469,079

734

100

734

100

734

100

734

100

2021ᖺ1᭶

451,904

734

100

734

100

734

100

734

100

2᭶

423,446

662

99

662

100

662

100

662

100

3᭶

459,876

734

100

734

100

734

100

730

100

5,581,275

8,569

100

8,569

100

8,568

100

8,561

100

ྜࠉィ

ͤࠉ ࡣࠊィ⟬ᶵ✌ാ⋡  㸸ィ⟬ᶵ✌ാ᫬㛫¹㸦㏻㟁᫬㛫㸦ᬺ᭶ᗘ㸧㸫ᐃᮇಖᏲ᫬㛫㸧࡛ࡍࠋ- 11 -

㻡㻚㻟䚷ィ⟬ᶵ฼⏝≧ἣ㻡㻚㻟㻚㻝䚷㻯㻼㼁౑⏝᫬㛫CPU౑⏝᫬㛫ᖺ᭶࣐ࢩࣥྡType-NF

GPU౑⏝᫬㛫*Type-NN*

Type-CC*

Type-CA*

Type-CA*

2020ᖺ4᭶

458,66166

13,656,841

65

2,805,492

74

764,68450

91,822

72

5᭶

681,40189

20,571,540

88

2,383,390

57

739,378

44

119,69485

6᭶

604,40982

19,346,102

86

3,162,594

78

797,898

49

131,764977᭶

641,405

84

21,094,996

90

3,429,924

82

574,09334

111,635

798᭶

672,791

88

21,127,885

91

3,526,461

84

493,71729

78,11855

9᭶

688,54493

21,386,023

95

3,372,368

83

515,19631

100,6537410᭶

674,75493

20,915,832

94

3,497,250

87

709,64344

78,28658

11᭶

716,469

96

22,569,582

99

3,952,709

96

1,197,038

72

93,22867

12᭶

695,749

91

22,363,127

96

3,424,678

82

1,130,844

67

118,066842021ᖺ1᭶

678,563

89

21,819,372

94

3,202,426

76

885,36952

98,02770

2᭶

592,488

86

20,428,380

97

3,322,171

88

686,70745

83,15765

3᭶

680,98489

22,104,033

95

3,700,921

88

809,347

48

97,04769

7,786,216

87

247,383,714

91

39,780,384

81

9,303,914

47

1,201,49773

ྜࠉィ

ͤࠉ&38᫬㛫ࠊ*38᫬㛫ࡢ༢఩ࡣ᫬㛫࡛ࡍࠋͤࠉ ࡣࠊ࣐ࣝࢳ&38ࡢィ⟬ᶵ࡟࠾ࡅࡿ&38ᙜࡓࡾࡢ&38✌ാ⋡  ࡛ࡍࠋ㻡㻚㻟㻚㻞䚷䝞䝑䝏䝆䝵䝤ฎ⌮௳ᩘࣂࢵࢳࢪࣙࣈฎ⌮௳ᩘ

ᖺ᭶
࣐ࢩࣥྡ

Type-NF

Type-NN

Type-CC

Type-CAྜ䚷ィ2020ᖺ4᭶

195

16,13739,466

10,51966,3175᭶

437

24,85528,636

4,049

57,9776᭶

353

20,46056,48920,607

97,9097᭶

900

19,882

84,55829,284

134,6248᭶

327

21,31989,93633,326

144,908

9᭶

689

21,51671,441

71,573

165,219

10᭶

1,146

24,89652,29546,510124,847

11᭶

1,419

35,995

92,14425,819155,377

12᭶

3,501

18,178112,119

64,115

197,9132021ᖺ1᭶

2,130

26,216

163,816

85,839278,0012᭶

6,388

30,354

74,14046,595

157,4773᭶

6,230

35,019121,685

97,960260,894

23,715294,827

986,725

536,196

1,841,463

ྜࠉィ- 12 -

㻡㻚㻠䚷䜽䝷䝇ู㻯㻼㼁౑⏝᫬㛫
PN large

PN smallPN corePN gpuQueue ྜィETC

⥲ྜィ2020ᖺ4᭶

453568:27:20

13661933:13:20

3031859:37:36

538316:22:25

17685677:40:41

0:00:00

17685677:40:41

5᭶

665052:13:20

20587888:30:40

2435847:44:36

686920:25:26

24375708:54:02

0:00:00

24375708:54:02

6᭶

538525:56:40

19411984:52:40

3227778:02:43

732713:59:55

23911002:51:58

0:00:00

23911002:51:58

7᭶

544319:11:20

21192081:56:40

3696634:21:57

307382:49:10

25740418:19:07

0:00:00

25740418:19:07

8᭶

637635:57:20

21163039:13:20

3728305:37:18

291871:50:03

25820852:38:01

0:00:00

25820852:38:01

9᭶

644861:14:40

21429705:54:40

3575629:13:54

311934:33:05

25962130:56:19

0:00:00

25962130:56:19

10᭶

485266:51:20

21105318:54:00

3776440:30:33

430451:55:04

25797478:10:57

0:00:00

25797478:10:57

11᭶

557467:38:00

22728582:56:00

4660193:09:43

489553:40:57

28435797:24:40

0:00:00

28435797:24:40

12᭶

571253:20:40

22487622:43:20

3760444:39:11

795077:34:17

27614398:17:28

0:00:00

27614398:17:28

2021ᖺ1᭶

635445:35:20

21862491:25:48

3516374:09:46

571419:41:41

26585730:52:35

0:00:00

26585730:52:35

2᭶

482197:58:40

20538670:07:20

3670327:19:52

338550:22:50

25029745:48:42

0:00:00

25029745:48:423᭶

474364:12:00

22310652:48:40

4033546:11:55

476721:37:49

27295284:50:24

0:00:00

27295284:50:24

6689958:36:40 248479972:36:28

43113380:39:04

5970914:52:42 304254226:44:54ྜࠉィ㻡㻚㻡䚷䜽䝷䝇ู䝆䝵䝤ฎ⌮௳ᩘ
PN large

PN smallPN corePN gpuྜࠉィ2020ᖺ4᭶

126

16,20642,994

6,991

66,3175᭶

190

25,102

29,564

3,121

57,9776᭶

53

20,76059,286

17,81097,9097᭶

156

20,626

94,233

19,609134,6248᭶

138

21,50895,565

27,697

144,908

9᭶

152

22,05380,63262,382

165,21910᭶

216

25,826

61,05537,750124,847

11᭶

344

37,070107,591

10,372

155,377

12᭶

3,005

18,674

122,289

53,945

197,9132021ᖺ1᭶

1,566

26,796

206,116

43,523

278,0012᭶

344

36,39882,92437,811

157,477

3᭶

2,178

39,071

158,047

61,598260,894

8,468

310,090

1,140,296

382,609

1,841,463

ྜࠉィ- 13 -

0:00:00 304254226:44:54

5.6. 䝆䝵䝤䛾ᐇ⾜≧ἣ- 14 -

- 15 -

 ㈨ᩱ
 ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮㐠Ⴀጤဨ


㮚㔝 ᬒᏊ

࠾ⲔࡢỈዪᏊ኱Ꮫ
ᇶᖿ◊✲㝔⮬↛⛉Ꮫ⣔

ᩍᤵ

ᑿᓮ Ὀຓ

ᮾி኱Ꮫ
≀ᛶ◊✲ᡤ

ᩍᤵ

᳃ ᐶᩄ

୰ኸ኱Ꮫ
⌮ᕤᏛ㒊

ᩍᤵ

ᮧୖ ៅ࿃

୰ኸ኱Ꮫ
⌮ᕤᏛ㒊

ᩍᤵ

ᮃ᭶ ᩔྐ

ி㒔኱Ꮫ
࢘࢖ࣝࢫ࣭෌⏕་⛉Ꮫ◊✲ᡤ

ᩍᤵ

Ụཎ ṇ༤

ศᏊ⛉Ꮫ◊✲ᡤィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮㸦⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ◊✲㡿ᇦ ィ⟬ศᏊ⛉Ꮫ◊✲㒊㛛㸧

ᩍᤵ

ᩧ⸨ ┿ྖ

ศᏊ⛉Ꮫ◊✲ᡤ⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ◊✲㡿ᇦ ⌮ㄽศᏊ⛉Ꮫ➨୍◊✲㒊㛛㸦ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮㸧

ᩍᤵ

ዟᮧ ஂኈ

ศᏊ⛉Ꮫ◊✲ᡤ⏕࿨๰ᡂ᥈✲ࢭࣥࢱ࣮㸦⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ◊✲㡿ᇦ ィ⟬ศᏊ⛉Ꮫ◊✲㒊㛛㸧㸦ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮㸧

෸ᩍᤵ

༡㇂ ⱥ⨾

ศᏊ⛉Ꮫ◊✲ᡤ⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ◊✲㡿ᇦ ⌮ㄽศᏊ⛉Ꮫ➨୍◊✲㒊㛛෸ᩍᤵ㟷ᮌ ୍ὒ

ᇶ♏⏕≀Ꮫ◊✲ᡤ⣽⬊⏕≀Ꮫ㡿ᇦ ᐃ㔞⏕≀Ꮫ◊✲㒊㛛

ᩍᤵ

ෆᒣ㑳ኵ

ᇶ♏⏕≀Ꮫ◊✲ᡤ⌮ㄽ⏕≀Ꮫ㡿ᇦ ࢤࣀ࣒᝟ሗ◊✲ᐊ

෸ᩍᤵ

໭ᇛᆂ୍

⏕⌮Ꮫ◊✲ᡤ
ࢩࢫࢸ࣒⬻⛉Ꮫ◊✲㡿ᇦ ⚄⤒ࢲ࢖ࢼ࣑ࢡࢫ◊✲㒊㛛

ᩍᤵ

⚟Ọ 㞞႐

⏕⌮Ꮫ◊✲ᡤ
ࢩࢫࢸ࣒⬻⛉Ꮫ◊✲㡿ᇦ ᚰ⌮⏕⌮Ꮫ◊✲㒊㛛෸ᩍᤵ

- 16 -

 ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮⫋ဨỤཎ ṇ༤ࢭࣥࢱ࣮㛗࣭ᩍᤵ

ᩧ⸨ ┿ྖ

ᩍᤵ

ዟᮧ ஂኈ

෸ᩍᤵ

▼⏣ ᖸᇛ

ຓᩍ

኱㔝 ேౝ

෸ᩍᤵ

ෆᒣ 㑳ኵ

෸ᩍᤵ

ᒾᶫ ᘓ㍜

ᢏ⾡⫋ဨ㸦⌜㛗㸧Ỉ㇂ ᩥಖᢏ⾡⫋ဨ㸦ᢏ⾡ᑓ㛛ဨ㸧ෆ⸨ ⱱᶞᢏ⾡⫋ဨ㸦ಀ㛗㸧⃝ ᫀᏕᢏ⾡⫋ဨ㸦୺௵㸧㛗ᒇ ㈗㔞ᢏ⾡⫋ဨ㸦୺௵㸧

⚄㇂ ᇶྖ

ᢏ⾡⫋ဨ

ᮌୗ ᩗṇ

ᢏ⾡⫋ဨ

▮㷂 ⛱Ꮚ

≉௵ᑓ㛛ဨ

Ᏹ㔝 ᫂Ꮚ

ᢏ⾡ᨭ᥼ဨ

㏆⸨ ┤Ꮚ

஦ົᨭ᥼ဨ

㏆⸨ ⣖Ꮚ

஦ົᨭ᥼ဨ

- 17 -

㻢㻚㻟㻌฼⏝⪅ᩘ䛸㻯㻼㼁᫬㛫䛾᥎⛣ィ⟬ᶵࢩࢫࢸ࣒㐠ࠉ㌿ࠉ᪉ࠉᘧ

1978ᖺᗘ

1979ᖺᗘ

1980ᖺᗘ

1981ᖺᗘ

1982ᖺᗘ

1983ᖺᗘ

1984ᖺᗘ

M-180

M-180

M-200H

M-200H

M-200H

M-200H

M-200H

2ྎ

㸰ྎ

M-180

M-180

2ྎ

2ྎ

2ྎ

␯⤖ྜ

␯⤖ྜ

␯⤖ྜ

␯⤖ྜ

㸱࢝᭶ࠉ᭷ே
63ࣉࣟࢪ࢙ࢡࢺᩘ

200Hࠉ↓ே㸷᭶࠿ࡽ↓ே
176

↓ࠉே

↓ࠉே

192

↓ࠉே

↓ࠉே

183

198

199

207

฼ࠉ⏝ࠉ⪅ࠉᩘ
ᶵࠉᵓࠉෆa

48

70

69

91

94

102

110

ᶵࠉᵓࠉእ

107

254

325

330

375

426

446

ྜࠉࠉࠉࠉࠉィ

155

334

394

421

469

528

556

✌ࠉാࠉ᫬ࠉ㛫
(᫬㛫)

1,087

6,071

6,553

6,721

6,305

6,170

6,316

CPU᫬㛫฼⏝⏦ㄳ(᫬㛫)(200Hᇶ‽)(200Hᇶ‽)(200Hᇶ‽)(200Hᇶ‽)(200Hᇶ‽)(200Hᇶ‽)(200Hᇶ‽)

⏦ࠉࠉࠉㄳ

929

4,666

11,033

10,23011,93813,053

14,799

チࠉࠉࠉྍ

816

3,171

7,427

8,306

10,141

10,091

10,768⥲౑⏝CPU᫬㛫b,c
(᫬㛫)

509

2,405

5,405

6,320

8,205

8,489

8,508

ࢪࣙࣈฎ⌮௳ᩘb

41,521

155,980

183,840

214,847

239,771

236,519

226,727

0

20

43

20

699

10

118

ࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛ᪂つⓏ㘓ᩘࢹ࣮ࢱ࣮࣋ࢫ᪂つⓏ㘓ᩘ

0

2

0

0

3

3

0

ࢭࣥࢱ࣮౑⏝ㄽᩥᩘd

0

24

93

118

190

185

202

ィ⟬ᶵࢩࢫࢸ࣒

1985ᖺᗘ

1986ᖺᗘ

1987ᖺᗘ

1988ᖺᗘ

1989ᖺᗘ

1990ᖺᗘ

(㹼11᭶)

M-680H

M-680H

M-680H

M-680H

M-680H

M-680H

M-200H

S-810/10(㹼1᭶)

S-820/80

S-820/80

S-820/80

S-820/802ྎ

␯⤖ྜ

S-810/10

␯⤖ྜ

␯⤖ྜ

␯⤖ྜ

␯⤖ྜ

␯⤖ྜ

(2᭶㹼)

(1᭶㹼)

S-820/80

M-680H␯⤖ྜ

1991ᖺᗘ

S-810/10
㐠ࠉ㌿ࠉ᪉ࠉᘧ

↓ࠉே

↓ࠉே

↓ࠉே

↓ࠉே

↓ࠉே

↓ࠉே

↓ࠉே

226

234

213

231

239

256

272

ᶵࠉᵓࠉෆa

130

141

143

137

146

140

158

ᶵࠉᵓࠉእ

464

496

520

515

544

593

623

ྜࠉࠉࠉࠉࠉィ

594

637

663

652

690

733

781

✌䚷ാ䚷᫬䚷㛫
(᫬㛫)

6,016

6,368

6,444

6,091

5,694

6,768

6,749

ࣉࣟࢪ࢙ࢡࢺᩘ
฼ࠉ⏝ࠉ⪅ࠉᩘ

CPU᫬㛫฼⏝⏦ㄳ(᫬㛫)(200Hᇶ‽)(200Hᇶ‽ / M-680Hᇶ‽)(M-680Hᇶ‽)(M-680Hᇶ‽)(M-680Hᇶ‽)(M-680Hᇶ‽)(M-680Hᇶ‽)⏦ࠉࠉࠉㄳ

15,536

33,832 / 8,458

9,880

12,43914,694

16,622

20,606チࠉࠉࠉྍ

12,08028,184 / 7,046

7,978

10,41812,347

14,626

17,846⥲౑⏝CPU᫬㛫b,c(᫬㛫)12,77020,092 / 5,023

6,624

7,872

8,300

11,975

11,874ࢪࣙࣈฎ⌮௳ᩘb274,431289,915

278,956

278,104

253,418

2,955,038

346,987

160

39

4

7

3

0

0

ࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛ᪂つⓏ㘓ᩘࢹ࣮ࢱ࣮࣋ࢫ᪂つⓏ㘓ᩘ

1

0

1

0

0

0

0

ࢭࣥࢱ࣮౑⏝ㄽᩥᩘd

206

237

223

211

218

248

229

aᶵᵓෆ฼⏝⪅࡟ࡣ࢔࢖ࢻࣝㄢ㢟ࡢࡓࡵࡢ㔜」ࢆྵࡵࡲࡏࢇࠋ
b&38᫬㛫ࠊ௳ᩘ࡜ࡶࣛ࢖ࣈࣛࣜ㛤Ⓨࠊࢭࣥࢱ࣮ᴗົ౑⏝ศ࡞࡝ࡍ࡭࡚ࢆྵࡳࡲࡍࠋ
c6ࠊ6ࡢ&38᫬㛫࡟ࡘ࠸࡚ࡣࠊࢫ࣮࢝ࣛ᫬㛫࡜࣋ࢡࢺࣝ᫬㛫ࡢ༢⣧࡞࿴࡛ࡍࠋ
dࢭࣥࢱ࣮ࢆ౑⏝ࡋࡓィ⟬࡟ᇶ࡙ࡃㄽᩥ࡜ࡋ࡚ࢭࣥࢱ࣮࡟ᥦฟࡉࢀࡓࡶࡢ࡛ࡍࠋ

- 18 -

1992ᖺᗘ

1993ᖺᗘ

1994ᖺᗘ

1995ᖺᗘ

1996ᖺᗘ

1997ᖺᗘ

1998ᖺᗘ

1999ᖺᗘ

M-680H

M-680H

M-680H(㹼11᭶)SX-3/34R

SX-3/34R

SX-3/34R

SX-3/34R

SX-3/34R

VPP5000

S-820/80

S-820/80(㹼12᭶)SX-3/34R

HSP(1᭶㹼)

HSP

HSP

HSP

(12᭶ࡲ࡛)

SGI2800,Origin3800

␯⤖ྜ

SX-3/34R(1᭶㹼)

HSP(1᭶㹼)

SP2(1᭶㹼)SX-5

SP2(1᭶㹼)ィ⟬ᶵࢩࢫࢸ࣒↓ࠉே㐠ࠉ㌿ࠉ᪉ࠉᘧ

SP2

SP2

SP2

SX-5

HPC(9᭶㹼)

HPC

HPC

SP2

SP2

SR2201(11᭶㹼)

SR2201

HPC

HPC

↓ࠉே

↓ࠉே

↓ࠉே

↓ࠉே
271

ࣉࣟࢪ࢙ࢡࢺᩘ

225

222

2000ᖺᗘ

Origin2000(10᭶䡚)

SR2201SX-5(3᭶䡚)

Origin2000

↓ࠉே

↓ࠉே

↓ࠉே

↓ࠉே

210

201

188

174

166

156

฼ࠉ⏝ࠉ⪅ࠉᩘ
ᶵࠉᵓࠉෆa

143

127

139

129

139

126

138

125

101

ᶵࠉᵓࠉእ

661

589

601

597

574

609

566

539

534

ྜࠉࠉࠉࠉࠉィ

804
7,156

726

740

716

713

735

6,689 M-680H⣔

5,722 SX-3/34R

8,352 SX-3/34R

8,425 SX-3/34R

8,494 SX3-3/34R

8,579 SX3-3/34R

6,365 VPP5000

SX-3/34R

2,101 SX-3/34R

8,506 HSP

8,293 HSP

8,431 HSP

8,513 SX-5

8,587 SX-5

8,301 SGI⣔

8,319

HSP

2,133 SP2

8,333 SP2

8,336 SP2

8,515 SP2

8,574 SP2

8,375 SX-5

8,496

SP2

2,022

HPC

4,872 HPC

8,501 HPC

8,590 HPC

8,363 SP2

8,492

3,561 SR2201

8,694 SR2201

8,381 HPC

8,490

3,570 Origin2000

8,380✌ ാ ᫬ 㛫(᫬㛫)

SR2201㻔㻥᭶䡚㻕

Origin2000

㻔㻝㻝᭶䡚㻕
CPU᫬㛫฼⏝⏦ㄳ(᫬㛫)(M-680Hᇶ‽)

635

664

704

M-680H⣔(M-680Hᇶ‽)(M-680Hᇶ‽)(HSPᇶ‽)(HSPᇶ‽)(HSPᇶ‽)(HSPᇶ‽)

8,234(SP2 Thinᇶ‽)(SP2 Thinᇶ‽)⏦ࠉࠉࠉㄳ

21,15318,311

21,78140,35858,42573,91076,804

97,788249,405チࠉࠉࠉྍ

19,11016,027

19,39337,44651,49958,65067,15979,964

209,393⥲౑⏝CPU᫬㛫b,c(᫬㛫)12,491

16,30624,781

156,076

207,790

262,365

273,575

239,671619,294ࢪࣙࣈฎ⌮௳ᩘb297,638

227,650

107,194

84,10270,30851,73845,17340,697

58,685

0

10

10

7

15

3

13

14

18

ࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛ᪂つⓏ㘓ᩘࢹ࣮ࢱ࣮࣋ࢫ᪂つⓏ㘓ᩘ

0

1

1

1

0

0

0

0

0

ࢭࣥࢱ࣮౑⏝ㄽᩥᩘd

282

267

306

275

279

331

347

347

391

2001ᖺᗘ

2002ᖺᗘ

2003ᖺᗘ

2004ᖺᗘ

2005ᖺᗘ

2006ᖺᗘ

2007ᖺᗘ

2008ᖺᗘ

VPP5000

VPP5000

VPP5000

VPP5000

VPP5000

VPP5000(5᭶ࡲ࡛)Altix4700

Altix4700

Altix4700

SGI2800,Origin3800

SGI2800,Origin3800

SGI2800,Origin3800

SGI2800,Origin3800

SGI2800,Origin3800

SGI2800,Origin3800

PRIMEQUESTPRIMEQUESTPRIMEQUEST

SX-5

SX-5

SX-7

SX-7

SX-7

(5᭶ࡲ࡛)

SX-7(1᭶䜎䛷)

SR16000

SR16000

SP2

SP2

TX-7

TX-7

TX-7

Altix4700(7᭶࠿ࡽ)TX-7(1᭶䜎䛷)

HPC

HPC

PRIMEQUEST(7᭶࠿ࡽ)

SR16000(3᭶䛛䜙)ィ⟬ᶵࢩࢫࢸ࣒

2009ᖺᗘ

SX-7
TX-7
↓ࠉே

↓ࠉே

↓ࠉே

㐠ࠉ㌿ࠉ᪉ࠉᘧ

↓ࠉே

↓ࠉே

↓ࠉே

↓ࠉே

154

132

↓ࠉே

↓ࠉே

148

144

ᶵࠉᵓࠉෆa

100

104

89

83

30

40

44

59

49

ᶵࠉᵓࠉእ

504

479

449

516

480

533

551

589

635

ࣉࣟࢪ࢙ࢡࢺᩘ

119

141

171

152

145

฼ࠉ⏝ࠉ⪅ࠉᩘ

604

ྜࠉࠉࠉࠉࠉィ
VPP5000✌ ാ ᫬ 㛫(᫬㛫)CPU᫬㛫฼⏝⏦ㄳ
(᫬㛫)

583

8,492 VPP5000

538

8,506 VPP5000

599

8,553 VPP5000

510

8,502 VPP5000

595

573

8,462 VPP5000

684

648

1,402 Altix4700

8,245 Altix4700

8,087 Altix4700

8,319

SGI⣔

8,422 SGI⣔

8,324 SGI⣔

8,545 SGI⣔

8,496 SGI⣔

8,492 SGI⣔

1,400 PRIMEQUEST

8,304 PRIMEQUEST

8,486 PRIMEQUEST

8,536

SX-5

8,558 SX-5

8,391 SX-7

8,524 SX-7

8,451 SX-7

8,492 Altix4700

6,196 SX-7

7,098 SR16000

8,261 SR16000

8,454

SP2

8,555 SP2

7,118 TX-7

8,525 TX-7

8,489 TX-7

8,501 PRIMEQUEST

6,336 TX-7

7,088

HPC

8,555 HPC

8,386

(SP2 Thinᇶ‽)(SP2 Thinᇶ‽)(TX-7ᇶ‽)(TX-7ᇶ‽)(TX-7ᇶ‽)

SX-7

8,399

TX-7

8,398

(TX-7ᇶ‽)(TX-7ᇶ‽)(SR16000ᇶ‽)(SR16000ᇶ‽)⏦ࠉࠉࠉㄳ

251,785

237,872

278,177

341,788414,643

702,270

1,005,486

1,224,945

1,433,895

チࠉࠉࠉྍ

234,866

229,401

277,697

321,796368,136

653,468

918,737

1,199,620

1,412,981⥲౑⏝CPU᫬㛫b,c(᫬㛫)678,128

2,030,643

1,785,877

1,762,818

1,992,205

4,384,464

6,307,008

12,579,635

11,954,215

ࢪࣙࣈฎ⌮௳ᩘb70,68055,52258,78428,96819,896

78,130140,250

149,342

149,177

4

15

5

4

4

21

18

22

20

ࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛ᪂つⓏ㘓ᩘࢹ࣮ࢱ࣮࣋ࢫ᪂つⓏ㘓ᩘ

0

0

0

0

0

0

0

0

0

ࢭࣥࢱ࣮౑⏝ㄽᩥᩘd

302

302

281

284

205

214

188

186

196

aᶵᵓෆ฼⏝⪅࡟ࡣ࢔࢖ࢻࣝㄢ㢟ࡢࡓࡵࡢ㔜」ࢆྵࡵࡲࡏࢇࠋ
b&38᫬㛫ࠊ௳ᩘ࡜ࡶࣛ࢖ࣈࣛࣜ㛤Ⓨࠊࢭࣥࢱ࣮ᴗົ౑⏝ศ࡞࡝ࡍ࡭࡚ࢆྵࡳࡲࡍࠋ
c6ࠊ6ࠊ6;ࠊ6;ࠊ6;ࠊ933ࡢ&38᫬㛫࡟ࡘ࠸࡚ࡣࠊࢫ࣮࢝ࣛ᫬㛫࡜࣋ࢡࢺࣝ᫬㛫ࡢ༢⣧࡞࿴࡛ࡍࠋ
dࢭࣥࢱ࣮ࢆ౑⏝ࡋࡓィ⟬࡟ᇶ࡙ࡃㄽᩥ࡜ࡋ࡚ࢭࣥࢱ࣮࡟ᥦฟࡉࢀࡓࡶࡢ࡛ࡍࠋ

- 19 -

2010ᖺᗘ

2011ᖺᗘ

2012ᖺᗘ

2013ᖺᗘ

2014ᖺᗘ

2015ᖺᗘ

2016ᖺᗘ

2017ᖺᗘ

Altix4700

Altix4700(1᭶䜎䛷)

SR16000(2᭶䜎䛷)

PRIMERGYPRIMERGYPRIMERGYPRIMERGYPRIMERGY(9᭶䜎䛷)

PRIMEQUESTPRIMEQUEST(1᭶䜎䛷)

PRIMERGY

UV2000

UV2000

UV2000

UV2000

UV2000(9᭶䜎䛷)

SR16000

SR16000

UV1000PRIMEHPC FX10PRIMEHPC FX10PRIMEHPC FX10PRIMEHPC FX10PRIMEHPC FX10PRIMERGY (2᭶䛛䜙)

PRIMEHPC FX10ィ⟬ᶵࢩࢫࢸ࣒

NEC LX(10᭶䛛䜙)

UV1000(2᭶䛛䜙)
PRIMEHPC FX10(2᭶䛛䜙)↓ࠉே㐠ࠉ㌿ࠉ᪉ࠉᘧ

↓ࠉே
170ࣉࣟࢪ࢙ࢡࢺᩘ

↓ࠉே
190

↓ࠉே
213

↓ࠉே
204

↓ࠉே
214

↓ࠉே
235

↓ࠉே
234

236

฼ࠉ⏝ࠉ⪅ࠉᩘ
ᶵࠉᵓࠉෆa

49

43

49

39

63

46

50

45

ᶵࠉᵓࠉእ

617

645

758

747

773

798

816

869

666

ྜࠉࠉࠉࠉࠉィ
Altix4700✌ ാ ᫬ 㛫(᫬㛫)CPU᫬㛫฼⏝⏦ㄳ
(᫬㛫)

688

8,513 Altix4700

807

786

836

844

866

914

7,148 SR16000

7,904 PRIMERGY

8,482 PRIMERGY

8,561 PRIMERGY

8,588 PRIMERGY

8,576 PRIMERGY

4,251

PRIMEQUEST

8,567 PRIMEQUEST

7,180 PRIMERGY

8,444 UV2000

8,037 UV2000

8,574 UV2000

8,470 UV2000

8,530 UV2000

4,262

SR16000

8,576 SR16000

8,752 UV1000

8,338 PRIMEHPC FX10

7,875 PRIMEHPC FX10

8,547 PRIMEHPC FX10

8,600 PRIMEHPC FX10

8,577 PRIMEHPC FX10

8,519

PRIMERGY

1,412 PRIMEHPC FX10

8,558

UV1000

1,412

PRIMEHPC FX10

1,428

-

(SR16000ᇶ‽)

-

4,209

NEC LX

-

-

-

-

-

⏦ࠉࠉࠉㄳ

1,712,430

1,738,115

8,007,910

13,388,725

14,299,976

176,636,204

251,118,128

264,312,932

チࠉࠉࠉྍ

1,581,450

1,675,950

7,832,630

12,841,960

14,147,404

171,317,964

213,838,230

253,788,270⥲౑⏝CPU᫬㛫b(᫬㛫)

12,232,544

14,958,012

50,685,364

90,703,069

95,012,014

102,022,406

113,368,880

186,692,673

ࢪࣙࣈฎ⌮௳ᩘb

143,132

204,864

496,719

516,481979,108

705,470

1,055,412

1,140,631

15

22

21

9

24

36

29

32

ࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛ᪂つⓏ㘓ᩘࢹ࣮ࢱ࣮࣋ࢫ᪂つⓏ㘓ᩘ

0

0

1

0

0

0

0

0

ࢭࣥࢱ࣮౑⏝ㄽᩥᩘd

193

231

257

260

253

210

253

328

2018ᖺᗘ

2019ᖺᗘ

2020ᖺᗘ

PRIMEHPC FX10

NEC LX

NEC LX(9݆ΉͲ)NEC LXィ⟬ᶵࢩࢫࢸ࣒↓ࠉே↓ࠉே㐠ࠉ㌿ࠉ᪉ࠉᘧ

↓ࠉே
268

248

ࣉࣟࢪ࢙ࢡࢺᩘ

271

฼ࠉ⏝ࠉ⪅ࠉᩘ
ᶵࠉᵓࠉෆa

52

51

57

ᶵࠉᵓࠉእ

933

997

1086

985

ྜࠉࠉࠉࠉࠉィ
PRIMEHPC FX10

4,392 NEC LX

NEC LX

8,525

1048

1143

8,402 NEC LX

8,568✌ ാ ᫬ 㛫(᫬㛫)CPU᫬㛫฼⏝⏦ㄳ
(᫬㛫)

-

-

-

⏦ࠉࠉࠉㄳ

307,426,854

362,766,273

394,146,128

チࠉࠉࠉྍ

292,639,800

331,660,029

356,884,313⥲౑⏝CPU᫬㛫b(᫬㛫)272,486,299

301,854,255

304,254,227

ࢪࣙࣈฎ⌮௳ᩘb

2,520,856

5,494,831

1,841,463

24

23

15

ࣛ࢖ࣈࣛࣜࣉࣟࢢ࣒ࣛ᪂つⓏ㘓ᩘࢹ࣮ࢱ࣮࣋ࢫ᪂つⓏ㘓ᩘ

0

0

0

ࢭࣥࢱ࣮౑⏝ㄽᩥᩘd

368

314

252

aᶵᵓෆ฼⏝⪅࡟ࡣ࢔࢖ࢻࣝㄢ㢟ࡢࡓࡵࡢ㔜」ࢆྵࡵࡲࡏࢇࠋ
b&38᫬㛫ࠊ௳ᩘ࡜ࡶࣛ࢖ࣈࣛࣜ㛤Ⓨࠊࢭࣥࢱ࣮ᴗົ౑⏝ศ࡞࡝ࡍ࡭࡚ࢆྵࡳࡲࡍࠋ
dࢭࣥࢱ࣮ࢆ౑⏝ࡋࡓィ⟬࡟ᇶ࡙ࡃㄽᩥ࡜ࡋ࡚ࢭࣥࢱ࣮࡟ᥦฟࡉࢀࡓࡶࡢ࡛ࡍࠋ

- 20 -

㸵◊✲᪋タࡢ⌧≧࡜ᑗ᮶ィ⏬㸦ศᏊ◊࣏࣮ࣜࢺࡼࡾ㌿㍕㸧
8-4

計算科学研究センター

計算科学研究センターは，2000 年度に分子科学研究所の電子計算機センターから岡崎共通研究施設の計算科学研究センターへの組織改組が行われ，現在は分子科学研究所，基礎生物学研究所，生理学研究所の３研究所により運営されている。従来の共同利用に加えて，理論，方法論の開発等の研究，さらに，研究の場の提供，ネットワーク業務の支援，人材育成等に取り組んでいる。2020 年度においても，計算物質科学スーパーコンピュータ共用事業や各種スクールの開催をはじめとした様々な活動を展開している。ここでは共同利用に関する活動を中心に，特に設備の運用等について記す。
2021 年３月現在の共同利用サービスを行っている計算機システムの概要を示す。本システムは，旧来「超高速分子シミュレータ」と「高性能分子シミュレータ」の２システムから構成されてきたが，2017 年 10 月の更新以降「高性能分子シミュレータ」の１システムに統合した。本シミュレータでは，いずれも量子化学，分子シミュレーション，
固体電子論などの共同利用の多様な計算要求に応えうるための汎用性があるばかりでなく，ユーザーサイドの PC ク
ラスタでは不可能な大規模計算を実行できる性能を有する。
高性能分子シミュレータは，主として日本電気製の LX シリーズで構成される 1077 ノードの共有メモリ型スカラ計算
機クラスタであり，全サーバは同一体系の CPU（Intel Xeon）および OS（Linux 3.10）をもとに，バイナリ互換性を保ち一体的に運用される。システム全体として総演算性能 4.24 PFlops で総メモリ容量 222 TByte 超である。LX シリーズのク
ラスタは運用形態を念頭に置いて２タイプから構成されている。１つは TypeN と呼ぶノード単位の利用形態向けクラス
タで，2.4 GHz のクロック周波数を持つ 40 コア，192 GB メモリ構成のノード 794 台と，メモリ構成を 768 GB に強化した 26 台からなる PC クラスタである。もう１つは TypeC と呼ぶコア単位の利用形態向けクラスタで，3.0 GHz のクロッ
ク周波数を持つ 36 コア，192 GB メモリ構成のノード 159 台と，24 コアに GPGPU を２基搭載した演算性能を強化したノード 98 台からなる PC クラスタである。インターコネクトは，Omni-Path アーキテクチャを採用し，全台数を 100 Gb/s で相互接続しており，大規模な分子動力学計算などノードをまたがる並列ジョブを高速で実行することができる。これら PC
クラスタは 9.4 PB の容量を持つ外部磁気ディスクを共有し，Lustre ファイルシステムを構成している。
ハードウェアに加え，利用者が分子科学の計算をすぐに始められるようにソフトウェアについても整備を行っている。量子化学分野においては，Gaussian 16，GAMESS，Molpro，Molcas，TURBOMOLE，分子動力学分野では，
Amber，NAMD，GROMACS などがインストールされている。これらを使った計算は全体の 1/3 強を占めている。
共同利用に関しては，2020 年度は 271 研究グループにより，総数 1,103 名（2021 年３月末現在）におよぶ利用者がこれらのシステムを日常的に利用している。近年，共同利用における利用者数が増加傾向にあり，このことは計算科学研究センターが分子科学分野や物性科学分野，生物物理分野において極めて重要な役割を担っており，特色のある計算機資源とソフトウェアを提供していることを示している。また最近は，錯体化学分野や有機化学分野など幅広い
分野の研究者の利用も増加している。
計算科学研究センターは，国家基幹技術の一つとして位置づけられているスーパーコンピュータ「富岳」成果創出
加速プログラム，科学技術人材育成のコンソーシアムの構築事業「計算物質科学人材育成コンソーシアム」，元素戦
略プロジェクト＜研究拠点形成型＞とも連携を行っている。これら３つの大規模並列計算を志向したプロジェクトを支援し，各分野コミュニティにおける並列計算の高度化へさらなる取り組みを促すことを目的として東北大学金属材料研究所，東京大学物性研究所，自然科学研究機構分子科学研究所が共同で「計算物質科学スーパーコンピュータ共用事業（SCCMS）」を運営しており，2020 年度はこれらプロジェクトにコンピュータ資源の一部（10% 以下）を提供・協力している。さらに，ハード・ソフトでの協力以外にも，分野振興および人材育成に関して，計算科学研究センター・296

研究施設の現状と将来計画- 21 -

ナノテクノロジープラットフォーム事業合同ワークショップ「データ科学に基づく理論・計算科学と実験科学の協働を目指して」と２つのスクール「第 10 回量子化学スクール」と「第 14 回分子シミュレーションスクール̶基礎から応用まで̶」を開催した。また，東北大学金属材料研究所，東京大学物性研究所，大阪大学ナノサイエンスデザイン
センターと協力し，我が国の最先端の計算物質科学技術を振興し，世界最高水準の成果創出と，シミュレーション技術，
材料情報科学技術の社会実装を早期に実現するため，計算物質科学協議会を設立・運営し，分野振興を行っている。

2020 年度

システム構成高性能分子シミュレータシステム 4.24 PFlops
クラスタ演算サーバ TypeN
型番：日本電気 LX 2U-Twin2 サーバ 406Rh-2
ＯＳ：Linux
コア数：31,760 コア（40 コア× 794 ノード）2.4 GHz
総理論性能：2,439 TFlops（3,072 GFlops × 794 ノード）
総メモリ容量：152 TB（192 GB × 794 ノード）
クラスタ演算サーバ TypeNF（メモリ強化）
型番：日本電気 LX 1U サーバ 110Rh-1
ＯＳ：Linux
コア数：1,040 コア（40 コア× 26 ノード）2.4 GHz
総理論性能：79 TFlops（3,072 GFlops × 26 ノード）
総メモリ容量：19 TB（768 GB × 26 ノード）
クラスタ演算サーバ TypeC
型番：日本電気 LX 1U サーバ 110Rh-1
ＯＳ：Linux
コア数：5,724 コア（36 コア× 159 ノード）3.0 GHz
総理論性能：549 TFlops（3,456 GFlops × 159 ノード）
総メモリ容量：30 TB（192 GB × 159 ノード）
クラスタ演算サーバ TypeCA（演算性能強化）
型番：日本電気 LX 4U-GPU サーバ 108Th-4G
ＯＳ：Linux
コア数：2,352 コア（24 コア× 98 ノード）3.0 GHz
総理論性能：226 TFlops（2,304 GFlops × 98 ノード）+ 944 TFlops（NVIDIA Tesla P100 × 192, V100 × 20）
総メモリ容量：19 TB（192 GB × 98 ノード）
外部磁気ディスク装置
型番：DDN SFA14KX
総ディスク容量：9.4 PB
高速ネットワーク装置
型番：Intel Omni-Path Architecture 100Gbps
フロントエンドサーバ
型番：日本電気 LX 2U-Twin2 サーバ 406Rh-2
ＯＳ：Linux
総メモリ容量：1,536 GB（192 GB × 8 ノード）
運用管理クラスタ
型番：日本電気 Express5800/R120g-1M
ＯＳ：Linux
総メモリ容量：1,024 GB（64 GB × 16 ノード）

研究施設の現状と将来計画- 22 -

297



II 㒊
┠       ḟ

1 2020 ᖺᗘ◊✲ㄢ㢟࠾ࡼࡧ฼⏝ሗ࿌᭩1.1 2020 ᖺᗘ◊✲ㄢ㢟୍ぴ࡜฼⏝ሗ࿌᭩ᥦฟ≧ἣ(๭ᙜⅬᩘ 30,000 Ⅼ௨ୗ) ··········· 11.2 2020 ᖺᗘ◊✲ㄢ㢟୍ぴ࡜฼⏝ሗ࿌᭩(๭ᙜⅬᩘ 30,000 Ⅼ㉸)·························· 7
2 2020 ᖺᗘィ⟬≀㉁⛉Ꮫࢫࣃࢥࣥඹ⏝஦ᴗ฼⏝ᯟ◊✲ㄢ㢟࠾ࡼࡧ฼⏝ሗ࿌᭩ ······· 490
3 ࣮ࣘࢨⓎ⾲ㄽᩥ
3.1 ࣮ࣘࢨㄽᩥ୍ぴ················································································ 521
3.2 ࣉࣟࢪ࢙ࢡࢺูㄽᩥูๅᥦฟ≧ἣ························································ 550㻝㻚 㻞㻜㻞㻜ᖺᗘ㻌◊✲ㄢ㢟䛚䜘䜃฼⏝ሗ࿌᭩ࠉᖺᗘ◊✲ㄢ㢟ࡢ࠺ࡕࠊ๭ᙜⅬᩘⅬ௨ୗࡢࣉࣟࢪ࢙ࢡࢺ࡟㛵ࡋ࡚ࡣ㡯࡟◊✲ㄢ㢟ྡࡢ୍ぴ࡜ࡋ࡚
グ㍕ࡋࡲࡋࡓࠋࡲࡓ๭ᙜⅬᩘⅬࢆ㉸࠼ࡿࡢࣉࣟࢪ࢙ࢡࢺ࡟㛵ࡋ࡚ࡣᥦฟࡉࢀࡓ฼⏝ሗ࿌᭩ࡢ඲ᩥࢆ㡯࡟ᥖ㍕ࡋࡲࡋࡓࠋ

㻝㻚㻝㻌㻌㻞㻜㻞㻜ᖺᗘ㻌◊✲ㄢ㢟୍ぴ䛸฼⏝ሗ࿌᭩ᥦฟ≧ἣ㻌㻔๭ᙜⅬᩘ㻌㻟㻜㻘㻜㻜㻜Ⅼ௨ୗ㻕ࠑศᏊ⛉Ꮫࠒ᪋タ฼⏝ $
௦⾲฼⏝⪅ྡ

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FE

᭷ᶵ໬ྜ≀࡟࠾ࡅࡿ⨨᥮ᇶຠᯝࡢ
ᚤどⓗᶵᵓ

㫽ྲྀ኱㝔
ᕤ

᪩℩ಟ୍


 㸭 

ࢡࣟࢥࣥ㓟⤖ᬗ࡟࠾ࡅࡿ㉥እࢫ࣌ࢡࢺࣝࡢ⌮ㄽ◊✲㧗࢚ࢿࣝࢠ࣮ຍ㏿ჾ
◊✲ᶵᵓ

ᒾ㔝ࠉ⸅


 㸭 

㟼ᒸ⌮ᕤ⛉኱⌮ᕤ㛵ᒣ⚽㞝 㸭 

໭㔛኱
⌮

▼ᕝ᫓ᶞ


 㸭 

᪥ᮏཎᏊຊ◊✲㛤Ⓨᶵᵓᩘ⣡ᗈဢ 㸭 

ⲡ㛫ࠉோ 㸭 

FH

FJ

FJ

FL

FO

FO

FO

FP

FR

FR

FS

㔠ᒓ㘒య࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Ỉ⣲⤖ྜࢡࣛࢫࢱ࣮࡟࠾ࡅࡿ㉥እㄏ㉳␗ᛶ໬཯ᛂࡢほ ࡜␗ᛶ໬⤒㊰ࡢ᥈⣴⳦㢮࣭ᆅ⾰㢮௦ㅰ≀ࡢᨺᑕᛶࢭࢩ
࣒࢘⵳✚ᶵᵓ࠾ࡼࡧᢠ࢘࢖ࣝࢫᶵ
⬟࡟㛵ࡍࡿィ⟬⛉Ꮫ◊✲ࢩࢫࢸ࣒ィ⟬⛉Ꮫࢭࣥࢱ࣮㸦࣓ࣥࣂ࣮ᩘ㸧

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

Ⰽ⣲ቑឤග㟁ᴟ࣭ගゐ፹ཬࡧኴ㝧㟁ụ➼ࡢィ⟬໬Ꮫⓗ◊✲⏘ᴗᢏ⾡⥲ྜ◊✲ᡤ

GࡲࡓࡣG㔠ᒓࢆྵࡴ」᰾࠾ࡼࡧ୕᰾㔠ᒓ㘒యࡢ㟁Ꮚ≧ែ

ᒱ㜧኱
ᕤ

ᾏ⪁ཎᫀᘯ


 㸭 

࢖ࣥࢱ࣮࢚࣓ࣞࣥࢺከ㔜⤖ྜࢆࡶࡘ᭷ᶵ࢖࢜ࣥࡢ཯ᛂᶵᵓ࡟㛵ࡍࡿ㔞Ꮚ໬Ꮫⓗ◊✲

ዉⰋዪ኱㝔
⮬↛⛉Ꮫ

➉ෆᏕỤ


 㸭 

ศᏊࢡࣛࢫࢱ࣮ࡢᗈᖏᇦ㧗ศゎ⬟᣺ືᅇ㌿ศග࡟ࡼࡿศᏊ㛫┦஫స
⏝ࡢ◊✲

ᮾᕤ኱
⌮

Ỉ℩㈼ኴ


 㸭 

㧗཯ᛂάᛶ࡞඾ᆺඖ⣲ཬࡧ㑄⛣㔠ᒓ㘒యࡢᵓ㐀࡜཯ᛂ࡟㛵ࡍࡿ⌮ㄽ
ィ⟬

ᮾᕤ኱
⌮

▼⏣ࠉ㇏


 㸭 

⸆≀࡜㣧㣗≀࡟ྵࡲࢀࡿ⏕⌮άᛶ≀㉁࡜ࡢ┦஫స⏝ゎᯒ

⚟ᒸ኱
⸆

ụ⏣ᾈே


 㸭 

పศᏊ㠀ᬗ㉁᭷ᶵ༙ᑟయᮦᩱࡢ⇕ⓗ࣭໬ᏛⓗᏳᐃᛶ࠾ࡼࡧ㟁Ⲵ㍺㏦≉ᛶ࡟㛵ࡍࡿィ⟬ᒣᙧ኱㝔᭷ᶵᮦᩱࢩࢫࢸ࣒

ᶓᒣ኱㍜ 㸭 

- 1 -

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FU

ศᏊ㛫┦஫స⏝⌮ㄽ࡜ࡑࡢศᏊࢡ
ࣛࢫࢱ࣮◊✲࡬ࡢᛂ⏝ศᏊ⛉Ꮫ◊✲ᡤᚤ⣽ᵓ㐀ࢆㄆ㆑ࡍࡿ㉸ศᏊ」ྜ⣔ࡢᵓ⠏࡜ᵓ㐀ゎᯒ

F\

F\

GF

GM

GS

GX

HE

HK

HK

HN

HS

HT

HT

HT

H[

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ᒾ⏣ᮎᘅ 㸭 

᪂₲኱㝔
⮬↛⛉Ꮫ

ᒾᮏࠉၨ


 㸭 

࢔ࢰ࢟ࣛࣝ㔠ᒓ㘒యࡢ㟁Ꮚ≧ែࡢ
')7ィ⟬

ᮾி⌮⛉኱
⌮

⛅ὠ㈗ᇛ


 㸭 

࢟ࣛࣝ㉸ศᏊ㞟ྜయࡢ⌮ㄽⓗ᳨ウ

ᮾ኱㝔
ᕤ

ఀ⸨႐ග


 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ཯ᛂᶵᵓࡢゎ᫂⏘ᴗᢏ⾡⥲ྜ◊✲ᡤᰰ἟ࠉឡ 㸭 

໬Ꮫ཯ᛂࡢDELQLWLRィ⟬࡟ࡼࡿ◊
✲

ឡ፾኱㝔
⌮ᕤ

㛗ᒸఙ୍


 㸭 

ศᏊ㌶㐨ἲ࡟ࡼࡿ཯ᛂண
࡜ࡍࡿ᪂᭷ᶵ཯ᛂࡢ㛤Ⓨ

ᮾ኱㝔
⌮

୰ᮧᰤ୍


 㸭 

ᾮ┦⢾㢮ศᏊࡢ;$6ࢫ࣌ࢡࢺࣝࢩ
࣑࣮ࣗࣞࢩࣙࣥ

ᮾ኱㝔᪂㡿ᇦ๰ᡂ⛉Ꮫబࠎᮌᓅᙪ 㸭 

ࢡࣛࢫࢱ࣮」ྜయࡢ཯ᛂᛶゎᯒ㇏⏣ᕤᴗ኱ࢡࣛࢫࢱ࣮◊✲ᐊᕷᶫṇᙪ 㸭 

㑄⛣⣔ิ࢖࢜ࣥࢆྵࡴ໬ྜ≀ࡢ཯ᛂไᚚ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᒱ㜧኱
ᆅᇦ⛉Ꮫ

࿴బ⏣⿱᫛


 㸭 

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿศᏊ
㞟ྜయࡢ◊✲

ྡྂᒇᩥ⌮኱ᮏከ୍ᙪ 㸭 

ศᏊ☢ᛶయࡢ⤫ィ⇕ຊᏛ

኱㜰ᕷ኱㝔
⌮

ሷぢ኱㍜


 㸭 

᫂ᫍ኱
⌮ᕤ

ᯇᮏ୍Ⴙ


 㸭 

⦰ྜከ⎔ⰾ㤶᪘໬ྜ≀࡟ᇶ࡙ࡃ᭷
ᶵⓎගᮦᩱࡢ㛤Ⓨ

ᮾி㎰ᕤ኱㝔ᕤ୰㔝ᖾྖ 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿⅣ⣲ཎᏊࢆ
ྵࡴศᏊࡢ㓟໬㑏ඖ཯ᛂ㐣⛬ࡢゎ
᫂

᪩኱
ᅜ㝿ᩍ㣴

✄ⴥ▱ኈ


 㸭 

*D1ࢆ⏝࠸ࡓḟୡ௦ࣃ࣮࣡ࢹࣂ࢖ࢫ
ࡢィ⟬⛉Ꮫ࡟ࡼࡿタィ

ྡ኱㝔
ᕤ

ⓑ▼㈼஧


 㸭 

ࢆᇶ┙࢚ࣀ࣮࢚ࣝࢫࢸࣝࡢ୙ᩧຍỈศゎ

- 2 -

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

H[

➨୍ཎ⌮ཬࡧྂ඾ศᏊືຊᏛィ⟬
࡟ࡼࡿ6L㛵㐃≀㉁ࡢᵓ㐀ᙧᡂࣉࣟࢭࢫ࡜㟁Ꮚ≀ᛶࡢゎ᫂⏘ᴗᢏ⾡⥲ྜ◊✲ᡤ⏕యศᏊ࠾ࡼࡧ⁐፹ࡢᵓ㐀ᶵ⬟┦
㛵ࡢゎ᫂

ID

IH

IJ

IK

IK

IK

IK

IO

IO

IO

IP

IP

IR

IR

IR

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧᳃ୗᚭஓ 㸭 

❧࿨㤋኱
⏕࿨⛉Ꮫ

㧘ᶫ༟ஓ


 㸭 

࣊࢟ࢧ࢔ࢨࢺࣜࣇ࢙ࢽࣞࣥ㟁Ⲵ⛣ື㘒యࡢᵓ㐀ホ౯

㛵すᏛ㝔኱
⌮ᕤ

⏣୰኱㍜


 㸭 

᣺㟁┦஫స⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ி኱⚟஭ㅬ୍グᛕ
◊✲ࢭࣥࢱ࣮

బ⸨ࠉᚭ 㸭 

㔞Ꮚ⛉Ꮫᢏ⾡
◊✲㛤Ⓨᶵᵓ

ᱜᗞࠉಇ 㸭 

ி኱㝔
ᕤ

㛵ࠉಟᖹ


 㸭 

໭㔛኱
⌮

ྜྷ⏣ࠉ⣧


 㸭 

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜ᶵ
ᲔᏛ⩦ࢆ⤌ࡳྜࢃࡏࡓࣉࣟࢸ࢖ࣥ
࢟ࢼ࣮ࢮ&ࣜ࢞ࣥࢻ⤖ྜ⬟ண ࣔࢹ
ࣝࡢ㛤Ⓨ

㤶ᕝ኱
㎰

ᰗ⏣ࠉு


 㸭 

ከᗙ㓄఩Ꮚ࡛ᵓ㐀つไࡉࢀࡓ㑄⛣㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀㸪㟁Ꮚ≧ែ࠾ࡼࡧ཯ᛂᛶ

ዉⰋዪ኱㝔
⮬↛⛉Ꮫ

ᾆࠉᗣஅ


 㸭 

㘒య㓄఩Ꮚࢆ⏝࠸ࡓࣛࣥࢱࣀ࢖ࢻ
㘒యࡢ☢Ẽⓗᛶ㉁

㔠ἑ኱
ᅜ㝿ᇶᖿ

୕ᶫ஢∞


 㸭 

」㞧࡞ᫍ㛫᭷ᶵศᏊ⏕ᡂ཯ᛂࡢ⌮
ㄽⓗ◊✲

ᮾὒ኱
⌮ᕤ

⏣௦ᇶ៞


 㸭 

㖟ࣄࢻࣜࢻࢼࣀࢡࣛࢫࢱ࣮ࡢᵓ㐀
ゎ᫂

ᗈ኱㝔
ඛ㐍⌮ᕤ

Ỉ⏣ࠉຮ


 㸭 ᪂つࣃ࢖ඹᙺ໬ྜ≀ࡢᵓ㐀≀ᛶ┦㛵ࡢゎ᫂࡟㛵ࡍࡿ⌮ㄽ◊✲

㜰኱㝔
⌮

ᒣୗ೺୍


 㸭 

ィ⟬໬Ꮫⓗᡭἲࢆ⏝࠸ࡓ᭷ᶵྜᡂ
཯ᛂࡢᶵᵓࠊ᭷ᶵ≀㉁ࡢ≀ᛶゎ᫂

៞᠕኱
⸆

ᮾᯘಟᖹ


 㸭 

Ⓨගᛶ㔠ᒓ㘒యࡢບ㉳≧ែࡢ◊✲

᪥ᮏᕤᴗ኱
ᕤ

኱⃝ṇஂ


 㸭 

ᶓ὾ᅜ኱㝔
ᕤ

኱㔝┿ஓ


 㸭 

࣓ࢳࣝࢢ࢔ࢽࣥຊሙࡢసᡂ᪂つȧඹᙺ⣔ࡢ≀ᛶ໬Ꮫ◊✲஧ᡂศᆺᾮᬗࡢᵓ㐀ゎᯒࢩࣜࢥࣥᇶᯈୖࡢ᭷ᶵศᏊ྾╔ᵓ㐀࡜㟁Ꮚ≧ែࡢゎᯒ

- 3 -

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IS

㉁㔞ศᯒ࡟࠾ࡅࡿ᭷ᶵ㐣㓟໬≀ࡢᏳᐃᛶࡢ⪃ᐹ

ᮾ㑥኱
་

ᒸ┿ᝆᏊ


 㸭 

᭷ᶵศᏊࡢගບ㉳≧ែ࡟࠾ࡅࡿᵓ
㐀ኚ໬ࡢ◊✲

໭኱㝔
⌮

ᑠ㛛᠇ኴ


 㸭 

ṍࢇࡔከ⎔ⰾ㤶᪘໬ྜ≀ࡢᵓ㐀࡜
ᛶ㉁

ᮾ㑥኱
⌮

Ώ㑔⥲୍㑻


 㸭 

㉸ศᏊ㘒య࡟㛵ࡍࡿ⇕ຊᏛⓗ◊✲

ᮾி㧗ᑓ

஭ᡭᬛோ


 㸭 

IS

IS

IT

IT

IU

IU

IU

IV

IV

IW

IX

IY

IY

IY

IZ

㸦࣓ࣥࣂ࣮ᩘ㸧

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

ᰂ㌾࡞㦵᱁࡟ࡼࡿᕧ኱㔠ᒓ㘒యᵓ㐀ࡢタィ࡟ྥࡅࡓィ⟬࡟ࡼࡿ㓄ᗙண ᪉ἲࡢ᳨ウ

࠾Ⲕ኱
ᇶᖿ◊✲㝔

୕Ꮿு௓


 㸭 

኱⭠⳦⬡㉁ศᏊࡢຊሙసᡂ

ᮾ኱⏕≀⏕⏘ᕤᏛ
◊✲ࢭࣥࢱ࣮

⠛⏣ᜨᏊ 㸭 

ග࣭☢Ẽ࣭㟁Ẽⓗ≉ᛶࢆ」ྜⓗ࡟♧ࡍ᪂つศᏊᛶ≀㉁ࡢ㛤Ⓨ

኱㜰ᗓ኱㝔
⌮

㓇ᕳ኱㍜


 㸭 

47$,0஧ඖ㛵ᩘゎᯒἲ࡟ࡼࡿ⤖ᬗ࠾ࡼࡧ୙Ᏻᐃ≀㉁୰࡟࠾ࡅࡿᙅ࠸┦஫స⏝ࡢゎᯒ

࿴ḷᒣ኱
ࢩࢫࢸ࣒

ᯘࠉ⪽Ꮚ


 㸭 

ȧඹᙺᣑᙇᆺ᭷ᶵᮦᩱࡢ㛤Ⓨ࡟㛵ࡍࡿ⌮ㄽィ⟬

ᮾி㒔❧⏘ᴗᢏ⾡◊✲ࢭࣥࢱ࣮ᑠỮె♸ 㸭 

㧗࿘ᮇ᪘ඖ⣲ࢆྵࡴ໬ྜ≀ࡢᵓ㐀≀ᛶ⌮ㄽィ⟬ᮾி㒔኱㝔㒔ᕷ⎔ቃ⛉Ꮫ℩㧗ࠉ΅ 㸭 

ࢳ࣮ࣔࣝࣈ࣮ࣝ࠾ࡼࡧࣈࣟࣔࢳ
࣮ࣔࣝࣈ࣮ࣝࡢ㟁Ꮚ≧ែゎᯒ

ᘯ๓኱
ᩍ⫱

ᓥ⏣ࠉ㏱


 㸭 

㑄⛣㔠ᒓࢲ࢖࢝ࣝࢥࢤࢼ࢖ࢻࡢ➨୍ཎ⌮ィ⟬ ,,

㜰኱⏘ᴗ⛉Ꮫ◊✲ᡤ⏣୰ៅ୍㑻 㸭 

඾ᆺඖ⣲ࡢ≉ᛶࢆά⏝ࡋࡓ᪂ᶵ⬟ȧඹᙺศᏊࡢ㛤Ⓨ

Ⲉᇛ㧗ᑓ

ỤᕝὈᬸ


 㸭 

⌮ㄽィ⟬࡟ඛᑟࡉࢀࡿ≉␗⎔ቃ࡛
Ⓨගࡍࡿ᪂つȧඹᙺ⣔ศᏊࡢ㛤Ⓨ

ྡ኱㝔
⌮

ᮧ஭ᚁྐ


 㸭 

ගㄏ㉳㐣Ώᵓ㐀ኚ໬ࢆ฼⏝ࡋࡓศᏊ㛫཯ᛂ㛤Ⓨ

ᮾ኱㝔
⥲ྜᩥ໬

ṇ஭ࠉᏹ


 㸭 

▷ᑑ࿨✀ࡸ⏺㠃໬Ꮫ✀ࡢ᣺ືࢫ࣌
ࢡࢺࣝゎᯒ

⟃Ἴ኱㝔
ᩘ⌮≀㉁

▼ᶫᏕ❶


 㸭 

- 4 -

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IZ

⌮ㄽィ⟬࡟ࡼࡿෆໟࣇ࣮ࣛࣞࣥࡢ
◊✲

ᮾ໭኱㝔
⌮

ᒸ⏣ὒྐ


 㸭 

ࢪࢳ࢔ࢩࢡࣟ࣌ࣥࢸࣥ⎔ࢺࣛ࢖࣐࣮㦵᱁ࢆ᭷ࡍࡿ▷Ἴ㛗㉥እග྾཰ᮦᩱࡢ㟁Ꮚ≧ែゎ᫂

㟼ᒸ኱㝔
ᕤ

᳜⏣୍ṇ


 㸭 

⁐ᾮ୰㔠ᒓ㘒యࡢ㟁Ꮚ≧ែ࡜཯ᛂᛶࡢ⌮ㄽⓗ◊✲

㜰኱㝔
ᕤ

ᑠᮡ೺ᩯ


 㸭 

')7ィ⟬ࢆ⏝࠸ࡓ཯ᛂᶵᵓࡢゎ᫂࡟ࡼࡿ㑅ᢥⓗ᭷ᶵྜᡂ཯ᛂࡢ㛤Ⓨ

ዉⰋᩍ⫱኱
⌮

ᒣᓮ⚈Ꮚ


 㸭 

➨୍ཎ⌮ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ
ᅛయ㓟໬≀ゐ፹ࡢᶵ⬟ゎ᫂

ᮾ኱㝔
ᕤ

୰ᒣࠉဴ


 㸭 

㧗࿘ᮇඖ⣲ྵࡴ㧗཯ᛂᛶ໬Ꮫ⤖ྜࡢ⌮ㄽⓗ◊✲

❧ᩍ኱
⌮

⟪ᾆ┿⏕


 㸭 ᪂つᶵ⬟ᛶ᭷ᶵⰍ⣲ࡢ㛤Ⓨ

ᒱ㜧኱
ᕤ

⯪᭥୍ṇ


 㸭 

ேᕤගྜᡂ࡟ྥࡅࡓ᭷ᶵ㔠᪘㘒యࡢ㟁Ꮚ≧ែ࡟㛵ࡍࡿ◊✲ᮾி㒔኱኱Ꮫᩍ⫱ࢭࣥࢱ࣮

❧ⰼࠉᏹ 㸭 ᪂つ཮ᴟᛶ᭷ᶵ඾ᆺඖ⣲໬ྜ≀ࡢ๰ᡂ࡜཯ᛂᛶ

໭㔛኱
⌮

ෆᒣὒ௓


 㸭 

')7FDOFXODWLRQRIWKH
GLIIXVLRQRIPHWKR[\VSHFLHVRQ
7L2  VXUIDFH໭኱ゐ፹⛉Ꮫ◊✲ᡤ/LX&DQ 㸭 

ࣆ࣮࣭ࣟࣝ㓟໬ࣉࣟࣆࣞࣥࢡࣛࢫ
ࢱ࣮ࡢ࢟ࣛࣝㄆ㆑ࡢ◊✲

㟼ᒸ኱
⌮

ᯇᮏ๛᫛


 㸭 

ᮾ኱
ᕤ

ᖹᯘ♸௓


 㸭 

」ᩘࡢ཯ⰾ㤶᪘㦵᱁ࢆ㞟✚ࡉࡏࡓȧ㟁Ꮚ⣔ࡢ㔞Ꮚ໬Ꮫィ⟬

ྡᕤ኱㝔
ᕤ

㧗ᮌᖾ἞


 㸭 

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜≀⌮໬Ꮫᐃ࡟ࡼࡿࣞࢡࢳࣥከ⢾㢮」ྜయ
ࡢ┦஫స⏝ゎᯒ࡜ᶵ⬟ᨵኚ

ᮾ኱
ᕤ

኱ᕝᑗᚿ


 㸭 

ࢧࣈࣘࢽࢵࢺ㞟✚ᆺࢼࣀࢧ࢖ࢬ✵Ꮝ㘒యࡢ⮬ᕫ㞟ྜ㐣⛬࠾ࡼࡧᶵ⬟
ࡢゎ᫂

ᮾ኱㝔
ᕤ

ᇽᮏᝆஓ


 㸭 ᪂つ㉸ཎᏊ౯ࣚ࢘⣲໬ྜ≀ࡢ᥈⣴

ᶓ὾ᅜ኱㝔
ᕤ

ಙ⏣ᑦẎ


 㸭 

IZ

IZ

I[

I\

I]

I]

JD

JD

JD

JD

JD

JD

JD

JE

JE

ࢱࣥࣃࢡ㉁㛫┦஫స⏝ࡢศᏊ㛫┦஫స⏝ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿண

- 5 -㸦࣓ࣥࣂ࣮ᩘ㸧

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

JE

ศᏊ⮬⏤ᗘ࡜ࢫࣆࣥࡢ⌮ㄽⓗ◊✲

ዉⰋዪ኱
⮬↛⛉Ꮫ

ᅵᑕὠᫀஂ


 㸭 

ᶵ⬟ᛶࣅࣆࣜࢻࢼ࣮ࢺ㓄఩Ꮚࢆ᭷ࡍࡿ㑄⛣㔠ᒓ㘒యゐ፹࡟ࡼࡿ࢔ࣝ
ࢥ࣮ࣝ⬺Ỉ⣲໬཯ᛂࡢᶵᵓ◊✲

ி኱㝔
ே㛫⎔ቃ

᪂ᯘ༟ஓ


 㸭 

࣐࢖ࢡࣟࣇ࣮ࣟ཯ᛂሙࢆ⏝࠸࡚๰〇ࡉࢀࡿ‽Ᏻᐃ㉸ศᏊᵓ㐀ࡢゎᯒி㒔ᗓ኱㝔⏕࿨⎔ቃ⛉Ꮫ

἟⏣᐀඾ 㸭 

7KHRUHWLFDOVWXGLHVRIOLJKWPDWWHULQWHUDFWLRQVLQ
PROHFXODUV\VWHPVி኱㝔ᕤ

1JX\HQ7KDQK
3KXF඾ᆺ㔠ᒓゐ፹཯ᛂࡢ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓ཯ᛂᶵᵓゎ᫂

㜰኱㝔
ᕤ

すᮏ⬟ᘯ


 㸭 

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡿ࢔࣑ࣟ࢖ࢻ࣌ࣉࢳࢻࡢᏳᐃ໬ᵓ㐀ࡢゎᯒᮾி⌮⛉኱㝔
㉥እ⮬⏤㟁Ꮚ࣮ࣞࢨ࣮
◊✲ࢭࣥࢱ࣮

ᕝᓮᖹᗣ 㸭 

㉸㧗㏿ศග࡜㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓගᶵ⬟ᛶศᏊࡢບ㉳≧ែࢲ࢖ࢼ࣑ࢡࢫࡢゎ᫂

஑኱㝔
⌮

ᐑ⏣₩ᚿ


 㸭 

⌮ㄽィ⟬ࢆ⏝࠸ࡓồ᰾ᛶࢥࣂࣝࢺ㘒యࡢゐ፹స⏝ࡢゎ᫂

ᗈ኱㝔
ඛ㐍⌮ᕤ

⡿ᒣබၨ


 㸭 

㔠ᒓ㘒యሙ࡟࠾ࡅࡿᑠศᏊࡢᤕ
ᤊ࣭άᛶ໬࡟㛵ࡍࡿィ⟬໬Ꮫⓗ⪃
ᐹ

ྡᕤ኱㝔
ᕤ

ᑠ⃝ᬛᏹ


 㸭 

㧗ศᏊྜᡂࢆᚿྥࡋࡓ᭷ᶵ⣲཯ᛂࡢ཯ᛂᶵᵓゎᯒ

⩌㤿኱㝔
⌮ᕤ

ぬ▱ுᖹ


 㸭 

࢔ࣝࢣࢽࣝࣇࣝ࢜ࣜࢻྠኈࡢ࣓ࢱ
ࢭࢩࢫ཯ᛂᐇ⌧ࡢྥࡅࡓ᪂つᨭᣢ㓄఩Ꮚࡢタィ

┦ᶍ୰ኸ
໬Ꮫ◊✲ᡤ

ୖᆅ㐩▮


 㸭 

࢖࣭࢜ࣥཎᏊཬࡧ࢖࣭࢜ࣥศᏊ⾪✺ࡢ⌮ㄽⓗ◊✲

ᐑᓮ኱
ᕤ

஬༑ᔒ᫂๎


 㸭 

ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

DK

(*6ࢆ⏝࠸ࡓ࣐࢞ࣥ⥺ㄏ㉳㝧㟁Ꮚᾘ⁛ィ ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᴟ➃⣸እග◊✲᪋タ

JE

JE

JE

JE

JE

JE

JF

JF

JF

JF

JF

㸦࣓ࣥࣂ࣮ᩘ㸧

‫ۑ‬

‫ۑ‬

‫ۑ‬
 㸭 
‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬



‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

ᡤෆ

- 6 -

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧ᖹࠉ⩏㝯Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧 㸭 
‫ۑ‬㻝㻚㻞㻌㻌㻞㻜㻞㻜ᖺᗘ㻌◊✲ㄢ㢟୍ぴ䛸฼⏝ሗ࿌᭩䚷㻔๭ᙜⅬᩘ㻌㻟㻜㻘㻜㻜㻜Ⅼ㉸㻕ࠑศᏊ⛉Ꮫࠒ᪋タ฼⏝ $
௦⾲฼⏝⪅ྡ

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FD

ศගἲ࡜ศᏊືຊᏛィ⟬㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓ⏕య㛵㐃ศᏊࡢືⓗ
ᵓ㐀ゎᯒ

బ㈡኱㝔
ᕤ

ᾏ㔝㞞ྖ


 㸭 

ศᏊෆ࠾ࡼࡧศᏊ㛫㟁Ꮚ⛣ືࡢศ
Ꮚ㌶㐨ἲ࡟ࡼࡿ◊✲

⚄ዉᕝ኱
⌮

⏣௰஧ᮁ


 㸭 

㝵ᒙ᪉⛬ᘧࢆ⏝࠸ࡓ㟁Ꮚࣇ࢛ࣀࣥ
┦஫స⏝࡟㛵ࡍࡿィ⟬◊✲㸸᭷ᶵኴ㝧㟁ụ࡟࠾ࡅࡿ࢚࢟ࢩࢺࣥ⛣ືཬࡧ࣍ࣝࢫࢱ࢖࣭ࣥࣁࣂ࣮ࢻᶍᆺ
࡬ࡢᛂ⏝

ி኱㝔
⌮

㇂ᮧྜྷ㝯


 㸭 

᭷ᶵࢣ࢖⣲໬ྜ≀ࡢᵓ㐀࡜ᛶ㉁

⩌㤿኱㝔
⌮ᕤ

ஂ᪂Ⲯ୍㑻


 㸭 

จ㞟ㄏ㉳Ⓨග࡟ࡘ࠸࡚ࡢ⌮ㄽⓗ◊
✲

༓ⴥᕤᴗ኱
ᕤ

ᒣᮏ඾ྐ


 㸭 

୕㔜㡯ᾘ⁛࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥ
ࡢࡓࡵࡢ㔠ᒓࢡࣛࢫࢱ࣮ቑឤ๣࡟
㛵ࡍࡿィ⟬⛉Ꮫⓗ◊✲

❧ᩍ኱
⌮

୕஭ṇ᫂


 㸭 

Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧ㞟ྜయࡢ㟁Ꮚ≧ែ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ࢔ࣉ
࣮ࣟࢳ

໭኱㝔
⌮

ຍ⸨ᫀᏊ


 㸭 

ศᏊ㓄ิ࡟ࡼࡗ࡚ไᚚࡉࢀࡓ᭷ᶵ
࣍࢘⣲㘒యࡢⓎⰍᶵᵓࡢゎ᫂

ྡᕤ኱
ᕤ

ᑠ㔝ඞᙪ


 㸭 

ග໬Ꮫ཯ᛂࡢไᚚ࡜ᛂ⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲㔞Ꮚ⛉Ꮫᢏ⾡
◊✲㛤Ⓨᶵᵓ

㯮ᓮࠉㆡ 㸭 

Ỉ⣲⤖ྜ⣔࡟࠾ࡅࡿග໬Ꮫ㐣⛬ࡢ
⌮ㄽⓗ◊✲

ᘯ๓኱㝔
⌮ᕤ

ᒣᓮ⚈ᖹ


 㸭 

ȧࢡࣛࢫࢱ࣮ศᏊࡢ㟁Ꮚ≀ᛶࡢゎ
᫂

㜰኱㝔
⌮

すෆᬛᙪ


 㸭 

࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ࠾ࡼࡧ❅໬࣍࢘⣲ࢼࣀࢳ࣮ࣗࣈࡢྜᡂ࣓࢝ࢽ
ࢬ࣒ゎ᫂࡟ྥࡅࡓ㔞Ꮚ໬Ꮫィ⟬࡜ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᮾ኱㝔
ᕤ

୸ᒣⱱኵ


 㸭 

᣺ື෇஧Ⰽᛶศගἲࡢ㉸ศᏊ࢟ࣛࣜࢸ࢕࡬ࡢᛂ⏝

ឡ፾኱㝔
⌮ᕤ

బ⸨ஂᏊ


 㸭 

ගᶵ⬟ᛶศᏊࡢ㟁Ꮚ≧ែ࣭ᵓ㐀࣭ࢫ࣌ࢡࢺࣝィ⟬

ᐊ⹒ᕤᴗ኱
ᕤ

㣤᳃ಇᩥ


 㸭 

FE

FE

GE

GI

GJ

GT

HX

H\

IG

IP

IQ

IR

IS

- 7 -

㸦࣓ࣥࣂ࣮ᩘ㸧





























௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IT

᪂つ࡞඾ᆺඖ⣲໬ྜ≀ࡢᵓ㐀࡜཯
ᛂᛶࡢ◊✲

Ꮫ⩦㝔኱
⌮

⊁㔝┤࿴


 㸭 ᪂つᶵ⬟ᛶȧඹᙺศᏊࡢྜᡂ࡜≀ᛶ࡟㛵ࡍࡿ◊✲

㜰኱㝔
ᇶ♏ᕤ

ΎỈ❶ᘯ


 㸭 

⣽⬊ෆࡢ㉸◲㯤ศᏊࡢ᣺ືゎᯒ

ᮾ໭኱㝔
⸆

ᐑ⏣኱㍜


 㸭 

ྡᕤ኱
ᕤ

୰ᮧಟ୍


 㸭 

㓄఩Ꮚࡢ᭱㐺໬࡟ࡼࡿ㧗άᛶ㔜ྜ
ゐ፹ࡢタィ

┦ᶍ୰ኸ
໬Ꮫ◊✲ᡤ

㛗ᒸṇᏹ


 㸭 

ከ᰾ᵓ㐀ࢆ᭷ࡍࡿ๓࿘ᮇ㑄⛣㔠ᒓ࢔ࣝ࢟ࣜࢹࣥ࠾ࡼࡧ࢔ࣝ࢟ࣜࢪࣥ
ࢡࣛࢫࢱ࣮ࡢྜᡂ

ᒸᒣ኱㝔
⮬↛⛉Ꮫ

㯮ᮌࠉᑲ


 㸭 

࢚ࢫࢸࣝࢲࣥࢫ཯ᛂࡢ఩⨨㑅ᢥᛶ࡟㛵ࡍࡿ⌮ㄽⓗ⪃ᐹ

᪩኱
ඛ㐍⌮ᕤ

ኴ⏣ⱥ௓


 㸭 

඾ᆺඖ⣲ࡢ≉ᛶࢆά⏝ࡋࡓ᭷ᶵ࢚
ࣞࢡࢺ࣑ࣟࣝࢿࢵࢭࣥࢫ⏝Ⓨගᮦ
ᩱࡢ㛤Ⓨ

Ⲉᇛ኱
ᕤ

࿃㒓཭ᏹ


 㸭 

Ⅳ⣲㙐ศᏊࡢỌஂ཮ᴟᏊ࣮࣓ࣔࣥ
ࢺࡢ෌ホ౯

ୖᬛ኱
⌮ᕤ

ஂୡಙᙪ


 㸭 

㔠ᒓ㓟໬≀ࢼࣀࢡࣛࢫࢱ࣮ࡢタィ࡜ࡑࡢ㟁Ꮚ≧ែゎᯒ

ᮾ኱㝔
ᕤ

㕥ᮌᗣ௓


 㸭 

᭷ᶵࣃࣛࢪ࣒࢘㘒యࡢゐ፹స⏝࡟
㛵ࡍࡿ◊✲

ᮾி㟁ᶵ኱
ᕤ

ᒣᮏဴஓ


 㸭 

୰㛫ⓗ࡞ࢫࣆࣥ≧ែࢆ⤒⏤ࡍࡿࢥࣂࣝࢺゐ፹཯ᛂࡢィ⟬໬Ꮫⓗᶵᵓ
ゎᯒ

໭኱㝔
⸆

ᑠᓥṇᐶ


 㸭 

IT

IV

IV

IW

IY

IZ

I[

I\

JD

JD

JF

᪂つ㧗ᶵ⬟ᛶࡢ୙ᩧゐ፹◊✲㸦࣓ࣥࣂ࣮ᩘ㸧

























᪋タ฼⏝ %
௦⾲฼⏝⪅ྡ

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FF

⏕యศᏊࡢᶵ⬟Ⓨ⌧཯ᛂ࡟㛵ࡍࡿ
⌮ㄽⓗ◊✲

༓ⴥ኱㝔
⸆

ᫍ㔝ᛅḟ


 㸭 

ゐ፹ศᏊ⣔࠾ࡼࡧ⏕యศᏊ⣔ࡢ㔞Ꮚ໬Ꮫ࡜཯ᛂືຊᏛ໭኱ゐ፹⛉Ꮫ◊✲ᡤ㛗㇂ᕝ῟ஓ 㸭 

FF

- 8 -

㸦࣓ࣥࣂ࣮ᩘ㸧௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FF

ᣑᙇ࢔ࣥࢧࣥࣈࣝἲ࡟ࡼࡿศᏊࢩ
࣑࣮ࣗࣞࢩࣙࣥ

ྡ኱㝔
⌮

ᒸᮏ♸ᖾ


 㸭 

」ྜ㟁Ꮚ⣔ࡢᵓ㐀ࠊ㟁Ꮚ≧ែࠊ཯ᛂ㐣⛬ࠊ⁐፹࿴ᵓ㐀࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ி኱⚟஭ㅬ୍グᛕ
◊✲ࢭࣥࢱ࣮

ᴬࠉⱱዲ
 㸭 

㔞Ꮚࢲ࢖ࢼ࣑ࢡࢫ࡟ࡼࡿືⓗ≀ᛶ㔞ࡢ⌮ㄽⓗ◊✲

㜰኱㝔
ᇶ♏ᕤ

୰㔝㞞⏤


 㸭 

࢝࢖ࣛࣝศᏊࡀసࡾฟࡍ㟁Ꮚ࢝࢖ࣛࣜࢸ࢕ࡢ⏕ᡂᶵᵓ࡜ሙࡢ㔞Ꮚㄽ࡟ᇶ࡙ࡃᒁᡤ≀⌮㔞࡟ࡼࡿ㔞Ꮚ≀
ᛶࡢ◊✲

ி኱㝔
ᕤ

℩Ἴ኱ᅵ


 㸭 

㧗཯ᛂᛶࡢࢪ࣎ࣛࣥ  ࣭$O࢔ࢽ࢜ࣥࡢᛶ㉁ࡢゎ᫂࠾ࡼࡧ࣓ࢱࣥࡢ&+⤖ྜάᛶ໬࡬ྥࡅࡓᆒ୍⣔ゐ፹タ
ィ

ྡ኱㝔
ᕤ

ᒣୗࠉㄔ


 㸭 

㔠ᒓ⺮ⓑ㉁ࡢ㟁Ꮚᵓ㐀ไᚚ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᗈᓥᕷ኱㝔
᝟ሗ⛉Ꮫ

㮚㔝ࠉඃ


 㸭 

⏕యศᏊࡢᵓ㐀࡜ᶵ⬟࡟㛵ࡍࡿ⌮
ㄽⓗ◊✲

ᗈᓥ኱㝔
⌮

㉥℩ࠉ኱


 㸭 

㔞Ꮚከᡂศ⣔ศᏊ⌮ㄽࢆ⏝࠸ࡓỈ⣲ࢲ࢖ࢼ࣑ࢡࢫ࡜ྠ఩యຠᯝࡢ⌮
ㄽⓗ◊✲

ᶓ὾ᕷ኱㝔
⏕࿨ࢼࣀࢩࢫࢸ࣒

❧ᕝோ඾ 㸭 

」㞧ศᏊ⣔ࡢ໬Ꮫ཯ᛂࢩ࣑࣮ࣗࣞ
ࢩࣙࣥி኱⚟஭ㅬ୍グᛕ
◊✲ࢭࣥࢱ࣮

㕥ᮌࠉ⪽ 㸭 

ᐩỌᆂ௓ 㸭 

FG

FG

FI

FI

FJ

FJ

FK

FL

FL

FL

FN

FN

FP

FP

」㞧ศᏊ⣔࡟࠾ࡅࡿࢸࣛ࣊ࣝࢶᖏ
࠿ࡽ㉥እ㡿ᇦࡢࢫ࣌ࢡࢺࣝゎᯒ⚄ᡞ኱ศᏊࣇ࢛ࢺࢧ࢖࢚ࣥࢫ
◊✲ࢭࣥࢱ࣮

㸦࣓ࣥࣂ࣮ᩘ㸧





















ᐦᗘỗ㛵ᩘἲィ⟬ࡢ᪂ࡓ࡞ᒎ㛤࡜ࢼࣀ⾲㠃࣭⏺㠃ᡂ㛗ᶵᵓࡢゎ᫂ྡ኱ᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒
◊✲ᡤ

ᢲᒣࠉ῟


 㸭 

㔞ᏊຊᏛ 40 ศᏊຊᏛ 00 ἲ࡟ࡼࡿࣁࣟ㓟⬺ࣁࣟࢤࣥ໬㓝⣲ࡢ཯ᛂᶵᵓゎᯒ

㛗὾ࣂ࢖࢜኱
ࣂ࢖࢜ࢧ࢖࢚ࣥࢫ

୰ᮧࠉ༟ 㸭 

㠉᪂ⓗ㔞Ꮚ⛉Ꮫ࡜኱つᶍࢩ࣑࣮ࣗࣞࢩࣙࣥ⛉Ꮫࡢ๰㐀㔞Ꮚ໬Ꮫ◊✲༠఍୰㎷ࠉ༤ 㸭 

⏕యศᏊ」ྜయ⣔ࡢ඲ཎᏊ࣭⢒ど໬ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲⚄ᡞ኱㝔ࢩࢫࢸ࣒᝟ሗ

⏣୰ᡂ඾ 㸭 

≉ᐃΰྜẚ࡛Ⓨ⌧ࡍࡿ≉␗≀ᛶࢆ฼⏝ࡋࡓ᪂ᮦᩱ๰ᡂࡢࡓࡵࡢ➨୍ཎ⌮ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜ᶵᲔ
Ꮫ⩦ࡢ㐃ᦠ

୰ኸ኱
⌮ᕤ

᳃ࠉᐶᩄ


 㸭 

- 9 -











௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FQ

⁐ᾮ⏺㠃ࡢᵓ㐀࡜ᶵ⬟ࡢィ⟬໬Ꮫ

ᮾ໭኱㝔
⌮

᳃⏣᫂ᘯ


 㸭 

᪘㔠ᒓ࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࡢάᛶホ౯࡜ࢩࢡࣟ࣌ࣥࢱࢪ࢚
ࣀࣥ㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࡢ㛤Ⓨ

ᮾ኱㝔
ᕤ

㔝ᓮிᏊ


 㸭 

ⰾ㤶᪘⁐፹࿴ࢡࣛࢫࢱ࣮ࡢගㄏ㉳⁐፹෌㓄ྥࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࢃࡿ⁐፹࿴ᵓ㐀᥈⣴

࠾Ⲕ኱
ᇶᖿ◊✲㝔

ᐑᓮ඘ᙪ


 㸭 

➨୍ཎ⌮཯ᛂࢲ࢖ࢼ࣑ࢡࢫ࡜ඛ㐍ⓗ㟁Ꮚ≧ែ⌮ㄽࡢከゅⓗᒎ㛤

໭኱㝔
⌮

Ṋḟᚭஓ


 㸭 

㉸⌫㠃᥈⣴ἲࢆ⏝࠸ࡓศᏊᵓ㐀ࠊ⤖ᬗᵓ㐀ࡢ᥈⣴

࿴ḷᒣ኱
ࢩࢫࢸ࣒

ᒣ㛛ⱥ㞝


 㸭 

ศᏊືຊᏛཬࡧ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓࢭ࣮ࣝࣟࢫ㛵㐃ศᏊ࠾ࡼࡧ⏕య㧗ศᏊࡢᵓ㐀࡜ᶵ⬟ࡢ◊✲

ᶓ὾ᅜ኱㝔
ᕤ

ୖ⏣୍⩏


 㸭 

㔞Ꮚ໬Ꮫ࡜⤫ィຊᏛ࡟ᇶ࡙ࡃ」㞧
໬Ꮫ⣔ࡢ⌮ㄽⓗ◊✲

ி኱㝔
ᕤ

బ⸨ၨᩥ


 㸭 

❧య㑅ᢥⓗ཯ᛂ࡟࠾ࡅࡿ⁐፹ຠᯝ࡜཯ᛂᶵᵓ࡟㛵ࡍࡿ⌮ㄽ◊✲㧗▱኱㝔⥲ྜே㛫⮬↛⛉Ꮫ㔠㔝኱ຓ 㸭 

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓ࣊ࣟࢼ࣑ࢻ㢮ࡢᢠ┿⳦స⏝࣓࢝ࢽࢬ
࣒ࡢゎ᫂

໭㝣኱
⸆

㰻⸨኱᫂


 㸭 

ᵓ㐀ከ⢾ᮦᩱ࠾ࡼࡧ㛵㐃ࢱࣥࣃࢡ㉁ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ᐑᓮ኱ᕤ‫‮‬஭ᩄᩥ
 㸭 

඲ཎᏊศᏊືຊᏛィ⟬ࡢ㧗ศᏊ◊
✲࡬ࡢᒎ㛤

ᮾ኱㝔
᪂㡿ᇦ๰ᡂ⛉Ꮫᒸᓮࠉ㐍 㸭 

Ỉ⁐ᾮ୰ࡢ㔜㔠ᒓ࢖࢜ࣥࡢάᛶⅣ࡟ᑐࡍࡿ྾╔ᣲືࡢゎᯒᚨᓥ኱㝔♫఍⏘ᴗ⌮ᕤ

ྜྷ⏣ࠉ೺ 㸭 

ከཎᏊศᏊ࠿ࡽ࡞ࡿ⁐㉁ࡢ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࢆṇ☜࡟ồࡵࡿ2=
⌮ㄽࡢ㛤Ⓨ

ឡ፾኱㝔
⌮ᕤ

ᐑ⏣❳ᙪ


 㸭 

ගྜᡂ㓟⣲Ⓨ⏕୰ᚰ&D0Q2ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࠊ㟁Ꮚ࣭ࢫࣆࣥ≧ែ࠾ࡼࡧ཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲㜰኱ࢼࣀࢧ࢖࢚ࣥࢫ
ᩍ⫱◊✲ࢭࣥࢱ࣮

ᒣཱྀࠉ඙ 㸭 

ࣃ࢖ඹᙺ⣔⎔≧໬ྜ≀ࡢྜᡂ◊✲
࡜ග≀ᛶ

໭㔛኱㝔
⌮

㛗㇂ᕝ┿ኈ


 㸭 

㠀ᖹ㠃ᆺࣃ࢖ඹᙺศᏊࡢᵓ㐀࡜≀
ᛶ

኱㜰ᗓ኱㝔
⌮

ὠ␃ᓮ㝧኱


 㸭 

FQ

FR

FU

FW

FW

FY

FY

FZ

FZ

FZ

F[

F\

F]

GD

GE

- 10 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

GF

ࢼࣀ࣮࣭࢝࣎ࣥ࢔࣑ࣀ㓟࣭ࢡࣛࢫࢱ࣮ࡢ཯ᛂືຊᏛࡢ㔞Ꮚ໬Ꮫⓗ◊
✲

㟁㏻኱㝔
᝟ሗ⌮ᕤ

ᒣ໭ెᏹ


 㸭 

࣑࢜ࢩࣥ9,ࡢ཯ᛂࢧ࢖ࢡࣝ඲యࡢ
ືⓗࣛࣥࢻࢫࢣ࣮ࣉ࡟ࡼࡿࢫࢸࢵ
ࣉ㐠ືᶵᵓࡢゎ᫂

ྡ኱㝔
ᕤ

ᑎ⏣ᬛᶞ


 㸭 

ࢱࣥࣃࢡ㉁࡜ศᏊ㞟ྜయࡢศᏊᶵ
⬟ࡢ⌮ㄽィ⟬

ி኱㝔
⌮

ᯘࠉ㔜ᙪ


 㸭 

⺮ⓑ㉁࡟ࡼࡿ'1$ຍỈศゎ࡟࠾ࡅࡿ
⁐፹ࡢᙺ๭

஑ᕤ኱㝔
᝟ሗᕤ

ධబṇᖾ


Ỉࠊịࠊࢡࣛࢫ࣮ࣞࢺࣁ࢖ࢻ࣮ࣞ
ࢺࡢᵓ㐀┦㌿⛣ࡢ⌮ㄽ◊✲

ᒸᒣ኱㝔
⮬↛⛉Ꮫ

ᯇᮏṇ࿴


 㸭 

㔞ᏊศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔
17&KHP࡟ࡼࡿࢼࣀࢧ࢖ࢬศᏊࡢศ
Ꮚᶵ⬟ࡢゎ࣭᫂タィ⌮໬Ꮫ◊✲ᡤ

୰ᔱ㝯ே 㸭 

⏕యศᏊࡢ࣐ࣝࢳࢥࣆ࣮࣐ࣝࢳࢫ
ࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᶓ὾ᕷ኱㝔
⏕࿨་⛉Ꮫ

᳃ḟࠉᆂ


 㸭 

⬺⁐፹࿴ຠᯝࢆ⪃៖ࡋࡓᡭἲ࡟ࡼ
ࡿᢠయ࡜⢾㙐㛫┦஫స⏝ࡢẚ㍑◊
✲

໭㔛኱
୍⯡ᩍ⫱

⬟Ⓩࠉ㤶


 㸭 

㌾;⥺ග⛉Ꮫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᗈᓥ኱㝔
⌮

㧗ᶫࠉಟ


 㸭 

໬Ꮫ཯ᛂࡢ㔞Ꮚࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ி኱ゐ፹࣭㟁ụࡢඖ⣲ᡓ␎◊✲ᣐⅬᒣୗ᫭୍ 㸭 

ศᏊ㌶㐨ィ⟬࡟ࡼࡿ᭷ᶵ཯ᛂ࠾ࡼ
ࡧ᭷ᶵศᏊᵓ㐀ࡢタィ࡜ゎᯒ

ᮾ኱㝔
⸆

኱࿴⏣ᬛᙪ


 㸭 

㑄⛣㔠ᒓ໬ྜ≀࠾ࡼࡧໟ᥋໬ྜ≀ࡢᵓ㐀࣭཯ᛂ࣭ศᏊ㛫┦஫స⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲࠾Ⲕ኱㝔ே㛫ᩥ໬๰ᡂ⛉Ꮫ㮚㔝ᬒᏊ 㸭 

ᾮయ࣭⏕యศᏊ࠾ࡼࡧ㛵㐃ศᏊ⣔ࡢᵓ㐀࣭ࢲ࢖ࢼ࣑ࢡࢫ࣭ศᏊ㛫┦஫స⏝࡜᣺ືࢫ࣌ࢡࢺࣝ

㟼ᒸ኱
ᕤ

㫽ᒃࠉ⫕


 㸭 

ศᏊ㞟ྜయࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ㸳

໭㔛኱
⌮

⡿⏣ⱱ㝯


 㸭 

ࢼࣀ࣐ࢸࣜ࢔ࣝཬࡧ⏕యศᏊࡢᶵ
⬟࣭≀ᛶ࣭཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽⓗ
◊✲

᪩኱
ඛ㐍⌮ᕤ

୰஭ᾈᕭ


 㸭 

ࢱࣥࣃࢡ㉁㛫┦஫స⏝ࡢ⢒ど໬ࣔࢹࣝࡢ㛤Ⓨ࡜㟁Ꮚఏ㐩⣔࡬ࡢᛂ⏝

㔠ἑ኱
⌮ᕤ

ᕝ୍ཱྀ᭸


 㸭 

GJ

GK

GK

GL

GM

GN

GV

GX

GZ

G[

HN

HP

HP

HS

HT

- 11 -

㸦࣓ࣥࣂ࣮ᩘ㸧






 㸭 


























௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

HV

ゐ፹ࢆ⏝࠸ࡓ໬Ꮫ཯ᛂᶵᵓࡢ⌮ㄽ
ⓗゎ᫂

Ⲉᇛ኱
⌮

᳃ࠉ⪷἞


ᶵ⬟ᛶ᭷ᶵᮦᩱࡢ㟁Ꮚ≀ᛶゎᯒ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ி኱㝔
ᕤ

ఀ⸨ᙲᾈ


 㸭 

ከඖ⣲ࢡࣛࢫࢱ࣮ࡢ㉥እゎ㞳ศගࡢࡓࡵࡢ㉥እࢫ࣌ࢡࢺࣝࡢண

ᮾ኱㝔
⥲ྜᩥ໬

ᕤ⸨ࠉ⪽


 㸭 

㔜ཎᏊࢆྵࡴ໬ྜ≀ࡢᇶᗏ࣭ບ㉳㟁Ꮚ≧ែ࡜ศᏊ≀ᛶ࡟㛵ࡍࡿ㔞Ꮚ
໬Ꮫィ⟬

ᮾி㒔኱㝔
⌮

Ἴ⏣㞞ᙪ


 㸭 

⏕య㉸ศᏊࡢ❧యᵓ㐀ኚ໬࡜ᶵ⬟

ᮾᕤ኱
⏕࿨⌮ᕤ

໭ᑿᙲᮁ


 㸭 

➨୍ཎ⌮ィ⟬࠾ࡼࡧ࣐ࢸࣜ࢔ࣝࢬ
࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿࢼࣀᵓ
㐀࠾ࡼࡧཎᏊᒙ≀㉁ࡢᙧᡂ࡜ᶵ⬟Ⓨ⌧࡟㛵ࡍࡿ◊✲

୕㔜኱㝔
ᕤ

⛅ᒣࠉ஽


 㸭 ࢡࣛࢫࢱ࣮࢖࢜ࣥࡢᗄఱᵓ㐀ࠊ཯ᛂᛶ࠾ࡼࡧ⾪✺᩿㠃✚ࡢィ⟬

ᮾ໭኱㝔
⌮

኱ୗ៞ḟ㑻


 㸭 

ࢱࣥࣃࢡ㉁ࡢᵓ㐀࡜ᶵ⬟ࡢ㛵㐃ᛶ

ி㒔ᗓ኱㝔
⏕࿨⎔ቃ

ࣜࣥࢺࢗࣝ࢜ࢺ
ṇ⨾ศᏊ㐠ື࡟㉳ᅉࡍࡿືⓗศᏊ㛫┦஫స⏝ࢆά⏝ࡋࡓᾮᬗࡢᶵ⬟㛤Ⓨ

㜰኱㝔
ᇶ♏ᕤ

ෆ⏣ᖾ᫂


 㸭 

ศᏊᛶᑟ㟁࣭☢ᛶᮦᩱ࡟㛵ࡍࡿ⌮
ㄽⓗ◊✲

ி኱㝔
⌮

୰㔝⩏᫂


 㸭 

࢞ࣛࢫ⣔࡟࠾ࡅࡿ㐜࠸ࢲ࢖ࢼ࣑ࢡ
ࢫࡢ⌮ㄽ࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲

㜰኱㝔
ᇶ♏ᕤ

㔠ࠉ㗰


 㸭 

㧗ศᏊᵓ㐀ኚ໬࡟࠾ࡅࡿỈࡢᙳ㡪ಙᕞ኱ᅜ㝿ࣇ࢓࢖ࣂ࣮ᕤᏛ
◊✲ᡤ

ᮃ᭶ᘓ∞


 㸭 

ཎᏊ᰾ࡢ㔞Ꮚຠᯝࢆ⪃៖ࡋࡓከᡂ
ศ⣔⌮ㄽ࡟ࡼࡿ໬Ꮫ཯ᛂゎᯒἲࡢᣑᙇ࡜ᛂ⏝ィ⟬

ᒱ㜧኱
ᕤ

Ᏹ⏣ᕝኴ㑻


 㸭 

㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜ࡑࡢ཯ᛂ
ᛶ

ᮾ኱㝔
⌮

ᑠᏳ႐୍㑻


 㸭 

➨୍ཎ⌮ィ⟬ᡭἲ࡟ᇶ࡙ࡃࢼࣀ㟁Ꮚᮦᩱࡢࣉࣟࢭࢫᶵ⬟ไᚚ࡟㛵ࡍ
ࡿ◊✲

ᓥ᰿኱
⥲ྜ⌮ᕤ

ᙳᓥ༤அ


 㸭 

➨୍ཎ⌮ศᏊືຊᏛࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ࡟ࡼࡿ+&OỈ⁐ᾮ⾲㠃࡛ࡢ
=XQGHO(LJHQᵓ㐀◊✲

ᐩᒣ኱
⌮ᕤ

▼ᒣ㐩ஓ


 㸭 

HW

HY

HZ

H]

H]

IE

IF

IF

IF

IF

IG

IG

IG

IG

IJ

- 12 -

㸦࣓ࣥࣂ࣮ᩘ㸧 㸭 













 㸭 


















௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IJ

ග㉳㟁ຊࢹࣂ࢖ࢫࡢ㟁Ⲵ⛣ື࣓࢝
ࢽࢬ࣒

᪥ᮏዪᏊ኱
⌮

ᮧᒸࠉᱻ


 㸭 

᭷ᶵศᏊ༙ᑟయ⭷୰ࡢ✚ᒙᵓ㐀Ḟ㝗ࡢ㟁Ꮚ≀ᛶࡢ◊✲

༓ⴥ኱㝔
⌮

୰ᒣ㝯ྐ


 㸭 

཯ᛂ⤒㊰⮬ື᥈⣴ࢆ⏝࠸ࡿゐ፹࣭Ⓨගᮦᩱࡢ⌮ㄽⓗ◊✲

៞᠕኱
⌮ᕤ

⏿୰⨾✑


 㸭 

࢖࢜ࣥᛶᾮయ࡟࠾ࡅࡿ࢖࢜ࣥఏᑟ
⋡ࠊෆ㒊⛣ືᗘࠊ࠾ࡼࡧ+DYHQẚࡢໟᣓⓗ◊✲㸯㸸࢖࢜ࣥ㉁㔞౫Ꮡᛶ

᪂₲኱
⌮

኱㫽⠊࿴


 㸭 

࣎࢘ࣝᆺඹᙺ໬ྜ≀ࡢ≀ᛶㄪᰝࠊ࠾ࡼࡧ㔠ᒓࢡࣛࢫࢱ࣮ゐ፹ࡢάᛶ
ホ౯◊✲

㜰኱㝔
ᕤ

Ḉ஭ⱥ༤


 㸭 

ࢪ࣮ࣚࢻࣅ࢔࣮ࣜࣝࢆ⏝࠸ࡓ$3(;཯ᛂࡢ཯ᛂᶵᵓゎ᫂࡜ࢼࣀ࣮࢝࣎
ࣥศᏊࡢᵓ㐀≀ᛶゎ᫂◊✲

ྡ኱㝔
⌮

ఀ⸨ⱥே


 㸭 

7KHRUHWLFDOVWXG\WRLPSURYH,U2[W\SHHOHFWURGHVIRUZDWHU
R[LGDWLRQᮾᕤ኱⌮-XKDV]*HUJHO\ 㸭 

ࢳ࢚࣮࢜ࢸࣝࢆ࢔࣮ࣥ࢝࡜ࡋ࡚ᣢ
ࡘ᭷ᶵ㔠ᒓศᏊ࣡࢖࣮ࣖࡢ㛤Ⓨᮾᕤ኱⛉Ꮫᢏ⾡๰ᡂ◊✲㝔⏣୰⿱ஓ 㸭 

ከᶵ⬟㓄఩Ꮚࢆࡶࡘ㔠ᒓ㘒యࡢᵓ㐀࠾ࡼࡧ཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽ◊✲⌮໬Ꮫ◊✲ᡤ

ὸᏊኊ⨾ 㸭 

ィ⟬ศᏊศගᏛ㸸ศᏊࡢᵓ㐀࠾ࡼࡧ཯ᛂ࡟㛵ࡍࡿィ⟬໬Ꮫ

࠾Ⲕ኱
⌮

ᖹ㔝ᜏኵ


 㸭 

㉁㔞ศᯒἲ࡟ࡼࡿ⏕యศᏊࡢẼ┦ศゎ㐣⛬࡟㛵ࡍࡿ◊✲

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

ὸᕝ኱ᶞ


 㸭 

ᶵᲔᏛ⩦࡟ࡼࡿ⁐፹࿴ࣔࢹࣝࡢᨵ
ၿ࡜㓟ゎ㞳ᐃᩘ࡬ࡢᛂ⏝

⟃Ἴ኱㝔
ᩘ⌮≀㉁

ᯇ஭ࠉ஽


 㸭 

ᾮయࡢ⤫ィຊᏛ⌮ㄽ࡟ࡼࡿ⏕యศᏊᶵ⬟ࡢゎᯒ

஑ᕞ኱㝔
⌮

ྜྷ⏣⣖⏕


 㸭 ᪂つȧ㟁Ꮚ⣔࢖࢜ࣥࡢタィ࣭ྜᡂࢆᇶ㍈࡜ࡋࡓ㉸ศᏊ㞟ྜయࡢ๰〇

❧࿨㤋኱
⏕࿨⛉Ꮫ

๓⏣኱ග


 㸭 

ࢱࣥࣃࢡ㉁ࡢᶵ⬟ࢆไᚚࡍࡿ࣌ࣉ
ࢳࢻ࣭ࢱࣥࣃࢡ㉁ࡢྜ⌮タィ

ᮾ኱㝔
ᕤ

᳃ᮏ῟ᖹ


 㸭 

᰾ኚ᥮⁐⼥ሷࢱ࣮ࢤࢵࢺ㛤Ⓨ࡟ྥࡅࡓ')7ศᏊືຊᏛィ⟬࡟ࡼࡿ⇕ຊ
Ꮫ㔞ホ౯

ᮾ໭኱㝔
ᕤ

᏷ᡞ༤⣖


 㸭 

IJ

IJ

IJ

IK

IK

IK

IL

IL

IL

IM

IM

IN

IN

IP

IP

- 13 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IQ

ᴟప Ẽ┦⣸እศග࡜)UDQFN&RQGRQࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ࣍
ࢫࢺѸࢤࢫࢺ໬ྜ≀ࡢໟ᥋ᵓ㐀ࡢ◊
✲

ᗈᓥ኱㝔
ඛ㐍

஭ཱྀెဢ


 㸭 

ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ㕲㘒య࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

໭㔛኱
⌮

⚄㇂ᫀᏹ


 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿගྜᡂỈศゎ཯ᛂࡢศᏊᶵᵓࡢゎ᫂

ྡ኱㝔
⌮

㔝ཱྀࠉᕦ


 㸭 

3G ,, ஧᰾㘒యࢆ⏝࠸ࡿගゐ፹ⓗ&+ሷ⣲໬཯ᛂࡢ㛤Ⓨᮾ኱⏕⏘ᢏ⾡◊✲ᡤᮧ⏣ࠉ្ 㸭 

」㞧࡛ከᵝ࡞ศᏊᵓ㐀࡜㟁Ꮚ≧ែ࠾ࡼࡧ໬Ꮫ཯ᛂ࡟㛵ࡍࡿ◊✲ி኱ゐ፹࣭㟁ụࡢඖ⣲ᡓ␎◊✲ᣐⅬ⚟⏣Ⰻ୍ 㸭 

⌮ㄽィ⟬࡞ࡽࡧ࡟ᶵᲔᏛ⩦ࢆ฼⏝ࡋࡓ᭷ᶵ༙ᑟయࠊゐ፹㛤Ⓨ

┦ᶍ୰ኸ
໬Ꮫ◊✲ᡤ

ᕭୖᖾ୍㑻


 㸭 

ィ⟬໬Ꮫࢆ฼⏝ࡋࡓ᭷ᶵ໬Ꮫ཯ᛂ
ᶵᵓࡢゎ᫂

எ༲◊✲ᡤ

㯮ෆᐶ᫂


 㸭 

ィ⟬໬Ꮫࢆ⏝࠸ࡓゐ፹ࡢ⌮ㄽタィ࠾ࡼࡧ᭷ᶵⓎගᮦᩱࡢ≀ᛶゎᯒ

໭኱㝔
ᕤ

ఀ⸨ࠉ⫕


 㸭 

᭤ࡆኚᙧ࡟㛵ࡍࡿᾮᬗᏳᐃᛶࡢศ
ᏊືຊᏛ࡟ࡼࡿ◊✲ᮾி㎰ᕤ኱㝔ᕤᆏᮏ㐨᫛ 㸭 

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿᢠయ
タィ

ᮾ኱㝔
ᕤ

㯮⏣኱♸


 㸭 

཯ᛂ⤒㊰⮬ື᥈⣴ἲࡢ㛤Ⓨ࡜ᛂ⏝

໭኱㝔
⌮

๓⏣ࠉ⌮


 㸭 

㑄⛣㔠ᒓゐ፹࡟ࡼࡿᑠศᏊάᛶ໬
ࡢ཯ᛂᶵᵓ࡟ࡘ࠸࡚ࡢ')7◊✲

஑኱,t&1(5ఀໃᕝ⨾✑ 㸭 ᶵᲔᏛ⩦ࢆ⏝࠸ࡓప⇕ఏᑟ⋡࣍࢖ࢫ࣮ࣛᆺ⇕㟁ኚ᥮ᮦᩱࡢ᥈⣴

ྡᕤ኱㝔
ᕤ

ᐑᓮ⚽ಇ


 㸭 

ᐇ㦂࡜ィ⟬࡟ࡼࡿ᭷ᶵ཯ᛂᶵᵓゎ
ᯒ

ᮾ኱㝔
⸆

⁪⏣ࠉⰋ


 㸭 

㟷Ⰽගཷᐜయ⺮ⓑ㉁࡟࠾ࡅࡿ⣸እ⥺ᦆയ'1$ࡢಟ᚟ᶵᵓࡢゎ᫂⌮໬Ꮫ◊✲ᡤ

బ⸨❳㤿 㸭 

0XOWLVFDOHPRGHOLQJRI
LQWHUVWHOODUUDGLFDOVSHFLHVRQZDWHULFH

໭኱
⛉Ꮫ◊✲ᡤ

IQ

IQ

IR

IR

IR

IS

IT

IU

IU

IU

IU

IU

IV

IV

IV

ప

- 14 -

㸦࣓ࣥࣂ࣮ᩘ㸧:0&
6DPHHUD































 㸭 
௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IW

ࢣ࢖㓟⣔⁐⼥యࡼࡾ⏕ࡎࡿ&D6L2
⤖ᬗ࡟࠾ࡅࡿ>6L2@㘒యᵓ㐀࡬ཬࡰࡍᅛ⁐ඖ⣲ࡢᙳ㡪

㜰኱㝔
ᕤ

㕥ᮌ㈼⣖


 㸭 

ศᏊືຊᏛィ⟬࡟ࡼࡿ㧗᥋╔⺮ⓑ㉁ࡢỈ୰᥋╔࣓࢝ࢽࢬ࣒ࡢゎ᫂

ྡ኱㝔
ᕤ

㕥ᮌ῟ᕧ


 㸭 

⏕≀ศᏊ⣔ࡢ㟁Ꮚᵓ㐀ཬࡧ཯ᛂᛶ
ࡢゎ᫂࡟ྥࡅࡓィ⟬໬Ꮫⓗゎᯒྡ኱ࢺࣛࣥࢫࣇ࢛࣮࣐ࢸ࢕ࣈ
⏕࿨ศᏊ◊✲ᡤᰗ஭ࠉẎ 㸭 

ศᏊືຊᏛἲࢆ⏝࠸ࡓ⏕యᕧ኱ศᏊࡢᣑᩓಀᩘࡢィ⟬㸸ኚᛶࡢຠᯝ

஑኱㝔
⌮

⛅ᒣࠉⰋ


 㸭 

⏕య⣔ࡸ⾲㠃⣔ࡢจ⦰⣔ࡢ➨୍ཎ⌮ィ⟬࡟ࡼࡿ㟁Ꮚ≧ែ࠿ࡽࡢᶵ⬟࣓࢝ࢽࢬ࣒ࡢゎ᫂⌮໬Ꮫ◊✲ᡤ

୰ᮧ᣺୍㑻 㸭 

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓᅛయ࣭ᾮయ⏺㠃࡟࠾ࡅࡿศᏊ
ᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫ

Ⲉᇛ኱
ᕤ

ᇛሯ㐩ஓ


 㸭 

ศᏊ㔠ᒓ㘒యࡢ⢭ᐦไᚚ࡟ᇶ࡙ࡃ
㓄ิ࣭✵㛫ࡢ๰ฟ

ᮾ໭኱
⌮

㛗⏣ᾈ୍


 㸭 ᪂つྜᡂ཯ᛂࡢ㛤Ⓨࢆᚿྥࡋࡓ⌮ㄽ໬Ꮫⓗ◊✲

ᮾ㎰኱
⏕࿨⛉Ꮫ

ᩧ⸨❳⏨


 㸭 

㟼㟁ሙ୰࡟࠾ࡅࡿศᏊ࢖࢜ࣥࡢ㍺㏦ࢲ࢖ࢼ࣑ࢡࢫ

㔠ἑ኱
⮬↛⛉Ꮫ

⋢⯓▱ஓ


 㸭 

ࢼࣀ࣮࢝࣎ࣥ࡜᭷ᶵ≀ࢆ⏝࠸ࡓᶵ⬟ᮦᩱࡢィ⟬໬Ꮫࢩ࣑࣮ࣗࣞࢩࣙ
ࣥ㧗ᗘ᝟ሗ⛉Ꮫᢏ⾡
◊✲ᶵᵓ

ᡭᓥṇ࿃


 㸭 

⭷㏱㐣࣌ࣉࢳࢻ࡟ᑐࡍࡿ⣽⬊⭷⾲㠃࡬ࡢ⛣ື㐣⛬࡟ᑐࡍࡿ⌮ㄽⓗ◊✲⟃Ἴ኱ィ⟬⛉Ꮫ◊✲
ࢭࣥࢱ࣮

す⃝ᏹ᫭


 㸭 

ຍỈศゎ㓝⣲ࢆ⏝࠸ࡿ㏿ᗘㄽⓗගᏛศ๭ࡢᶵᵓゎ᫂࡜ྜᡂ໬Ꮫⓗᛂ
⏝

㜰኱㝔
⸆

㉥஭࿘ྖ


 㸭 

Ẽ┦ศᏊࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜ศᏊ㛫┦஫స⏝ࡢ⌮ㄽⓗゎᯒ࡜࣮ࣞࢨ࣮ศග◊✲

ᮾ໭኱㝔
⌮

ᯇ⏣Ḡஅ


 㸭 

㧗ᴟᛶᾮᬗ໬ྜ≀ࡢศᏊືຊᏛࢩ
࣑࣮ࣗࣞࢩࣙࣥ㸰஑኱ඛᑟ≀㉁໬Ꮫ◊✲ᡤዟᮧὈᚿ 㸭 

6+ࢻ࣓࢖ࣥࢆ༢≉␗ⓗ࡟άᛶ໬ࡍ
ࡿࣔࢳ࣮ࣇࡢ㛤Ⓨ

ᮾ኱㝔
ᕤ

ᱵ᰿㍤᮶ே


 㸭 

ᕤᴗཎᩱࢆ฼⏝ࡋࡓ⢭ᐦ໬Ꮫኚ᥮
཯ᛂࡢ㛤Ⓨ

㜰኱
ᕤ

⏕㉺ᑓ௓


 㸭 

IW

IX

IX

IX

IX

IX

IY

IY

IZ

IZ

IZ

I[

I[

I[

I[

- 15 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































௦⾲฼⏝⪅ྡⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

I\

⏕య࣭㧗ศᏊ⮬ᕫ㞟ྜ⣔ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ

ྡ኱㝔
ᕤ

⠛⏣ࠉ΅


 㸭 

ᶵ⬟ᛶศᏊ㞟ྜయࡢศᏊືຊᏛ◊✲㸸ࢼࣀ⏺㠃࡟࠾ࡅࡿᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࡢゎᯒරᗜ┴኱㝔ࢩ࣑࣮ࣗࣞࢩࣙࣥ

㮖ὠோᚿ 㸭 

ேᕤගྜᡂࡢࡓࡵࡢ⏺㠃ࡢ◊✲࡜ᙉ┦㛵ࢯࣝࣂ࣮ࡢ᳨ド

⚄ᡞ኱
⛉Ꮫᢏ⾡
࢖ࣀ࣮࣋ࢩࣙࣥኳ⬟⢭୍㑻 㸭 

ᐇ㦂࡜ィ⟬ࡢ⼥ྜ࡟ࡼࡿẼ┦⏕యศᏊࡢ⢭ᐦᵓ㐀Ỵᐃ㸸ศᏊㄆ㆑ᶵ
ᵓࡢゎ᫂࡟ྥࡅ࡚

ᮾᕤ኱⛉Ꮫᢏ⾡๰ᡂ◊✲㝔ᖹ⏣ᆂ♸ 㸭 

࢖࢜ࣥᛶⰍ⣲⤖ᬗࢆྵࡴ᪂つȧ㟁Ꮚ⣔ࡢྜᡂ࡜㓄ิไᚚᒣᙧ኱㝔᭷ᶵᮦᩱࢩࢫࢸ࣒

ᒣ㛛㝠ᖹ 㸭 

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡿ㧗ศᏊᾮᬗ࠾ࡼࡧࣔࢹࣝᾮᬗ໬
ྜ≀ࡢ⇕ఏᑟ≉ᛶゎᯒ

ᮾᕤ኱
≀㉁⌮ᕤ

ྂᒇ⚽ᓠ


 㸭 

࣐࢝ࣝࣥ ࡟࠾ࡅࡿ࢟ࣕࣅࢸ࣮
ࢩࣙࣥࡢศᏊືຊᏛィ⟬

ᮾ኱
≀ᛶ◊✲ᡤ

㔝ཱྀ༤ྖ


 㸭 ᚤどⓗᵓ㐀࠿ࡽ⪃࠼ࡿࢱࣥࣃࢡ㉁ࡢሷᯒ࣭⁐ゎ

஑⏘኱
⌮ᕤ

ᮎᯇᏳ⏤⨾


✀ࠎࡢศᏊࡢཎᏊ㛫ຊ㢧ᚤ㙾ീࡢ
⌮ㄽィ⟬

㔠ἑ኱
ࢼࣀ⏕࿨⛉Ꮫ

Ⅳ❤ாྖ 㸭 

㍈ᛶ࢟ࣛࣝ࡞ⓎගⰍ⣲ࡢບ㉳≧ែ
ᵓ㐀ࡢゎ᫂

ᒸᒣ኱㝔
⮬↛⛉Ꮫ

㧗▼࿴ே


 㸭 

㉸▷࣮ࣞࢨ࣮ࣃࣝࢫࢆ⏝࠸ࡓࢼࣀศᏊࡢ཯ᛂືຊᏛ࢖࣓࣮ࢪࣥࢢ⌮ㄽ⌮໬Ꮫ◊✲ᡤ

ᒣᓮࠉ㤾 㸭 

6WUXFWXUDOPHFKDQLVPRI7FHOODFWLYDWLRQ㜰኱ᚤ⏕≀⑓◊✲ᡤ)ORULV-DQ
YDQ(HUGHQࢺࣜࢳ࣒࣮࢘࣋ࢱᔂቯࡢ⏕య㧗ศᏊ࡬ࡢᙳ㡪᰾⼥ྜ⛉Ꮫ◊✲ᡤ࣊ࣜ࢝ࣝ◊✲㒊୰ᮧᾈ❶ 㸭 

㔠ᒓ᭷ᶵᵓ㐀య࡟ࡼࡿỈྠ఩యศᏊㄆ㆑ಙᕞ኱ඛ㗦ᮦᩱ◊✲ᡤ⏣୰⚽ᶞ 㸭 

ᣑᙇ࢔ࣥࢧࣥࣈࣝἲࢆ⏝࠸ࡓ⢾㙐ࢡࣛࢫࢱࡢ❧యᵓ㐀ண་⸆ᇶ┙◊✲ᡤ๰⸆ࢹࢨ࢖ࣥ
◊✲ࢭࣥࢱ࣮

ᮤࠉ⚽ᰤ 㸭 

ࢩࣗ࢘ࢻ࢔ࢬࣜࣥ0HWኚ␗యࡢ
4000ィ⟬

Ⲉᇛ኱
⌮ᕤ

ᒣཱྀᓧⱥ


 㸭 

I\

I\

I\

I\

I\

I]

I]

I]

I]

I]

I]

I]

I]

JD

JE

- 16 -

㸦࣓ࣥࣂ࣮ᩘ㸧














 㸭 







 㸭 










ᡤෆ
ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

DD

จ⦰⣔࡟࠾ࡅࡿ⦆࿴࠾ࡼࡧ཯ᛂࢲ
࢖ࢼ࣑ࢡࢫࡢ⌮ㄽ◊✲⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ」㞧⣔ࡢ㔞Ꮚ≧ែ⌮ㄽࡢ㛤Ⓨ࡜୙ᆒ୍⣔ゐ፹࠾ࡼࡧගᶵ⬟ࢩࢫࢸ࣒
⣔࡬ࡢᛂ⏝

DG

DG

DI

DI

DI

DJ

DJ

DJ

DK

DK

DK

DK

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ᩧ⸨┿ྖ 㸭 

ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮Ụཎṇ༤ 㸭 

ࢱࣥࣃࢡ㉁จ㞟ࡢศᏊࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ

⏕࿨๰ᡂ
᥈✲ࢭࣥࢱ࣮

ዟᮧஂኈ 㸭 

ᰂᵓ㐀ࢆᣢࡘ࣐ࣝࢳࢻ࣓࢖ࣥࢱࣥ
ࣃࢡ㉁ࡢᵓ㐀✵㛫᥈ᰝࡢࡓࡵࡢศ
Ꮚࢩ࣑࣮ࣗࣞࢩࣙࣥ

⏕࿨๰ᡂ᥈✲ࢭࣥࢱ࣮

ຍ⸨᫭୍ 㸭 

ศᏊືຊᏛィ⟬࡜㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿᾮయࡢศᏊ㛫┦஫స⏝ࡢ◊✲

ගศᏊ⛉Ꮫ

㛗ᆏᑗᡂ


 㸭 

ィ⟬ᶵ࠾ࡼࡧ⏕໬Ꮫᐇ㦂࡟ࡼࡿࢱ
ࣥࣃࢡ㉁ศᏊࢹࢨ࢖ࣥ

⏕࿨๰ᡂ᥈✲ࢭࣥࢱ࣮

ྂ㈡ಙᗣ
 㸭 

ᫍ㛫✵㛫࡟࠾ࡅࡿ⎔≧ศᏊࡢ⏕ᡂ
⤒㊰᥈⣴

࢔ࢫࢺࣟ
ࣂ࢖࢜ࣟࢪ࣮
ࢭࣥࢱ࣮

ᑠᯇࠉຬ


 㸭 

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ࢖࢜
ࣥᾮయࡢ◊✲⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ▼⏣ᖸᇛ 㸭 

ศᏊ⣔࡟࠾ࡅࡿ☢ᛶ࠾ࡼࡧࣇ࢛ࣀ
ࣥ≀ᛶࡢ➨୍ཎ⌮ィ⟬⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ༡㇂ⱥ⨾ 㸭 

㟁Ꮚ≧ែィ⟬࡟ࡶ࡜࡙ࡃపḟඖ㛤ẆศᏊ⣔≀㉁ࡢᵓ㐀≀ᛶ┦㛵ࡢゎ ⏕࿨࣭㘒యศᏊ⛉Ꮫ
᫂

ⲡᮏဴ㑻


 㸭 

኱つᶍ*:%6(ἲ࡟ࡼࡿ㠀ࣇ࣮ࣛࣞࣥ㟁Ꮚ࢔ࢡࢭࣉࢱ࣮ኴ㝧㟁ụࡢ⏺
㠃㟁Ⲵ⛣ື≧ែࡢゎᯒ⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ⸨⏣㈗ᩄ
ࢺ࣏ࣟࢪ࢝ࣝȧඹᙺศᏊࡢᵓ㐀࡜≀ᛶ⏕࿨࣭㘒యศᏊ⛉Ꮫ㑄⛣㔠ᒓ㘒యゐ፹ࢆ⏝࠸ࡿ᭷ᶵ཯
ᛂࡢ཯ᛂᶵᵓ◊✲ගศᏊ⛉Ꮫ

- 17 -

℩ᕝὈ▱

㧗㇂ࠉග





















 㸭 
 㸭 
 㸭 
ࠑᇶ♏⏕≀Ꮫࠒ᪋タ฼⏝ %
ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

TF

ᚤᑠ⟶ࡢࢩ࣮࣒㡿ᇦ࡟࠾ࡅࡿᵓ㐀㞟ᅋࡢศᏊືຊᏛィ⟬ゎᯒಙᕞ኱㎰ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

RD

῝ᒙᏛ⩦࡟ࡼࡿࣄࢺࡢ▱ぬ࢔ࣝࢦࣜࢬ࣒ࡢ᥈ồ

⚄⤒⏕⌮Ꮫ◊✲ᐊ௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧ᱵ⃝බ஧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧 㸭 ᡤෆ௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ώ㎶ⱥ἞


Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧 㸭 
ࠑ⏕⌮Ꮫࠒ
ᡤෆࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

LD

ḟඖ05,࡟ࡼࡿ⬻ࡢᶵ⬟ཬࡧᵓ㐀
ゎᯒ

ᚰ⌮⏕⌮Ꮫ

LD

ᶵᲔᏛ⩦ࢆ⏝࠸ࡓᶵ⬟ⓗ05,ࢹ࣮ࢱ⏕యᶵ⬟᝟ሗゎᯒᐊゎᯒ

- 18 -

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧⚟Ọ㞞႐ 㸭 ㏆ῧ῟୍
 㸭 





 

/
 Dynamic Structures of Biological Molecules Revealed by Spectroscopy,
Quantum Chemical Calculations, and Molecular Dynamics Simulations¡Ó ×h¿¥ ±¹ÚTËrtªztÑÛ1²´°¯[w]sb!]sÏ']skÎ«p*b]XRÁ¯+HCM]X'Íqje]X!$$]saÏÄW-,
1Ì

{r]s

Ø.g+%

oiÃ£b4B19J!]s2kÎ«p']sÏÄÒ!w!!5M>1ÌÅµct¯.³¯f*Y,²´.À



¬U]s

yÊ]s5M>b¯)

~b4B19JÄ

²´Åµ
²´!PXgw5M>1Ì4B19JNMR 4B19J½¶5M>1Ì.yÊ

HCM4B19J'HCMXtÄ]sb_tÅµÔsctÅµ.V­Åµct¯.­]sb_tÅµ! Amber16 .­·Ï.^Ï3DFKN3GM.À]sb_tÅµ),4;7A3G79.^ÏÑS.x}ÖªÉÚDFTÛnÔsctÚQMÛÅµf*k*5M>1ÌÑ].]s_tÚMMÛ¯»À4B19J

ÔsctÅµ! Gaussian16 .­3

Åµ.À,) QM/MM Åµ.

²´


2JNA!©¼Õ®

ZÙHCM]XÂº'HCMXt

ÚROAÛ]XÂºÕ®.À

$$¬UÖÐÇ#­+|}!Õ«89H@LNJÚ?IMÛ.®½l&3/<=18I01LE'K6;NJ.®½l&¬§mL:A3M]Xt(+ÏÄ.À$3/<=18I01LE RcaE !·Ï.)¤¢Ï+`Q£.]sb_tÅµ(*À$ NMR 4B19J.Ä+®½l

L9Mc¨)®Á+

4("ªÉÅµ



+



,)

!OÆ

(A

d¾É$!¸È®Á\¦v¹$!QuNagae, T., Unno, M., Koizumi, T., Miyanoiri, Y., Fujisawa, T., Masui, K., Kamo, T., Wada, K., Eki, T., Ito, Y.,

Hirose, Y., Mishima, M. Proc. Natl. Acad. Sci. USA 118, e2024583118 (2021)
Nakamizo, Y., Fujisawa, T., Kikukawa, T., Okamura, A., Baba, H., Unno, M. Phys. Chem. Chem. Phys. 23,
2072-2079 (2021)
Matsuo, J., Kikukawa, T., Fujisawa, T., Hoff, W. D., Unno, M. J. Phys. Chem. Lett. 11, 8579-8584 (2020)
Fujisawa, T., Unno, M. In Molecular and Laser Spectroscopy: Advances and Applications: Volume 2; Gupta, V. P.
& Ozaki, Y. Eds.; Elsevier Inc.; pp 41-82 (2020)- 19 -

Ў‫܇‬ϋấợỎЎ‫᧓܇‬ᩓ‫܇‬ᆆѣể҄‫ܖ‬Ӓࣖೞನỉᄂᆮᴾᵧᶌᶒᶐᵿᴾ ᴾ ᵿᶌᶂᴾᵧᶌᶒᶃᶐᵋᵫᶍᶊᶃᶁᶓᶊᵿᶐᴾ ᾒᾷᾰ῁ᾶᾴᴾ ᵲᶐᵿᶌᶑᶄᶃᶐᴾᵿᶌᶂᴾᵫᶃᶁᶆᵿᶌᶇᶑᶋᴾᶍᶄᴾ
ᵡᶆᶃᶋᶇᶁᵿᶊᴾ ᵰᶃᵿᶁᶒᶇᶍᶌᴾ ᴾ ᴾ     ‫⏣ۑ‬௰஧ᮁ 㸦⚄ዉᕝ኱Ꮫ ⥲ྜ⌮Ꮫ◊✲ᡤ㸧

1㸬◊✲┠ⓗࠊෆᐜ

ࢢࣜࢽ࣮ࣖ཯ᛂ࡞࡝㟁Ꮚ⛣ືࢆక࠺໬Ꮫ཯ᛂࡢ࣓࢝ࢽࢬ࣒ ໬Ꮫ཯ᛂࡢึᮇẁ㝵࡛ࠊ㟁Ꮚ⛣ືࢆక࠺཯ᛂ࡛ࡣࠊࣛࢪ࢝ࣝ≧ែࢆ⤒⏤ࡍࡿሙྜ࡜ࠊࣛࢪ࡛࢝ࣝ࡞ࡃ
㟁Ꮚᑐࡀ⛣ືࡋ࡚཯ᛂࡀ㐍⾜ࡍࡿሙྜ࡜࠶ࡾࠊ཯ᛂ୰㛫యࡢᵓ㐀ࡣ ࡑࢀࡒࢀ࡟
ࡘ࠸࡚ࠊ␗࡞ࡗ࡚࠸ࡿࠋᐇ㦂౛࡜ࡋ࡚ࡣࠊከࡃࡢ౛ࡀሗ࿌ࡉࢀ࡚࠸ࡿࡀࠊ࡝࠺࠸࠺
᮲௳࡛ࠊ࡝ࡕࡽࡢ⤒㊰ࢆ࡜ࡿࡢ࠿࡟ࡘ࠸࡚ࠊࡼࡃศ࠿ࡗ࡚࠸࡞࠿ࡗࡓࠋࡑࢀࡒࢀࡢ
ሙྜ࡟ࡘ࠸࡚ࠊ཯ᛂ୰㛫యࡢᵓ㐀ࢆศᏊ㌶㐨ィ⟬ࢆࡶ࡜࡟ࡋ࡚ࠊ᫂ࡽ࠿࡟ࡋ࡚཯
ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋ࡚ࠊᐇ㦂࡛ሗ࿌ࡉࢀ࡚࠸ࡿ཯ᛂ㏿ᗘࡢ್࡜ẚ㍑ࡋ
࡚ࠊ཯ᛂ࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ ࢢࣜࢽ࣮ࣖ཯ᛂ௨እ࡛ࡶࠊ+HFN཯ᛂ࡞࡝
ࡲࡔࡣࡗࡁࡾࡋ࡚࠸࡞࠸౛ࡶ࠶ࡿࡢ࡛ࠊࡑࢀࡽ࡟ࡘ࠸࡚ࡶ◊✲ࡋ࡚࠸ࡿࠋ
ࢥࣟࢼ࢘࢖ࣝࢫ࡜࣡ࢡࢳࣥࡢ཯ᛂ ᫖ᖺ᮶ୡ⏺ⓗ࡟ࢥࣟࢼ࢘࢖ࣝࢫࡢឤᰁࡀ኱ࡁ࡞ၥ㢟࡟࡞ࡾࠊ࣡ࢡࢳࣥࡢ㛤Ⓨࡀ㐍ࡵࡽࢀ࡚࠸ࡿࡀࠊ࢘࢖ࣝࢫ࡜࣡ࢡࢳࣥࡢసࡿ」ྜయࡢᵓ㐀ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ
⤖ྜࡢศᏊ㛫ຊ࡜ࡋ࡚ࡣࠊ㓟ሷᇶ⤖ྜ࡟ࡼࡿ࠿ࠊỈ⣲⤖ྜ࡟ࡼࡿ࠿ࡢ୧᪉ࡀ⪃࠼ࡽࢀࡿࡢ࡛ࠊ࡝ࡕࡽࡀ㔜せ࡞ࡢ࠿࡟ࡘ࠸࡚ࠊ఍ྜయࡢᵓ㐀ࢆࡶ࡜࡟ࡋ࡚ࠊ◊✲ࡋࡓࠋ࢘࢖ࣝࢫࡶ࣡ࢡࢳࣥࡶከࡃࡢ࢔࣑ࣀ㓟࠿ࡽ࡞ࡿࠊ኱ࡁ࡞ศᏊ࡛࠶ࡿࡢ࡛ࠊᚑ᮶
ࡢࢥࣥࣆ࣮ࣗࢱ࣮ࡢィ⟬㏿ᗘ࡛ࡣࠊ࡞࠿࡞࠿⤖ᯝࡀ࡛࡞࠿ࡗࡓ࡜ᛮࢃࢀࡿࡀࠊᖾ
࠸᫖ᖺ᮶ィ⟬㏿ᗘࡀ㏿ࡃ࡞ࡗࡓࡢ࡛ࠊ᭷⏝࡞⤖ᯝࡀᚓࡽࢀࡿࡼ࠺࡟ィ⟬ࢆ⾜ࡗ࡚ࡁࡓࠋ࢘࢖ࣝࢫࡶ࣡ࢡࢳࣥࡶ኱ࡁ࡞ศᏊ࡛࠶ࡿࡀࠊ࣡ࢡࢳࣥࡀ࢘࢖ࣝࢫ࡟⤖ྜࡍࡿ㒊఩ࢆ᥎ᐃ࡛ࡁࢀࡤࠊ⤖ྜຊࡢ኱ࡁࡉࢆィ⟬࡛ࡁࡿࡶࡢ࡜⪃࠼࡚ࠊィ⟬ࢆ⥆ࡅ࡚࠸ࡿࠋィ⟬᪉ἲࡣࠊ*DXVVLDQJ࡛ࠊᇶᗏ㛵ᩘࡣ %/<3J࡛ࠊ࡝࠺࠸࠺ศᏊ
㛫ຊࡀࡶࡗ࡜ࡶ㔜せ࡛࠶ࡿ࠿ࢆࠊ᥈ồࡋ࡚࠸ࡿࠋ

Ⓨ⾲ ฟ∧ணᐃ ⏣௰ࠊ ᯇᮏ  *ULJQDUG ཯ᛂࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࡢㄽᩥࢆసᡂ୰࡛࠶ࡿࠋ

- 20 -

㝵ᒙ᪉⛬ᘧࢆ⏝࠸ࡓ㟁Ꮚࣇ࢛ࣀࣥ┦஫స⏝࡟㛵ࡍࡿィ⟬◊✲㸸᭷ᶵኴ㝧㟁ụ࡟࠾ࡅࡿ࢚࢟ࢩࢺࣥ⛣ືཬࡧ࣍ࣝࢫࢱ࢖࣭ࣥࣁࣂ࣮ࢻᶍᆺ࡬ࡢᛂ⏝Calculation of electron-phonon interactions using hierarchical equationsof motion with applications to organicphotovoltaic cells and theHolstein-Hubbard model‫ۑ‬㇂ᮧ ྜྷ㝯ࠊ୰ᮧ ΎேࠊMauro Cainelliࠊ㧘ᶫ ⚽㢧ࠊ㉿ ⌔ᘏ㸦ி㒔኱Ꮫ㸧1◊✲┠ⓗ
BEDT-TTF ࡸ C60 ࡜࠸ࡗࡓ᭷ᶵఏᑟయ࡛ࡣࠊ
ᒁᡤⓗ࡞࢜ࣥࢧ࢖ࢺࡢ㟁Ꮚ-㟁Ꮚ(e-e)┦஫స⏝࡜㟁Ꮚ-᱁Ꮚ(e-ph)┦஫స⏝ࡀ➇ྜࡋ࡚࠾ࡾࠊࡇࢀ࡟⏤᮶ࡍࡿ」㞧࡞≀ᛶࡀࡳࡽࢀࡿࠋ㏆ᖺ࡛ࡣࠊࡇࢀࡽ᭷ᶵ໬ྜ≀࡟࣮ࣞࢨ࣮
ࣃࣝࢫࢆᙜ࡚ࡿ࡜ࠊ⤯⦕య-ᑟయ┦㌿⛣ࡸᑟయ-㉸ఏᑟయ┦㌿⛣ࡀ㉳ࡇࡿࡇ࡜ࡶሗ࿌ࡉࢀ࡚࠾ࡾࠊ┈ࠎࡢὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋࡇࡢࡼ࠺࡞≀ᛶࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ᵝࠎ࡞ᩘ್ィ⟬ࡀ࡞ࡉࢀ࡚ࡁࡓࡀࠊࡑࡢከࡃࡀᖹ⾮≧ែ࡟࠾ࡅࡿ㟼ⓗ࡞ࡶࡢ࡟㝈ࡽࢀ࡚࠾ࡾࠊගㄏ㉳ࡋࡓບ㉳⣔ࡢ᣺ࡿ⯙࠸ࡸࠊࡑࢀࡀᇶᗏ≧ែ࡬࡜⦆࿴ࡍࡿ㐣⛬࡞࡝ࡣṤ࡝ㄪ࡭ࡽࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊࡇࢀࡽ᭷ᶵఏᑟయ࡜ࡑࢀ࡟⤖ྜࡍࡿ⎔ቃ(=⇕ᾎ)࡟ຍ࠼࡚ࠊ᭷ᶵఏ
ᑟయࢆບ㉳ࡍࡿእ㒊㟁ሙࢆ⪃៖ࡋࡓᶍᆺࢆ⪃࠼ࠊ⣔ࢆ㥑ືࡋ㧗࢚ࢿࣝࢠ࣮≧ែ࡬࡜ᑟࡃእሙ࡜ࠊ⣔࠿ࡽ࢚ࢿࣝࢠ࣮ࢆዣ࠸ཤࡿ⇕ᾎࡀ࡝ࡢࡼ࠺࡟ᙳ㡪ࢆཬࡰࡋ࠶ࡗ࡚࠸ࡿࡢ࠿ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ࣍ࣝࢫࢱ࢖࣭ࣥࣁࣂ࣮ࢻ(HH)ᶍᆺ࡜࿧ࡤࢀࡿ e-eࠊe-ph ┦஫స⏝୧᪉ࢆྵࡴᶍᆺࢆᑐ㇟࡟ᩘ್ィ⟬ࢆ⾜࠺ࠋ

HH ᶍᆺ࡟ᑐࡍࡿ⇕ᾎࡢຠᯝࡣࠊ㝵ᒙᆺ㐠ື᪉⛬ᘧ࡜࿧ࡤࢀࡿ㐃❧᫬㛫ᚤศ᪉⛬ᘧࢆᩘ್✚ศࡋࠊᐇ᫬㛫ࢲ࢖ࢼ࣑ࢡࢫࢆィ⟬ࡍࡿࡇ࡜࡟ࡼࡗ࡚᫂ࡽ࠿࡟ࡍࡿࠋ౑⏝ࡍࡿࡢࡣ⏦ㄳ⪅ࡀ⊂⮬࡟㛤Ⓨࡋࡓ」ᩘࣀ࣮ࢻୖ࡛ື
సࡍࡿࣉࣟࢢ࣒࡛ࣛ࠶ࡿࠋගᏛఏᑟᗘࢆィ⟬ᑐ㇟࡜ࡋࠊ⪃࠼࡚࠸ࡿ HH ᶍᆺࡀᑟయ/⤯⦕య/㉸ఏᑟయࡢ࠸ࡎࢀ
࡟࠶ࡿ࠿ࡢᣦᶆ࡜ࡍࡿࠋ⇕ᾎ࡜⤖ྜࡋࡓ HH ᶍᆺ࡟ᑐࡍࡿእሙࡢຠᯝࡶࡲࡓࠊගᏛఏᑟᗘࢆ⏝࠸࡚ホ౯ࡍࡿࠋ
HH ᶍᆺࡢࢧ࢖ࢺᩘ࡟ࡼࡿࢲ࢖ࢼ࣑ࢡࢫࡢኚ໬ࡶィ⟬ࡍࡿࠋ3◊✲ᡂᯝ㟁Ꮚ 2 ࢧ࢖ࢺ࠿ࡽ࡞ࡿ HH ᶍᆺࡢᩘ್ィ⟬ࢆ⾜࠸ࠊe-e ┦஫స⏝ࡀ e-ph ┦஫స⏝࡜࡯ࡰ➼ࡋࡃࠊ➇ྜࡍࡿࡼ࠺࡞ሙྜ࡟᭱ࡶᑟయ࡟㏆࠸≧ែ࡟࡞ࡾࠊe-e-┦஫స⏝ࡀ e-ph ┦஫స⏝ࡼࡾࡶᑠࡉ࠸ࠊᡈ࠸ࡣ኱ࡁ࠸ሙྜ࡟
ࡣ⤯⦕య࡟㏆࡙ࡃࡇ࡜ࢆ♧ࡋࡓࠋࡇࢀࡣඛ⾜◊✲[1]࡜୍⮴ࡍࡿࡶࡢ࡛࠶ࡾࠊᮏ◊✲ᡭἲࡢጇᙜᛶࡀ♧ࡉࢀࡓࠋ
HH ᶍᆺࢆእሙ࡛㥑ືࡍࡿሙྜ࡟ࡣࠊ2 ࡘࡢሙྜࡀ⪃࠼ࡽࢀࡿࠋ୍ࡘࡣࠊ㟁Ꮚࢆ┤᥋ບ㉳ࡍࡿࡶࡢ࡛࠶ࡾࠊ
ࡶ࠺୍ࡘࡣ㟁Ꮚ࡟⤖ྜࡋࡓ᱁Ꮚࢆບ㉳ࡍࡿࡶࡢ࡛࠶ࡿࠋ㟁Ꮚࢆ┤᥋ບ㉳ࡍࡿࡶࡢ࡛ࡣࠊᏙ❧ࣁࣂ࣮ࢻᶍᆺࡀ
㉸ఏᑟయ࡟࡞ࡿࡇ࡜ࡀඛ⾜◊✲[2]࡛♧ࡉࢀ࡚࠸ࡓࠋᮏ◊✲࡛ࡣࠊࡇࡢ㟁Ꮚບ㉳ࣁࣂ࣮ࢻᶍᆺࡀ᱁Ꮚ࡜⇕ᾎ࡟᫹ࡉࢀࡓሙྜ࡝ࡢࡼ࠺࡟࡞ࡿ࠿ࢆ᫂ࡽ࠿࡟ࡋࡓࠋe-e ┦஫స⏝ࡀ e-ph ┦஫స⏝ࡼࡾࡶᑠࡉ࠸ࠊᡈ࠸ࡣྠ⛬ᗘࡢሙྜ࡟ࡣගᏛఏᑟᗘ࡟ኚ໬ࡣぢࡽࢀ࡞࠿ࡗࡓࠋ୍᪉࡛ࠊe-e ┦஫స⏝ࡀ e-ph ┦஫స⏝ࡼࡾࡶ኱ࡁ࠸ሙྜ࡟
ࡣࠊHH ᶍᆺࡣᑟయ࡟㏆௜࠸ࡓࠋ㟁Ꮚࢆ┤᥋ບ㉳ࡋ᱁Ꮚࡢ≧ែ࡟ὀ┠ࡋ࡞࠸ࡼ࠺࡞≧ἣ࡛ࡣࠊ᱁Ꮚ㒊ศࢆ᪂ࡓ࡟⇕ᾎ࡜ぢ೴ࡍࡇ࡜ࡀฟ᮶ࡿࠋࡇࡢࡼ࠺࡟⪃࠼ࡿࡇ࡜࡟ࡼࡾࠊ⇕ᾎ࡜ᙉࡃ┦஫స⏝ࡍࡿࣁࣂ࣮ࢻᶍᆺࡣࠊ

- 21 -

ࢡ࣮ࣟࣥ᩺ຊࡀ⣔-⇕ᾎ࢝ࢵࣉࣜࣥࢢࡼࡾࡶᙉ࠸ሙྜ࡟ࡢ
ࡳ㉸㟁ᑟ≧ែ࡟࡞ࡾࠊࡑ࠺࡛࡞࠸ሙྜ࡟ࡣ┦㌿⛣ࡣ㉳ࡇࡽ࡞࠸ࠊ࡜࠸࠺ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
᱁Ꮚࢆእሙ࡟ࡼࡗ࡚ບ㉳ࡍࡿィ⟬࡛ࡣࠊගᏛఏᑟᗘࡢࣆ
࣮ࢡ఩⨨࡟ኚ໬ࡣぢࡽࢀ࡞࠿ࡗࡓࠋእሙࡢ࿘Ἴᩘࡀ᱁Ꮚࡢ
࿘Ἴᩘ࡜୍⮴ࡍࡿ≧ἣ࡛ࡣࠊࣆ࣮ࢡࡢ㧗ࡉࡀᴟ➃࡟పࡃ࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࢀࡣࠊ᱁Ꮚࡢບ㉳࡟ࡼࡗ࡚ᐇ
ຠⓗ࡞ࢡ࣮ࣟࣥ཯Ⓨࡀᙅࡲࡾࠊ㟁Ꮚࡢ⛣ືࡀ㜼ᐖࡉࢀࡿࡇ
࡜ࡀཎᅉ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ᱁Ꮚບ㉳࡟ࡼࡿ㉸ఏᑟ≧ែࡢⓎ⌧ࡣඛ⾜◊✲[3]࡛ሗ࿌ࡉࢀ࡚࠸ࡿࡀࠊHH ᶍᆺ࡟ࡼࡿ

ᅗ 1.

4 ࢧ࢖ࢺ HH ᶍᆺࡢ⦆࿴

ᥥീ࡛ࡣࡇࢀࢆㄝ࡛᫂ࡁ࡞࠸ࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ
⌧ᐇ⣔ࡢ࠺ࡕ 2 ࢧ࢖ࢺ HH ᶍᆺ࡛グ㏙࡛ࡁࡿࡶࡢࡣᑡᩘ࡛࠶ࡾࠊᐇ㦂࡜ࡢᑐᛂ௜ࡅࡸࢧ࢖ࢬຠᯝࡢ᳨ドࡢ
ほⅬ࠿ࡽࠊ4 ࢧ࢖ࢺ HH ᶍᆺࡢィ⟬ࡀᚲせ࡛࠶ࡿ࡜⪃࠼ࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ⏦ㄳ⪅ࡢ◊✲ᐊ࡟࠶ࡿ PC ࡛ࡣィ⟬⬟ຊࡀ㊊ࡾ࡞࠿ࡗࡓࡓࡵࠊ㈗ࢭࣥࢱ࣮ࡢィ⟬ᶵࢆ࠾೉ࡾࡍࡿ㐠ࡧ࡜࡞ࡗࡓࠋ
㝵ᒙᆺ㐠ື᪉⛬ᘧࡢᩘ್ィ⟬࡛ࡣࠊࠕ㝵ᒙࡢ῝ࡉࠖ࡜࿧ࡤࢀࡿࣃ࣓࣮ࣛࢱࡀ࠶ࡾࠊ⇕ᾎࡢᗘࡀ㧗࠸࡯࡝ࠊ

ࡲࡓ⣔-⇕ᾎ㛫ࡢ⤖ྜᙉᗘࡀᙉ࠸࡯࡝ࠕ῝ࡉࠖࡀᚲせ࡜࡞ࡿࠋ㝵ᒙࡢ῝ࡉࡀ῝࠸࡯࡝ࠊィ⟬࡟せࡍࡿ⾜ิࡢࢧ࢖ࢬࡀ኱ࡁࡃ࡞ࡾࠊィ⟬ࢥࢫࢺࡀୖ᪼ࡍࡿࠋ2 ࢧ࢖ࢺ HH ᶍᆺ࡜ྠࡌࣃ࣓࣮ࣛࢱࢆ⏝࠸࡚ 4 ࢧ࢖ࢺ HH ᶍᆺࡢィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊィ⟬ࡀ㏵୰࡛Ⓨᩓࡋࡓࠋ2 ࢧ࢖ࢺ⣔࡛ࡢⓎᩓࡢᣲືࢆㄪᰝࡋࡓ࡜ࡇࢁࠊ4 ࢧ࢖ࢺ⣔࡛ࡣ⣔-⇕ᾎ㛫ࡢᐇຠⓗ࡞⤖ྜᙉᗘࡀ኱ࡁࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
ඛ㏙ࡢ㏻ࡾࠊ⣔-⇕ᾎ㛫ࡢ┦஫స⏝ࡀ኱ࡁ࠸ሙྜ࡟ࡣ㝵ᒙࡢ῝ࡉࢆ῝ࡃࡋ࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࠋࡋ࠿ࡋ࡞ࡀࡽࠊ
4 ࢧ࢖ࢺ HH ᶍᆺࡢィ⟬࡛ࠊࡇࢀ௨ୖ࡟㝵ᒙࢆ῝ࡃࡍࡿࡇ࡜ࡣィ⟬㈨※ࡢほⅬ࠿ࡽ㞴ࡋ࠿ࡗࡓࠋࡑࡇ࡛ࠊHHᶍᆺ࡜⇕ᾎ࡜ࡢ⤖ྜᵝᘧࢆኚ࠼ࠊィ⟬ᑐ㇟ࡢぢ┤ࡋࢆ⾜ࡗࡓࠋィ⟬ࢥࢫࢺࡣᢚ࠼ࡽࢀࠊ࣓ࣔࣜᚲせ㔞ࡢほⅬ࠿ࡽࡣ 1 ࣀ࣮ࢻ࡛༑ศ࡛࠶ࡗࡓࡀࠊィ⟬᫬㛫▷⦰ࡢࡓࡵ࡟㈗ࢭࣥࢱ࣮ࡢィ⟬ᶵࢆ౑⏝ࡋࡓࠋ⇕ᾎ௜ࡁ 4 ࢧ࢖
ࢺ HH ᶍᆺࡀ௵ពࡢึᮇ≧ែ࠿ࡽᖹ⾮≧ែ࡟⦆࿴ࡍࡿᵝᏊࢆᅗ 1 ࡟♧ࡍࠋࡇࡢᚋࠊගᏛఏᑟᗘࢆィ⟬ࡋࡓࡀࠊィ⟬ᚋ࡟ࣉࣟࢢ࣒ࣛ୰࡟ㄗࡾࡀ࠶ࡗࡓࡇ࡜ࢆⓎぢࡋࡓࠋࡇࡢࡓࡵࠊගᏛఏᑟᗘࡢࢢࣛࣇࡣ๭ឡࡍࡿࠋㄗࡾ࡟
Ẽ௜࠸ࡓࡢࡣ 2021 ᖺ 4 ᭶࡟ධࡗ࡚࠿ࡽࡔࡗࡓࡓࡵࠊᮏ⏦ㄳศ࡛ࡢ෌ィ⟬ࡣ⾜࠼࡞࠿ࡗࡓࠋ௒ᅇồࡵࡓᖹ⾮≧ែࢆඖࢹ࣮ࢱ࡜ࡋࡓ෌ィ⟬ࡣࠊ2021 ᖺᗘ⏦ㄳศࡢ㈗ࢭࣥࢱ࣮ィ⟬ᶵ࡛⾜ࡗࡓࠋ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
3 ࡛㏙࡭ࡓ⤖ᯝࢆ᮶ᖺ࡟ᘏᮇࡉࢀ࡚࠸ࡿບ㉳Ꮚࡸ㟁Ꮚ⛣ືࢆᑐ㇟࡜ࡋࡓ Santa Fe2020 ࡟࠾࠸࡚Ⓨ⾲ணᐃ࡛࠶ࡿࠋ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
3 ࡛㏙࡭ࡓ෌ィ⟬⤖ᯝࢆྵࡵࡓㄽᩥࢆ J. Chem. Phys ࡟㸴᭶ጞࡵ࡟ submit ࡍࡿணᐃ࡛‽ഛ୰࡛࠶ࡿࠋ

ཧ⪃ᩥ⊩[1] M. Tezuka, R. Arita, and H. Aoki, Phys. Rev. B 76, 155114 (2007).
[2] T. Kaneko, T. Shirakawa, S. Sorella, and S. Yunoki, Phys. Rev. Lett. 122, 077002 (2019).
[3] M. Mitrano et al., Nature 530, 461 (2016).

- 22 -

᭷ᶵࢣ࢖⣲໬ྜ≀ࡢᵓ㐀࡜ᛶ㉁Structures and Properties of Organosilicon Compounds‫ஂۑ‬᪂ Ⲯ୍㑻ࠊⳢ㔝 ◊୍㑻ࠊ㧗ᶫ 㞞ⱥࠊ὾㔝 㖟Ἑࠊᮏ㛫 㱟ஓࠊᒾ⏣ ࿴ဢࠊᕝ࿴⏣ ඃ㤶㔛ࠊ⏣୰ ᬛ኱㸦⩌㤿኱Ꮫ኱Ꮫ㝔⌮ᕤᏛᗓ㸧1◊✲┠ⓗ࣓࣌ࣝࢳࣝ࢜ࣜࢦࢩࣛࣥࡀࢣ࢖⣲༢ศᏊ⭷ࡸ஧ศᏊ⭷ࢆᙧᡂࡍࡿ࠿࡝࠺࠿᳨ウࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ࣓࣌ࣝࢳࣝࢹ࢝ࢩࣛࣥࡢᵓ㐀᭱㐺໬ࠊ㟁Ⲵศᕸࡣ Gaussian ࢆ⏝࠸࡚ィ⟬ࡋࡓࠋࡲࡓࠊ࣓࣌ࣝࢳࣝࢹ࢝ࢩࣛ

ࣥ 2 ศᏊࡢ㊥㞳ࢆኚ໬ࡉࡏ࡚ࠊ࢚ࢿࣝࢠ࣮ࡀ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿ࠿ Gaussian ࢆ⏝࠸࡚ィ⟬ࡋࡓࠋ3◊✲ᡂᯝ␯Ỉᛶࡢ㙐࡟ぶỈᇶࡀ⤖ྜࡋࡓ୧ぶ፹ᛶ≀㉁ࡣ༢ศᏊ⭷㸦Langmuir–Blodgett ⭷㸧ࡸ஧ศᏊ⭷㸦⬡㉁஧ศᏊ

⭷㸧ࢆᙧᡂࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࢀ࡟ᑐᛂࡍࡿࢣ࢖⣲༢ศᏊ⭷ࡸ஧ศᏊ⭷ࡣ࡛ࡁࡿࡢ࠿ࠊ⯆࿡ࡀࡶࡓࢀࡿࠋᮏ◊✲࡛ࡣぶỈᇶࢆࡶࡓ࡞࠸࣓࣌ࣝࢳࣝ࢜ࣜࢦࢩࣛࣥࡀᐜ᫆࡟༢ศᏊ⭷ࡸ஧ศᏊ⭷ࢆᙧᡂࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡍ࡞ࢃࡕ࣓࣌ࣝࢳࣝࢹ࢝ࢩࣛࣥࡢ࣊࢟ࢧࣥ⁐ᾮࢆỈ㠃ୖ࡟⁲ୗࡍࡿ࡜ࠊ⁐ᾮࡢ⃰ᗘࡸᗘࢆไᚚࡍࡿ

ࡇ࡜࡟ࡼࡗ࡚ࠊ༢ศᏊ⭷ࡸ஧ศᏊ⭷ࡀ⏕ᡂࡍࡿࠋ⌮ㄽィ⟬ࡢ⤖ᯝࠊ࣓࣌ࣝࢳࣝࢹ࢝ࢩࣛࣥࡢࢣ࢖⣲ཎᏊ࡜࣓ࢳࣝᇶࡢ㛫࡟ࡣẚ㍑ⓗ኱ࡁ࡞ศᴟࡀぢࡽࢀࠊࡑࢀ࡟ࡼࡗ࡚ศᏊ㛫┦஫స⏝ࡀാࡁࠊศᏊࡀᖹ⾜࡟㓄ิࡋ࡚༢ศᏊ⭷ࡸ஧ศᏊ⭷ࢆᙧᡂࡍࡿ࡜⪃࠼ࡽࢀࡿࠋࡑࡢࡓࡵ࣓࣌ࣝࢳࣝ࢜ࣜࢦࢩ࡛ࣛࣥࡣࠊ୧ぶ፹ᛶ≀㉁࡜ࡣ␗࡞
ࡿཎ⌮࡟ࡼࡗ࡚⭷ᙧᡂࡀ㉳ࡇࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

water

water
monolayer4bilayerⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ۻ‬1) ஂ᪂Ⲯ୍㑻㸪ྂࡃ࡚᪂ࡋ࠸࣏ࣜࢩࣛࣥ, ࢜ࣜࢦࢩࣛࣥࡢ◊✲, ➨ 24 ᅇࢣ࢖⣲໬Ꮫ༠఍ࢩ࣏ࣥࢪ࣒࢘, ࢜ࣥࣛ࢖ࣥ㛤ദ㸪2020 ᖺ 11 ᭶ 6 ᪥㸦ᣍᚅㅮ₇㸧㸬

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ۻ‬1) S. Kyushin, Y. Kurosaki, K. Otsuka, H. Imai, S. Ishida, T. Kyomen, M. Hanaya, H. Matsumoto, Nature Commun.
2020, 11, 4009㸦Featured Article ࡟᥇ᢥ㸧㸬2) S. Kyushin, K. Mizoguchi, T. Tanaka, T. Yamanobe, K. Hayashi, Organometallics 2020, 39, 4651㸦Cover Art ࡟᥇ᢥ㸧㸬- 23 -

จ㞟ㄏ㉳Ⓨග࡟ࡘ࠸࡚ࡢ⌮ㄽⓗ◊✲Theoretical Study on the Aggregation-Induced Emission‫ۑ‬ᒣᮏ ඾ྐ㸦༓ⴥᕤᴗ኱Ꮫ㸧

1

◊✲┠ⓗ

㏆ᖺ㸪༢య࡛ࡣⓎගࡋ࡞࠸ࡀ㸪ศᏊࡀከᩘจ㞟ࡍࡿ࡜Ⓨගࡍࡿ≉ᛶࢆᣢࡘ⺯ගⰍ⣲ࡀὀ┠ࡉࢀ࡚࠸ࡿࠋࡇࡢ
⌧㇟ࡣจ㞟ㄏ㉳Ⓨග࡜࿧ࡤࢀ࡚࠸ࡿࠋࢩ࢔ࣀࢫࢳࣝ࣋ࣥㄏᑟయࡢ CN-MBE ࡣจ㞟ㄏ㉳Ⓨගࢆ♧ࡍ⺯ගⰍ⣲࡛࠶ࡾ㸪⁐ᾮ୰࡟ศᩓࡋࡓ≧ែ࡛ࡢ⺯ග㔞Ꮚ཰⋡㸦ȍ㸧್ࡣ 0.001 ࡛࠶ࡿࡀ㸪จ㞟ࡋ࡚ᚤ⢏Ꮚࡸ⤖ᬗ࡟࡞ࡿ࡜
ȍ್ࡣ 0.69 ࡲ࡛ቑ኱ࡍࡿࠋࡇࡢ CN-MBE ࡟ࡣ E య࡜ Z యࡢ 2 ✀㢮ࡢ␗ᛶయࡀ࠶ࡾ㸪ࡇࡢ 2 ࡘࡢ␗ᛶయࡢ࠺
ࡕจ㞟ㄏ㉳Ⓨගࡀほࡉࢀࡿࡢࡣ E యࡢࡳ࡛࠶ࡾ㸪Z యࡣ⤖ᬗᵓ㐀࡛ࡶⓎගࡀほࡉࢀ࡞࠸ࠋࡇࡢࡼ࠺࡟

CN-MBE ࡣจ㞟≧ែ࡟࠾ࡅࡿග≀ᛶࡀࡑࢀࡒࢀࡢ␗ᛶయ࡛኱ࡁࡃ␗࡞ࡿࡀ㸪ࡑࡢศᏊᶵᵓࡣ᫂ࡽ࠿࡛ࡣ࡞࠿
ࡗࡓࠋᮏ◊✲࡛ࡣ CN-MBE ࡀ♧ࡍจ㞟ㄏ㉳Ⓨගࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚㸪ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓゎᯒࢆ࠾ࡇ࡞ࡗࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲCN-MBE ࡢ㟁Ꮚ≧ែࡣࢫࣆࣥ཯㌿ᆺ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘ㸦SF-TD-DFT㸧ἲࢆ⏝࠸࡚ゎᯒࡋࡓࠋࣉࣟࢢ࣒ࣛ࡟
ࡣ GAMESS ࢆ⏝࠸ࡓࠋCN-MBE ࡢບ㉳≧ែ⦆࿴㐣⛬࡟క࠺⮬⏤࢚ࢿࣝࢠ࣮ኚ໬࡟ࡘ࠸࡚㸪QM/MM ⮬⏤࢚ࢿࣝࢠ࣮ᦤືἲࢆ⏝࠸࡚ゎᯒࡋࡓࠋࣉࣟࢢ࣒ࣛ࡟ࡣ Amber20 ࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆゎᯒࡋࡓ⤖ᯝ㸪E యࡢሙྜ㸪จ㞟య୰࡛ࡣගບ㉳ᚋ㸪ศᏊᵓ㐀ࡢኚ໬㸦C=C ⤖ྜ㒊ศࡢᅇ㌿㸧ࢆ⤒࡚෇㗹஺ᕪ࡟⮳ࡿ⤒㊰ࡀ࢚ࢿࣝࢠ࣮ⓗ࡟ⴭࡋࡃ୙฼࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࡢ
ࡇ࡜࠿ࡽ㸪E యࡢሙྜ㸪จ㞟ᵓ㐀࡛ࡣ↓㍽ᑕ࡟⦆࿴ࡍࡿ⤒㊰ࡀⴭࡋࡃᢚไࡉࢀ࡚࠸ࡿࡓࡵ࡟ᙉ࠸Ⓨගࢆ♧ࡍ࡜⪃࠼ࡽࢀࡿࠋ୍᪉࡛ Z యࡢจ㞟యࡀගບ㉳ࡉࢀࡓ࡜ࡁ࡟ࡣ㸪ᆶ┤ບ㉳ࡋࡓ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤㠃ୖ
ࡢᆅⅬ࠿ࡽࣂࣜ࢔ࣞࢫ࡛෇㗹஺ᕪ࡬࡜ࡍࡳࡸ࠿࡟⦆࿴ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋZ యࡀจ㞟ㄏ㉳Ⓨගࢆ♧ࡉ࡞࠸ཎᅉࡣ㸪จ㞟య୰࡛࠶ࡗ࡚ࡶẚ㍑ⓗᐜ᫆࡟ C=C ⤖ྜ㒊఩ࡢᅇ㌿㐠ືࡀ㉳ࡇࡿࡇ࡜࡛ࡍࡳࡸ࠿࡟࣏ࢸࣥ
ࢩࣕࣝ᭤㠃ୖࡢ෇㗹஺ᕪ࡟฿㐩ࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡾ㸪↓㍽ᑕ࡛⦆࿴ࡍࡿࡓࡵ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬Yamamoto, Norifumi, “Free energy profile analysis to identify factors activating the aggregation-induced emissionof a cyanostilbene derivative”, Phys. Chem. Chem. Phys., Vol. 23, pp. 1317-1324 (2021),
doi: 10.1039/D0CP04246C- 24 -

୕㔜㡯ᾘ⁛䜰䝑䝥䝁䞁䝞䞊䝆䝵䞁䛾䛯䜑䛾㔠ᒓ䜽䝷䝇䝍䞊ቑឤ๣㻌䛻㛵䛩䜛ィ⟬⛉Ꮫⓗ◊✲㻌㻯㼛㼙㼜㼡㼠㼍㼠㼕㼛㼚㼍㼘㻌㼟㼠㼡㼐㼥㻌㼛㼚㻌㼙㼑㼠㼍㼘㻌㼏㼘㼡㼟㼠㼑㼞㻌㼟㼑㼚㼟㼕㼠㼕㼦㼑㼞㼟㻌㼒㼛㼞㻌㼠㼞㼕㼜㼘㼑㼠㻌㼒㼡㼟㼕㼛㼚㻌㼡㼜㼏㼛㼚㼢㼑㼞㼟㼕㼛㼚㻌‫୕ۑ‬஭ṇ᫂㸦❧ᩍ኱Ꮫ⌮Ꮫ㒊㸧1◊✲┠ⓗ୕㔜㡯୕㔜㡯ᾘ⁛࡟ᇶ࡙ࡃࣇ࢛ࢺࣥ࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥ㸦77$8&㸧ࡣࠊኴ㝧ග⛬ᗘࡢᙅ࠸ග࡛ࡶ

㧗ຠ⋡࡞࢔ࢵࣉࢥࣥࣂ࣮ࢪࣙࣥࡀྍ⬟࡛࠶ࡿࡇ࡜࠿ࡽ㠉᪂ⓗ࡞࢚ࢿࣝࢠ࣮ኚ᥮ᢏ⾡࡜ࡋ࡚ὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ77$8& ࡢ୕㔜㡯ቑឤ๣࡜ࡋ࡚ᶵ⬟ࡍࡿ㓄఩Ꮚಖㆤ㈗㔠ᒓࢡࣛࢫࢱ࣮࡟ᑐࡋ࡚⣔⤫ⓗ࡞⌮ㄽィ⟬ࢆᐇ᪋ࡋࠊᇶᗏ≧ែ࠾ࡼࡧບ㉳୍㔜㡯࣭୕㔜㡯≧ែ࡟࠾ࡅࡿᏳᐃᵓ㐀ࠊᇶᗏ≧ែ࠿ࡽྛບ
㉳≧ែ࡬ࡢ㟁Ꮚ㑄⛣ࡢ≉ᛶ㸦㑄⛣࢚ࢿࣝࢠ࣮ࠊ㑄⛣࣮࣓ࣔࣥࢺࠊ᣺ືᏊᙉᗘࠊ඲㟁Ꮚᕪศᐦᗘ࡞࡝㸧ࢆ᫂ࡽ࠿࡟ࡋࠊ୕㔜㡯ቑឤ๣࡜ࡋ࡚ᶵ⬟ࡍࡿ୍㐃ࡢ㓄఩Ꮚಖㆤ㔠ᒓࢡࣛࢫࢱ࣮࡟࠾ࡅࡿ୕㔜㡯≧ែ⏕ᡂຠ⋡ࡀࠊ㟁Ꮚບ㉳≧ែࡢ≉ᛶ࡜࡝ࡢࡼ࠺࡞㛵ಀᛶࢆᣢࡗ࡚࠸ࡿ࠿᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ⏦ㄳ⪅ࡽࡀ᪤࡟ 77$8& ࡢቑឤ๣࡜ࡋ࡚ᶵ⬟ࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓ㔠ᒓࢡࣛࢫࢱ࣮㸦;$J ; 3G$J

3W$X ࠊ$Jࠊ$Xࠊ$Xࠊ$X&X㸧࡟ᑐࡋ࡚ࠊ*DXVVLDQ ࢆ⏝࠸ࡓᐦᗘỗ㛵ᩘ㸦')7㸧ἲ࠾ࡼࡧ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘ㸦7'')7㸧ἲ࡟ࡼࡿ⌮ㄽィ⟬ࢆᐇ᪋ࡋࡓࠋලయⓗ࡟ࡣࠊ  ⁐ ፹ ຠᯝࢆྲྀࡾධࢀࡓᇶᗏ≧ែࡢᏳᐃᵓ㐀ࡢ᥈⣴㸦ᵓ㐀᭱㐺໬࡜ᇶ‽᣺ືゎᯒ㸧ࠊ2) ບ㉳୍㔜㡯࠾ࡼࡧບ㉳୕㔜㡯≧ែ࡬ࡢᆶ┤㑄⛣࢚ࢿࣝࢠ࣮ࠊ㑄⛣࣮࣓ࣔࣥࢺࠊ᣺ືᏊᙉᗘࠊ  ບ㉳୍㔜㡯≧ែࡢᏳᐃᵓ㐀ࡢホ౯ࢆᐇ᪋ࡋࡓࠋ

3◊✲ᡂᯝ
;$J ; 3G$J3W$X ࡜ $J ࡢ 6 ≧ែࡘ࠸࡚ࡣࠊ㉸ཎᏊ㌶㐨࡟ᇶ࡙࠸࡚ゎ㔘ࡉࢀࡿ㟁Ꮚᵓ㐀ࡀᚓ

ࡽࢀࠊ3' 㑄⛣࡟ᇶ࡙࠸࡚⏕ᡂࡍࡿບ㉳୍㔜㡯≧ែ࡜ບ㉳୕㔜㡯≧ែࡢ㛫࡛ࢫࣆࣥ㌶㐨┦஫స⏝
㸦62&㸧⾜ิせ⣲ࡀࢮ࡛ࣟࡣ࡞࠸ࡇ࡜ࡀ (O6D\HG ๎࡟ᇶ࡙ࡃ⪃ᐹ࠿ࡽ♧၀ࡉࢀࡓࠋࡲࡓࠊ$X ࡣ┤᥋
62& ࡀྍ⬟࡛࠶ࡿࡢ࡟ᑐࡋࠊ$X ࡣ┤᥋ 62& ࡀ୙ྍ⬟࡞㟁Ꮚᵓ㐀ࢆᣢࡘࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊࢡࣛࢫࢱ࣮࡟࠾ࡅࡿ୕㔜㡯⏕ᡂຠ⋡ࡢ኱ࡁࡉࡢഴྥ࡜ᐃᛶⓗ࡟ࡼࡃᑐᛂࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ


4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬Ag25 ࢡࣛࢫࢱ࣮ࡢග≀ᛶ࡟ᑐࡍࡿ࢝࢘ࣥࢱ࣮࢖࢜ࣥࡢᙳ㡪㸪㧗ᶫ┤ஓ࣭᪂ᇼె⣖࣭୕஭ṇ᫂㸪ࢼࣀᏛ఍➨ 18 ᅇ኱఍㸪2020 ᖺ 5 ᭶‫ ۻ‬Ag29 ࢡࣛࢫࢱ࣮ࡢⓎගᛶ࣭ᖹ⾮≉ᛶ࡟ᑐࡍࡿ࣍ࢫࣇ࢕ࣥ➨஧㓄఩Ꮚࡢຠᯝ㸪㧗ᒣ❳୍࣭᪂ᇼె⣖࣭୕஭ṇ᫂㸪ࢼࣀᏛ఍➨ 18 ᅇ኱఍㸪2020 ᖺ 5 ᭶‫୍࡛ࣥ࢖ࢪࢱࣈۻ‬㒊⨨᥮ࡋࡓ⎔≧࣊࢟ࢧ-2,7-࢔ࣥࢺ࢚ࣜࣞࣥࢳࢽࣞࣥㄏᑟయࡢྜᡂ࡜[10]CPP ໟ᥋㸪⡿㇂ᶞ࣭ᯇᮌὒ᠇࣭᪂ᇼె⣖࣭୕஭ṇ࣭᫂ⱴཎᰤ୍࣭ᒣᏊⱱ࣭ᑠᯘ೺஧㸪᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍㸪2021
ᖺ3᭶
5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬³6LQJOH3ODWLQXP$WRP'RSLQJWR6LOYHU&OXVWHUV(QDEOHV1HDULQIUDUHGWR%OXH3KRWRQ8SFRQYHUVLRQ´<1LLKRUL<:DGD00LWVXL Angew. Chem. Int. Ed.   Selected as Hot paper & Frontispiece‫ۻ‬³6\QWKHVLVDQG3URSHUWLHVRID&\FORKH[D$QWKU\OHQH(WK\Q\OHQH'HULYDWLYH´+0DWVXNL.2NXER<7DNDNL
< 1LLKRUL00LWVXL (.D\DKDUD6<DPDJR ..RED\DVKL Angew. Chem. Int. Ed.  - 25 -

Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧ㞟ྜయࡢ㟁Ꮚ≧ែ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ࢔ࣉ࣮ࣟࢳ
Theoretical approach on electronic states of luminescent metal
complexes and their assembled systems‫ۑ‬ຍ⸨ ᫀᏊ㸪㰻⸨ ኱ᑗ㸪㏆⸨ ᪩⍛㸪ᜏᡂ 㧗ᘯࠊ㰻⸨᭸ஓࠊྜྷ⏣ ᑗᕫ㸪ᑠᯘ ཌᚿ㸦໭ᾏ㐨኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲㝔໬Ꮫ㒊㛛㸧1◊✲┠ⓗࠊෆᐜ
Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧࢡࣛࢫࢱ࣮ࡣࠊ᭷ᶵ EL ⣲Ꮚࡸࢭࣥࢧ࣮࡞࡝ࡢᮦᩱ࡜ࡋ࡚ࡶ⯆࿡῝ࡃࠊάⓎ࡞◊✲ࡀᒎ㛤ࡉࢀ࡚࠸ࡿࠋ㧗ຠ⋡࡞Ⓨගᛶ㔠ᒓ㘒య㛤Ⓨࡢࡓࡵ࡟ࡣࠊ㔞Ꮚ཰⋡ࠊⓎගᑑ࿨ࠊⓎග࢚ࢿࣝࢠ࣮ࠊගᏳ
ᐃᛶ➼ࢆไᚚࡍࡿせᅉࢆゎ᫂ࡋࡓศᏊタィࡀᚲせ࡛࠶ࡿࠋࡑࡇ࡛ᮏᥦ᱌࡛ࡣࠊ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿᇶᗏ≧ែ࠾ࡼࡧບ㉳≧ែࡢᵓ㐀ࡸ㟁Ꮚ≧ែࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚◊✲ࢆᐇ᪋ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ᑐ㇟࡜ࡍࡿ㘒యࡣࠊᮏ◊✲ࢢ࣮ࣝࣉ࡛㛤ⓎࡋࡓⓎගᛶⓑ㔠(II)㘒యࡸ㖡(I)㘒య➼࡛࠶ࡿࠋึࡵ࡟ࠊึᮇ

ᵓ㐀ࡢᵓ⠏ࡣࠊX ⥺ᵓ㐀ゎᯒ࡟ࡼࡾỴᐃࡋࡓᗙᶆࢆ⏝࠸࡚⾜࠸ࠊᵓ㐀᭱㐺໬ࡋࡓࠋᐦᗘỗ㛵ᩘἲ (DFT)ࢆ⏝࠸࡚ᇶᗏ≧ែࢆィ⟬ࡋࡓࠋḟ࡟ࠊ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲ(TD-DFT)ࢆ⏝࠸࡚ࠊᆶ┤ບ㉳≧ែࢆィ⟬ࡋࡓࠋࡇࢀ
࡟ࡼࡾప࠸ࣞ࣋ࣝࡢບ㉳≧ែࡢ᝟ሗࢆᚓࠊ୺せ࡞ບ㉳≧ែ࡟ࡘ࠸࡚ࡣ᭱㐺໬ࢆ⾜ࡗࡓࠋᇶᗏ≧ែ࡜ບ㉳≧ែࡢヲ⣽࡞グ㏙ࢆ㏻ࡌ࡚྾཰࠾ࡼࡧⓎගࢫ࣌ࢡࢺࣝࡢゎ᫂ࢆ⾜࠸ࠊ㧗Ⓨගࡸ࣮࢝ࣛࢳ࣮ࣗࢽࣥࢢࢆᐇ⌧ࡍࡿࡓࡵࡢศᏊᵓ㐀ணࢆ⾜࠸ࠊᐇ㦂໬Ꮫࡢࣇ࢕࣮ࢻࣂࢵࢡ࡟฼⏝ࡋࡓࠋ DFT ࠾ࡼࡧ TD-DFT ィ⟬࡟ࡣ Gaussian 09

ࡲࡓࡣ Gaussian 16 ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

3.1 ᙉⓎගᛶ N-࣊ࢸࣟ⎔≧࢝ࣝ࣋ࣥⓑ㔠(II)㘒యࡢⓎග≉ᛶ࣭ⓎගⰍไᚚᙜ◊✲ᐊ࡛㛤ⓎࡋࡓᙉⓎගᛶࡢ N-࣊ࢸࣟ⎔≧࢝ࣝ࣋ࣥⓑ㔠(II)㘒య⩌࡟ࡘ࠸࡚ࠊࡑ
ࡢⓎග≉ᛶࡢヲ⣽࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋ≉࡟ࠊྑᅗࡢⓑ㔠(II)㘒యࡢ⤖ᬗ࡟࠾࠸࡚ࠊ
⨨᥮ᇶࡢᔞ㧗ࡉ࡟ࡼࡗ࡚㘒య㛫ࡢ✚ᒙࡀኚ໬ࡋࠊⓎගⰍࡀ㉥Ⰽ࠿ࡽ㟷Ⰽࡲ࡛ᖜᗈࡃࢳ
࣮ࣗࢽࣥࢢྍ⬟࡛࠶ࡿࡇ࡜ࢆぢฟࡋࡓࠋࡑࡇ࡛ບ㉳≧ែ࡟ࡘ࠸࡚ศගᏛⓗᐇ㦂࡜࡜ࡶ࡟⌮ㄽィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊࡇࢀࡽࡢ㘒యࡢ᭱పບ㉳≧ែࡣࠊ༢ศᏊ≧ែ࡟࠾࠸࡚ࡣ⨨᥮ᇶࡢᙳ㡪ࢆཷࡅ࡞࠸୍᪉࡛ࠊ✚ᒙࡋࡓ≧ែ࡛ࡣ㢧ⴭ࡟⨨᥮ᇶࡢᙳ㡪ࢆཷࡅࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡇࢀࡣࠊ⁐ᾮ୰࡛ࡣ⨨᥮ᇶࡢᙳ㡪ࡀᑠࡉ࠸୍᪉࡛⤖ᬗ≧ែ࡛ࡣ⨨᥮ᇶ࡟ࡼࡗ࡚ⓎගⰍࡀ኱ࡁࡃኚ໬ࡍࡿ࡜࠸࠺ᐇ㦂⤖ᯝࢆࡼࡃ෌⌧ࡍࡿィ⟬⤖ᯝ࡛࠶ࡿࠋࡇࢀ࠿ࡽࠊ⤖ᬗ୰࡟࠾ࡅࡿⓎගⰍࢳ࣮ࣗࢽࣥࢢࡀ⨨᥮ᇶࡢ㟁Ꮚⓗຠᯝ࡛ࡣ࡞ࡃ
㘒య㛫ࡢ✚ᒙࡢኚ໬࡟⏤᮶ࡍࡿࡇ࡜ࡀ❧ドࡉࢀࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ㧗ຠ⋡᭷ᶵ EL⣲Ꮚࢆ㛤Ⓨࡍࡿࡓࡵࡢ㔜せ࡞ᣦ㔪ࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋ

3.2 ከᏍᛶⓑ㔠(II)㘒యࣇ࣮࣒࣮ࣞ࣡ࢡࡢⓎග≉ᛶᙜ◊✲ᐊ࡛㛤ⓎࡋࡓⓎගᛶࡢࢩࢡ࣓ࣟࢱ࣮ࣞࢺᆺⓑ㔠(II)㘒య⩌࡟ࡘ࠸࡚ࠊࡑࡢⓎග≉ᛶࡢヲ⣽࡟ࡘ࠸᳨࡚

- 26 -

ウࢆ⾜ࡗࡓࠋ౛࠼ࡤࠊྑᅗࡢỈ⣲⤖ྜ㒊఩ࢆᑟධࡋࡓࢩࢡ࣓ࣟࢱ࣮ࣞࢺᆺⓑ㔠(II)㘒
య࡟࠾࠸࡚ࠊ㏻ᖖࡢ⤖ᬗ໬᪉ἲ࡜ᾮᾮ⏺㠃ୖ࡟࠾ࡅࡿ⤖ᬗ໬᪉ἲ࡜࡛ᚓࡽࢀࡿ⤖ᬗࡢ⣽Ꮝᛶ࠾ࡼࡧⓎග≉ᛶࡀ␗࡞ࡿࡇ࡜ࢆぢฟࡋࡓࠋࡑࡇ࡛ࠊࡇࡢⓎග≉ᛶࡢヲ⣽ࢆ᳨ウࡍࡿࡓࡵ࡟ࠊ༢ศᏊ≧ែ࠾ࡼࡧ⤖ᬗ୰࡟࠾ࡅࡿ㞟✚≧ែ࡟ࡘ࠸࡚⌮ㄽィ⟬࡟ࡼࡾບ㉳≧ែࢆồࡵࡓࠋࡑࡢ⤖ᯝࠊⓑ㔠㛫࡟┦஫స⏝ࢆᣢࡓ࡞࠸㯤Ⰽ⤖ᬗ㸦ྑᅗࠊྑ෗┿㸧ࡢ
Ⓨග࡟ࡣ୺࡜ࡋ࡚㓄఩Ꮚ୰ᚰࡢ 3ʌʌ*ບ㉳≧ែࡀ኱ࡁ࡞ᐤ୚ࢆ♧ࡍࡢ࡟ᑐࡋࠊⓑ㔠㛫࡟┦஫స⏝ࢆࡶࡘ࢜ࣞࣥࢪⰍ⤖ᬗ㸦ྑᅗࠊᕥ෗┿㸧ࡣⓑ㔠㛫ࡢ཯⤖ྜᛶ㌶㐨࠿ࡽ㓄఩Ꮚࡢ ʌ*㌶㐨࡬ࡢ㑄⛣࡟⏤᮶ࡍࡿ㞟✚Ⓨගࢆ♧ࡍࡇ࡜ࡀ❧ドࡉࢀࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊගᶵ⬟ᛶ่࣭⃭ᛂ⟅ᛶࡢከᏍᛶᮦᩱࢆ㛤Ⓨࡍࡿୖ࡛㔜せ࡞▱ぢࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ⏣ྜྷۻ‬ᑗᕫࠊᮌᮧ ┿⌮ࠊᑠᯘ ཌᚿࠊຍ⸨ ᫀᏊ, "ᾮᾮ⏺㠃ࢆ฼⏝ࡋࡓከᏍᛶⓑ㔠(II)㘒య⤖ᬗࡢ๰〇࡜Ⓨග≉ᛶไᚚ", 2020 ᖺ web ග໬Ꮫウㄽ఍, 1C04 (࢜ࣥࣛ࢖ࣥ㛤ദ࣭2020/9/9-11).
‫ۻ‬S. Kondo, M. Yoshida, A. Kobayashi, M. Kato, "Photophysical properties and vapor response of a coordinatively
unsaturated mononuclear Cu(I) complex in crystal and thin film states", 2020 ᖺ web ග໬Ꮫウㄽ఍, 1C06 (࢜ࣥࣛ࢖ࣥ㛤ദ࣭2020/9/9-11).
‫ۻ‬㰻⸨ ኱ᑗࠊྜྷ⏣ ᑗᕫࠊᑠᯘ ཌᚿࠊຍ⸨ ᫀᏊ, "ᙉⓎගᛶⓑ㔠(II)㘒యࡢ⵨Ẽㄏ㉳༢⤖ᬗ-༢⤖ᬗᵓ㐀㌿⛣࡜࣋࢖࣏ࢡ࣑ࣟࢬ࣒", 㘒య໬Ꮫ఍➨ 70 ᅇウㄽ఍, 2PF-29 (࢜ࣥࣛ࢖ࣥ㛤ദ࣭2020/9/28-30).
‫ۻ‬బࠎᮌ ࡇࡢࠊྜྷ⏣ ᑗᕫࠊᑠᯘ ཌᚿࠊຍ⸨ ᫀᏊ, "ᙉⓎගᛶ Pt(II)㘒య㞟✚యࡢྜᡂ࡜ࢺ࣑ࣜ࣎ࣝࢿࢵ
ࢭࣥࢫ", ໬Ꮫ⣔Ꮫ༠఍໭ᾏ㐨ᨭ㒊 2021 ᖺ෤Ꮨ◊✲Ⓨ⾲఍, 1C06 (࢜ࣥࣛ࢖ࣥ㛤ദ࣭2021/1/26-27).
‫ۻ‬㰻⸨ ኱ᑗࠊྜྷ⏣ ᑗᕫࠊᑠᯘ ཌᚿࠊຍ⸨ ᫀᏊ, " C^N^C ୕ᗙ㓄఩Ꮚࢆ᭷ࡍࡿⓎගᛶ N-࣊ࢸࣟ⎔≧࢝ࣝ࣋ ࣥ ⓑ 㔠 (II)㘒 య ࡢ ྜ ᡂ ࡜ ග ≀ ᛶ ", ᪥ ᮏ ໬ Ꮫ ఍ ➨ 101 ᫓ Ꮨᖺ ఍ , P02-3vn-23 ( ࢜ ࣥࣛ ࢖ ࣥ 㛤 ദ ࣭
2021/3/19-22).

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬D. Saito, T. Ogawa, M. Yoshida, J. Takayama, S. Hiura, A. Murayama, A. Kobayashi, M. Kato, "Red to Blue
Intense Luminescence Based on the Superfine Control of Metal-Metal Interactions for Self-assembled Platinum(II)Complexes", Angew. Chem. Int. Ed. 2020, 59, 18723–18730.

‫ۻ‬A. Kobayashi, T. Ehara, M. Yoshida, M. Kato, "Quantitative Thermal Synthesis of Cu(I) Coordination Polymers
That Exhibit Thermally Activated Delayed Fluorescence", Inorg. Chem. 2020, 59, 9511–9520.

‫ ۻ‬M. Kimura, M. Yoshida, S. Fujii, A. Miura, K. Ueno, Y. Shigeta, A. Kobayashi, M. Kato, "Liquid-liquidInterface-promoted Formation of a Porous Molecular Crystal Based on a Luminescent Platinum(II) Complex",
Chem. Commun. 2020, 56, 12989–12992.

‫ۻ‬S. Kondo, N. Yoshimura, M. Yoshida, A. Kobayashi, M. Kato, "Vapochromic Luminescence of a Spin-coated
Copper(I) Complex Thin Film by the Direct Coordination of Vapour Molecules", Dalton Trans. 2020, 49,
16946–16953.

‫ ۻ‬M Yoshida, V. Sääsk, D. Saito, N. Yoshimura, J. Takayama, S. Hiura, A. Murayama, K. Põhako-Esko, A.
Kobayashi, M. Kato, "Easily Fabricated and Bright Phosphorescent Platinum(II) Complex Thin-films with
Mechano- and Thermo-responsiveness", manuscript in preparation.

- 27 -

ศᏊ㓄ิ࡟ࡼࡗ࡚ไᚚࡉࢀࡓ᭷ᶵ࣍࢘⣲㘒యࡢⓎⰍᶵᵓࡢゎ᫂
Study on coloring mechanisms of organoboron complexes controlled
by molecular arrangements
‫ۑ‬ᑠ㔝

1

ඞᙪ㸦ྡྂᒇᕤᴗ኱Ꮫ㸧◊✲┠ⓗࠊෆᐜ
㏆ᖺࠊᅛయ≧ែ࡛ᙉࡃⓎගࡍࡿจ㞟ㄏ㉳Ⓨග㸦Aggregation-Induced Emission: AIE㸧ࡀὀ┠ࡉࢀ࡚࠾ࡾࠊᅛయ

ࡢⓎගࡸⓎⰍ࡟㛵ࡍࡿ◊✲ㄽᩥࡀከᩘሗ࿌ࡉࢀ࡚࠸ࡿࠋᙜ◊✲ᐊ࡛ࡣࠊศᏊ⛉Ꮫ࡟ࡼࡗ࡚ࢸࢡࣀࣟࢪ࣮ࡸ⏘ᴗ࡟㈉⊩ࡍࡿࡇ࡜ࢆ┠ⓗ࡟ࠊ᭷ᶵ༙ᑟయࡸᶵ⬟ᛶⰍ⣲ࡢ◊✲㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓࠋࡑࡢ୰࡛ࠊ࠶ࡿ᭷ᶵ࣍࢘⣲໬ྜ≀ࡢᮎ➃࢔ࣝ࢟ࣝ㙐㛗ࢆኚ࠼ࡿ࡜ࠊ῝⣚࠿ࡽ࢜ࣞࣥࢪⰍ࡬ᅛయⰍࡀ㢧ⴭ࡟ኚ໬ࡍࡿ⌧㇟ࢆぢฟࡋࡓࠋࡇ
ࡢ⌧㇟ࡣᮎ➃࢔ࣝ࢟ࣝ㙐㛗ࡢኚ໬࡟ࡼࡗ࡚
⤖ᬗࡢศᏊ㓄ิࡀኚ໬ࡋࠊࡑࢀࡀᅛయⰍࡢ㐪࠸࡜ࡋ࡚⌧ࢀ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ࠊ
ࡇࢀࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡟ᐇ㦂࡜⌮ㄽࡢ୧㠃࠿ࡽ᳨ドࡋࡓࠋ2

R = MeR = EtR = PrR = Buᅗ㸯. ࣍࢘⣲㘒యㄏᑟయࡢᅛయ⏬ീ◊✲᪉ἲࠊィ⟬᪉ἲ㸺ᐇ㦂ࡢ㒊㸼
(1) ᮎ➃࢔ࣝ࢟ࣝ㙐㛗ࡢ␗࡞ࡿ᭷ᶵ࣍࢘⣲໬ྜ≀ࢆྜᡂࡋࡓࠋ
(2) ⁐ᾮ࡜ᅛయࡢ UV-vis ࢫ࣌ࢡࢺࣝࢆ

ᐃࡋࠊ྾཰Ἴ㛗࡜ᮎ➃࢔ࣝ࢟ࣝ㙐㛗ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

(3) ༢⤖ᬗ X ⥺ᵓ㐀ゎᯒ࡟ࡼࡾྛ໬ྜ≀ࡢศᏊ㓄ิ࡜ศᏊ㛫㊥㞳ࢆㄪᰝࡋࡓࠋ
㸺⌮ㄽィ⟬ࡢ㒊㸼(4) Gaussian 16 ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ TDDFT ィ⟬ࢆ⾜࠸ࠊศᏊ༢⊂࡛ࡢ UV-vis ࢫ࣌ࢡࢺࣝࢆࢩ࣑࣮ࣗࣞࢩࣙࣥࡋࡓࠋ(5) ⤖ᬗᵓ㐀࠿ࡽ஧㔞యࢆᢳฟࡋࠊࡇࡢ⤖ᬗᗙᶆࢆ⏝࠸࡚ UV-vis ࢫ࣌ࢡࢺࣝࢆᚓࡓࠋ
(6) (5)࡛ホ౯ࡋࡓ஧㔞య࡟ࡘ࠸࡚ࡉࡽ࡞ࡿᣑ኱ࢆ᳨ウࡋࠊከ㔞యࡢィ⟬ࢆ⾜ࡗࡓࠋ(7) ༢㔞య࣭஧㔞య࣭ከ㔞య࡟ࡘ࠸࡚ࠊࡑࢀࡒࢀᮎ➃࢔ࣝ࢟ࣝ㙐㛗ࡢຠᯝࢆ᳨ウࡋࡓࠋ(8) ᮎ➃࢔ࣝ࢟ࣝ㙐㛗࡟ࡼࡗ࡚ᅛయⰍࡀኚ໬ࡍࡿ⌧㇟ࢆ⪃ᐹࡋࡓࠋ3◊✲ᡂᯝᮏ◊✲࡛ࡣ⤖ᬗᵓ㐀࡟⏤᮶ࡍࡿග྾཰≉ᛶࢆㄪᰝࡍࡿࡓࡵ࡟ࠊ࣍࢘⣲㘒యㄏᑟయࢆྜᡂࡋ X ⥺⤖ᬗᵓ㐀ゎᯒࢆ⾜ࡗࡓࠋ㸲✀㢮ࡍ࡭࡚ࡢ⤖ᬗᵓ㐀ゎᯒ࡟ᡂຌࡋࠊศᏊ㓄ิࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡇࡢ⤖ᯝࠊࡍ࡭࡚࡟࠾࠸࡚
ศᏊࡢ㓄ิᵝᘧࡀ␗࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢࡓࡵࠊ༢ศᏊ࠾ࡼࡧศᏊ㞟ྜయ࡟ࡘ࠸࡚ TDDFT ィ⟬ࢆ⾜࠸
UV-vis ࢫ࣌ࢡࢺࣝࢆࢩ࣑࣮ࣗࣞࢩࣙࣥࡋࡓࠋᚓࡽࢀࡓࢫ࣌ࢡࢺࣝࡢ᭱኱྾཰Ἴ㛗ࢆᅗ㸰࡟♧ࡍࠋ༢ศᏊ࠿ࡽ
2(ᒙ)×2(ิ)ศᏊࣘࢽࢵࢺࡲ࡛ࡢィ⟬࡛ࡣࠊᐇ㦂ࢆ෌⌧ࡍࡿ⤖ᯝࡣᚓࡽࢀ࡞࠿ࡗࡓࠋ୍᪉ࠊ2×3 ศᏊࡢィ⟬⤖ᯝ࡛ࡣࠊᐇ㦂ࢆࢧ࣏࣮ࢺࡍࡿ᭱኱྾཰Ἴ㛗ࡢࢩࣇࢺࡀᚓࡽࢀࡓࠋࡉࡽ࡟ศᏊᩘࢆቑࡸࡋࡓ 2×5 ศᏊࡸ 3×2- 28 -

ศᏊ࡛ࡣᐇ㦂࡜␗࡞ࡿ⤖ᯝࢆᚓࡓࡀࠊ3×3 ศᏊ࡛ࡣᐇ㦂ࢆࢧ࣏࣮ࢺࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋᅗ㸱࡟ᐇࡢᅛయ

UV-vis ࢫ࣌ࢡࢺࣝ࡜ࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝࢆ♧ࡋࡓࠋ3×3 ศᏊࣘࢽࢵࢺࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝࡣᴫࡡᐇ㦂ࢫ࣌ࢡࢺࣝࢆᨭᣢࡍࡿࡶࡢ࡛࠶ࡗࡓࠋ
3×3 ศᏊࣘࢽࢵࢺࡢᵓ㐀ࢆゎᯒࡋࡓ⤖ᯝࠊedge-to-edge ࡛స⏝ࡍࡿศᏊ㛫Ỉ⣲⤖ྜ࡛ 3 ิࡢศᏊ㓄ิࡀᙧᡂࡉࢀࠊࡑࢀࡀ 3 ᒙ࡟✚ᒙࡋ࡚࠸ࡓࠋࡇࡢࡓࡵࠊᅛయⰍ࡟ᙳ㡪ࢆཬࡰࡍᅉᏊ࡜ࡋ࡚ḟࡢ㸰Ⅼࡀ᫂ࡽ࠿࡟࡞ࡗ
࡚ࡁࡓࠋձศᏊ㛫Ỉ⣲⤖ྜ࡛ᙧᡂࡉࢀࡓ 3 ิࡢศᏊࣘࢽࢵࢺࡀἼ㛗ࢩࣇࢺࡢ༢఩࡟࡞ࡗ࡚࠸ࡿࠊղࡇࡢศᏊ
ࣘࢽࢵࢺࡀ✚ᒙࡍࡿࡇ࡜࡛ࢩࣇࢺᖜࡀቑ኱ࡍࡿࠋ௒ᚋࠊࡇࡢ㸰Ⅼࢆ᳨ドࡋ࡞ࡀࡽ◊✲ࢆ㐍ࡵࡿணᐃ࡛࠶ࡿࠋ

ᅗ㸰. ྛㄏᑟయ࠾ࡅࡿ᭱኱྾཰Ἴ㛗ࡢィ⟬್

a)b)

ᅗ㸱. UV-vis ࢫ࣌ࢡࢺࣝ:a)ⷧ⭷ࠊb) 3×3 ศᏊࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬᳃⩏㈗(2021)㸬ྡྂᒇᕤᴗ኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉ಟኈㄽᩥ㸦㠀බ㛤㸧.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Y. Kojima, S. Sugiura, K. Suzuki, Y. Yisilamu, K. Ono, “Synthesis and n-Type Semiconducting Properties ofBis(dioxaborin) Compounds Containing a ʌ-Extended 2,2'-Bithiophene Structure”, in preparation.
‫ۻ‬Y. Sakura, F. Yumioka, T. Funaki, K. Ono, “Synthesis and Photovoltaic Properties of Boron ȕ-Ketoiminate Dyes
Forming a Linear Donor-ʌ-Acceptor Structure”, Chem. Asian J. 2020, 15, 1982–1989.

- 29 -

ග໬Ꮫ཯ᛂࡢไᚚ࡜ᛂ⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical study on the control and application of photochemical reactions۵㯮ᓮ ㆡࠊబ఑ ┒ஂ㸦㔞Ꮚ⛉Ꮫᢏ⾡◊✲㛤Ⓨᶵᵓ㸧◊✲┠ⓗࠊෆᐜᮏ◊✲ࡣḟࡢ஧ࡘࡢࣉࣟࢪ࢙ࢡࢺ࠿ࡽᡂࡿ㸸㸦㸧㉸▷ࣃࣝࢫ࣮ࣞࢨ࣮࡟ࡼࡿ㔞Ꮚไᚚ㸹  㓟ᛶ⁐ᾮ୰࡛ࡢ࢖࢜ࣥ㘒యࡢᵓ㐀◊✲ࠋ㸦㸧࡛ࡣࠊ/L&O ศᏊࡢΰྜ≀ /L&O ࡜ /L&O ࡢྠ఩య㑅ᢥⓗศᏊ㓄ྥࢆᐇ⌧ࡍࡿ᭱㐺ไᚚࣃࣝࢫࡢ⟬ฟࢆ┠ⓗ࡜ࡍࡿࠋ㸦㸧࡛ࡣࠊ  ࣮ࣞࢨ࣮ᚤ⢏Ꮚ໬ἲ࡟ࡼࡿ 3G ศ㞳ᶵᵓࡢゎ᫂ࠊ ࣏ࣜࣔࣜࣈࢹࣥ㓟ࡢᏳᐃᵓ㐀᥈⣴࠾ࡼࡧศගࢹ࣮ࢱィ⟬ࠊࢆ┠ⓗ࡜ࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ㸦㸧୍ගᏊ࠾ࡼࡧ஧ගᏊ㐣⛬ࢆ⪃៖ࡋࡓࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸࡚ࠊ/L&O ศᏊࡢྠ఩య㑅ᢥⓗ࡞ศᏊ㓄ྥࢆᐇ⌧ࡍࡿ᭱㐺㟁ሙࢆ᭱㐺ไᚚ⌮ㄽ࡟ࡼࡾồࡵࡿࠋἼ᮰ࡢ᫬㛫Ⓨᒎィ⟬ࡣࠊ᣺ື࡜ᅇ㌿ࢆ⪃៖ࡋࡓ஧ḟඖࡢVSOLWRSHUDWRU ἲ࡟ࡼࡾ⾜࠺ࠋ㸦㸧0ROSUR ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࠊ>3G&O@㘒యࡢບ㉳≧ែ࣏ࢸࣥࢩࣕࣝࢆ
஧ḟඖࣔࢹࣝࢆ⏝࠸࡚ィ⟬ࡍࡿࠋィ⟬᪉ἲࡣ 05&,ࠊᇶᗏ㛵ᩘࡣ 3G ࡟ DXJFFS97=33ࠊ&O ࡟ DXJFFS97= ࢆ⏝࠸ࡿࠋ  *DXVVLQ ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࠊ03DXJFFS9'= ࣞ࣋ࣝࡢィ⟬࡟ࡼࡾᙉ㓟ᛶ⁐ᾮ୰࡛ࡢᏑ
ᅾࡀண᝿ࡉࢀࡿ 0R ஧㔞యࠊ0R ༢㔞యࡢᏳᐃᵓ㐀᥈⣴ࢆ⾜࠺ࠋ◊✲ᡂᯝ 㸦㸧᭱㐺ไᚚィ⟬ࡢ⤖ᯝࠊྠ఩య㑅ᢥⓗศᏊ㓄ྥࢆ㧗ຠ⋡࡛ᐇ⌧ࡍࡿ᭱㐺ࣃࣝࢫࡀᚓࡽࢀࡓࠋࡇࡢ࡜ࡁᚓ
ࡽࢀࡓࣃࣝࢫࡣࠊ୍ගᏊ㐣⛬࡜஧ගᏊ㐣⛬ࡀ┦஌ⓗ࡟స⏝ࡍࡿ⌮᝿ⓗ࡞ࡶࡢ࡛࠶ࡗࡓࠋ(2-1) >3G&O@㘒యࡢບ㉳≧ែ࣏ࢸࣥࢩࣕࣝ㠃ࢆࠊ&O&O ㊥㞳࡜ࡑࡢ୰Ⅼ࠿ࡽ 3G ࡲ࡛ࡢ㊥㞳ࡢ஧ኚᩘ㛵ᩘ࡜ࡋ࡚ィ⟬ࡋࡓࠋᖹ⾮᰾㓄⨨㸦ṇ᪉ᙧࠊ'K㸧࡟࠾࠸࡚ᇶᗏ≧ែ࡜ࡢ㛫࡟኱ࡁ࡞㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺࢆᣢࡘບ㉳≧ែ࣏ࢸࣥࢩࣕࣝ㠃ࡢᙧ≧࠿ࡽࠊගゎ㞳㐣⛬ࡢ⤖ᯝ 3G&O&O&Oࡀ⏕ᡂࡍࡿྍ⬟ᛶࡀ㧗࠸ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ  ᫖ᖺᗘࡲ࡛
0R ஧㔞య࡜ࡋ࡚>0R2 +2 @0R ༢㔞య࡜ࡋ࡚>0R2 +2 @ࢆ᝿ᐃࡋ࡚◊✲ࢆ㐍ࡵ࡚ࡁࡓࡀࠊࡇࢀ࡛ࡣ࠺
ࡲࡃ ;$)6 ࢹ࣮ࢱࡀゎ㔘࡛ࡁ࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊ௒ᖺᗘ᪂ࡓ࡟ 0R ༢㔞యࡢೃ⿵࡜ࡋ࡚>+0R2 +2 @ࢆྲྀࡾධ
ࢀゎᯒࢆ⾜ࡗࡓ⤖ᯝࠊ㓟⃰ᗘ࡟౫Ꮡࡋࡓ ;$)6 ࢫ࣌ࢡࢺࣝᙧ≧ኚ໬ࢆ࠺ࡲࡃㄝ᫂ࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ࡋ࡞ۻ‬

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬బ఑ࠊⶇ⏣ࠊᯇᮧࠊ㰻⸨ࠊ୰すࠊ㎷ࠊ኱ሙ$SSOLFDWLRQRIDQ$XJPHQWDWLRQ0HWKRGWR0&5$/6$QDO\VLVIRU ;$)6DQG5DPDQ'DWD 0DWULFHV LQWKH 6WUXFWXUDO&KDQJHRI ,VRSRO\PRO\EGDWHV $QDO\WLFDO
6FLHQFHV  ‫ۻ‬㯮ᓮࠊ୰すࠊబ఑ࠊ኱ሙࠊ͆$ELQLWLR05&,VWXG\RQSRWHQWLDOHQHUJ\FXUYHVIRUGRXEOH&OORVVIURPWKH SDOODGLXPWHWUDFKORULGHDQLRQ3G&OѸ͆&KHP3K\V/HWW  - 30 -

Ỉ⣲⤖ྜ⣔࡟࠾ࡅࡿග໬Ꮫ㐣⛬ࡢ⌮ㄽⓗ◊✲Theoretical studies on photochemical processes in hydrogen-bonded
systems‫ۑ‬ᒣᓮ ⚈ᖹࠊఀ⸨ ᖾᫍ㸦ᘯ๓኱㝔⌮ᕤ㸧1◊✲┠ⓗᮏㄢ㢟࡛ࡣࠊศᏊෆ࣭ศᏊ㛫ࡢỈ⣲⤖ྜࢆᣢࡘ᭷ᶵ໬ྜ≀࡟ࡘ࠸࡚ࠊගບ㉳ࡋࡓ࡜ࡁ࡟㉳ࡇࡿ࡜ࡉࢀࡿᵝࠎ࡞㐣⛬ࡢᶵᵓࢆศᏊ࡛ࣞ࣋ࣝ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ◊✲ࢆ㐙⾜ࡋ࡚࠸ࡿࠋ2020 ᖺᗘࡣࠊ࢖ࣥࢹ࢕ࢦ
࡜ࡑࡢ⨨᥮యࡢග␗ᛶ໬࡟㛵ࡍࡿ㔞Ꮚ໬Ꮫィ⟬ࢆ㔜Ⅼⓗ࡟ᐇ᪋ࡋࡓࠋ
࢖ࣥࢹ࢕ࢦࡣࠊศᏊࡢ୰ኸ࡟Ⅳ⣲̺Ⅳ⣲㛫஧㔜⤖ྜࢆᣢࡘ࡟ࡶ࠿࠿ࢃࡽࡎࠊࢩࢫ̺ࢺࣛࣥࢫග␗ᛶ໬ࢆ㉳ࡇࡉ࡞࠸ࠋ୍᪉ࠊ࢖ࣥࢹ࢕ࢦࡣศᏊෆỈ⣲⤖ྜࢆᙧᡂࡋ࡚࠾ࡾࠊࡇࡢỈ⣲ࢆࣇ࢙ࢽࣝᇶ➼࡛⨨᥮ࡍࡿ࡜ග␗
ᛶ໬ࢆ㉳ࡇࡍࡼ࠺࡟࡞ࡿࠋࡇࡢ཯ᛂᛶࡢ㐪࠸࡟ࡣศᏊෆỈ⣲⤖ྜࡢ᭷↓ࡀᙳ㡪ࡍࡿ࡜⪃࠼ࡽࢀࡿࡀࠊ㐪࠸ࢆ⏕ࡌࡉࡏࡿලయⓗ࡞ᶵᵓࡣศ࠿ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊ࢖ࣥࢹ࢕ࢦ࠿ࡽ 2 ಶࡢ࣋ࣥࢮࣥ⎔ࢆ๐㝖ࡋࡓࣔࢹࣝศ
Ꮚࠊ࠾ࡼࡧࡑࡢࢪ࣓ࢳࣝ⨨᥮యࡢࢩࢫ̺ࢺࣛࣥࢫග␗ᛶ໬࡟ࡘ࠸࡚࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ィ⟬ࢆ⾜࠸ࠊ཯ᛂᛶࡢ㐪࠸ࢆ᳨ウࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ࢖ࣥࢹ࢕ࢦࡢࣔࢹࣝศᏊ࠾ࡼࡧࡑࡢ⨨᥮యࡢ 1ʌʌ*≧ែ࡟ࡘ࠸࡚ࠊ୰ኸࡢ C=C ⤖ྜ࿘ࡾࡢࡡࡌࢀゅࢆ཯ᛂᗙᶆ࡜ࡍࡿ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤⥺ࢆィ⟬ࡋࡓࠋCASSCF ἲ࡛ 1ʌʌ*≧ែࡢᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊᚓࡽࢀࡓᵓ
㐀࡟࠾࠸࡚ MS-CASPT2 ἲ࡛࢚ࢿࣝࢠ࣮ࢆ෌ィ⟬ࡋࡓࠋ࠸ࡎࢀࡢィ⟬࡟ࡘ࠸࡚ࡶࠊactive ✵㛫ࡣ (2,2) ࡘࡲࡾ
2 㟁Ꮚ 2 ㌶㐨࡜ࡋࡓࠋ௨ୖࡢィ⟬࡟ Molpro 2018.2 ࢆ౑⏝ࡋࡓࠋ

3◊✲ᡂᯝ
MS-CASPT2 ࡟ࡼࡿ࣏ࢸࣥࢩࣕࣝィ⟬ࡢ⤖ᯝࠊග␗ᛶ໬ࡢ࢚ࢿࣝࢠ࣮㞀ቨࡀ࢖ࣥࢹ࢕ࢦࡢࣔࢹࣝศᏊ࡛ 1.10

eVࠊ⨨᥮య࡛ 0.69 eV ࡜ồࡵࡽࢀࡓࠋࡇࡢ⤖ᯝࡣࠊ⨨᥮࡟ࡼࡾග␗ᛶ໬ࡀࡼࡾ㉳ࡇࡾࡸࡍࡃ࡞ࡿ࡜࠸࠺ほ஦ᐇࢆᨭᣢࡋ࡚࠸ࡿࠋ୍᪉࡛ࠊ࠸ࡎࢀࡢศᏊ࡟࠾࠸࡚ࡶࠊC=C ⤖ྜࡀ⣙ 90° ࡡࡌࢀࡓᵓ㐀࡛ 1ʌʌ*≧ែ࡜ᇶᗏ≧ែࡢ࣏ࢸࣥࢩࣕࣝ᭤㠃㛫ࡢ෇㗹஺ᕪ࡟฿㐩ࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡣࠊࡓ࡜࠼↓⨨᥮ࡢ࢖ࣥࢹ࢕ࢦ࡛ࡶ
㧗࢚ࢿࣝࢠ࣮ບ㉳࡟ࡼࡗ࡚ග␗ᛶ໬ࡀ㉳ࡇࡾ࠺ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠾ࡾࠊほ⤖ᯝ࡜཯ࡋ࡚࠸ࡿࠋ௒ᚋࡢ◊✲࡟࠾࠸࡚ࠊࡼࡾ኱ࡁ࡞ active ✵㛫࡛ィ⟬ࢆ⾜࠺➼ࡢࡉࡽ࡞ࡿ᳨ウࡀᚲせ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 31 -

ȧࢡࣛࢫࢱ࣮ศᏊࡢ㟁Ꮚ≀ᛶࡢゎ᫂Investigation of the electronic properties of pi-cluster molecules‫ۑ‬すෆ ᬛᙪࠊ㛗⏫ ఙᏹࠊஂಖ Ꮥྐ㸦኱㜰኱Ꮫ㸧1◊✲┠ⓗᮏ◊✲࡛ࡣࠊȧ㟁Ꮚࡀ㇏ᐩ࡞ⰾ㤶⎔ࢆศᏊෆ࡟ᐦ࡟㞟✚ࡉࡏࡓ໬ྜ≀ࠕSࢡࣛࢫࢱ࣮ศᏊࠖࡢྜᡂ࡜ࡑࡢ≀ᛶࡢゎ᫂ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋⰾ㤶⎔ࢆⅣ⣲ཎᏊࡢࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫ༙ᚄࡢ࿴ࡼࡾࡶ▷࠸㊥㞳࡛ᐦ࡟㞟✚໬ࡉࡏࡿࡇ࡜࡛ࠊⰾ㤶⎔ྠኈ࡟ඹ᭷⤖ྜࢆ௓ࡉ࡞࠸㞟✚໬࡟ࡼࡿSඹᙺ⣔ࡢᣑᙇࢆಁࡍࡇ࡜ࡀྍ⬟࡜࡞ࡿࠋ᭱㏆
࡛ࡣⅣ໬Ỉ⣲ࣛࢪ࢝ࣝ࡜࠸ࡗࡓ཯ᛂᛶ໬Ꮫ✀ࡀᙧᡂࡍࡿȪࢲ࢖࣐࣮ࡸȧࢲ࢖࣐࣮࡟࠾ࡅࡿȧ㟁Ꮚ㞼ࡀᐦ࡞⎔ቃࢆᣢࡘ໬ྜ≀࡟ࡘ࠸࡚ࡶ◊✲ࢆᒎ㛤ࡋ࡚࠸ࡿࠋᙜヱᖺᗘ࡟࠾࠸࡚ࡣࠊ࢔ࣥࢺࣛࢭࣥ஧㔞య࠿ࡽᡂࡿ⎔≧ȧࢡࣛࢫࢱ࣮1 ࡜ࡑࡢග␗ᛶయ 1’ࡢ⇕࡟ࡼࡿ␗ᛶ໬ᣲື࡟ࡘ࠸࡚㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ࣉࣟࢢ࣒ࣛࡣ Gaussian16 ࢆ౑⏝ࠋᇶᗏ≧ែ࡟࠾ࡅࡿᵓ㐀᭱㐺໬ࡣ(U)M06-2X ỗ㛵ᩘࢆ⏝࠸࡚ホ౯ࢆ⾜ࡗࡓࠋᇶᗏ㛵ᩘࡣ 6-31G(d,p)ࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

ྑ࡟ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡓ␗ᛶ໬๓ᚋࡢ࢚ࢿࣝࢠ࣮┦㛵ᅗࢆ♧ࡍࠋ1’࠿ࡽ 1 ࡟ᡠࡿ㝿ࠊ஧ࡘ࠶ࡿ༢⤖ྜࡣẁ㝵ⓗ࡟㛤⿣ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࠊࡇࢀࡣᐇ㦂್࡜㠀ᖖ࡟Ⰻ࠸୍⮴ࢆࡋࡓࠋࡉࡽ࡟㑄⛣≧ែ࡛ࡣ⯆࿡῝࠸஦࡟ 85㸣ࡢ㧗࠸㛤Ẇࣅࣛࢪ࢝ࣝᛶࢆ♧ࡍࡇ࡜ࡀศ࠿ࡗࡓࠋ

4

Ⓨ⾲ᐇ⦼

‫[ۻ‬1] 㛗⏫ఙᏹ࣭すෆᬛᙪ࣭బ⸨࿴ಙ࣭ஂಖᏕྐ
ࠕ❅⣲ཎᏊࢆᑟධࡋࡓȧᣑᙇᆺࢺࣜࣇ࢙ࢽ࣓ࣝࢳࣝࣛࢪ࢝ࣝࡢྜᡂ࡜≀ᛶࠖ  ᇶ♏᭷ᶵ໬Ꮫ఍ ➨ 0 ᅇⱝᡭ࢜ࣥࣛ࢖ࣥࢩ࣏ࣥࢪ࣒࢘㸦2020 ᖺ㸧‫[ۻ‬2] ┦ཎᫍᩯ࣭すෆᬛᙪ࣭ஂಖᏕྐ
ࠕ࢔ࣥࢺࣜࣝ㦵᱁࡛ȧᣑᙇࡋࡓ Chichibabin's Ⅳ໬Ỉ⣲ࡢྜᡂ࡜ᛶ㉁ࠖ
  ᪥ᮏ໬Ꮫ఍ ➨ 101 ᅇ᫓Ꮨᖺ఍ ᇶ♏᭷ᶵ໬Ꮫウㄽ఍㸦2021 ᖺ㸧‫[ۻ‬3] すෆᬛᙪ࣭┦ཎᫍᩯ࣭ஂಖᏕྐ
ࠕ࢔ࣥࢺࣜࣝ㦵᱁࡛ȧᣑᙇࡋࡓ Thiele's Ⅳ໬Ỉ⣲ࡢྜᡂ࡜ᛶ㉁ࠖ
  ᪥ᮏ໬Ꮫ఍ ➨ 101 ᅇ᫓Ꮨᖺ఍ ᇶ♏᭷ᶵ໬Ꮫウㄽ఍㸦2021 ᖺ㸧‫[ۻ‬4] ㉥⃝ຬᶞ࣭すෆᬛᙪ࣭ஂಖᏕྐ
ࠕ࢔ࣥࢺࣛࢭࣥ㦵᱁ࢆᇶ┙࡜ࡋࡓࣛࢲ࣮≧ȧࢡࣛࢫࢱ࣮ศᏊࡢྜᡂ࡜ᛶ㉁ࠖ
  ᪥ᮏ໬Ꮫ఍ ➨ 101 ᅇ᫓Ꮨᖺ఍ ᇶ♏᭷ᶵ໬Ꮫウㄽ఍㸦2021 ᖺ㸧

5

ฟ∧ᐇ⦼

‫[ۻ‬1] T. Nishiuchi, K. Kisaka, T. Kubo
“Synthesis of Anthracene-Based Cyclic π-Clusters and Elucidation of their Properties Originating from Congested
Aromatic Planes”

Angew. Chem. Int. Ed. 2021, 60, 5400-5406.

- 32 -

 ' )  $ !,"&#+("#  






  

*%





bw'OBM8;2HO? h Áarh  Àj´NÀe¹n­ag« |ÂÁ  #4M@LO6 ¥aA%§8;2HO?

#il  h g«Â£8;2HO?h¾ Á h ·¡ºv°pd~#¹qar±¦¯ Á h#f[\q`^r,DHLO,IM¯Â

+<K6¸a)J.1O   c&1;OKd~#Á#311*#- #¯Â ! ¾Á  %/ mz¾Á. cq  " C4M,GK#Á.)J.1O
&1;OKd~#´¹\t¿}d~µ ¯ÂÁ il h¶¢#Á =3*O-#f[\q`^r,DHLO,IMÂ  cqTW 0&#5 C4M,GKÁ cq &01.'' C4M,GKÁRª½\q½^ &--#0%
.-&1 C4M,GK#Â´¹\k#Xt¿}  .)J.1O&1;
OKd~UQÂ.    .         #¤Á]y{¨"Á*(30&   &1;O
K$06$K5>7\¯¶¢#¯

Âa&:

K(OZV  &Ád~ & Â h\q`^r,DHLO,IM¨# *(Â  ilÁ £¨±¦#¼oÁ  cq#Y©,DHLO,IM#  !Á        £¨sx»q#®u _ Â¨Á   hF'9/E

¬ } Â







*(30& -#/1).21.'(0.42)



1*,3+#2*.-# #22)& *-*2*#+12#2&#-%$#'2&0-1

P²¤¨#³SsÂUP- 33 -

᣺ື෇஧Ⰽᛶศගἲࡢ㉸ศᏊ࢟ࣛࣜࢸ࢕࡬ࡢᛂ⏝Application of Vibrational Circular Dichroism for Supramolecular
Chirality‫ۑ‬బ⸨ ஂᏊ㸦ឡ፾኱Ꮫ኱Ꮫ㝔⌮ᕤᏛ◊✲⛉㸧1◊✲┠ⓗ࢟ࣛࣝศගἲࡢ୍ࡘ࡛࠶ࡿ᣺ື෇஧Ⰽᛶ㸦VCD㸧ἲ࡛ࡣࠊ㉥እ㡿ᇦࡢ෇஧Ⰽᛶࢆ᳨ฟࡍࡿࠋࡑࡢ≉ᚩ࡜ࡋ࡚ࠊྛᇶ‽᣺ື࡟ࡘ࠸࡚ࡢከ㔞ࡢ᝟ሗࢆᚓࡿࡇ࡜ࡀ࡛ࡁࠊ࡯࡜ࢇ࡝ࡍ࡭࡚ࡢ≀㉁࡟㐺⏝࡛ࡁࡿࡇ࡜࡛࠶ࡿࠋ
ࡋ࠿ࡋᛂ⏝౛ࡣ⣸እ㡿ᇦࡢ෇೫ග

ᐃ㸦ECD㸧࡟ẚ㍑ࡋ࡚᱁ẁ࡟ᑡ࡞࠸ࠋࡑࡢ୺࡞⌮⏤ࡣࠊVCD ࢩࢢࢼࣝࡢ

ᙉᗘࡀ㠀ᖖ࡟ᑠࡉ࠸ࡇ࡜࡛࠶ࡿࠋᮏ⏦ㄳ⪅ࡽࡣࢤࣝᙧᡂ㐣⛬ࡸ㔠ᒓ㓄఩࡟ࡼࡗ࡚ VCD ࢩࢢࢼࣝࡀ㢧ⴭ࡟ቑ኱ࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋ௨ୖࡢࣈ࣮ࣞࢡࢫ࣮ࣝࢆࡶ࡜࡟ࠊVCD ἲࢆࢤࣝࠊ࢟ࣛࣝ⤖ᬗࠊᾮᬗࠊከ᰾㔠ᒓ㘒యࠊᅛయ࡞࡝ࡢ㉸ศᏊ⣔࡬㐺⏝ࡋ࡚᮶ࡓࠋVCD ἲࢆά⏝ࡍࡿ࡟ࡣࠊ⌮ㄽィ⟬ࢆ⏝࠸࡚ࠊᐇ㦂࡜⌮ㄽࢆẚ㍑ࡋࠊࡑ
ࡢヲ⣽ᵓ㐀ࢆỴᐃࡍࡿᚲせࡀ࠶ࡿࠋᮏ◊✲࡛ࡣ୺࡟࢖ࣜࢪ࣒࢘㘒యࡢບ㉳≧ែࡢィ⟬ࠊ࢟ࣛࣝ㘒యྠኈࡢ┦஫స⏝ࠊࡑࢀࡽࡢ VCD ィ⟬ࠊCu 㘒యࡢ୙ᩧྜᡂ࡬ࡢᛂ⏝ࢆ┠ᣦࡋࡓィ⟬ࠊ࠾ࡼࡧࢪ࣌ࣉࢳࢻࡢ᣺ື෇஧Ⰽ
ᛶࡢィ⟬࡟฼⏝ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 16 ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࠊB3LYP/6-31G(d,p) 㸦C, H, O, N㸧, SDD 㸦Ru, Ir, Ni, Cu ࡞࡝ࡢ㔠ᒓ㸧࡛ࣞ࣋ࣝᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊࡑࡢᚋ࡟ VCD ィ⟬ࢆ࠾ࡇ࡞ࡗࡓࠋ࣌ࣉࢳࢻᵓ㐀ண3

ࡸ VCD ィ⟬ࡶ࠾ࡇ࡞ࡗࡓࠋ

◊✲ᡂᯝᮏ◊✲࡛ࡣ࢔࣑ࣀ㓟ࡢ࢟ࣛࣜࢸ࢕࡟╔┠ࡋࡓศගἲ࡜ࡋ࡚ᅛయ᣺ື෇஧Ⰽᛶ㸦SD-VCD㸧ἲࢆ㐺⏝ࡋࡓࠋᮏᖺᗘࡣ≉࡟୙ᩧྜᡂࢆ┠ᣦࡋࡓ Cu 㘒య࡜ᇶ㉁ࡢ┦஫స⏝࡟㛵ࡋ࡚ィ⟬ࢆ࠾ࡇ࡞ࡗࡓࠋVCD ࡢィ⟬ࢆ࠾ࡇ࡞࠸࢔࢟ࣛࣝศᏊࡢ࢟ࣛࣝㄏᑟࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊྛ✀࢔࣑ࣀ㓟ࡸࢪ࣌ࣉࢳࢻ࡬ࡢᛂ⏝ࢆ࠾ࡇ࡞࠸ࠊᅛయ࡟࠾ࡅࡿ㉸ศᏊᵓ㐀ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ୺࡞ᡂᯝ࡜ࡋ࡚௨ୗࡢㄽᩥ࡞࡝࡟Ⓨ⾲ࡋࡓࠋⓎ⾲ᐇ⦼
1. Vibrational Circular Dichroism towards Asymmetric Catalysis: Chiral Induction in Substrates Coordinatedwith Copper(II) Ions
Hisako Sato, Kazuyoshi Takimoto, Jun Yoshida and Akihiko Yamagishi
Phys. Chem. Chem. Phys. 2020, 22, 24393 – 24398.
2. Multidimensional Vibrational Circular Dichroism Apparatus Equipped with Quantum Cascade Laser andits Use for Investigating Some Peptide Systems Containing d-Amino Acids
Hisako Sato*, Masaru Shimizu, Keisuke Watanabe, Jun Yoshida, Izuru kawamura, Jun Koshoubu,
Anal. Chem. Analytical Chemistry 2021, 93, 5, 2742-2748.季ʤJST, Ѭඦ୉͵ʹͲϕϪηϨϨʖηʥ

- 34 -

ගᶵ⬟ᛶศᏊࡢ㟁Ꮚ≧ែ࣭ᵓ㐀࣭ࢫ࣌ࢡࢺࣝィ⟬Calculations of electronic states, structure, and spectra ofphotofunctional molecules‫ۑ‬㣤᳃ ಇᩥ㸦ᐊ⹒ᕤᴗ኱Ꮫ㸧1◊✲┠ⓗ
7,7,8,8-ࢸࢺࣛࢩ࢔ࣀ࢟ࣀࢪ࣓ࢱࣥ(TCNQ)ࡣࠊ௦⾲ⓗ࡞㟁Ꮚ࢔ࢡࢭࣉࢱ࣮ศᏊࡢࡦ࡜ࡘ࡛࠶ࡾࠊ᭷ᶵఏᑟయ

ࡢ㛤Ⓨ࡟࠾࠸࡚㠀ᖖ࡟㔜せ࡞ศᏊ࡛࠶ࡿࠋ฼⏝⪅ࡣᵝࠎ࡞⁐፹୰࡟࠾ࡅࡿ TCNQ ࡢศග◊✲ࢆ⾜࠸ࠊ⺯ග㔞Ꮚ཰⋡ࡀ⁐፹ࡢᴟᛶ࡟኱ࡁࡃ౫Ꮡࡋࠊ⇕άᛶ໬㐜ᘏ⺯ගࢆ♧ࡍࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ࡚࠸ࡿࠋࡇࢀࡽࡢᐇ㦂⤖ᯝࢆ⌮ゎࡍࡿࡓࡵ࡟ࠊTCNQ ࡢᇶᗏ≧ែ࠾ࡼࡧ୕㔜㡯≧ែࢆྵࡴບ㉳≧ែࡢ࢚ࢿࣝࢠ࣮‽఩࡜ᵓ㐀ࡢィ⟬ࢆ⾜࠺ࡇ࡜ࡀᚲせ࡛࠶ࡾࠊ2019 ᖺᗘࡢィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮᪋タ฼⏝࡟᥇ᢥࡉࢀ DFT ィ⟬ࢆ⾜ࡗࡓࠋᮏᖺᗘࡣ๓
ᅇࡢィ⟬ࢆⓎᒎࡉࡏࠊࢡࣛࢫࢱ࣮ᒎ㛤ἲ࡛࠶ࡿ CC2 ἲ࡞࡝ࢆ⏝࠸࡚ࠊศᏊᵓ㐀ࠊࢫ࣌ࢡࢺࣝࠊ࠾ࡼࡧࢫࣆࣥ
㌶㐨┦஫స⏝ࡢィ⟬ࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ
Turbomole, ORCA, ࠾ࡼࡧ Gaussian 16 ࣉࣟࢢ࣒ࣛࢆィ⟬࡟౑⏝ࡋࡓࠋCC2 ィ⟬࡟ࡣ Turbomole ࢆ⏝࠸ࠊ

CC2/aug-cc-pVTZ ࡛ࣞ࣋ࣝᇶᗏ≧ែ࡜ບ㉳≧ែࡢᵓ㐀᭱㐺໬ࠊ࠾ࡼࡧᆶ┤㑄⛣࢚ࢿࣝࢠ࣮ࡢィ⟬ࢆ⾜ࡗࡓࠋࢫࣆࣥ㌶㐨┦஫స⏝ࡢィ⟬ࡣ ORCA ࢆ⏝࠸ࠊM06-2X/6-311++G(d,p)ࣞ࣋ࣝࡢ TD-DFT ἲ࡟ࡼࡾ⾜ࡗࡓࠋࡉࡽ
࡟ᇶᗏ≧ែࡢᵓ㐀᭱㐺໬ࢆ MP2/aug-cc-pVTZ ࡛ࣞ࣋ࣝ Gaussian 16 ࢆ⏝࠸࡚⾜ࡗࡓࠋ3◊✲ᡂᯝCC2 ィ⟬࡟ࡼࡾண⾲ 1. ບ㉳≧ែࡢᑐ⛠ᛶ࡜࢚ࢿࣝࢠ࣮ࠊ᣺ືᏊᙉᗘ
ࡉࢀࡓບ㉳≧ែࡢᑐ⛠ᛶ

Excited states (symmetry)E / eVf࡜ᆶ┤㑄⛣࢚ࢿࣝࢠ࣮ࡢ್ࢆࠊ⾲㸯࡟♧ࡍࠋ୍㔜ଵ ሺ ଵଷ୳ ሻ

3.292

1.301

㡯≧ែ࡜୕㔜㡯≧ែࡢ㛫ࡢࢫࣆࣥ㌶㐨┦஫స⏝ଶ ሺ ଵଵ୥ ሻ

3.811

0.000

ࡢ኱ࡁࡉࢆィ⟬ࡋࡓ࡜ࡇࢁࠊ⣙ 1 cm ௨ୗ࡜࡞ࡾ

ଵଷ ሺ ୥ ሻ

4.402

0.000

ᑠࡉ࠸ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡉࡽ࡟ࠊT1 ≧ែ࡜ଵ ሺ ଷଷ୳ ሻ

1.336

S0 ≧ែࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࡣ 0.98 eV ࡜ᑠࡉ࠸ଷଶ ሺ ଵ୥ ሻ

3.283

ଷ

3.657

–1

ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

4ଷ ሺ ୥ ሻⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
մ[1] 㣤᳃ಇᩥࠊ2020 ᖺᗘ᪥ᮏศගᏛ఍໭ᾏ㐨ᨭ㒊ࢩ࣏ࣥࢪ࣒࢘ (2021 ᖺ 1 ᭶ 15 ᪥ࠊ࢜ࣥࣛ࢖ࣥ)ࠊ௚Ⓨ⾲

ᐇ⦼㸳௳ࠋ

5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
մ[1] Iimori, T. Comput. Theor. Chem. 1199, 113211 (2021). մ[2] Iimori, T., Sugawa, H. & Uchida, N. J. Phys. Chem.

B 124, 8317-8322 (2020).[3] Iimori, T., Torii, Y., Ishikawa, T. & Tamai, N. J. Phys. Chem. B 124, 7918-7928 (2020).

- 35 -











Study on structure and reactions of novel main group element
compoundsÁ`Îµ«¼HÎÇfMÎ¡kydÎKSÎj\X¶Î^¸cÎKEmMÎ
Ë¶ÎKcÎ«LÎÅzÎEÅcÌg¨ÄcgÍ

1

¢
t

$Ze¿OvÀYr D©#}UbT¥Y]¢oJ

ºq·[pq%iÉx! ¢%iÉ´¯¤GÈ!

¢o¬ Ê_~UbT¥Y]° ºq·%®x# %#!UbT¥Y] ÃF#[p¾rqY*7@-C%´¯¤[p®x%u2¢w¯¤wGaussian 16 Rev.B.01 %Q B3LYP/6-31G+(d,p) B3LYP/6-31G+(d)

¯¤ "

3

¿nº|½Y%¬{Y]

 B3PW91/6-31G+(d,p) DFT

ÃF#[p¾rº%¢s
E±¯¤w?B−;)¥¦]/(¥−¥¦]%Y]%#UbT¥Y]|½

Yº%9AB3'&¹»*7@-CÆªWl%²R>0+@s?,B5+2:?B.¾rºqY*7@-C%iÉ¦%]³x #4

%x! ­i§Ih
“;19'8<>C4¿Oe%}#(?0)=0+@<6@ÂP]sq·”, ÇfM, µ«¼H,Á`ÎÂPYgN£ 70 a°´N(2020).

5Vi§Ih
"Photocatalytic Giese-type Reaction Using Alkylsilicates Bearing C,O-Bidentate Ligands", T. Morofuji, Y. Matsui,

M. Ohno, G. Ikarashi, N. Kano, Chem. Eur. J., 27, 6713-6718 (2021).
"Synthesis, Structure and Properties of a Boron-substituted Phosphorane Bearing N,O-Bidentate Ligands", N. J.
O’Brien, Y. Koda, H. Maeda, N. Kano, Polyhedron, 185, 114841 (2020).
"Arylation of Aryllithiums with S-Arylphenothiazinium Ions for Biaryl Synthesis", T. Morofuji, T. Yoshida, R.
Tsutsumi, M. Yamanaka, N. Kano, Chem. Commun., 56, 13995-13998 (2020).
"Terminal-oxidant-free Photocatalytic C–H Alkylations of Heteroarenes with Alkylsilicates as Alkyl Radical
Precursors", G. Ikarashi, T. Morofuji, N. Kano, Chem. Commun., 56, 10006-10009 (2020).
"Promiscuous Enzymes Cooperate at the Substrate Level En Route to Lactazole A", A. A. Vinogradov, M.
Shimomura, N. Kano, Y. Goto, H. Onaka, H. Suga, J. Am. Chem. Soc., 142, 13886-13897 (2020).

- 36 -᪂つᶵ⬟ᛶȧඹᙺศᏊࡢྜᡂ࡜≀ᛶ࡟㛵ࡍࡿ◊✲
6\QWKHVLVDQG3URSHUWLHVRI1RYHO)XQFWLRQDOʌ&RQMXJDWHG0ROHFXOHV‫ۑ‬ΎỈ ❶ᘯࠊὠ⏣ ▱ᣅࠊụ⏣ ⩧ࠊ᭷ᕝ ᚸࠊ኱ᅬ ᙬ℩ࠊ㉺ᬛ ຬኴࠊ㤶ᒣ ⥤㡢ࠊὠ⏣ ✑㤶ࠊᯘ⏣ 㞞❶ࠊⱱᗞ ᘯ࿴ࠊ᳃⭜ ဴஓࠊᶓ⏣ ⾨ࠊᮤ ᮾⅡࠊ᪂㇂ ு㸦኱㜰኱Ꮫ኱Ꮫ㝔ᇶ♏ᕤᏛ◊✲⛉㸧 ◊✲┠ⓗࠊෆᐜ㟁Ꮚࢻࢼ࣮࡜㟁Ꮚ࢔ࢡࢭࣉࢱ࣮ࢆ኱ࡁ࡞஧㠃ゅࢆ௓ࡋ࡚┦஫స⏝ࡉࡏࡓࠊ㛤Ẇᛶࢆ᭷ࡍࡿȧඹᙺ཮ᛶ࢖࢜
ࣥࢆタィ࣭ྜᡂࡋࠊ㛤Ẇᛶࢆᐇ㦂ⓗ࠾ࡼࡧィ⟬⛉Ꮫⓗ࡟᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡟◊✲ࢆ⾜ࡗࡓࠋ ◊✲᪉ἲࠊィ⟬᪉ἲ*DXVVLDQ ࢆ⏝࠸࡚ࠊᐦᗘỗ㛵ᩘἲ %/<3* GS  ࡛ィ⟬ࢆ⾜ࡗࡓࠋ㛢Ẇ࡜㛤Ẇࡢ୍㔜㡯࠾ࡼࡧ୕㔜㡯ࡢᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ᭱㐺໬ࡋࡓᵓ㐀ࢆ⏝࠸࡚ࠊ໬Ꮫࢩࣇࢺ್ࠊ1,&6 ್ࠊບ㉳࢚ࢿࣝࢠ࣮ࠊศᏊ㌶㐨ࠊࢫࣆࣥᐦᗘࠊ⾲㠃㟁Ⲵࠊ㛤Ẇᛶࡢィ⟬ࢆ⾜ࡗࡓࠋ ◊✲ᡂᯝ
ࣇ࢙ࢼࢪࢽ࣒࢘ࢆᇶ┙࡜ࡍࡿȧඹᙺ཮ᛶ࢖࢜ࣥ  ࢆタィ࣭ྜᡂࡋࡓࠋ㔞Ꮚ໬Ꮫィ⟬ࡼࡾࠊ཮ᛶ࢖࢜ࣥᵓ
㐀࡟ຍ࠼࡚㛤Ẇᵓ㐀ࡢᐤ୚ࡀ࠶ࡿ࡜ண᝿ࡉࢀࡓࠋȧඹᙺ཮ᛶ࢖࢜ࣥࡣ +202 ࡜ /802 ࡢ࢚ࢿࣝࢠ࣮ᕪࡀ
⣙ H9 ࡜㠀ᖖ࡟ᑠࡉࡃࠊ㏆㉥እ㡿ᇦ QP ௨ୖ  ࡢ྾཰࡜୧ᛶࡢ㓟໬㑏ඖ≉ᛶࢆ♧ࡋࡓࠋ105 ࢩࢢࢼࣝࡢࣈ࣮ࣟࢻࢽࣥࢢ࠿ࡽ㛤Ẇᛶࡀ♧၀ࡉࢀࡓࡀࠊ(65 ࡛ࡣ୕㔜㡯✀⏤᮶ࡢࢩࢢࢼࣝࡣほ ࡉࢀ࡞࠿ࡗࡓࠋ

 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬1LWURJHQ&RQWDLQLQJ3RO\F\FOLF=ZLWWHULRQZLWK6LQJOHW%LUDGLFDO&KDUDFWHU6KLPL]X$$ULNDZD66KLQWDQL5
7KHWK,QWHUQDWLRQDO6\PSRVLXPRQ2UJDQLF5HDFWLRQV ,625  ᖺ  ᭶  ᪥ࠊᶓ὾ࠊཱྀ㢌Ⓨ⾲ ᪂ᆺࢥࣟࢼࡢᙳ㡪࡛ண✏㞟ࡢࡳ  ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬+202í/802 (QHUJ\*DS 7XQLQJ RI ȧ̻&RQMXJDWHG =ZLWWHULRQV &RPSRVHG RI (OHFWURQ'RQDWLQJ $QLRQ DQG(OHFWURQ$FFHSWLQJ&DWLRQ6KLPL]X$,VKL]DNL<+RULXFKL6+LURVH70DWVXGD.6DWR+<RVKLGD-J. Org.
Chem.86í

- 37 -

⣽⬊ෆࡢ㉸◲㯤ศᏊࡢ᣺ືゎᯒ
Analysis of vibrational bands of supersulfide compounds in cells‫ۑ‬ᐑ⏣ ኱㍜ࠊᙳᒣ ⳀἋࠊ㧗ᶫ ኱ᬛࠊ୰ᯘ Ꮥ࿴㸦ᮾ໭኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲⛉㸧
1◊✲┠ⓗࠊෆᐜ
 ㏆ᖺࠊ◲㯤ཎᏊࡀ┤㙐≧࡟ከᩘ㐃⤖ࡋࡓ໬ྜ≀࡛࠶ࡿࠕ㉸◲㯤ศᏊࠖࡀࣄࢺࢆࡣࡌࡵ࡜ࡍࡿ့ங㢮ࡢ⏕యෆ࡟ぢ࠸ࡔࡉࢀࠊ⏕࿨ᶵ⬟ࢆᢸ࠺᪂ࡓ࡞໬ྜ≀࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡇࢀࡲ࡛࡟⏕⣽⬊ෆࡢ㉸◲㯤ศᏊࢆᐃ㔞ⓗ࡟ᐃࡍࡿᡭἲࡣ☜❧ࡉࢀ࡚࠾ࡽࡎࠊ㉸◲㯤ศᏊࡢ⏕⌮ᶵ⬟࡟ᑐࡍࡿᙺ๭ࡣ୙᫂៖࡞ࡲࡲ

࡛࠶ࡿࠋࡑࡇ࡛ᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣࠊ⏕⣽⬊ෆ࡟࠾ࡅࡿ㉸◲㯤ศᏊࡢᙺ๭ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊ࣐ࣛࣥศ
ගἲࢆ⏝࠸ࡓ⏕⣽⬊ෆ࡟࠾ࡅࡿ㉸◲㯤ศᏊࡢᐃἲࡢ☜❧ࢆ㐍ࡵ࡚࠸ࡿࠋᮏ◊✲࡟࠾࠸࡚ࡣࠊ⏕⣽⬊ෆࡢ㉸◲㯤ศᏊࡢᵓ㐀ࡸ཯ᛂᛶ࡟ࡘ࠸࡚ࡼࡾヲ⣽࡞⌮ゎࢆᚓࡿࡓࡵࠊ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓ㉸◲㯤ศᏊࡢ❧యᵓ㐀ࡸ㟁Ⲵᐦᗘศᕸࡢ᳨ウࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊ⣽⬊≧ែࢆ⮬ືุู࡛ࡍࡿࢩࢫࢸ࣒ࢆ⏝࠸࡚⣽⬊≧ែ࡜㉸◲㯤ศᏊࡢ⃰ᗘ➼ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊTensorFlow ࢆ⏝࠸ࡓ AI ࡢ㛤Ⓨࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬࡟ࡣࠊGaussian 16 ࢆ⏝࠸ࡓࠋAb initio MO ィ⟬ࡢ୍ࡘ࡛࠶ࡿᐦᗘỗ㛵ᩘἲࢆ⏝࠸࡚ࠊᵓ㐀᭱㐺໬࡜᣺ືᩘィ⟬ࢆ⾜࠸ࠊ⏕⣽⬊ෆ࡟࠾ࡅࡿ㉸◲㯤ศᏊࡢ❧యᵓ㐀ࢆᶍ⣴ࡋࡓࠋ⁐፹ຠᯝࢆྲྀࡾධࢀࡓィ⟬
࡟ࡣࠊIEFPCM ࢆ⏝࠸ࡓࠋࡲࡓࠊNatural Population Analysis ࡟ࡼࡾ㉸◲㯤ศᏊࡢ㟁Ⲵᐦᗘศᕸࢆㄪ࡭ࡓࠋ
AI ࡢ㛤Ⓨ࡟ࡣࠊ
TensorFlow ࢆ⏝࠸ࡓࠋ࣐ࣛࣥ࢖࣓࣮ࢪࣥࢢ࡟ࡼࡗ࡚ᚓࡽࢀࡿከᩘࡢ࣐ࣛࣥࢫ࣌ࢡࢺࣝ࠿ࡽࠊ
⣽⬊ෆࡢ≉ᐃࡢ㡿ᇦ㸦⣽⬊㉁ࡸ᰾㸧࡟ᑐᛂࡍࡿࢫ࣌ࢡࢺࣝࢆ⮬ືⓗ࡟ᢳฟࡍࡿࣔࢹࣝࢆᵓ⠏ࡋࡓࠋ3◊✲ᡂᯝ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾࠊ㉸◲㯤ศᏊࡣᮎ➃ࡢ࢝ࣝ࣎ࢽࣝᇶྠኈࡀỈ⣲⤖ྜࡋ࡚⎔≧ᵓ㐀ࢆᙧᡂࡍࡿࡇ࡜࡛Ᏻ

ᐃ໬ࡉࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࢀࡣࠊᚑ᮶ࡢ◲㯤໬ྜ࡛࠶ࡿࢩࢫࢳࣥ࡞࡝࡛ࡣぢࡽࢀ࡞࠸≉ᚩ࡛࠶ࡾࠊ㉸◲㯤ศᏊࡢ㧗࠸཯ᛂᛶ࡟ᐤ୚ࡍࡿྍ⬟ᛶࡀ࠶ࡿࠋࡲࡓࠊ㉸◲㯤ศᏊࡣศᏊෆ࡟ṇ࡟Ⲵ㟁ࡍࡿ◲㯤ཎᏊ࡜㈇࡟Ⲵ
㟁ࡍࡿ◲㯤ཎᏊࡢ୧᪉ࢆᣢࡘࡇ࡜ࡀࢃ࠿ࡗࡓࠋ㉸◲㯤ศᏊࡣࠊồ᰾ᛶ࡜ồ㟁Ꮚᛶࡢ୧᪉ࢆ♧ࡍ࡜࠸࠺ࣘࢽ࣮
ࢡ࡞ᛶ㉁ࢆࡶࡘࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࡀࠊୖグࡢ⤖ᯝࡣࠊࡑࢀࢆᨭᣢࡍࡿ⤖ᯝ࡛࠶ࡿࡇ࡜ࢆ♧၀ࡍࡿࠋ௒ᚋࠊ
㉸◲㯤ศᏊࡢ཯ᛂᛶࡸ⏕໬Ꮫ཯ᛂࡢᶵᵓ࡞࡝࡟ࡘ࠸࡚ QST ἲ࡞࡝ࢆ⏝࠸࡚᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆணᐃࡋ࡚࠸ࡿࠋ
TensorFlow ࢆ⏝࠸ࡿࡇ࡜࡛ࠊ࣐ࣛࣥ࢖࣓࣮ࢪ࠿ࡽ⣽⬊୰ࡢ≉ᐃࡢ㡿ᇦ࡟࠾ࡅࡿࢫ࣌ࢡࢺࣝࢆ⮬ືⓗ࡟཰㞟ࡍࡿࣔࢹࣝࡢᵓ⠏࡟ᡂຌࡋࡓࠋ኱㔞ࡢࢫ࣌ࢡࢺࣝࢆ㧗㏿࠿ࡘຠ⋡ⓗ࡟ྲྀᚓ࡛ࡁࡿࡇ࡜ࡣࠊ௒ᚋࠊ⣽⬊ෆࡢ≧ែࢆࣔࢽࢱࣜࣥࢢࡍࡿୖ࡛᭷⏝࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 38 -᪂つ㧗ᶵ⬟ᛶࡢ୙ᩧゐ፹◊✲
Development of novel high functional asymmetric catalysts‫ۑ‬୰ᮧ ಟ୍㸦ྡྂᒇᕤᴗ኱Ꮫ㸧1◊✲┠ⓗ࣭ෆᐜ
᪂ࡋࡃタィ࣭ྜᡂࡋࡓ୙ᩧゐ፹࡟㛵ࡋ࡚ࠊᵓ㐀ࡢ᭱㐺໬ࢆ⾜࠸ࠊゐ፹άᛶ࡜ࡢ㛵㐃ᛶࢆㄪᰝࡍࡿ࡜࡜ࡶ
࡟ࠊᚓࡽࢀࡓ❧య㑅ᢥᛶࡢⓎ⌧ᶵᵓࡢゎ᫂࡟ᙺ❧࡚ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 16 ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝୗᅗ㸯ࡢゐ፹ศᏊ࡟㛵ࡋ࡚ࠊィ⟬ࢆ⾜࠸ࠊ᭱㐺ᵓ㐀ࡢኚ໬➼ࢆ⪃ᐹࡋࡓࠋࡲࡓࠊ୙ᩧྜᡂ཯ᛂ࡟࠾ࡅࡿ
୰㛫య㘒యࡢᏳᐃᛶ࠾ࡼࡧࠊࡑࡢ❧య㑅ᢥᛶⓎ⌧ᶵᵓࡢゎ᫂ࢆ⾜ࡗࡓ㸦ୗᅗཧ↷㸧ࠋࡉࡽ࡟࠸ࡃࡘ࠿ࡢ୙
ᩧྜᡂ཯ᛂ࡟࠾ࡅࡿ୙ᩧゐ፹࡜㑄⛣ᵓ㐀ࡢィ⟬ࢆ⾜ࡗࡓࠋ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
2021 ᖺᗘ୰࡟ 2 ሗࡢㄽᩥࢆⓎ⾲ணᐃ㸦ㅰ㎡ࢆグ㍕ணᐃ㸧ࠋ- 39 -

㓄఩Ꮚࡢ᭱㐺໬࡟ࡼࡿ㧗άᛶ㔜ྜゐ፹ࡢタィ
Design of a high-performance polymerization catalyst by modification ofligand-structure‫ۑ‬㛗ᒸ ṇᏹ㸦┦ᶍ୰ኸ໬Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
࢚ࢳࣞࣥ࡜D-࢜ࣞࣇ࢕ࣥ࡜ࡢඹ㔜ྜయࡣࠊ࢚ࢳࣞࣥࡢ༢⊂㔜ྜయ࡜ẚ㍑ࡋࠊ⇕ⓗ࣭ᶵᲔⓗࡀ≉ᛶ኱ࡁࡃኚ

໬ࡍࡿࠋ୰࡛ࡶ࣓ࢱࣟࢭࣥゐ፹࡟ࡼࡾ〇㐀ࡉࢀࡓඹ㔜ྜయࡣࠊࡇࢀࡽࡢD-࢜ࣞࣇ࢕ࣥࡢᑟධຠᯝ࡟ຍ࠼࡚ࠊ
ศᏊ㔞ศᕸࡢ⊃࠸ඹ㔜ྜయࢆ୚࠼ࡿࡇ࡜ࡀ≉ᚩ࡜ࡉࢀ࡚࠸ࡿࠋࡇࢀࡲ࡛࡟ࠊ࣓ࢱࣟࢭࣥゐ፹ࡢ㓄఩Ꮚᵓ㐀࡟࠾ࡅࡿ❧యⓗ࡞せᅉ࡜ඹ㔜ྜᛶࡢ㛵ಀ࡟ࡘ࠸࡚᫂ࡽ࠿࡟ࡉࢀ࡚ࡁࡓࡀࠊ㓄఩Ꮚࡢ㟁Ꮚⓗ≉ᛶ࡜ࡢ㛵ಀ࡟ࡘ࠸࡚ࡣࠊ༑ศ࡟᫂ࡽ࠿࡟ࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊ㟁Ꮚⓗ≉ᛶࡢほⅬ࠿ࡽ㧗࠸ඹ㔜ྜᛶࢆ᭷ࡍࡿ࣓ࢱࣟࢭࣥ
ゐ፹ࡢᑟฟࢆ┠ⓗ࡜ࡋࠊ⨨᥮ᇶࡢᙳ㡪ࢆㄪᰝࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 16 program ࢆ⏝࠸ࠊDFT ἲ࡟ࡼࡗ࡚ᵓ㐀᭱㐺໬࠾ࡼࡧ᣺ືィ⟬ࢆ⾜ࡗࡓࠋィ⟬ᡭἲ࡜ࡋ࡚ࡣࠊTPSSTPSS / cc-pVDZ-(PP) ࢆ᥇⏝ࡋࠊ࢚ࢳࣞࣥ࠾ࡼࡧࣉࣟࣆࣞࣥࡢᤄධ࡟࠾ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡋ
ࡓࠋ㟁Ꮚⓗ≉ᛶࡢ␗࡞ࡿ㓄఩Ꮚࢆࡶࡘࢪࣝࢥࣀࢭࣥゐ፹࡟ᑐࡋ࡚ࠊ୍㐃ࡢィ⟬ࢆ⾜࠸ࠊඹ㔜ྜᛶ࡟ࡘ࠸࡚᥎
ᐹࡋࡓࠋ

3

◊✲ᡂᯝ
R1

࢖ࣥࢹࢽࣝᇶࡢ 4 ఩࡟ࣇ࢙ࢽࣝᇶࠊ࢖ࢯ
R1

R1

ࣉࣟࣆࣝᇶࠊࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝᇶ࠾ࡼࡧࢪ
Me
Me Si

࡟ࡘ࠸࡚࢚ࢳࣞࣥ࠾ࡼࡧࣉࣟࣆࣞࣥࡢᤄධ
཯ᛂࢆゎᯒࡋࠊάᛶ໬࢚ࢿࣝࢠ࣮ࡢᕪ

G (kcal mol–1 )࣓ࢳࣝ࢔࣑ࣀᇶࢆ᭷ࡍࡿࢪࣝࢥࣀࢭࣥ 1–5(''G) ࢆ⟬ฟࡋࡓ (ᅗ)ࠋࡑࡢ⤖ᯝࠊࢪ࣓ࢳ
ࣝ࢔࣑ࣀᇶࢆ 2 ࡘ᭷ࡍࡿࢪࣝࢥࣀࢭࣥ 4࡟࠾࠸࡚ࠊ''G ࡢపୗࡀほᐹࡉࢀࡓࠋࡋࡓ
ࡀࡗ࡚ࠊ㓄఩Ꮚࡢ㟁Ꮚ౪୚ᛶࢆ㧗ࡵࡿࡇ࡜࡛ࠊ

Zr

Me
Me Si

H

Me
Me Si

Zr

‡

R

Zr
R

R2
C-propene (R = Me)

R2

R2

A

R

B

''G

R1
C-ethylene (R = H)

R = H or Me(R = R2 = Ph): 3.4 kcal/mol
1 1(R = R2 = i
2 1Pr): 3.8 kcal/mol(R = R2 = CF
3 1
: 4.4 kcal/mol
3)(R = R2 = NMe
4 1
2)
(R1 =
= CF : 3.2 kcal/mol
2
5
NMe2, R3) : 4.3 kcal/mol

D-࢜ࣞࣇ࢕ࣥࡢᤄධࡶ㐍⾜ࡋࡸࡍࡃ࡞ࡾࠊඹ
㔜ྜᛶࡀྥୖࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ୍᪉ࠊ㟁ᅗ㸬㔜ྜ࡟࠾ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮

Ꮚồᘬᛶᇶ࡛࠶ࡿࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝᇶࡢᑟ
ධࡣࠊ''G ࢆቑ኱ࡉࡏࠊඹ㔜ྜᛶࢆపୗࡉࡏࡿഴྥ࡟࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᮏ⤖ᯝ࡟ࡘ࠸࡚ࡣࠊᏛ఍࡟࡚Ⓨ⾲ணᐃ࡛࠶ࡿࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ᮏ⤖ᯝ࡟ࡘ࠸࡚ࡣࠊ㛵㐃ࡍࡿ໬ྜ≀ࡢㄽᩥࢆ‽ഛ୰࡛࠶ࡿࠋ

- 40 -

Me
Me Si

Zr

R2
D

R

- 41 -

- 42 -











THEORETICAL STUDY OF THE REGIOSELECTIVITY IN ESTER DANCEREACTION
 (

1 #%!



$ 

 "-$),.



5:>J<M:h! .gr0¿¢"dr¨stX³É"Í]0´v.
·Ógk"bq`Á«h#·Ó¡P"³m bqÃ"Ô0o !bq`±kX³"'o.h.h!+U"h#w^. Ï X³!³m0«
 ·Ógk0¯\!k. iµ . ·Ó¡P"³m"bq`Á«h#§yÂP-~#grËÀË"{nm ÆÊ hW0¹.(e¨ h"
Ì§

&/

|©­u#¶!Ì§CI93H»p0£.·Ó5:>J(Ar-COOAr')"5:>JÔ(COOAr')0Î °P!«fÕ1,2-Á«Ö.5:>J<M:h0ºa/#»p¨gk!Ña.Ã"O.5:>JÔ0·Ó¡P 1,2-Á«.c"[.»p¨ ·Ógk"bq`ÁXh#T&%1[   h}z¼ .,!5:>J<M:0Ä²Å¸.·Ó5:>J"5:>JÔ0 1,3-Á«.h)R¥c(ºa©­¾Ò#¢"dr¨st*È«0Ëqgr½®!+º¬)-5:>J<M:h"X³É0´v.

2 #%+&©­! ._"Ëqdr½®!# Gaussian 16 FL7IH0Z£jbq"ÃÇg½®#
PM6B3LYP/ 6-31G(d)CBS-QB3 Ð½®KGJ0P¸O½®!# CBS-QB3 0£ 

3 #%
O

5:>J<M:h"X³É

OPh¢"dr¨st
!

O

OPh

=BN?(1n)"h# 2n 0//S¢Q .NO

10 mol% PdCl2
20 mol% dcypt
K2CO3 (0.5 equiv)m-xylene (0.8 mL)
140 °C, 24 h

1bO

2a: 85%
ΔG: –3.7 kcal/mol

OPh

O
OPh

+
N
1b: 20%,/.X³¦Y 2a "6E:OPh+
1a: 7%

1a×-@D?5N?(1a)"h#Ëqgr½®0£ 1a OPhm-xylene (0.8 mL)
150 °C, 24 h´vD4AJ-¦Y 2a 0D4AJ2;A8O

10 mol% PdCl2
20 mol% dcypt
K2CO3 (0.5 equiv)N2b: 57%
ΔG: –0.5 kcal/mol
ThermodynamicallyFavorable¶¤5BJ6N0®a±S¢,/. 2a # 1a $6E:¶¤5BJ6N

3.7 kcal/mol xdr¨!+-st² 1b X³¦Y 2b "6E:¶¤5BJ6N0®a"±S¢
,/. 2b "6E:¶¤5BJ6N# 1b +-) 0.5 kcal/mol xdr¨!+-stVP"±- 43 -

 ,5:>J<M:h#dr¨!+-st X³¦Y S¢,/. ªl/4 *'1) (6@G7 2G:C <?), 649'K %&>%" %3!$&E*
I5;%F0H.DAJ+/-=  81B-  &#& 2)  2

G:C (6@G7 <?), 649'K %&>%" %3!$&E*I5;%F0H.DAJ+/-=  81B- 

5

' &#&Matsushita, K.; Takise, R.; Muto, K.; Yamaguchi, J. Sci. Adv. 2020, 6, eaba7614.
Tanaka, S.; Asako, T.; Ota, E.; Yamaguchi, J. Chem Lett. 2020, 49, 918–920.
Uehara, T. N.; Takao, S.; Matsuo, H.; Saito, A.N.; Ota, E.; Ono, A.; Itami, K.; Kinoshita, T.; Yamaguchi, J.;
Nakamichi, N. BioRxiv. 2020, preprint
Asako, S.; Suzuki, T.; Tanaka, S; Ota, E.; Yamaguchi, J. “Synthesis of Decaarylanthracene with Nine Different
Substituents” J. Org. Chem. 2020, 85, 15437-15448.

- 44 -

඾ᆺඖ⣲ࡢ≉ᛶࢆά⏝ࡋࡓගᶵ⬟ᛶศᏊࡢ㛤Ⓨ
Development of Optofunctional Molecules
by Taking Advantage of Main Group Elements‫ۑ‬࿃㒓 ཭ᏹ㸪Ọ⏣ ṇ࿴㸪ᑠụ ⣧ᖹ㸦Ⲉᇛ኱㝔⌮ᕤ㸧1◊✲┠ⓗᡃࠎࡣ඾ᆺඖ⣲ࡢ≉ᛶࢆά⏝ࡍࡿࡇ࡜࡛῝㉥Ⰽ㹼㏆㉥እⓎගࠊ෇೫ගⓎගࠊ㧗㍤ᗘ࢚ࣞࢡࢺ࣑ࣟࣝࢿࢵࢭ

ࣥࢫࠊ࠾ࡼࡧపᒅᢡ⋡࣭పㄏ㟁⋡࡜࠸ࡗࡓ✀ࠎࡢගᏛ≉ᛶࢆ᭷ࡍࡿ᭷ᶵᮦᩱࡢ㛤Ⓨࢆ⾜ࡗ࡚࠸ࡿࠋᮏ◊✲࡛ࡣ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓගᶵ⬟ᛶศᏊࡢタィࢆ⾜࠺࡜࡜ࡶ࡟ࠊᮦᩱࡢᵓ㐀࣭≉ᛶࡢゎᯒࢆᐇ᪋ࡍࡿࠋᮏᖺᗘ
ࡣ⣸㹼㏆㉥እ࡟⮳ࡿᗈ⠊࡞Ἴ㛗ᇦ࡛ࡢ⺯ගⓎග≉ᛶࢆᣢࡘྵ࣍࢘⣲ඹᙺศᏊࡢศᏊタィ࡜㟁Ꮚ≧ែゎᯒࢆ୰ᚰⓗ࡟ᐇ᪋ࡋࡓࡢ࡛ሗ࿌ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
DFT ィ⟬㸦୺࡟ B3LYP/6-311g(d)㸧࡟ࡼࡿᵓ㐀᭱㐺໬࡜ TD-DFT ィ⟬㸦୺࡟ B3LYP/6-311+g(d)㸧࡟ࡼࡿບ㉳≧ែィ⟬ࢆ⾜ࡗࡓࠋィ⟬࡟ࡣ Gaussian 16 (Rev. C.01)ࢆ⏝࠸ࡓࠋࡲࡓ⇕άᛶ໬㐜ᘏ⺯ග≉ᛶࡢホ౯ࡢࡓࡵ࡟
ORCA (4.2.1)ࢆ⏝࠸ࡓ spin-orbit coupling ィ⟬ࢆ⾜ࡗࡓࠋィ⟬ࣔࢹࣝࡢసᡂཬࡧ⤖ᯝࡢྍど໬࡟ࡣ GaussView(ver. 6.1.1)ࢆ฼⏝ࡋࡓࠋ3◊✲ᡂᯝⰋዲ࡞⺯ගⓎග≉ᛶࢆᣢࡘࣇ࢙ࢼࢨ࣎ࣜࣥ㸦ࢪ࣋ࣥࢰ࢔ࢨ࣎ࣜࣥ㸧ࢆࣛࢲ࣮ᆺȧඹᙺ⣔࡟⤌ࡳ㎸ࢇࡔࠕࣛࢲ࣮ᆺ࢔ࢨ࣎ࣜࣥࠖ࡟ᑐࡋࠊ✀ࠎࡢ Pd ゐ፹཯ᛂࢆά⏝ࡍࡿࡇ࡜࡛ඹᙺ⣔ࢆᣑᙇࡋࡓ᪂つ࣍࢘⣲ⓎගศᏊࢆ
DFT ࠾ࡼࡧ TD-DFT ィ⟬࡟ࡼࡗ࡚タィࡋࡓࠋタィࡋࡓྵ࣍࢘⣲ඹᙺศᏊࡢᗄࡘ࠿࡟ࡘ࠸࡚ᐇ㝿࡟ྜᡂࡋග≀ᛶࢆホ౯ࡋࠊ᪤Ꮡࡢࣇ࢙ࢼࢨ࣎ࣜࣥ⣔Ⓨගయ࡟ẚ࡭Ⓨගࡢ㛗Ἴ㛗໬࣭㧗ຠ⋡໬ࢆ㐩ᡂࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋヲ⣽ࡣⓎ⾲ᐇ⦼࡜ฟ∧ᐇ⦼࡛බ⾲ࡋࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Ọ⏣ ṇ࿴࣭࿃㒓 ཭ᏹ࣭⚟ඖ ༤ᇶࠊC-H άᛶ໬-ศᏊෆ⎔໬཯ᛂࢆ౑ࡗࡓඹᙺᣑᙇ࢔ࢨ࣎ࣜࣥࡢྜᡂ࡜

ᛶ㉁ࠊ➨ 10 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2020ࠊ2020 ᖺ 10 ᭶ 20㹼22 ᪥ࠊ࢜ࣥࣛ࢖ࣥ㛤ദ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬M. Nagata, T. Agou et al., Synthesis of Carbazole-Fused Azaborines via a Pd-Catalyzed C-H

Activation-Cyclization

Reaction,

BulletinoftheChemical10.1246/bcsj.20200129.

- 45 -

Society

of

Japan

2021,

94,

21-23.

DOI:

C5N ࡢỌஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ෌ホ౯
Reevaluation of the permanent dipole moment of C5N‫ஂۑ‬ୡ ಙᙪࠊᑠᒣ ㈗⿱㸦ୖᬛ኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ

࠙┠ⓗࠚከཧ↷㓄⨨㛫┦஫స⏝㸦MRCI㸧ἲࢆ⏝࠸࡚ࠊ┤⥺Ⅳ⣲㙐ศᏊ C5N ࡢṇ☜࡞Ọஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࢆ
ồࡵࠊࡑࢀࢆ⏝࠸࡚ C5N ࡢᫍ㛫✵㛫࡟࠾ࡅࡿᏑᅾ㔞␗ᖖࡢၥ㢟ࢆゎᾘࡍࡿࠋ࠙ෆᐜࠚ┤⥺Ⅳ⣲㙐ศᏊࡣࠊᫍ㛫ศᏊ࡜ࡋ࡚௦⾲ⓗ࡞໬Ꮫ✀࡛࠶ࡾࠊᫍ㛫໬Ꮫ࡟࠾࠸࡚Ⅳ⣲ࡢ୺せ࡞Ꮡᅾᙧែ
࡜ࡋ࡚ࡢᙺ๭ࢆᯝࡓࡍࠋⅣ⣲㙐ศᏊࡣ୍⯡ⓗ࡟Ⅳ⣲㙐ࡀఙࡧࡿ࡯࡝ࡑࡢᏑᅾ㔞ࡀῶᑡࡍࡿࠋࡋ࠿ࡋࠊ୍㒊ࡢศᏊ✀࡟ࡘ࠸࡚ࠊᏑᅾ㔞ࡢ⌮ㄽィ⟬್࠿ࡽ኱ࡁࡃ㐓⬺ࡋࡓ್ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ౛࠼ࡤࠊᮎ➃ࡀỈ⣲ࡢ CnH
㸦n = 1, 2, 3…㸧⣔ิ࡟࠾࠸࡚ࠊC4H ࡔࡅࡀ␗ᖖ࡟኱ࡁ࡞Ꮡᅾ㔞ࢆ♧ࡍࠋࡇࡇ࡛ࠊ㟁Ἴᮃ㐲㙾࡛ほࡉࢀࡓศᏊ

ࡢ㍤⥺࠿ࡽᫍ㛫✵㛫࡟࠾ࡅࡿᏑᅾ㔞ࢆぢ✚ࡿ࡟ࡣࠊࡑࡢศᏊࡢỌஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢṇ☜࡞್ࡀᚲせ࡜࡞ࡿࠋࡋ࠿ࡋࠊCnH ࡢࡼ࠺࡞ࣛࢪ࢝ࣝ✀ࡣࠊᐇ㦂ⓗ࡟Ọஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࢆỴᐃࡍࡿࡇ࡜ࡀ㞴ࡋ࠸ࡓࡵࠊ୍
⯡ⓗ࡟㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿண᝿್ࡀゎᯒ࡟⏝࠸ࡽࢀࡿࠋ࡜ࡇࢁࡀ C4H ࡣ㟁Ꮚᇶᗏ≧ែࡢࡍࡄ㏆ࡃ࡟ບ㉳≧ែࡀᏑᅾࡋࠊࡑࢀࡽࡢ┦஫స⏝࡟ࡼࡗ࡚Ọஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ್ࡀ኱ࡁࡃኚ໬ࡍࡿࠋࡋ࠿ࡋࠊᚑ᮶ࡢ㔞Ꮚ໬Ꮫィ⟬ࡣࡇࡢ┦஫స⏝ࢆ⪃៖ࡋ࡚࠾ࡽࡎࠊỌஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢṇ☜࡞್ࢆィ⟬࡛ࡁ࡚࠸࡞࠿ࡗࡓࠋᡃࠎ
ࡣඛ⾜◊✲࡛ࠊࡇࡢ㟁Ꮚ≧ែ㛫ࡢ┦஫స⏝ࢆ⪃៖ࡋࡓ MRCI ἲࢆ⏝࠸࡚ࠊC4H ࡢỌஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢṇ☜࡞್ࢆ⟬ฟࡋࡓ[1]ࠋࡑࡢ⤖ᯝࠊC4H ࡢᏑᅾ㔞ࡀሗ࿌ࡉࢀ࡚࠸ࡓ್ࡼࡾࡶ 2.4 ಸ኱ࡁ࠸ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ ᭱㏆ࠊᮎ➃ࡀ❅⣲ࡢ C5N ࠾ࡼࡧࡑࡢ㝜࢖࢜ࣥ✀ C5NѸࡢศᏊ㞼 TMC-1 ࡛ࡢึ᳨ฟࡀሗ࿌ࡉࢀࡓ[2]ࠋࡋ࠿ࡋࠊ
ࡑࡢᏑᅾ㔞ࡢẚ (C5N/C5NѸ)ࡣ 2.3 ࡟ࡶ࡞ࡾࠊ➼౯㟁ᏊศᏊ࡛࠶ࡿ C6H ࡢẚ (C6H/C6HѸ=16)࡟ẚ࡭࡚᫂ࡽ࠿࡟
ᑠࡉ࠿ࡗࡓࠋࡇࢀࡣ C5N ࡢᏑᅾ㔞ࡀ C5NѸ࡟ẚ࡭࡚␗ᖖ࡟ᑡ࡞࠸ࡇ࡜ࢆព࿡ࡍࡿࠋࡇࡢศᏊࡶ C4H ࡜ྠᵝ࡟㟁Ꮚᇶᗏ≧ែࡢࡍࡄ㏆ࡃ࡟ບ㉳≧ែࡀᏑᅾࡍࡿࠋࡇࢀࡽ≧ែ㛫ࡢ┦஫స⏝ࡀỌஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ್࡟ᙳ
㡪ࢆ୚࠼ࠊ⤖ᯝ࡜ࡋ࡚ C5N ࡢᏑᅾ㔞ࢆ㐣ᑠホ౯ࡋ࡚࠸ࡿ࡜ண᝿ࡉࢀࡿࠋࡋ࠿ࡋࠊC5N ࡣ C4H ࡟ẚ࡭࡚㔜ཎᏊࡀ஧ಶቑ࠼ࡓࡇ࡜࡛ィ⟬᫬㛫ࡀᣦᩘ㛵ᩘⓗ࡟ቑຍࡋ࡚ࡋࡲ࠸ࠊᡃࠎࡢィ⟬ᶵࢧ࣮ࣂ࣮࡛ࡣィ⟬᏶஢ࡲ࡛࡟୍
ᖺ௨ୖ࠿࠿ࡿ࡜ぢ✚ࡽࢀࡓࠋࡑࡇ࡛ᮏ⏦ㄳㄢ㢟࡛ࡣࠊศᏊ⛉Ꮫ◊✲ᡤࡢ኱つᶍィ⟬ᶵࢧ࣮ࣂ࣮ࢆά⏝ࡋࠊC5N
ࡢᐇຠⓗ࡞Ọஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࢆィ⟬ࡋࠊᏑᅾ㔞␗ᖖࢆ᪩ᮇ࡟ゎᾘࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓࠋ ᮏ⏦ㄳㄢ㢟࡛ࡣ C5N ࡜୪⾜ࡋ࡚ᮎ➃ࡀỈ⣲ࡢ CnH ⣔ิࡢ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢィ⟬ࡶ⾜ࡗࡓࠋࡇࡢ⣔ิ࡛ࡣ≉࡟Ⅳ⣲ᩘ n ࡀ 8 ௨ୖࡢศᏊ✀࡟ࡘ࠸࡚ࠊ㧗⢭ᗘࡢ㔞Ꮚ໬Ꮫィ⟬ࡀ⾜ࢃࢀ࡚࠸࡞࠸ࠋࡑࡢࡓࡵࠊᫍ㛫✵㛫࡟࠾ࡅࡿࡇࢀࡽศᏊ✀ࡢṇ☜࡞Ꮡᅾ㔞ࡢ⟬ฟࡀ࡛ࡁ࡞࠿ࡗࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ Ọஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢィ⟬ࡣࠊ㔞Ꮚ໬Ꮫィ⟬ࢯࣇࢺMOLPRO [3]ࢆ⏝࠸ࡓࠋࡲࡎࠊ㟁Ꮚ≧ែ㛫ࡢ┦஫స⏝ࢆ⪃៖ࡋ࡞࠸RCCSD(T)/cc-pVTZ࡛ࣞ࣋ࣝࠊC5Nࡢ㟁Ꮚᇶᗏ≧ែ26+ࡢ᭱Ᏻᐃᵓ㐀ࢆィ⟬ࡋࡓࠋḟ࡟ᚓࡽࢀࡓศ
Ꮚᵓ㐀ࢆึᮇ್࡟ࡋ࡚ࠊ㟁Ꮚ≧ែ㛫ࡢ┦஫స⏝ࢆ⪃៖ࡋࡓMRCI/cc-pVTZ࡛ࣞ࣋ࣝࠊᇶᗏ≧ែࡢ᭱Ᏻᐃᵓ㐀࠾ࡼࡧỌஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࢆィ⟬ࡋࡓࠋࡑࡢ㝿ࠊෆ᰾ࡢ1V–10V㌶㐨ࡣᅛᐃࡋ࡚ࠊ11V–V࠾ࡼࡧ1S–Sࢆάᛶ✵㛫࡟ྲྀࡗࡓࠋCnH⣔ิ࡟ࡘ࠸࡚ࡣRCCSD(T)/cc-pVQZ࡛ࣞ࣋ࣝィ⟬ࢆ⾜ࡗࡓࠋ- 46 -

3◊✲ᡂᯝᮏ◊✲࡛ᚓࡽࢀࡓ MRCI/cc-pVTZ ࡛ࣞ࣋ࣝࡢ C5N ࡢ᭱Ᏻᐃᵓ㐀ࢆᅗ 1 ࡟♧ࡍࠋⅣ⣲㙐ศᏊࡣ୍⯡ⓗ࡟┤⥺ᵓ㐀ࡀ᭱Ᏻᐃ࡛࠶ࡿࡀࠊC5N ࡢሙྜࠊ㟁Ꮚ≧ែ㛫ࡢ┦஫స⏝࡟ࡼࡗ࡚᭤ࡀࡗࡓᵓ㐀ࡀ᭱Ᏻᐃ࡟࡞ࡗࡓࠋࡑࡢ
Ọஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡣ 2.55 D ࡜ぢ✚ࡽࢀࡓࠋࡇࡢ್ࡣࡇࢀࡲ࡛࡟㟁ἼኳᩥᏛ࡛⏝࠸ࡽࢀ࡚࠸ࡓ್ 3.385 D[4]
ࡢ 1/1.3 ࡛࠶ࡿࠋࡇࡢ್ࢆ⏝࠸࡚ TMC-1 ࡛ࡢ C5N/C5NѸẚࢆ෌ィ⟬ࡍࡿ࡜ 4.1 ࡜࡞ࡾࠊሗ࿌್ࡢ஧ಸ㏆ࡃ࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊࡇࡢ್ࡣ Cernicharo ࡽࡢ TMC-1 ࡟࠾ࡅࡿ C5N/C5NѸẚࡢ⌮ㄽண᝿್ࡢୗ㝈[2]࡜ㄗᕪ⠊ᅖෆ୍࡛⮴ࡋࡓࠋࡋ࠿ࡋࠊࡇࡢ್ࡣ C6H ࡢẚ 16 ࡟ẚ࡭࡚ࡲࡔ኱ࡁ࠸ࠋ௒ᅇࡢィ⟬ࡣάᛶ✵㛫ࢆ㝈ᐃࡋ࡚࠸ࡿࡓࡵࠊỌஂ཮ᴟᏊ࣮࣓ࣔࣥࢺ࡬ࡢ㟁Ꮚ≧ែ㛫ࡢ┦஫స⏝ࢆ༑ศ࡟⪃៖࡛ࡁ࡚࠸࡞࠸ྍ⬟ᛶࡀ࠶ࡿࠋ
άᛶ✵㛫ࡢࡉࡽ࡞ࡿᣑᙇࡀ⌧ᅾࡢィ⟬ࣉࣟࢢ࣒ࣛ࠾ࡼࡧ฼⏝ྍ⬟࡞࣓࣮࡛ࣔࣜᐇ⾜ྍ⬟࠿᳨ウ୰࡛࠶ࡿࠋᅗ 1.

C5N ࡢ᭱Ᏻᐃᵓ㐀

CnH ⣔ิ࡟ࡘ࠸࡚ n=10 ࡲ࡛᭱Ᏻᐃᵓ㐀࡜Ọஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢィ⟬ࡀ⤊஢ࡋࡓ (⾲ 1)ࠋศᏊᵓ㐀࠿ࡽồࡵࡽࢀࡓᅇ㌿ᐃᩘࡀᐇ㦂್ࢆࡼࡃ෌⌧ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊ཮ᴟᏊ࣮࣓ࣔࣥࢺ࡟ࡘ࠸࡚ࡶ㧗࠸⢭ᗘ࡛ண᝿࡛ࡁ
ࡓ࡜࠸࠼ࡿࠋ௒ᚋࡣᫍ㛫✵㛫࡛ࡲࡔほ⾜࠺ணᐃ࡛࠶ࡿࠋ

ሗ࿌ࡀ࡞࠸ C11H ௨ୖ࡟ࡘ࠸࡚ࡶࠊ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ㧗⢭ᗘィ⟬ࢆ

⾲ 1. CnH ࡢᅇ㌿ᐃᩘ࡜཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ㔞Ꮚ໬Ꮫィ⟬ࡢ⤖ᯝศᏊ✀ᅇ㌿ᐃᩘ㻛㻹㻴㼦
ᐇ㦂್䛸䛾ㄗᕪ㻛㻑
㻞㻚㻟㻤㻞
㻙㻜㻚㻡
㻯㻡 㻴
㻝㻚㻟㻣㻢
㻙㻝㻚㻝
㻯㻢 㻴
㻜㻚㻤㻣㻜
㻙㻜㻚㻢
㻯㻣 㻴
㻜㻚㻡㻤㻟
㻙㻜㻚㻤
㻯㻤 㻴
㻜㻚㻠㻝㻜
㻙㻜㻚㻣
㻯㻥 㻴
㻜㻚㻞㻥㻥
㻙㻜㻚㻣
㻯㻝㻜㻴
ィ⟬䝺䝧䝹䛿㻾㻯㻯㻿㻰㻔㼀㻕㻛㼏㼏㻙㼂㻽㼆

4཮ᴟᏊ䝰䞊䝯䞁䝖㻛㻰
㻠㻚㻤㻢
㻡㻚㻢㻟
㻡㻚㻤㻤
㻢㻚㻡㻤
㻢㻚㻢㻣
㻣㻚㻟㻡

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬ᫍ㛫≀㉁࣮࣡ࢡࢩࣙࢵࣉ 2021㸦໭ᾏ㐨኱Ꮫ㸧࠾ࡼࡧ Internal symposium of molecular spectroscopy 2022 ࡛ࡢⓎ⾲ࢆணᐃ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Astrophysical journal ࡛ࡢฟ∧ࢆணᐃཧ⪃ᩥ⊩[1] Oyama et al, 2020, ApJ, 890, 39. [2] Cernicharo et al., 2020, A&A. 641, L9. [3] MOLPRO 2012, version 2012.1,
a package of ab initio programs, ed. H.-J. Werner et al. [4] Botschwina, 1996, Chem. Phys. Lett. 259, 627.

- 47 -













Design of metal oxide nanoclusters
and analysis of their electronic states
(,$&

1

,

'

%*

)+


¹¿4JN@`{±ëèe¯*®¦xçV{²ë,/M*ñ¾( %'ëèe¯<?3H69Nm*Ñ ü½öë,/M  ý½öTPë,/M*ñ¾´½ëx¢¤áÚØ#jË' )&em¯ ëça$Æ°´×z
X²\×zX²ºÁ*» *& "¦­zQëèe¯<?3H69N
í,/M*g( %'Oæí ä[)í<?3H69N*m( # (em¯­ªQ#ù*'jÔ\ôu°´nh*( *Ó_( ¹¿ê{e~ØÃ%' ÒmWò{±*&(#\¯*Ü!( *¶µ2#
¹¿]ØÃ* Gaussian 16 @L4HD*²Ñ`{¤áb¥fÇ X È¤áÖ %&)¥*Y²`{¤áâe*Ñ©ð CAM-B3LYP *²vð`{¤áâe Si  O  6-31G*Ag  W  LanL2DZ ECP *².>J2NØ
Ã TD-DFT ØÃSi  6-31G*O  6-31+G*Ag  W  LanL08(d)*²

3


Â±Ém9M46:Mèe¯ú[Si3W27O95]18–û^æíþ¢3H69N*#¤áúAg7; s 1ûí3
H69NæVèe±*we¤áâe*Ñl± (¤á$.>J2N*¨ßÇ¡í 7 ¢3H69N{Ag7}5+èe±'+=/M]W[Ag7(Si3W27O95)]13–(»q)

Ç¡fÇÿÈ¤áÖ ù`ÖËÞê` [Å` &)(èe±#¸·Ç¡

em¯

+7;=;IJQ (nh6A3;J420 nm õÐnh Õ¬)ús 2aû" ­ª* 7 ïóÊ#nh6A3;Jweem¯s  í<?3H69N@.A
9M46:Mèe¯Òm¤á 

­ªQ

#|t (  ` ¤áâe¥*² TD-DFT ØÃ*Ñ nh³*Ü!420 nm nhHOMO  LUMOHOMO  LUMO+3HOMO  LUMO+9 ã¼³ ){Ag7}5+3H69N&9M46:Mèe¯ø£ òÏ¼c{Ag7}5+3H69N^- 48 -

òÏ¼c³(  `"300 nm & 400 nm  nh{Ag7}5+3H69N
&9M46:Mèe¯ø£ òÏ¼c³(  »)TD-DFT Ç¡&0-6ðúFWHM
= 0.40 eVû%'6A3;J5CFKN5GM*Ñ÷µ&)nh6A3;JÎ OÌús 2bû Ç¡%'í<?3H69N9M46:Mèe¯ÒmWí<?3H69N&9
M46:Mèe¯ °´òÏ¼c°*#  `'\¯$\gÍo )((                             )s   ( +7;=;IJQ (nh6A3;J(b) TD-DFT ØÃ%(nh6A3;J5CFKN5GMÇ¡

4 "!
& 'Äé Zyå ì S « Ûk i pRCIM4±BI/18E9KN;^d)í<?
3H69Nà§m¤áwD e~UÀ} U /MH,M

& ' ,49(75%54,8(95 58:1, ":?:10 (?:>(%(3(.:*/0 C$297(89()2, "02;,7 (45*2:89,78 4*(68:2(9,+ <09/04
#70;(*(49(*:4(7>!52>5=53,9(2(9,8D îWe~UÀ  rÙÝU /MH,M

5





!
& 'C4$297(89()2,"3(22@.A(45*2:89,7<09/04(#70(4.:2(75225<!52>5=53,9(2(9,7(3,<571D
%54,8(9595%515.(<(%(3(.:*/0":?:10
      B  & 'C52,*:2(7>)70+5-(49530*(22>!7,*08,"02;,7(45*2:89,7(4+!52>5=53,9(2(9,8-57 2,(;(.,0495
!759548(4+2,*97548D
%54,8(95"%(3(?5,%515.(<(%(3(.:*/0":?:10
      

(40,



& ' C0.(4+07,*9,+ 6675(*/ 04 !52>5=53,9(2(9, ">49/,808 573(9054 5- ( ,< 0;(*(49 (*:4(7>
!52>5=5352>)+(9,&G!5

F
' D

0%(3(.:*/0":?:10
    B & ' C 6759,*904. .75:6 897(9,.> 95 (**,88 89()2, 2(*:4(7> 652>5=5352>)+(9,8 -57 04975+:*04. 3:2904:*2,(7 3,9(2*2:89,78D
003)5%(3(.:*/0":?:10
 

B

- 49 -

᭷ᶵࣃࣛࢪ࣒࢘㘒యࡢゐ፹స⏝࡟㛵ࡍࡿ◊✲
Study on Catalysis of Organopalladium Complexes‫ۑ‬ᒣᮏ ဴஓࠊΎỈ ᮍ⣖㸦ᮾி㟁ᶵ኱Ꮫ㸧1◊✲┠ⓗ ⏦ㄳ⪅ࡽࡣ N-࣊ࢸࣟ⎔࢝ࣝ࣋ࣥ㸦NHC㸧ࢆᨭᣢ㓄఩Ꮚ࡜ࡍࡿ᭷ᶵࣃࣛࢪ࣒࢘㘒యࢆ⏝࠸ࡓ᭷ᶵ࣍࢘⣲໬ྜ≀ࡢ࢝ࣝ࣎ࢽࣝ໬ྜ≀࡬ࡢ 1,2-௜ຍ཯ᛂࢆ㛤Ⓨࡋ࡚࠸ࡿࠋࡇࡢ཯ᛂࡢゐ፹ࢧ࢖ࢡࣝࡣࠊ᭷ᶵࣃࣛࢪ࣒࢘㘒య࡜᭷ᶵ࣍࢘⣲໬ྜ≀ࡢࢺࣛࣥࢫ࣓ࢱ
ࣝ໬ࢆ⤒ࡿࢪ࢔࣮ࣜࣝࣃࣛࢪ࣒࢘㘒యࡢ⏕ᡂ(i)ࠊࡘ࡙ࡃ࢝ࣝ࣎ࢽࣝ໬ྜ≀࡬ࡢ࢔࣮ࣜࣝᇶࡢᤄධ(ii)࡜࢔ࣝࢥ࢟ࢩࣃࣛ
ࢪ࣒࢘࡜᭷ᶵ࣍࢘⣲໬ྜ≀ࡢࢺࣛࣥࢫ
࣓ࢱࣝ໬࡟ࡼࡿࢪ࢔࣮ࣜࣝࣃࣛࢪ࣒࢘
㘒యࡢ෌⏕(iii)࡜᝿ᐃࡉࢀࡿ㸦ᅗ 1㸧ࠋᮏ◊✲࡛ࡣࡑࡢゐ፹཯ᛂᶵᵓࡢ⌮ㄽ໬Ꮫᅗ 1㸬ⓗ࡞ゎ᫂ࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬ࡣࡍ࡭࡚ Gaussian 16 ࢆ⏝࠸࡚⾜ࡗࡓࠋỗ㛵ᩘ࡜ࡋ࡚ B3LYP ࢆ⏝࠸ࠊᇶᗏ㛵ᩘ࡜ࡋ࡚ࡣࠊHࠊ

CࠊBࠊNࠊOࠊS ࡟㛵ࡋ࡚ࡣ 6-31G(d)ࢆࠊPd ࡟ LanL2DZ ࢆ⏝࠸ࡓࠋ㑄⛣≧ែࡢᵓ㐀ࡣ IRC ィ⟬࡛☜ㄆࡋࡓࠋ3◊✲ᡂᯝ
ᅗ 1 ࡟♧ࡋࡓࣃࣛࢪ࣒࢘㘒య࡜ࣇ࢙ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࡢࢺࣛࣥࢫ࣓ࢱࣝ໬ࠊ࣋ࣥࢬ࢔ࣝࢹࣄࢻ࡬ࡢࣇ

࢙ࢽࣝᇶࡢᤄධࠊ࢔ࣝࢥ࢟ࢩࣃࣛࢪ࣒࢘㘒య࡜ࣇ࢙ࢽࣝ࣎ࣟࣥ㓟࢚ࢫࢸࣝࡢࢺࣛࣥࢫ࣓ࢱࣝ໬ࡢࡑࢀࡒࢀࡢ
⤒㊰࡟ࡘ࠸࡚ࠊNHC ࡟ᑐࡋ࡚ࢩࢫࡢ఩⨨ࡼࡾࡶࢺࣛࣥࢫࡢ఩⨨࡛⏕ࡌࡿ᪉ࡀ࢚ࢿࣝࢠ࣮ⓗ࡟᭷฼࡛࠶ࡿࡇ࡜
ࡀ☜ㄆ࡛ࡁࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬ዟ⏣ 㞝ኴࠊచ㔝 㱟ࠊΎỈ ᮍ⣖ࠊᒣᮏ ဴஓࠊ͆ࣄࢻࣟ࢟ࢩᇶ࡛ᯫᶫࡋࡓ NHC 㓄఩ࢩࢡ࣓ࣟࢱࣝ໬ࣃ
ࣛࢪ࣒࢘㘒యࡢゐ፹స⏝͇ ᪥ᮏ໬Ꮫ఍ ➨ 101 ᫓Ꮨᖺ఍ (2021)ࠊ2021 ᖺ 3 ᭶ 20 ᪥ࠊZOOM

5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
⌧ᅾࠊᢞ✏‽ഛࢆࡋ࡚࠾ࡾࠊᖺෆࡢᢞ✏ࢆணᐃࡋ࡚࠸ࡿࠋ

- 50 -

୰㛫ⓗ࡞ࢫࣆࣥ≧ែࢆ⤒⏤ࡍࡿࢥࣂࣝࢺゐ፹཯ᛂࡢィ⟬໬ᏛⓗᶵᵓゎᯒTheoretical investigation of cobalt-catalyzed reactions involving
non-integral spin states‫ۑ‬ᑠᓥṇᐶࠊྜྷ㔝㐩ᙪࠊ෠⏣Ọᕼࠊ⚄ᒣ㣁リࠊຍ⸨ె⨾ࠊ㛵᰿኱ᆅࠊబ⸨ಇኴ㸦໭ᾏ㐨኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲㝔㸧1◊✲┠ⓗᡃࠎࡣගゐ፹࡜ࢥࣂࣝࢺゐ፹ࡢ༠ാゐ፹⣔ࢆ⏝࠸ࡓࠊỈ⣲ཎᏊ⛣ືࢆ㘽཯ᛂ࡜ࡍࡿ࢔ࣝࢣࣥࡢࣄࢻࣟᐁ⬟ᇶ໬཯ᛂࡢ㛤Ⓨࢆ⾜ࡗ࡚࠸ࡿࠋࡇࡢ཯ᛂ⣔࡛ࡣỈ⣲ཎᏊ⛣ື࡟క࠸ࠊ㛢Ẇ⣔࠿ࡽࣛࢪ࢝ࣝ࣌࢔ࡀⓎ⏕ࡍࡿᶵᵓ࡟࡚཯ᛂࡀ㐍⾜ࡍࡿࠋࡇࡢᶵᵓࢆ୰㛫ⓗ࡞ࢫࣆࣥ≧ែࡢྲྀࡾᢅ࠸࡟㓄៖ࡋࡓ DFT ィ⟬࡟ࡼࡾゎᯒࡋࠊ཯ᛂ
ᶵᵓ࡟㛵ࡍࡿ▱ぢࢆ⋓ᚓࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚タᐃࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ
GRRM14 ࠾ࡼࡧ GRRM17 ࢆ⏝࠸ࠊࢥࣂࣝࢺࣄࢻࣜࢻ㘒య࠿ࡽ✀ࠎࡢ୙άᛶ࢔ࣝࢣࣥ࡬ࡢỈ⣲ཎᏊ⛣ືẁ㝵ࡢ㑄⛣≧ែࠊ࠾ࡼࡧ IRC ࡢ DFT ィ⟬ࢆ⾜ࡗࡓࠋ࠸ࡎࢀࡢィ⟬ࡶ GRRM ࡢ stable=opt ࢜ࣉࢩࣙࣥࢆ౑⏝ࡋࠊἼື㛵ᩘࡢᏳᐃᛶࢆ୍ᐃࡢィ⟬ࢫࢸࢵࣉࡈ࡜࡟☜ಖࡋࡓࠋࡇࢀ࡟ࡼࡾ㛢Ẇ✀࠿ࡽࣛࢪ࢝ࣝ࣌࢔ࡀⓎ⏕ࡍࡿ㐣⛬࡛⏕ࡌࡿ୰㛫ⓗ࡞ࢫࣆࣥ≧ែࢆᣢࡘ໬Ꮫ✀ࢆࠊᐇ㦂⣔࡟㏆࠸ᙧ࡛ྲྀࡾᢅ࠸࡛ࡁࡿ࡜᝿ᐃࡋࡓࠋ

3◊✲ᡂᯝ
DFT ィ⟬ࡢ⤖ᯝࠊ୙άᛶ࢔ࣝࢣࣥ࡬ࡢࢥࣂࣝࢺࣄࢻࣜࢻ࠿ࡽࡢỈ⣲ཎᏊ⛣ືࢆ㉳Ⅼ࡜ࡍࡿ㸰✀ࡢ཯ᛂ࡟ࡘ

࠸࡚ࠊỈ⣲ཎᏊ⛣ື㐣⛬ࡢ㑄⛣≧ែ࡜ IRC ࡢᑟฟ࡟ᡂຌࡋࡓࠋᚓࡽࢀࡓィ⟬⤖ᯝࡣᐇ㦂⤖ᯝ࡜ᩚྜࡋࠊGRRM
ࡢ stable=opt ࢜ࣉࢩࣙࣥࢆ⏝࠸ࡓ୰㛫ⓗ࡞ࢫࣆࣥ≧ែࡢྲྀࡾᢅ࠸ᡓ␎ࡢጇᙜᛶࢆ♧ࡍࡇ࡜ࡀ࡛ࡁࡓ࡜⪃࠼࡚࠸ࡿࠋࡲࡓỈ⣲ཎᏊ⛣ື㐣⛬ࡢ๓ᚋ࡛㉳ࡇࡿ㐃⥆཯ᛂࡢ㑄⛣≧ែ࠾ࡼࡧ IRC ࡢᑟฟࡶేࡏ࡚ᐇ᪋ࡋࠊከẁ㝵཯ᛂࡢ඲యീࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡟ࡶᡂຌࡋࡓࠋࡇࢀࡽࡢ཯ᛂ࡟㛵ࡋ࡚ࡣ⌧ᅾᐇ㦂໬Ꮫⓗ࡞᳨ウࡀ⤊஢ࡋḟ➨ࠊィ⟬⤖ᯝࢆ஺࠼࡚Ꮫ఍࠾ࡼࡧㄽᩥⓎ⾲ࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
◊✲ᡂᯝࡢ㡯࡛㏙࡭ࡓ㸰✀ࡢ཯ᛂ࡟㛵ࡋࠊ⌧ᅾࡲ࡛ࡢᐇ㦂ⓗ᳨ウ࡟ࡘ࠸࡚㸰௳ࡢᏛ఍Ⓨ⾲ࢆ⾜ࡗࡓࠋx᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍ [A21-2am-11] ග㓟໬㑏ඖゐ፹࡜ࢥࣂࣝࢺゐ፹ࡢ༠ാ࡟ࡼࡿ HAT ␗ᛶ໬ࢆ⏝࠸ࡓከ⨨᥮࢚ࢼ࣑ࢻྜᡂ㸦Ⓨ⾲⪅㸸Ύ㔝భ௓ࠊ௚ 5 ྡ㸧x᪥ᮏ⸆Ꮫ఍➨ 141 ᖺ఍ [28V05-pm02S] ග㓟໬㑏ඖゐ፹/ࢥࣂࣝࢺゐ፹ࡢ༠ാ࡟ࡼࡿ⎔ቃㄪ࿴ᆺศ
Ꮚෆ HAT ࣄࢻࣟ࢔࣮ࣜࣝ໬཯ᛂ㸦Ⓨ⾲⪅㸸ᒣཱྀඃ෤ࠊ௚ 5 ྡ㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
GRRM ࢆ⏝࠸ࡓ DFT ィ⟬࡟ࡼࡿỈ⣲ཎᏊ⛣ືࡢ཯ᛂᶵᵓゎᯒ࡟ࡘ࠸࡚ࠊ௨ୗࡢㄽᩥⓎ⾲ࢆ⾜ࡗࡓࠋxKamei, Y. et al. “Silane- and peroxide-free hydrogen atom transfer hydrogenation using ascorbic acid andcobalt-photoredox dual catalysis” Nat. Commun. 2021, 12, article number: 966.

- 51 -

⏕యศᏊࡢᶵ⬟Ⓨ⌧཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDOUHVHDUFKRQUHDFWLRQPHFKDQLVPVLQELRPROHFXOHV‫ۑ‬ᫍ㔝 ᛅḟࠊຍⱱ ኱ᆅࠊᏱబ⨾ ⍆ࠊ㯮⏣ ᆂ୍ࠊ㒌 Ⰿࠊᓥ⏣ ୍⚽ࠊ㺞㺖㺹㺻㺟㺊㺻㺞㺡㺼㺆㸦༓ⴥ኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲㝔㸧◊✲┠ⓗࠊෆᐜ
ᢠయศᏊࡣ㧗࠸ぶ࿴ᛶ࡜≉␗ᛶ࡛ᶆⓗศᏊ࡟⤖ྜࡍࡿࠋࣔࣀࢡ࣮ࣟࢼࣝᢠయࡣࠊ⒴ࠊ㛵⠇⅖ࠊႍᜥࠊ஝Ⓞࠊ

࢘࢖ࣝࢫឤᰁࠊ࠾ࡼࡧ⛣᳜ᣄ⤯཯ᛂࢆྵࡴᗈ⠊࡞἞⒪ศ㔝࡛౑⏝ࡉࢀࡿࡓࡵࠊ་⸆ရ࡜ࡋ࡚㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࠋ୍⯡࡟ࠊᢠయ་⸆ࡣᶆⓗ࡟ᑐࡍࡿ≉␗ⓗࡀ㧗ࡃࠊపศᏊ໬ྜ≀ࡼࡾࡶ๪స⏝ࡀᑡ࡞࠸ࠋࡲࡓࠊ
⾑୰༙ῶᮇࡀ㛗࠸ࡇ࡜ࡀ⸆๣࡜ࡋ࡚᭷฼࡛࠶ࡿࠋ⌧ᅾࠊࣔࣀࢡ࣮ࣟࢼࣝᢠయࡣࠊ་⸆ရࠊ་Ꮫⓗデ᩿ࠊ࠾ࡼࡧ⏕≀Ꮫⓗ◊✲࡟࠾࠸࡚ࠊᴟࡵ࡚㔜せ࡞ᶵ⬟ᛶศᏊ࡟࡞ࡗ࡚࠸ࡿࠋ㧗࠸≉␗ᛶ࡜ぶ࿴ᛶࢆᣢࡘᢠయࡢྜ⌮ⓗ࡞タィࡢࡓࡵ࡟ࡣࠊᢠཎ̺ᢠయ┦஫స⏝ࡢ࣓࢝ࢽࢬ࣒ࢆヲ⣽࡟⌮ゎࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋᮏ◊✲ࡢ┠ⓗࡣࠊィ⟬ᶵゎᯒ࡟ࡼࡾᢠཎ̺ᢠయ┦஫స⏝ࡢ≉ᛶࢆゎᯒࡍࡿࡇ࡜࡛࠶ࡿࠋศᏊຊᏛ 00 ィ⟬ἲࢆ⏝࠸࡚ࠊࣄࢺ
ࡲࡓࡣ࣐࢘ࢫᢠయ࡟ᑐࡍࡿ  ࡢᢠཎ̺ᢠయ」ྜయࡢゎᯒࢆヨࡳࡓࠋ00 ィ⟬ࡣࠊཎᏊ㛫ࡢຊሙ࡟ᇶ࡙࠸࡚
࢚ࢿࣝࢠ࣮᭱ᑠ໬ᵓ㐀ࢆィ⟬ࡋࠊ᭱㐺໬ᵓ㐀࡟࠾ࡅࡿ࢚ࢿࣝࢠ࣮࡜ᵓ㐀࡟㛵ࡍࡿᛶ㉁ࢆồࡵࡿィ⟬࢔ࣉ࣮ࣟࢳ࡛࠶ࡿࠋࡇࡢィ⟬⤖ᯝ࠿ࡽࠊᢠయศᏊࡢᢠཎ࡜ࡢ⤖ྜࢆ⤫ィ࡟ㄪ࡭ࡓࠋ
◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ࣔࢹࣝࡢᵓ⠏; ⥺⤖ᬗᵓ㐀࠿ࡽᢠཎᢠయ」ྜయࡢ୕ḟඖཎᏊᗙᶆࢆᵓ⠏ࡋࡓࠋ
ࢱࣥࣃࢡ㉁ᵓ㐀ࢹ࣮ࢱࣂࣥࢡ 3'% ࠿ࡽࠊ ࡢ」ྜయᵓ㐀ࢆ௨ୗࡢᇶ‽࡛ྲྀᚓࡋࡓࠋ  ࣄࢺཪࡣ࣐࢘ࢫ⏤᮶ࡢᢠయࠊ  ; ⥺ᅇᢡࡢศゎ⬟ࡣ ௨ୗࠊ ᢠཎࡢṧᇶᩘࡣ  ௨ୖࠊ  ⤖ᬗᵓ㐀ࡣከᩘࡢḞኻṧᇶࢆྵࡲ࡞࠸ࠋ
࠸ࡃࡘ࠿ࡢ」ྜయࡣࠊ
ZIEࠊ
ZIFࠊZIGࠊ࠾ࡼࡧ ZIH ࡞࡝ࠊྠࡌ✀㢮ࡢᢠཎ࠾ࡼࡧᢠయศᏊ࠿ࡽᵓᡂࡉࢀࡿࠋࡇࡢࡼ࠺࡞」ྜయࡢ⤖ᬗᵓ㐀ࡶ  ࣔࢹࣝ୰࡟㔜」ࡋ࡚ྵࡵ࡚࠸ࡿࠋ」ྜయࡢึᮇᵓ㐀ࡣࠊḞᦆ࢔࣑ࣀ㓟ṧᇶ࡜Ỉ⣲ཎᏊࢆ௜ຍࡋ
࡚౑⏝ࡋࡓࠋ」ᩘࡢᢠཎ̺ᢠయ」ྜయࡀ⤖ᬗࡢ㠀ᑐ⛠༢఩⬊࡟ྵࡲࢀࡿሙྜࠊ᭱ึࡢ࣌࢔ࢆ㑅ᢥࡋࡓࠋཌࡉ ࡢỈࡢᒙࢆ」ྜయࡢ࿘ࡾ࡟⏕ᡂࡋ࡚ィ⟬ࡋࡓࠋ⤖ྜࢫࢥ࢔࡜Ỉ⣲⤖ྜࡢィ⟬
$PEHU7RROV ࢆ౑⏝ࡋ࡚ࠊ00 ィ⟬ࡢධຊࢹ࣮ࢱࢆసᡂࡋࡓࠋ00 ィ⟬࡟ࡼࡾࠊ」ྜయᵓ㐀ࢆ᭱㐺໬ࡋࡓࠋ$0%(5II6% ຊሙࢆศᏊෆ┦஫స⏝ࡢィ⟬࡟㐺⏝ࡋࠊ⊂⮬㛤ⓎࡋࡓຊሙࢆศᏊ㛫┦஫స⏝ࡢホ౯ィ⟬࡟౑⏝ࡋࡓࠋඹᙺ໙㓄ἲ࡟ࡼࡾ࢚ࢿࣝࢠ࣮᭱ᑠ໬ࢆ  ࢧ࢖ࢡࣝ⾜ࡗࡓࠋཎᏊ఩⨨࡟㛵ࡍࡿไ⣙ࢆタᐃࡏࡎ࡟࢚ࢿࣝࢠ࣮᭱ᑠ໬ࢆ⾜ࡗࡓࠋศᏊ㛫┦஫స⏝ࡢᙉࡉࡣຊሙ࡛ホ౯ࡋࡓ࢚ࢿࣝࢠ࣮ࡢ࿴࡛୚࠼ࡽࢀࡿࠋᮏ◊✲࡛ࡣࠊࡑࡢ኱ࡁࡉࢆ⤖ྜࢫࢥ࢔࡜ࡍࡿࠋศᏊ㛫┦஫స⏝࡟㛵ࡍࡿຊሙ࡛ࡣࠊཎᏊ㛫ࡢ࣏ࢸࣥࢩࣕࣝࡣ࣮ࣔࢫ
ᆺ㛵ᩘ࡟ࡼࡗ࡚グ㏙ࡉࢀࠊࣃ࣓࣮ࣛࢱࡣཎᏊᆺࡢ࠶ࡽࡺࡿ⤌ࡳྜࢃࡏ࡟ᑐࡋ࡚ᐃ⩏ࡋ࡚࠶ࡿࠋ⤖ྜࢫࢥ࢔ࡣ
ཎᏊࢱ࢖ࣉ࡟ࡼࡾ␯Ỉᛶ┦஫స⏝࡜ぶỈᛶ┦஫స⏝࡟ศࡅࡽࢀࡿࠋ␯Ỉᛶ┦஫స⏝ࡣ YDQGHU:DDOV ┦஫స⏝࡟ࠊ␯Ỉᛶ┦஫స⏝ࡣ㟼㟁┦஫స⏝࡟ᑐᛂࡍࡿࠋ⤖ྜࢫࢥ࢔ࡣࡑࢀࡒࢀࡢཎᏊࡢᐤ୚࡟ศࡅࡿࡇ࡜ࡶ࡛ࡁ

- 52 -

ࡿࠋ&'5 ࣮ࣝࣉ࡟࠾ࡅࡿྛ࢔࣑ࣀ㓟ṧᇶࡢฟ⌧㢖ᗘࢆࠊ඲  ࡢᢠయ࡟ࡘ࠸࡚ྜィࡋࡓṧᇶࡢ⥲ᩘࡢᖹᆒ್
࠿ࡽィ⟬ࡋࡓࠋ&'5 ࡟࠾ࡅࡿṧᇶࡢᖹᆒ㢖ᗘࢆࠊᢠయࡢ඲࢔࣑ࣀ㓟ṧᇶࡢᏑᅾ㔞࡜ẚ㍑ࡋࡓࠋࡉࡽ࡟ࠊṧᇶࡢ㢖ᗘࢆ┿᰾⏕≀ࡢ୍⯡ⓗ࡞ࢱࣥࣃࢡ㉁ࡢᖹᆒᏑᅾ㔞࡜ẚ㍑ࡋࡓࠋࡲࡓపศᏊ㔞໬ྜ≀࡜ࡑࡢᶆⓗࢱࣥࣃࢡ㉁࡜ࡢ」ྜయ࡟࠾ࡅࡿ㓝⣲ࡢ⤖ྜ࣏ࢣࢵࢺ࡟࠾ࡅࡿฟ⌧㢖ᗘ࡜ẚ㍑ࡋࡓࠋ




◊✲ᡂᯝ
ᅗ  D ࡣࠊ⤖ྜࢫࢥ࢔࡟ᑐࡍࡿྛ࢔࣑ࣀ㓟ṧᇶࡢᐤ୚ࢆ♧ࡋ࡚࠸ࡿࠋ7\U ࡢ㈉⊩ࡣ㝿❧ࡗ࡚࠸ࡿࠋ6HUࠊ$VQࠊ$VS ཬࡧ $UJ ࡣ࠿࡞ࡾ኱ࡁ࡞ᐤ୚ࢆ♧ࡋࡓࠋ7KUࠊ7USࠊ*OX ࡶ࠶ࡿ⛬ᗘᐤ୚ࡋ࡚࠸ࡿࠋ௚ࡢ  ࢔࣑ࣀ㓟ṧᇶ࠿ࡽࡢᐤ୚ࡣᑠࡉ࠸ࠋ≉࡟ࠊ7\U ࡜ 7US ࡢࡳࡀᐤ୚ࡢ㧗࠸  ṧᇶࡢ୰࡛ࠊ࠶ࡿ⛬ᗘࡢ␯Ỉᛶ┦஫స⏝ࢆᣢࡗ࡚࠸ࡓࠋ⤖ྜࢫࢥ࢔ࡢ⣙  ࡣࡇࢀࡽࡢ㧗࠸ᐤ୚ࢆࡍࡿ  ṧᇶ࡟ࡼࡿࡶࡢ࡛࠶ࡿࠋ
&'5 ࣮ࣝࣉ୰ࡢྛ࢔࣑ࣀ㓟ṧᇶࡢฟ⌧㢖ᗘࢆᅗ  E ࡟♧ࡍࠋ6HU ࡜ 7\U ࡢᏑᅾࡣⴭࡋࡃ኱ࡁ࠸ࠋࡑࡢฟ⌧㢖ᗘࢆ୍⯡ⓗ࡞ࢱࣥࣃࢡ㉁ࠊᢠయ඲యࠊ」ྜయࡢ⤖ྜ࣏ࢣࢵࢺ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊ6HU ࡜ 7\U ࡢᏑᅾ㔞ࡣ୍⯡ⓗ࡞ࢱࣥࣃࢡ㉁࡟ẚ࡭࡚ &'5 ࡛㧗࠸ഴྥࡀ࠶ࡗࡓࠋࡇࢀࡽ  ṧᇶࡣ㠀Ⲵ㟁ᴟᛶഃ㙐ࢆࡶࡘࠋ≉࡟ࠊ7\U ࡢᏑᅾࡣ୍⯡ⓗ࡞ࢱࣥࣃࢡ㉁࡟ẚ࡭࡚  ಸቑຍࡋࡓࠋ୍᪉ࠊ$VS ௨እࡢⲴ㟁ṧᇶ࡛ࡣࠊ୍⯡ࢱࣥࣃࢡ㉁࡟ẚ࡭࡚㢧ⴭ࡞పୗࡀほᐹࡉࢀࡓࠋ ࡘࡢ㠀ᴟᛶṧᇶࠊ3URࠊ9DOࠊ/HX ࡢᏑᅾࡶⴭࡋࡃప࠸ࠋᢠయศᏊ඲య࡜ẚ㍑ࡋ
࡚ 7\U ࡢฟ⌧ࡣⴭࡋࡃ㧗࠸ࠋ ࡘࡢ㠀ᴟᛶṧᇶࠊ3URࠊ9DOࠊ/HX ࡢᏑᅾࡶⴭࡋࡃప࠸ࠋ໬ྜ≀ࢱࣥࣃࢡ㉁」ྜయࡢ⤖ྜ࣏ࢣࢵࢺ࡜ẚ㍑ࡋ࡚ࠊ6HU ࡟ࡣ㢧ⴭ࡞㐪࠸ࡀࡳࡽࢀࡿࠋᢠཎᢠయ⏺㠃࡟࠾ࡅࡿ 6HU ࡢᏑᅾࡣࠊ໬
ྜ≀ࢱࣥࣃࢡ㉁⏺㠃࡜ẚ㍑ࡋ࡚  ಸቑຍࡍࡿࠋⰾ㤶᪘ṧᇶࡢฟ⌧ࡣࠊ໬ྜ≀ࢱࣥࣃࢡ㉁」ྜయࡢ⤖ྜ࣏ࢣࢵࢺ࡛㧗࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ7\U ௨እࡢᢠཎᢠయ」ྜయ࡛ࡣⰾ㤶᪘ṧᇶࡢᏑᅾࡣ㧗ࡃ࡞࠸ࠋࡑࡢ௦ࢃࡾࠊ
㠀Ⲵ㟁ᴟᛶṧᇶ࡛࠶ࡿ 7KUࠊ$VQࠊ*OQ ࡢฟ⌧ࡀᢠయ &'5 ࡛ቑຍࡍࡿࠋ
ᅗ  E ࡣࠊ⤖ྜࢫࢥ࢔ࡢྛṧᇶ࡬ࡢ⥲࿴࡜ࡋ࡚ィ⟬ࡉࢀ࡚࠸ࡿࡢ࡛ࠊࡇࡢ್ࢆṧᇶࡢᩘ࡛๭ࡗࡓࠋࡍ࡞ࢃࡕࠊᅗ  F ࡢ⤖ྜࢫࢥ࢔ࡣࠊ ṧᇶᙜࡓࡾࡢᐤ୚ࢆ⾲ࡍࠋ7\Uࠊ7USࠊ$VSࠊ*OXࠊ$UJࠊ$VQ ࡣ㔜せ࡛࠶ࡾࠊ⤖ྜࢫࢥ࢔ࡣ ᮍ‶࡛࠶ࡾࠊ⤖ྜ࡟ᐤ୚ࡍࡿࡇࢀࡽࡢ㔜せ࡞  ࢔࣑ࣀ㓟ṧᇶࡢ๭ྜࡣ ࢆ㉸࠼ࡿࠋ6HU
࡜ 7KU ࡣ &'5 ࡟ከࡃྵࡲࢀ࡚࠸ࡿࡢ࡛ࠊ㔜せ࡞  ಶࡢ࢔࣑ࣀ㓟ṧᇶ࠿ࡽࡣ㝖እࡉࢀࡿࠋ
&'5 ୰ࡢ࠸ࡃࡘ࠿ࡢṧᇶࡣࠊᢠయศᏊࡢᢠཎㄆ㆑ࢻ࣓࢖ࣥࡢ㦵᱁ࢆᙧᡂࡍࡿࡓࡵ࡟ෆഃ࡟఩⨨ࡍࡿࡢ࡛ࠊ
&'5 ୰ࡢࡍ࡭࡚ࡢṧᇶࡀᢠཎ࡜᥋ゐࡍࡿࢃࡅ࡛ࡣ࡞࠸ࠋࡑࡇ࡛ࠊᢠཎ࡜᥋ゐࡍࡿ࢔࣑ࣀ㓟ṧᇶࡢฟ⌧㢖ᗘࢆ෌ィ⟬ࡋࡓࠋฟ⌧㢖ᗘࡣࠊᅗ  E ࡢ⤖ᯝ࡜࡯ࡰ୍⮴ࡋࡓࠋ7\U ࡜ 7US ࡟ࡣࢃࡎ࠿࡞㐪࠸ࡀぢࡽࢀࠊࡇࢀࡽ ࡘࡢṧᇶࡢῶᑡࡣ௚ࡢṧᇶ࡟ẚ࡭࡚኱ࡁࡃ࡞࠸ࠋᚑࡗ࡚ࠊ7\U ࡜ 7US ࡣ &'5 ࡢ᥋ゐ⏺㠃࡟఩⨨ࡍࡿྍ⬟ᛶࡀ㧗࠸ࠋ⤖ྜࢫࢥ࢔࡟ᑐࡍࡿྛ࢔࣑ࣀ㓟ṧᇶࡢᐤ୚ࡶࠊᅗ  F ࡟♧ࡋࡓࡶࡢ࡜࡯ࡰ୍⮴ࡍࡿࠋ7\U ࡜ 7US ࡢฟ⌧㢖ᗘࡣ㐺ᗘ࡟ῶᑡࡋ࡚࠸ࡿࡢ࡛ࠊ7US ࡢ  ṧᇶ࠶ࡓࡾࡢᐤ୚ࡣ $UJ ࡟ẚ࡭࡚┦ᑐⓗ࡟ప࠸ࠋᚑࡗ࡚ࠊ$UJ ࡣࠊ ṧᇶᙜࡓࡾࡢ⤖ྜࢫࢥ࢔࡛ࡣࠊᐤ୚ࡀ㧗࠸ṧᇶ࡜࡞ࡿࠋ7\Uࠊ7USࠊ$VSࠊ*OXࠊ$UJࠊ$VQ ࡣ㔜せ࡞  ࢔࣑ࣀ㓟ṧᇶ࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀ࡚࠾ࡾࠊ⥲⤖ྜࢫࢥ࢔ࡢ ࢆ༨ࡵ࡚࠸ࡓࠋ
&'5 ࡟࠾ࡅࡿ࢔࣑ࣀ㓟ṧᇶ࡬ࡢỈ⣲⤖ྜࡢᩘࡣࠊ7\Uࠊ$VQࠊ$VS ࠾ࡼࡧ 6HU ࡢ㡰࡛㢧ⴭ࡛࠶ࡗࡓࠋ㠀Ⲵ㟁ᴟᛶṧᇶ࠿ࡽࡢỈ⣲⤖ྜࡢᩘࡣⲴ㟁ᴟᛶṧᇶࡢᩘࡢ  ಸ࡛࠶ࡿࠋ&'5 ࡟࠾ࡅࡿ㠀Ⲵ㟁ᴟᛶṧᇶࡢᏑᅾࡣࠊᢠཎ
࡜ᢠయ࡜ࡢ㛫ࡢᙧ≧┦⿵ᛶࢆಁ㐍ࡍࡿࠋᢠཎ࡜ᢠయ㛫ࡢ &'5 ࡟࠾ࡅࡿ┤᥋Ỉ⣲⤖ྜࡣ୺࡟㔜㙐࡛ほᐹࡉࢀࠊ᭱▷Ỉ⣲⤖ྜࡣ୺࡟㔜㙐࡛ほᐹࡉࢀࡓࠋపศᏊ㔞໬ྜ≀࡜ࡑࡢᶆⓗࢱࣥࣃࢡ㉁࡜ࡣᑐ↷ⓗ࡟ࠊᢠཎᢠయ」ྜ
యࡢᙧᡂࡣ୺࡟ぶỈᛶ┦஫స⏝࡟㉳ᅉࡍࡿࠋᚑࡗ࡚ࠊぶỈᛶ┦஫స⏝࡜ᙧ≧┦⿵ᛶࡀࠊ୺࡟ᢠཎࡢᢠయㄆ㆑
࡟㛵୚ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋ

- 53 -ᅗ 㸸 D ⤖ྜࢫࢥ࢔࡟ᑐࡍࡿྛ࢔࣑ࣀ㓟ṧᇶࡢᐤ୚ࠋぶỈᛶ┦஫స⏝ ㉥ ࡜␯Ỉᛶ┦஫స⏝ ỈⰍ ࡢࢫࢥ࢔ࢆṧᇶࡈ࡜࡟✚ࡳ㔜ࡡ࡚⾲♧ࠋ E &'5 ࣮ࣝࣉ୰ࡢྛ࢔࣑ࣀ㓟ṧᇶࡢฟ⌧㢖ᗘࠋ F ⤖ྜࢫࢥ࢔࡟ᑐࡍࡿྛṧᇶࡢᖹᆒᐤ୚
⋡ࠋ⤖ྜࢫࢥ࢔ࢆฟ⌧㢖ᗘ࡛๭ࡾ⟬ࡋࡓ್ࠋ- 54 -

⤖ᬗᵓ㐀࠿ࡽࣔࢹࣝ໬ࡋࡓ  ࡢᢠཎᢠయ」ྜయ࡟ࡘ࠸࡚ศᏊຊᏛィ⟬ࢆ⾜ࡗࡓ⤖ᯝࠊ௨ୗࡢ▱ぢࢆᚓࡓࠋ+ ࡜ + ࡢ &'5 ࡣᢠཎ࡜ᢠయࡢ⤖ྜぶ࿴ᛶ࡟኱ࡁࡃᐤ୚ࡋ࡚࠸ࡿࠋ7\U ࡢᐤ୚ࡣࡍ࡭࡚ࡢṧᇶࡢ୰࡛᭱ࡶ㧗࠸ࠋ␯Ỉᛶ┦஫స⏝࡟ẚ࡭࡚ぶỈᛶ┦஫స⏝ࡀᨭ㓄ⓗ࡛࠶ࡗࡓࠋ6HU ࡣ &'5 ࣮ࣝࣉ࡟࠾ࡅࡿฟ⌧㢖ᗘ࡟࠾࠸࡚ࠊ
࢔࣑ࣀ㓟ṧᇶࡢ୰࡛᭱ࡶ㧗࠸ᖹᆒ㔞ࢆ♧ࡍࠋ6HU ࡜ 7\U ࡣࠊ/ ࡜ +&'5 ࣮ࣝࣉ࡟ࡑࢀࡒࢀ㧗࠸༨᭷⋡࡛⌧ࢀࡿࠋᢠయ୰ࡢ 6HU ࡜ 7\U ࡢᖹᆒᏑᅾ㔞ࡣ୍⯡ⓗ࡞ࢱࣥࣃࢡ㉁ࡼࡾࡶከ࠸ࠋ6HU ࡜ 7\U ࡣศᏊㄆ㆑࡟ᚲ㡲࡛࠶ࡿࡀࠊ≉␗ᛶ࡜ぶ࿴ᛶ࡟ᑐࡍࡿᙺ๭ࡣ␗࡞ࡿࠋ6HU ࡣᢠཎᢠయ㛫ࡢ┤᥋ࡢỈ⣲⤖ྜࡢᩘࡀᑡ࡞ࡃࠊ⤖ྜࢫࢥ࢔࡬ࡢᐤ୚ࡀᑠࡉ࠸ࡇ࡜࠿ࡽุ᩿ࡍࡿ࡜ࠊ6HU ࡣぶ࿴ᛶ࡛ࡣ࡞ࡃ≉␗ᛶ࡟㛵୚ࡋ࡚࠸ࡿࠋഃ㙐࡟ⰾ㤶⎔ࢆࡶ
ࡘ 7US ࡸ 3KH ࡣ + ࡸ + ࡞࡝ࡢ㔜㙐࡟ࡶከࡃࡳࡽࢀࡿࡀࠊ⤖ྜࢫࢥ࢔࡬ࡢᐤ୚ࡣ኱ࡁࡃ࡞࠸ࠋࡇࢀࡽࡢ▱ぢࡣ㧗ぶ࿴ᛶᢠయࡢタィࢆྜ⌮໬ࡍࡿࡢ࡟ᙺ❧ࡘ࡜ᮇᚅࡉࢀࡿࠋ
Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫@>ۻ‬ᫍ㔝ᛅḟ+,9 ㏫㌿෗㓝⣲ 51DVH+ άᛶ㜼ᐖ⸆ࡢ㛤Ⓨ㺂᪥ᮏ⸆Ꮫ఍➨  ᖺ఍ࠊᗈᓥ ࢜ࣥࣛ࢖ࣥ
 ‫@>ۻ‬㒌Ⰿࠊ௚(OHFWURVWDWLF3RWHQWLDOVDURXQGWKH3URWHLQV3UHIHUDEO\&U\VWDOOL]HGE\$PPRQLXP6XOIDWHࠊ ᖺᗘィ⟬㺜㺻㺞㺎㺃㺣㺧㺡㺖㺪㺽㺵㺍㺢ྜྠ ZDNXVKRࠊᒸᓮ ࢜ࣥࣛ࢖ࣥ  ‫@>ۻ‬ႛḠᝋࠊ௚$QDO\VLVRIELQGLQJPRGHVRIDQWLJHQDQWLERG\FRPSOH[HVE\PROHFXODUPHFKDQLFVFDOFXODWLRQ㺂 ᖺᗘィ⟬㺜㺻㺞㺎㺃㺣㺧㺡㺖㺪㺽㺵㺍㺢ྜྠ ZDNXVKRࠊᒸᓮ ࢜ࣥࣛ࢖ࣥ  ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

>@ 0RUL ' <RQHGD 7 6X]XNL 0 +RVKLQR 7 1H\D 6  'HSURWHFWLRQ RI D EHQ]\O XQLW LQGXFHV D ʌDURPDWLF PDFURF\FOHRIR[\S\ULSHQWDSK\ULQ  ZLWKVWURQJ1,5DEVRUSWLRQ2UJ%LRPRO&KHP
  GRLGREN>@ 6KLUD\DQDJL7$RNL6)XMLPRUL6:DWDQDEH.$LGD7+LUDVDZD0.XPDJDL.+RVKLQR7,WR.  'HWHFWLRQ RI $EDFDYLU,QGXFHG 6WUXFWXUDO $OWHUDWLRQV LQ +XPDQ /HXNRF\WH $QWLJHQ%  8VLQJ
3KDJH'LVSOD\%LRO3KDUP%XOO  GRLESEE
մ>@&KDQWDGHH 76LULUDN-+RVKLQR73KDHFKDPXG7$XJPHQWDWLYHPROHFXODUDVSHFWIRUSKDVHLQYHUVLRQRI YDQFRP\FLQ K\GURFKORULGHORDGHG IDWW\ DFLG LQ VLWX IRUPLQJ PDWULFHV 0DWHULDOV  'HVLJQ   GRLMPDWGHV>@ .RED\DVKL 6 +LZDVD 7 ,VKLJH 7 .DQR 0 +RVKLQR 7 5DKPXWXOOD % 6HLPL\D 0 6KLPDGD +

1RPXUD ) 0DWVXEDUD + 0DWVXVKLWD .  $QWL),5ǻH[RQ DXWRDQWLERG\ DV D QRYHO LQGLFDWRU IRU EHWWHU
RYHUDOOVXUYLYDOLQJDVWULFFDQFHU&DQFHU6FL±  GRLRUJFDV
մ>@ *XR < 4X / 1LVKLGD 1 +RVKLQR 7  (OHFWURVWDWLF 3RWHQWLDOV DURXQG WKH 3URWHLQV 3UHIHUDEO\&U\VWDOOL]HGE\$PPRQLXP6XOIDWH&U\VW*URZWK'HV±  GRLDFVFJGF
մ>@1XNDJD0<RRQ0-7DUDFLOLD0$+RVKLQR7%HFND6$=HLVHU(7-RKQVRQ-53DSS:DOODFH.0$VVHVVLQJWKH3RWHQF\RIȕ/DFWDPDVH ,QKLELWRUVZLWK'LYHUVH,QDFWLYDWLRQ 0HFKDQLVPVDJDLQVWWKH
3HQ$ &DUEDSHQHPDVH IURP%XUNKROGHULD PXOWLYRUDQV $&6 ,QIHFW 'LV  0DU  GRLDFVLQIHFGLVF
մ>@ 4X / 4LDR ; 4L ) 1LVKLGD 1 +RVKLQR 7  $QDO\VLV RI %LQGLQJ 0RGHV RI $QWLJHQ$QWLERG\&RPSOH[HVE\0ROHFXODU0HFKDQLFV&DOFXODWLRQ-&KHP,QIRUP0RGHOGRLDFVMFLPF

- 55 -

ゐ፹ศᏊ⣔࠾ࡼࡧ⏕యศᏊ⣔ࡢ㔞Ꮚ໬Ꮫ࡜཯ᛂືຊᏛ
Quantum Chemistry and Reaction Dynamic of
Catalytic and Biological Systemsࠐ㛗㇂ᕝ ῟ஓ㸪㣤⏣ ೺஧㸪㧗 ᩄ㸪0DQXVVDGD5DWDQDVDN㸪5DWWDQDZDOHH5DWWDQDZDQ㸪ᐑᓮ ⋹㸪㉿ 㯪᫂㸪'DQMR3XULR'H&KDYH]㸪ಖᆏ 㱟㸪኱ᇛ ᾏ㸪 ཎ ෽ử㸦໭ᾏ㐨኱Ꮫゐ፹⛉Ꮫ◊✲ᡤ㸧◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࣉࣟࢪ࢙ࢡࢺ࡟ࡼࡾᐇ᪋ࡋࡓ◊✲ࡢ୰࠿ࡽḟࡢࢸ࣮࣐࡟ࡘ࠸࡚ࠊࡑࡢ⤖ᯝࢆሗ࿌ࡍࡿࠋ 3W ⾲㠃࡟྾╔ࡋࡓศᏊ࡟ᑐࡍࡿ⨨᥮ᇶࡢຠᯝࡢ 1%2 ゎᯒ࡟ࡘ࠸࡚
 ஧ᐁ⬟ᛶ࣏ࣝࣇ࢕ࣜࣥゐ፹࡟ࡼࡿ஧㓟໬Ⅳ⣲࡜࢚࣏࢟ࢩࢻࡢඹ㔜ྜ཯ᛂᶵᵓ࡟㛵ࡍࡿ◊✲ 0J ,, 㘒య࡟ࡼࡿ࢚ࢫࢸࣝ஺᥮཯ᛂᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲  ᾮయ࢖ࣥࢪ࣒࢘࡟ࡼࡿ࣓ࢱࣥ⬺Ỉ⣲࢝ࢵࣉࣜࣥࢢࡢゐ፹ᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲  㖟㓟໬ࢳࢱࣥ⏺㠃࡛ࡢගㄏ㉳㟁Ꮚ⛣ືࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲  ⣔㛫஺ᕪࢆྵࡴ໬Ꮫ཯ᛂ⤒㊰ࡢ⮬ືỴᐃἲ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲◊✲᪉ἲࠊィ⟬᪉ἲ   ࡢ◊✲࡟ࡣ 9$63*DXVVLDQ ࢆ౑⏝ࡋࡓ   ࡢ◊✲࡟ࡣ *DXVVLDQ ࢆ౑⏝ࡋࡓ   ࡢ◊✲࡟ࡣ *DXVVLDQ ࢆ౑⏝ࡋࡓ    ࡢ◊✲࡟ࡣ &3. ࢆ౑⏝ࡋࡓ   ࡢ◊✲࡟ࡣ㸪6$/021 ࢆ౑⏝ࡋࡓ   ࡢ◊✲࡟ࡣ  *DXVVLDQ ࢆ౑ࡗ࡚࢚ࢿࣝࢠ࣮໙㓄ࢆィ⟬ࡋ㸪࢜ࣉࢸ࢕࣐࢖ࢨ࣮࡟ࡣ◊✲ᐊ࡛㛤Ⓨࡋࡓࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࡓ



◊✲ᡂᯝ
 3W ⾲㠃࡟྾╔ࡋࡓศᏊ࡟ᑐࡍࡿ⨨᥮ᇶࡢຠᯝࡢ 1%2 ゎᯒ࡟ࡘ࠸࡚1DWXUDO%RQG2UELWDO 1%2 $QDO\VLV ⮬↛㌶㐨ゎᯒἲࡣ⮬↛⤖ྜ㌶㐨

ࢆィ⟬ࡍࡿࡇ࡜࡛ࠊᏙ❧ศᏊෆ࡜ศᏊ㛫ࡢ┦஫స⏝࡞࡝ࢆᐃ㔞ⓗ࡟ㄝ᫂ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋᮏ◊✲࡛ࡣ 1%2 ἲࢆ⏝࠸࡚ࠊ࿘ᮇቃ⏺᮲௳ࢆ⏝࠸ࡓ⾲㠃ィ⟬࡟ᛂ⏝ࡋࠊ3W ⾲㠃ࡀᢸᣢࡋࡓ࢔࣮ࣜࣝ࢖ࢯࢩ࢔ࢽࢻศᏊ
ࡢศᏊ᣺ືཬࡧ㟁Ꮚ≧ែ࡟୚࠼ࡿᙳ㡪ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡑࡢ⤖ᯝࠊ࢔࣮ࣜࣝ࢖ࢯࢩ࢔ࢽࢻศᏊࡢ 1& ⤖ྜᙉᗘࡣ⨨᥮ᇶࡔࡅ࡛ࡣ࡞ࡃࠊ⾲㠃࡜ศᏊ㛫ࡢȧ㏫౪୚࡜Ȫ౪୚࡟ࡶᙳ㡪ࢆ࠺ࡅࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸦ᅗ 㸧ࠋ1& ⤖ྜᙉᗘࡣఙ⦰᣺ື࡜┦㛵ࡀ࠶ࡿࡓࡵࠊ1%2 ゎᯒ⤖ᯝ࠿
ࡽ 1& ఙ⦰᣺ືഴྥࢆண ࡍࡿྍ⬟ᛶࢆ♧ࡋࡓࠋ- 56 -

ᅗ  ,QWHUDFWLRQ EHWZHHQ DU\O
LVRF\DQLGHPROHFXOHVDQG3WVXUIDFH  ஧ᐁ⬟ᛶ࣏ࣝࣇ࢕ࣜࣥゐ፹࡟ࡼࡿ஧㓟໬Ⅳ⣲࡜࢚࣏࢟ࢩࢻࡢඹ㔜ྜ཯ᛂᶵᵓ࡟㛵ࡍࡿ◊✲ᒸᒣ኱Ꮫ౫㤿◊✲ᐊ࡜ᮾி኱Ꮫ㔝ᓮ◊✲ᐊࡀ㛤Ⓨࡋࡓ࣏ࣝࣇ࢕ࣜࣥゐ፹ࡣᶆグࡢ཯ᛂ࡛ୡ⏺᭱㧗Ỉ‽ࡢ72) ࢆ♧ࡋࡓ㸦ᅗ  ᕥ㸧ࠋᮏ◊✲࡛ࡣྠ཯ᛂࡢ཯ᛂᶵᵓ࡟㛵ࡍࡿඹྠ◊✲ࢆᐇ᪋ࡋࡓࠋ≉ᚩⓗ࡞ゐ፹ᵓ㐀࡟ࡘ࠸࡚ࠊ L ࣏ࣝࣇ࢕ࣜࣥ㓄఩Ꮚ࡟࠾ࡅࡿ $O࢖࢜ࣥࡀࠊồ᰾ᨷᧁࢆཷࡅࡓᚋࡢ୙Ᏻᐃ࡞࢚࣏࢟ࢩࢻ༢㔞య࢔ࢽ࢜ࣥࢆᏳᐃ໬ࡍࡿࡇ࡜ࠊ LL ᅄ⣭࢔ࣥࣔࢽ࣒࢘ࢆྵࡴ⨨᥮ᇶࡣࠊ஧㓟໬Ⅳ⣲࡜࢝ࢵࣉࣜࣥࢢࡋࡓᚋࡢ࢔ࢽ࢜ࣥ
✀ࢆ㟼㟁ⓗ࡟Ᏻᐃ໬࡛ࡁࠊ㔠ᒓ୰ᚰ࠿ࡽࡢ⬺㞳ࢆಁ㐍ࡍࡿࡇ࡜㸦ᅗ  ྑ㸧ࠊ LLL ๪཯ᛂ࡛࠶ࡿ⎔≧࣮࢝࣎ࢿ࣮
ࢺ⏕ᡂࡣ࢚ࢿࣝࢠ࣮ⓗ࡟୙฼࡜࡞ࡿࡇ࡜➼ࡀ ')7 ィ⟬࡟ࡼࡗ࡚♧ࡉࢀࡓࠋ
 0J ,, 㘒య࡟ࡼࡿ࢚ࢫࢸࣝ஺᥮཯ᛂᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ྡྂᒇ኱Ꮫ▼ཎ◊✲ᐊࡀ㛤Ⓨࡍࡿ 0J ,, ࢔ࣜࣝ࢜࢟ࢩࢻゐ፹࡟ࡼࡿ࢚ࢫࢸࣝ஺᥮཯ᛂ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚
ඹྠ◊✲ࢆᐇ᪋ࡋࡓࠋᇶ㉁ࡢỈ㓟ᇶ࠿ࡽ࢔ࣜࣝ࢜࢟ࢩࢻ㓄఩Ꮚࡀࣉࣟࢺࣥࢆᘬࡁᢤࡃ㐣⛬࡜࢔ࢡࣜࣝ㓟࣓ࢳࣝ࡬ࡢồ᰾ᨷᧁࡀ༠ዌⓗ࡟㉳ࡁࡿࡇ࡜࡛ࠊᇶ㉁ࡢồ᰾ᛶࡀ㧗ࡲࡾάᛶ໬㞀ቨࡀపୗࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸦ᅗ
㸧
ࠋ









ᅗ  /HIW  3RO\FDUERQDWH V\QWKHVLV ZLWK &2 DQGR[LGH
FDWDO\]HG
E\ELIXQFWLRQDOF\FORKH[HQH
$O ,,, SRUSK\ULQFRPSOH[ 5LJKW $WUDQVLWLRQVWDWHIRU&2
ERQGIRUPDWLRQEHWZHHQFDUERQDWHDQG&+2PRQRPHUᅗ . 7UDQVLWLRQ VWDWH IRU FRQFHUWHGQXFOHRSKLOLF DWWDFN RI 3K2+ WR PHWK\ODFU\ODWH FDWDO\]HG E\ D 0J ,, 
DU\OR[LGHVFRPSOH[  ᾮయ࢖ࣥࢪ࣒࢘࡟ࡼࡿ࣓ࢱࣥ⬺Ỉ⣲࢝ࢵࣉࣜࣥࢢࡢゐ፹ᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ᮾᕤ኱࣭ᒣ୰◊✲ᐊ࡟࠾࠸࡚ࠊ㔠ᒓ࢖ࣥࢪ࣒࢘ᾮయゐ፹࡟ࡼࡿ࣓ࢱࣥࡢ⬺Ỉ⣲ከ㔞໬཯ᛂࡀሗ࿌ࡉࢀࡓࠋ
ᡃࠎࡣࠊ')7 ィ⟬࡜➨୍ཎ⌮ 0' ィ⟬ࢆ⏝࠸࡚ࠊྠ཯ᛂࡢ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆヨࡳ࡚࠸ࡿࠋᐇ㦂ࡀ⾜ࢃࢀࡿ. ࡟࠾࠸࡚࢖ࣥࢪ࣒࢘ࡣᾮయ࡛࠶ࡿࡓࡵࠊẼᾮ⏺㠃ࡢ➨୍ཎ⌮ 0' ィ⟬࡜ EOXHPRRQ ࢔ࣥࢧࣥࣈࣝἲ࡟
ࡼࡗ࡚ྛ཯ᛂ⣲㐣⛬ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋᅗ  ࡟࣓ࢱࣥࡢゎ㞳྾╔㸪 /DQJPXLU+LQVKHOZRRG ᶵᵓࠊ
(OH\5LGHDO ᶵᵓ࡟ࡼࡿ࣓ࢱࣥ࢝ࢵࣉࣜࣥࢢࡢάᛶ໬࢚ࢿࣝࢠ࣮ࠊỈ⣲Ⓨ⏕ᶵᵓࡢάᛶ໬࢚ࢿࣝࢠ࣮࡞࡝ࢆࡲ
࡜ࡵࡓࠋᚊ㏿ẁ㝵ࡣ࣓ࢱࣥࡢ &+ ゎ㞳࡛࠶ࡗࡓࡀࠊ⏺㠃࡟࠾ࡅࡿ &+,Q ✀࡝࠺ࡋ࡟ࡼࡿ࣓ࢱࣥ࢝ࢵࣉࣜࣥࢢ
࡜ &+,Q ✀࡜ +,Q ✀࡟ࡼࡿ &+ ෌⤖ྜࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡣࡑࢀࡒࢀ N-PROࠊN-PRO ࡛࠶ࡾࠊ࡯ࡰ
➼ࡋ࠸⤖ᯝ࡟࡞ࡗࡓࠋ௚᪉࡛ࠊ&+,Q ✀࡜ +,Q ✀ࡢ 0' ࢺࣛࢪ࢙ࢡࢺ࣮ࣜࢆゎᯒࡍࡿ࡜ࠊ&+,Q ✀ࡣ⏺㠃࡟ศᕸࡍࡿࡢ࡟ᑐࡋ࡚ࠊỈ⣲ཎᏊࡣ࢖ࣥࢪ࣒࢘ᾮయ୰࡟ᐜ᫆࡟⁐ࡅ㎸ࡴࡇ࡜ࡀほᐹࡉࢀࡓࠋᚑࡗ࡚ࠊ⏺㠃࡟࠾ࡅࡿỈ⣲ཎᏊ⃰ᗘࡀపୗࡍࡿࡇ࡜࡛ࠊ&+ ෌⤖ྜࡢ㢖ᗘࡀᢚไࡉࢀ࡚ࠊ࣓ࢱࣥ࢝ࢵࣉࣜࣥࢢࡀಁ㐍ࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ࣓ࢳࣝࣛࢪ࢝ࣝࡀⓎ⏕ࡋ࡚ࠊẼ┦࠿ࡽ &+,Q ✀ࢆᨷᧁࡍࡿ (OH\5LGHDO ᶵᵓ࡟ࡘ࠸࡚ࡣࠊ
࣓ࢳࣝࣛࢪ࢝ࣝࡀẼ┦࡟⬺㞳ࡍࡿ࢚ࢿࣝࢠ࣮ࡀ኱ࡁ࠸ࡇ࡜ࠊ&+,Q ✀ࢆᨷᧁࡍࡿ࡜ඃඛⓗ࡟Ỉ⣲ᘬࡁᢤࡁࡀ
㉳ࡁࡿࡇ࡜ࡀศ࠿ࡗࡓࠋᚑࡗ࡚ࠊ/DQJPXLU+LQVKHOZRRG ᶵᵓࡀඃඛⓗ࡟ᶵ⬟ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ

- 57 -

  㟁ᅽࡢ༳ຍ࡟ࡼࡿ㟁Ꮚ≀ᛶኚ໬ࡢ࣓࢝ࢽࢬ࣒
ࢢࣛࣇ࢙ࣥ࡜ᵝࠎ࡞᭷ᶵศᏊ࠿ࡽ࡞ࡿ⣔࡟ࡘ࠸࡚ࠊࢢࣛࣇ࢙ࣥ㟁ᴟࡢᶵ⬟ࢆไᚚࡍࡿ࡜࠸࠺ほⅬ࠿ࡽ◊✲ࡀ⾜ࢃࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ᭷ᶵศᏊࢆࢢࣛࣇ࢙ࣥ࡟✚ᒙࡍࡿࡇ࡜࡛㟁ᅽ౫Ꮡᛶࡀ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿࡢ࠿ࠊ
࣓࢝ࢽࢬ࣒ࡢヲ⣽ࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠿ࡗࡓࠋᡃࠎࡣࠊ㟁ᅽࡢ༳ຍ࡟࡜ࡶ࡞࠺㟁Ꮚࡢὶฟධ࡜㟁ᴟ㟁ሙࡢ୧⪅ࢆྲྀࡾ㎸ࢇ࡛㟁Ꮚ≀ᛶࢆィ⟬ࡍࡿ⊂⮬ࡢ⌮ㄽⓗᡭἲࢆ⏝࠸࡚ࠊ㟁ᅽ౫ᏑᛶࢆཎᏊࡸ㟁Ꮚࡢ࡛ࣞ࣋ࣝ᫂ࡽ
࠿࡟ࡋ࡚ࡁࡓࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊS ࢻ࣮ࣆࣥࢢ࡟ᗈࡃ౑ࢃࢀ࡚࠸ࡿ᭷ᶵศᏊ )7&14 ࡀࢢࣛࣇ࢙ࣥ࡟྾╔ࡋࡓ⣔ࢆᑐ㇟࡜ࡋ࡚ࠊ㟁ᅽ౫Ꮡᛶࡢィ⟬ࢆ⾜ࡗࡓࠋࡑࡋ࡚㟁ᅽࡢ༳ຍ࡟ࡼࡿ㟁Ꮚᐦᗘኚ໬ࢆゎᯒࡋࡓ࡜ࡇࢁࠊ
)7&14ࢢࣛࣇ࢙ࣥ⏺㠃ࡢ㟁Ⲵศᕸࡀ㟁ᴟ㟁ሙ࡟ࡼࡗ࡚Ỵᐃ࡙ࡅࡽࢀ࡚࠸ࡿ࡜࠸࠺ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
















ᅗ  $ SODXVLEOH PHFKDQLVP RI WKHPHWKDQHWRHWKDQH FRQYHUVLRQ E\ WKH OLTXLGLQGLXP FDWDO\VW 1XPEHUV DUH FDOFXODWHG
DFWLYDWLRQ IUHH HQHUJ\ N-PRO XQLW  DW  .
REWDLQHGE\EOXHHQVHPEOHFDOFXODWLRQVᅗ  *UDSKHQH)7&14 HOHFWURGH XQGHUYROWDJHELDV  ⣔㛫஺ᕪࢆྵࡴ໬Ꮫ཯ᛂ⤒㊰ࡢ⮬ືỴᐃἲ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲㛤Ẇ㟁Ꮚ⣔ࢆ♧ࡍࡇ࡜ࡀከ࠸㑄⛣㔠ᒓ࡛ࡣ㸪」ᩘࡢ
ࢫࣆࣥ≧ែࡀ㏆᥋ࡋࡓ࢚ࢿࣝࢠ࣮㡿ᇦ࡟Ꮡᅾࡍࡿࡇ࡜
ࡀ▱ࡽࢀ࡚࠸ࡿ㸬ࡇࢀࡽࡢ㑄⛣㔠ᒓࡀゐ፹ࡍࡿ໬Ꮫ཯
ᛂ࡟࠾࠸࡚ࡣ㸪᭱Ᏻᐃ࡞ࢫࣆࣥ≧ែࡀ཯ᛂࡢ๓ᚋ࡛␗
࡞ࡿࡓࡵ㸪⣔㛫஺ᕪࢆ⤒ࡿ཯ᛂ⤒㊰ࢆồࡵࡿ᪉ἲࡢ㛤Ⓨࡀᚲせ࡛࠶ࡿ㸬ᮏ◊✲࡛ࡣࠊ1XGJHG(ODVWLF%DQG 1(% ἲ࡟⣔㛫஺ᕪⅬࢆ᭱㐺໬ࡍࡿᶵ⬟ࢆ௜୚ࡋࡓࠋࡍ࡞ࢃࡕࠊ」ᩘࡢࢫࣆࣥ
≧ែࡢ࢚ࢿࣝࢠ࣮㠃ࡀ஺ᕪࡍࡿ㡿ᇦ࡛ࡣࠊ⣔㛫஺ᕪⅬ
0LQLPXP (QHUJ\ ,QWHU6\VWHP &URVVLQJ SRLQW 0(,6& ࢆ᭱㐺໬ࡋࠊࡑࢀ௨እ࡛ࡣ 1(% ࡢ࢔ࣝࢦࣜࢬ࣒࡟ᚑ࠸࣏
ࢸࣥࢩࣕࣝ㠃ୖࡢ࢚ࢿࣝࢠ࣮ᴟᑠ⤒㊰ࢆồࡵࡿࡇ࡜ࡀᅗ 5HDFWLRQSDWKZD\RI&R+FDWDO\]HGPHWKDQHDFWLYDWLRQ WZRLPDJHV,BDQG,BZHUHRSWLPL]HG
DV 0(,6& SRLQWV DQG RQH LPDJH ,B ZDVRSWLPL]HGDV76 ྍ⬟࡟࡞ࡗࡓࠋᅗ㸴࡟ &R+࡬ࡢ࣓ࢱࣥゎ㞳྾╔࡟ᛂ⏝ࡋࡓ⤖ᯝࢆ♧ࡍࠋ,B ࠾ࡼࡂ ,B ࡛ࡣ⣔㛫஺ᕪⅬࢆࠊ,B ࡛ࡣ㑄⛣≧ែࢆ⮬ືⓗ࡟ồࡵࡿࡇ࡜ࡀ࡛ࡁࡓࠋ

- 58 -

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ


























‫ۻ‬6\QWKHVLVRIVLO\OIRUPDWHVIRUPDPLGHVDQGDOGHK\GHVYLDVROYHQWIUHHRUJDQRFDWDO\WLFK\GURVLO\ODWLRQRI&2
70XUDWD0+L\RVKL05DWDQDVDN-+DVHJDZD7(PD&KHP&RPPXQ  '2,'&&'‫ۻ‬4XDQWXPFKHPLFDOVWXG\RIVXEVWLWXHQWHIIHFWVRQ&1ERQGLQDU\OLVRF\DQLGHPROHFXOHVDGVRUEHGRQWKH3WVXUIDFH
%:DQJ0*DR.8RVDNL77DNHWVXJX
3K\V&KHP&KHP3K\V  '2,'&3$$OXPLQXPSRUSK\ULQVZLWKTXDWHUQDU\DPPRQLXPKDOLGHVDVFDWDO\VWVIRUFRSRO\PHUL]DWLRQRIF\FORKH[HQHR[LGHDQG
&2 0HWDO±OLJDQG FRRSHUDWLYH FDWDO\VLV >6HOHFWHG DV %DFN &RYHU@ - 'HQJ 0 5DWDQDVDN < 6DNR + 7RNXGD &
0DHGD-+DVHJDZD.1R]DNL7(PD &KHP6FL  '2,'6&+
$6\VWHPDWLF6WXG\RQWKH$EVRUSWLRQ)HDWXUHVRI,QWHUVWHOODU,FHVLQ3UHVHQFHRI,PSXULWLHV3 *RUDL 0 6LO $ 'DV % 6LYDUDPDQ 6 . &KDNUDEDUWL 6 ,RSSROR & 3X]]DULQL = .DQXFKRYD $ 'DZHV 0
0HQGROLFFKLR*0DQFLQL9%DURQH11DNDWDQL76KLPRQLVKL1-0DVRQ
$&6(DUWK6SDFH&KHP  '2,DFVHDUWKVSDFHFKHPF
'HORFDOL]DWLRQ(IIHFW3URPRWHGWKH,QGRRU$LU3XULILFDWLRQYLD8QORFNLQJ'LUHFWO\5LQJRSHQ3DWKZD\RI7ROXHQH
:4X3:DQJ0*DR-+DVHJDZD=6KHQ4:DQJ5/L'=KDQJ(QYLURQ6FL7HFKQRO  '2,DFVHVWF
‫(ۻ‬OHFWULF)LHOG(IIHFWRQ*UDSKHQH2UJDQLF,QWHUIDFHXQGHU%LDV9ROWDJH .,LGD&KHP/HWW  '2,FO
‫=ۻ‬HROLWHVXSSRUWHGXOWUDVPDOOQLFNHODVFDWDO\VWIRUVHOHFWLYHR[LGDWLRQRIPHWKDQHWRV\QJDV
6<DVXGD52VXJD<.XQLWDNH..DWR$)XNXRND+.RED\DVKL0*DR-+DVHJDZD50DQDEH+6KLPD6
7VXWVXPLQDL7<RNRL &RPPXQ&KHP  '2,V
6HOI$VVHPEOHG 0XOWLOD\HU ,URQ   1DQRSDUWLFOH &DWDO\VW IRU /LJDQG)UHH &DUERQ±&DUERQ&DUERQ±1LWURJHQ
%RQG)RUPLQJ5HDFWLRQV 7$NL\DPD<:DGD0<DPDGD<6KLR7+RQPD66KLPRGD.7VXUXWD<7DPHQRUL++DQHRND76X]XNL.+DUDGD+7VXUXJL.0DVKLPD-+DVHJDZD<6DWR0$ULVDZD2UJ/HWW  '2,DFVRUJOHWWF
6SLQ̺LQYHUVLRQPHFKDQLVPVLQ2ELQGLQJWRDPRGHOKHPHFRPSRXQG$SHUVSHFWLYHIURPQRQDGLDEDWLFZDYHSDFNHWFDOFXODWLRQV>6HOHFWHGDV&RYHU,PDJH@ .6DLWR<:DWDEH70L\D]DNL77DND\DQDJL-+DVHJDZD-&RPSXW&KHP  '2,MFF
‫[(ۻ‬WHQGLQJ1XGJHG(ODVWLF%DQG0HWKRGWR5HDFWLRQ3DWKZD\V,QYROYLQJ0XOWLSOH6SLQ6WDWHV
/=KDR.:DWDQDEH11DNDWDQL$1DND\DPD;;X-+DVHJDZD-&KHP3K\V  '2,
‫ۻ‬0HFKDQLVWLF 6WXG\ RQ 'HR[\GHK\GUDWLRQ DQG +\GURJHQDWLRQ RI 0HWK\O *O\FRVLGHV WR 'LGHR[\ 6XJDUV RYHU
5H2[3G&H2FDWDO\VW -&DR07DPXUD5+RVDND$1DND\DPD-+DVHJDZD<1DNDJDZD.7RPLVKLJH
$&6&DWDO  '2,DFVFDWDOF
‫&ۻ‬DWDO\WLF 0HFKDQLVP RI /LTXLG0HWDO ,QGLXP IRU 'LUHFW 'HK\GURJHQDWLYH &RQYHUVLRQ RI 0HWKDQH WR +LJKHU+\GURFDUERQV < 1LVKLNDZD < 2KWVXND + 2JLKDUD 5 5DWWDQDZDQ 0 *DR $ 1DND\DPD - +DVHJDZD ,
<DPDQDND $&62PHJD  '2,DFVRPHJDF
,QFUHDVHLQ&2UHGXFWLRQUDWHYLDRSWLFDOQHDUILHOGHIIHFW 7<DWVXL<1DNDPXUD<6X]XNL70RULPRWR<.DWR0
<DPDPRWR7<RVKLGD:.XUDVKLJH16KLPL]X<1HJLVKL.,LGD.1REXVDGD
-1DQRSKRWRQLFV  '2,-13
‫&ۻ‬KHPRVHOHFWLYH7UDQVHVWHULILFDWLRQRI0HWK\O 0HWK DFU\ODWHV&DWDO\]HGE\6RGLXP , RU0DJQHVLXP ,, $U\OR[LGHV>3UHVV 5HOHDVHG@ - 1J + $ULPD 7 0RFKL]XNL . 7RK . 0DWVXL 0 5DWDQDVDN - +DVHJDZD 0 +DWDQR .
,VKLKDUD $&6&DWDO  '2,DFVFDWDOF
‫ۻ‬2QWKH(OHFWURQLF6WUXFWXUH2ULJLQRI0HFKDQRFKHPLFDOO\,QGXFHG6HOHFWLYLW\LQ$FLG&DWDO\]HG&KLWLQ+\GURO\VLV
>6HOHFWHGDV6XSSOHPHQWDU\&RYHU@ '3'H&KDYH]+.RED\DVKL$)XNXRND-+DVHJDZD-3K\V&KHP$  '2,DFVMSFDF7XQLQJ 7UDQVLWLRQ (OHFWULF DQG 0DJQHWLF 'LSROH 0RPHQWV >@+HOLFHQHV 6KRZLQJ ,QWHQVH &LUFXODUO\ 3RODUL]HG/XPLQHVFHQFH +.XER7+LURVH71DNDVKLPD7.DZDL-+DVHJDZD.0DWVXGD-3K\V&KHP/HWW  '2,DFVMSFOHWWF
&DWDO\WLF$FWLYLW\RI*ROG&OXVWHUV6XSSRUWHGRQK%1$X  6XUIDFHIRU+\GURJHQ(YROXWLRQ5HDFWLRQ 0*DR0
1DNDKDUD$/\DOLQ77DNHWVXJX -3K\V&KHP&  '2,DFVMSFFF
0HFKDQLVPRIWKH$V\PPHWULF'HK\GUDWLYH$OO\ODWLYH&\FOL]DWLRQRI$OFRKROVWR&\FOLF(WKHUV&DWDO\]HGE\D&S5X
&RPSOH[RIWKH&KLUDO3LFROLQLF$FLG7\SH/LJDQG&O1DSK3\&22+,VDʌ$OO\O,QWHUPHGLDWH3UHVHQW"
<6X]XNL6,ZDVH05DWDQDVDN-+DVHJDZD67DQDND0.LWDPXUD%XOO&KHP6RF-SQ  '2,EFVM
‫ۻ‬0HFKDQLVWLF 6WXG\ RI &+ %RQG $FWLYDWLRQ E\ 2 RQ 1HJDWLYHO\ &KDUJHG $X &OXVWHUV  D'HK\GURJHQDWLRQ RI
0HWK\OSLSHULGRQHE\6XSSRUWHG$X&DWDO\VWV 50L\D]DNL;-LQ'<RVKLL7<DWDEH7<DEH10L]XQR.
<DPDJXFKL-+DVHJDZD &DWDO6FL7HFKQRO,QSUHVV  '2,'&<*‫'ۻ‬HVLJQ DQG 3UHGLFWLRQ RI +LJK 3RWHQW DQVD=LUFRQRFHQH &DWDO\VW IRU 2OHILQ 3RO\PHUL]DWLRQV &RPELQHG ')7&DOFXODWLRQVDQG4635$SSURDFK 05DWDQDVDN-+DVHJDZD93DUDVXN
1HZ-&KHP  '2,'1--‫ۻ‬$7ULDG)OXRUHQRQH'HULYDWLYH%HDULQJ7ZR,PLGD]ROH*URXSV7KDW6ZLWFKHVEHWZHHQ7KUHH6WDWHVE\%DVHDQG$FLG
6WLPXOL <:DQJ10DLW\/=KDR0.UDPHU-+DVHJDZD<6KLFKLEX..RQLVKL;:DQJ=6RQJ0%DQGR
71DNDQR &KHP/HWWLQSUHVV  '2,FO
,RQLF/LTXLGVWDELOL]HG6LQJOHDWRP5K&DWDO\VWDJDLQVW/HDFKLQJ
6'LQJ0+XHOVH\+$Q4+H+$VDNXUD0*DR-+DVHJDZD77DQDND1<DQ&&6&KHPLQSUHVV  - 59 -







Molecular simulations by generalized-ensemble algorithms
 ÊûĵÐÿºţjËĔ§¹ıŔÎĕďëÀĀÕŵĦ¾ÎƇĦĎࠉࠉࠉࠉࠉࠉࠉİƄĶ¨§ĦºÁE^hgRE]ÈĀìÔƈ£ºƉƋ ƊĲĺįĮgÄ ûĲĺ'ļi'įĉ(Úþ'ãĒ'¯Ɓ9ù6×$E\_dhE`fĒ9ziĤ4'GfSBŤ'Ļxćŭpė9Ō%6"!

5!$GfSBŤ'å5Ī.%ż6Ĝ¿ĮŋÆ9Œ
9ä

6

"%3

ļ

÷È=PcAhćŭ9ç)

"1įĮ"6¼3*¼ž®

¼ķ¿'Ĳĺ%(º$¯Ɓ½³67('3$¹ōħÒŖſŀ%(=PcAhĆÈĠßęí%½³60%Úþ'E\_dhE`fãĒ9ĥ

(E\_dhE`f7

4'=PcAhĆÈĠß%ĩ--Şłā9Ç-"%Ŧ­6á

(E\_dhE`f=PcAhĆÈĠß%ĩ-6'9Ģŏű6"!6æÖ:fDfUcĒ
(generalized-ensemble algorithm)"ņĸ76ãĒ9'«ƃ%Űĥ6"9éªĈdhE`f%Űĥƈ÷ũ'Řş"({)tl9ě7$¼ķ¿E\_

ÊûBiophysics and

Physicobiology 16, 344-366 (2019)ƉûĲĺ'įĮ(¼E\_dhE`f%35ø$æÖ:fDfUc
Ē9õ%źĬ"!

6ƌƊĲĺðĒgřľðĒ á(æÖ:fDfUcĒ"ņĸ76×$E\_dhE`fãĒ9¼ķ¿E\_dhE`f+Űĥ6"9éĄ74'{"[cI?QO?cĒƈmulticanonical algorithmƉ2dVb?qêĒ

ƈreplica-exchange methodƉ$#'øÝ9Ĵ""1%74'¼¿ĒĞ9źĬ5õ%ïæÖ:fDfUcĒ9źĬ5

ğ%1999Ï%źĬdVb?qê¼¿Ē(üĦÊûChem. Phys. Lett. 314, 141 (1999))('Űĥ'Äò'0%±ŽĮ%ÑĲĺē9ŝŦá

747ĝĬĮ$(2000 Ï%źĬæÖ:fDfUcĒ(¹ċdVb?qêĒdVb?

qê[cI?QO?cĒ[cI?QO?cdVb?qêĒdVb?qêĚâĒ$#)9ƅz6""1%ï×$æÖ:fDfUcĒ9źĬğ%Ï¹ċdVb?qêĒ¹ċ[cI?QO?cĒ¹ċĚâĒ'iŎš'ÂÓ%à74'iŮ'ãĒźĬ%i'59(ČÊûJ. Chem. Phys. 130, 214105 (2009))ûĨŠ(őĭŤ'å5Ī.9n«ƃ"ŃńĨŠ9ŉ5Ū{÷ũ!(35ÍÑŹŻ

¼ķ¿E\_dhE`f'«ƃ%Lh[9æº)őĭŤ+'Ő}ŕ¼'NJ@fCE\_dhE`f%á

źĬdVb?qêD

fVcĒ9ŰĥÈ¼'ł¢ćŭ'pė%à2 ċdVb?qêĒ%36NJ@fCE\_
dhE`f35È¼'ł¢ōħ=PcAh'řľĒ1éĄõ%7-!(n%¿%µ¼E\_dhE`f9Œ
¼ā95 áÏÅÒĐżíĒ(DFT)2×ł¢ũwÅÒĐżíĒ(DFTB)!Ŷ

7æÖ:fDfUcĒ'źĬ%1à'ðĒ'ğÛ(úćŭ"ğÂ'1'9ĥ5ñı'ÃƆłā%¤safH]$úćŭ4E\_dhE`f9»06"%- 60 -

6

3$Ŵ.(iƍ ƊĲĺàā
ûÏÒ1ûĲĺįĮ'0%Ĉ$řľ9Œ':cKR;[hīĬī'­'i"SBŤŷĠ'ą'3

47

6':\e;NXhGƈAƉ "¦)76Gf%$:\e;NŇŅØà76"!

ğ%Ŵŗ"7ł¢6"%3ŋ6'ƌċĂØà!

ƌûį':\e;NŇŅØà'Ă9y6"!

Œ'řľ'śŁ%

9z
ê

6:\e;NŇŅ'vŹ%
6:\e;NŇŅ% A

67(ñ%Øà7$6 A42 ':\e;NŇŅƋû"Ƌ|' A42 'ŀ%"06ãĒ"Ŵŗ$àā9tl%ū,66á

'ƌċĂØà'¼E\_dhE`f9(Ŭmłā9¶¥óÏÒ'¶¥ö%ö

(æÖ:fDfUcĒ'Ƌ!

(42 |':\Qų4

'!!(Ŀ%-

6 Replica-Exchange with Solute Tempering 2 (REST2)

:\e;NŇŅk!(A42 WbJBFćŭ9Øà7EhMćŭ%¸ƌċĂØàů/"Ĵ©7ƈîġ 5 "Ğ7Ɖ ĚâĒƈSimulated TemperingƉ([cI?O?cĒ2dVb?qêĒ""1%Ñz87
Ö:fDfUcĒ!

6dVb?qêĒ(ĘE\_dhE`f$!

6æ

$5ûřľ9ÃŒ!6ĚâĒ2[cI?QO?cĒ!(ûřľ'%E\_dhE`f'Ŵ.­¼9đÂ6přľ9ŒÜŗ6ŀŖſ%$6%7

'přľ9à6'Ɓ$5ôŻ1-'¯Ɓ9ù60%ĚâĒ!(dVb?qêĚâĒƈMitsutake and Okamoto, Chem.

Phys. Lett. 332, 131 (2000)Ɖ[cI?QO?cĒ!(dVb?qê[cI?QO?cĒƈSugita andOkamoto, Chem. Phys. Lett. 329, 261 (2000)éĄ7ƈ74'ðĒ'¹ċ+'iŎ(tl!Œ87
Mitsutake and Okamoto, J. Chem. Phys. 130, 214105 (2009)ƉiðĚâĒ!(õ%Į%Ŵ.­¼9õï

ŒðĒ1źĬ7ƈNguyen, Okamoto, and Derreumaux, J. Chem. Phys. 138, 061102 (2013)Ɖ7%35ĚâĒ'Ŵ.­¼'đÂÄò%$Ś!

6ûÏ('÷Ù'ðĒ9¹ċ%æ

Ö6"%àƈîġ 8Ɖ'!tl%Ŀ%¶¥6¹ċĚâĒ%
ĖĽ²:fDfUc%

({"

Ľ

ĖÒ"²'ƌċĚâĒƈMori and Okamoto, J. Phys. Soc. Jpn. 79, 074003(2010)Ɖ9èĥ'ãĒ!(ĖÒ)5!$²!1afH]<>hBŦ5ĖÒ ²%
6ƌċafH]<>hB9Ãģ6"!6'·¢Ŵ.­¼(AUFōħ=PcAhg(,P)!œ"!Į%Ŵ.­¼9đÂ6'%tl'Ĺ9řľ6Üŗ

6

ĖÒ T 'õï'·¢

² P 'õï'·¢

!H (=fGcThV (xĹ9œá(74'Ĺ9tl'¡ØÓ!ũw6"%

- 61 -

'ãĒ'øÝ9Ĵ0%:\Qųí 10 |'ÈYVIN chignolin 9 923 |'ď¼'m%Ŋ

ŀ%6ƌċĚâ¼¿E\_dhE`f9Œ-(ĖÒ( 5 |'~²( 4 |''·¢%LFME\_dhE`f9Œ°Ƌ%AUFōħ=PcAh'E\_dhE`f'ôŻĬÉ""1%ýĊĈ9Ĵ

°ƋƊchignolin %6ĖÒ²ĚâĒ'Ŵ.­¼đÂE\_dhE`f1 nsec -!%­¼ý
Ŵ.­¼'Ŵ.

6"6-đÂ76"9ĳŜ'!ûřľ9tl'3%ŒĖÒ( 300K 4 450K 'Ż% 16 |'~9ĥÞ²( 0.1MPa 4 420MPa 'Ż% 15 |'~9ĥÞ°ƌ%łā9Ĵ°ƌƊchignolin %6ĖÒ²ĚâE\_dhE`f%6(a)ĖÒ"²'Ųč(b)ĖÒ"²'Ì(c)ĖÒ T=300K %6ÃƆćŭ4'ăƌoÎ´ŧƀ'Ì(d)'E\_dhE`f'ĖÒ T=300K² P=1 bar %6nŸ'ćŭƈťƉ9 NMR ÃƆłāƈƂƉ"Ŵ&°- 62 -

 tk4r¬źĬïãĒ'øÝĴ7

Ǝ ƊĬœÃň±ŽuŢ1.

ĀŨÊû CompPhys20, Leipzig, Germany, December 3-5, 2020 (Zoom Conference).

2.

Êû

The 34th Annual CSP Workshop, Athens, Georgia, USA, February 22-25, 2021 (Zoom Conference).

ƏƊĞÃňŘş3.

Êû  A A PPS Bulletin 30, 34-40 (2020).

šî4.

ÿÊû   Journal of Chemical Physics 152, 194108 (11 pages) (2020).

5.

ŵĦ¹ıÊû         

A CS Chemical Neuroscience 11, 2989-2998 (2020).

6.

ZfHhjËÊû   

BBA – General Subjects 1864, 129654 (11 pages) (2020).

7.

ĀŨÊû   Journal of Chemical Physics 154, 044503 (11 pages) (2021).

8.

§ĦÊû   

Molecular Physics e1904156 (9 pages) (2021).

- 63 -

」ྜ㟁Ꮚ⣔ࡢᵓ㐀ࠊ㟁Ꮚ≧ែࠊ཯ᛂ㐣⛬ࠊ⁐፹࿴ᵓ㐀࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Study of Geometries, Electronic Structures, Reactions, andSolvation of Complex Systems‫ۑ‬ᴬ ⱱዲࠊỌ℩ ⱱࠊடᑿ ⫕ࠊ㧗ᮌᮃ, Bo Zhu, JiaJia Zheng, Zhao Peng, Li Qiao-Zhi㸦ி㒔኱Ꮫ ゐ፹࣭㟁ụඖ⣲ᡓ␎◊✲ࣘࢽࢵࢺ㸧1◊✲┠ⓗࠊෆᐜ
㑄⛣㔠ᒓඖ⣲ࡣVS㌶㐨࡟ຍ࠼ࠊG㌶㐨ࡀཎᏊ౯㌶㐨࡜࡞ࡿࠋGẆࡣᡂศࢆᣢࡕࠊࡑࡢ⤖ᯝࠊ⤖ྜᛶࠊ཯⤖ྜᛶ㌶㐨࡜࡜ࡶ࡟ࠊ⤖ྜ࡟㛵୚ࡋ࡞࠸㠀⤖ྜᛶG ㌶㐨ࡀᏑᅾࡍࡿࡓࡵࠊGG ㌶㐨࢚ࢿࣝࢠ࣮ᕪࡀᑠࡉ࠸࡜ゝ࠺≉ᚩࡀ࠶ࡾࠊከᵝ࡞ཎᏊ౯≧ែࠊ㓟໬ᩘࠊࢫࣆࣥ≧ែࢆ࡜ࡿࡇ࡜ࡀྍ⬟࡟࡞ࡿࠋࡑࡢࡼ࠺࡟ከᵝ࡞㟁Ꮚ≧ែࢆᣢࡕᚓࡿ㑄⛣㔠ᒓඖ⣲࡜᭷ᶵᐁ⬟ᇶࠊ㧗࿘ᮇ඾ᆺඖ⣲ࡸ඾ᆺ㔠ᒓඖ⣲໬Ꮫ✀࡞࡝ࢆྠ᫬࡟ྵࡴ G 㟁Ꮚ」ྜ⣔ࡣࠊ㟁Ꮚ≧ែࡢከᵝᛶࡀ୍ᒙ㇏࠿࡟࡞ࡾࠊᰂ㌾࡞㟁Ꮚ≧ែࢆྲྀࡾ࠼ࡿࡼ࠺࡟࡞ࡿࠋG࡞ᵓ㐀ࠊ⤖ྜࠊศᏊ≀ᛶࠊ཯ᛂᛶࢆ♧ࡍࡢࡣࡑࡢ⤖ᯝ࡛࠶ࡿࠋᚑࡗ࡚ࠊG㟁Ꮚ」ྜ⣔ࡀከᵝ

㟁Ꮚ」ྜ⣔ࡣศᏊᛶゐ፹ࠊᅛయゐ፹ࠊ㔠ᒓ㓝⣲ࠊኴ㝧㟁ụࡢቑឤ๣ࠊ᭷ᶵ (/ ࡢⓎග⣲ᏊࠊศᏊ☢▼࡞࡝࡜ࡋ࡚ࠊ⌧௦ࡢ໬Ꮫࡢ୰ᚰⓗ࡞◊✲ᑐ㇟࡜࡞ࡗ࡚࠸ࡿࠋࡑࢀࡽࡢᵓ㐀ࠊศᏊ≀ᛶࠊᶵ⬟ࠊ཯ᛂᛶࡣᇶ♏໬Ꮫࠊᛂ⏝໬Ꮫ࠸ࡎࢀ࡟࠾࠸࡚ࡶ㔜せ࡛࠶ࡿࠋࡑࢀࡽࡢᶵ⬟࡜ G 㟁Ꮚ」ྜ⣔ࡢ㟁Ꮚ≧ែ࡜ࡣᐦ᥋࡟┦㛵ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊG 㟁Ꮚ」ྜ⣔ࡢ໬Ꮫࢆ㟁Ꮚㄽ࡟ᇶ࡙࠸࡚ゎ᫂ࡋࠊணG

ࡍࡿࡇ࡜ࡣࠊ⌮ㄽ໬Ꮫ࣭ィ⟬໬Ꮫศ㔝ࡢ୰ᚰㄢ㢟ࡢ୍ࡘ࡜ࡶゝ࠼ࡿࠋ

㟁Ꮚ」ྜ⣔ࡢ㟁Ꮚ≧ែࡣᨃ⦰㏥⣔࡛࠶ࡿࡇ࡜ࡶከࡃࠊࡲࡓࠊ⁐፹ຠᯝࡸ⤖ᬗຠᯝࡀ኱ࡁ࠸ࡇ࡜࠿ࡽࠊ࿘

ᅖࡢຠᯝࢆྲྀࡾ㎸ࢇࡔୖ࡛ࠊ኱つᶍ࡞㧗⢭ᗘ㟁Ꮚ≧ែィ⟬ࢆ⾜࠺ᚲせࡀ࠶ࡿࠋᚑࡗ࡚ࠊ᪂ࡋ࠸⌮ㄽィ⟬ἲࡶᚲせ࡜ࡉࢀࠊྠ᫬࡟ィ⟬⤖ᯝࡢṇࡋ࠸ゎᯒἲࡶᚲせ୙ྍḞ࡛࠶ࡿࠋ໬Ꮫ⤖ྜࡸ཯ᛂ㐣⛬࡟ᑐࡍࡿ᪂ࡋ࠸どⅬࠊ᪂ࡋ࠸ᴫᛕࡶᚲせ࡜ࡉࢀࡿሙྜࡶከ࠸ࠋᐇ㝿ࠊ᭱㏆ὀ┠ࡉࢀ࡚࠸ࡿ㔠ᒓᚤ⢏Ꮚࡸ㔠ᒓࢡࣛࢫࢱ࣮ࠊ㔠ᒓ㘒యࡢ㞟ྜయ࡛࠶ࡿ02) PHWDORUJDQLFIUDPHZRUN ࠊ⤖ᬗ࡛࠶ࡾ࡞ࡀࡽᵓ㐀ኚ໬ࡸᶵ⬟ࡢእ㒊่⃭ኚ໬ࢆ♧ࡍࢯࣇࢺࢡࣜࢫࢱࣝ࡟ࡣࠊࡇࢀࡲ࡛ࡢศᏊ⛉Ꮫⓗ⌮ゎࢆ㉸࠼ࡿࡶࡢࡀከࡃࠊᇶ♏࠾ࡼࡧᛂ⏝ศ㔝࡛ G 㟁Ꮚ」ྜ⣔ࡣศᏊ⛉Ꮫ◊✲ࠊ⌮ㄽ໬Ꮫ㺃ィ⟬໬Ꮫ◊✲ࡢ㔜せ࡞ࢱ࣮ࢤࢵࢺ࡛࠶ࡿࠋ
ᡃࠎࡣࠊࡇࢀࡲ࡛㑄⛣㔠ᒓඖ⣲ࡸ㧗࿘ᮇ඾ᆺඖ⣲ࢆ࠿ࡂᡂศ࡜ࡍࡿ」ྜ㟁Ꮚ⣔ࡢ㟁Ꮚ≧ែ⌮ㄽ◊✲ࢆ⾜࠸ࠊከᵝ࡞ᵓ㐀ࡸࡇࢀࡲ࡛ࡢ⪃࠼᪉࡛ࡣㄝ࡛᫂ࡁ࡞࠸᪂ࡋ࠸ᵓ㐀ࠊ໬Ꮫ⤖ྜࠊ㇏࠿࡞໬Ꮫ཯ᛂᛶࠊゐ፹స⏝ࢆ㟁Ꮚ≧ែ࡟ᇶ࡙࠸࡚ゎ᫂ࡋࠊ⌮ㄽⓗண࡟ࡶᡂຌࡋ࡚ࡁࡓࠋ ᖺᗘࡣࠊ L  㘒యゐ፹ࠊ᭷ᶵ㔠ᒓ໬Ꮫ཯ᛂ㛵ಀ࡛ࡣ,U㺂5K5X㘒య࡟ࡼࡿ࣓ࢱࣥࡢVS&+⤖ྜࡢ࣎ࣜࣝ໬ゐ፹཯ᛂࡢ཯ᛂᶵᵓ࡜ゐ፹άᛶࢆᨭ㓄ࡍࡿᅉᏊࡢゎ᫂ࠊ5K$O┤᥋⤖ྜࢆᣢࡘ㘒య࡟ࡼࡿ&)⤖ྜάᛶ໬཯ᛂࡢ≉ᚩゎ᫂ࠊ LL  㔠ᒓ㘒యࡢᵓ㐀࡜⤖ྜ࡟㛵ࡍࡿ◊✲࡛ࡣࠊ᭱㏆ࠊሗ࿌ࡉࢀࡓ5K$O┤᥋⤖ྜࢆࡶࡘ5K , 㘒య࡬ࡢᇶ㉁ࡢ㓄఩ࡢከᵝᛶࢆ㟁Ꮚ≧ែ࠿ࡽ᫂ࡽ
࠿࡟ࡋࠊLLL  㔠ᒓᚤ⢏Ꮚ㛵ಀ࡛ࡣࠊ3G࠾ࡼࡧ5Kᚤ⢏Ꮚୖ࡛ࡢࣉࣟࣆࣞࣥ㓟໬཯ᛂࡢ཯ᛂᶵᵓ࡜άᛶࡢẚ㍑ࠊ
5Xࢆࢥ࢔ࠊⓑ㔠ࢆࢩ࢙ࣝ࡜ࡍࡿ5X#3Wᚤ⢏Ꮚ࠾ࡼࡧ3Wᚤ⢏Ꮚ࡛ࡢ㓟⣲ศᏊάᛶ໬཯ᛂࡢ཯ᛂᶵᵓ࡜཯ᛂᛶ
ࡢẚ㍑ࠊ LY  ศᏊᛶ⤖ᬗ㛵ಀ࡛ࡣࠊ3W ,, 㘒యࡢศᏊᛶ⤖ᬗ࡛ࡢ྾཰ࢫ࣌ࢡࢺࣝࠊບ㉳≧ែᵓ㐀ࠊⓎගࢫ࣌ࢡࢺࣝࡢ

2ᗘ౫Ꮡᛶࢆゎ᫂ࡋࡓࠋ⣬㠃ࡢ㒔ྜୖࠊ୍㒊ࢆ㝖࠸࡚ࠊ௨ୗ࡟ᴫせࢆ㏙࡭ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ㑄⛣㔠ᒓ㘒యࡸࡑࡢゐ፹཯ᛂࡢ⌮ㄽⓗ◊✲࡛ࡣࠊDFTἲ࡟ࡼࡾᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ࢚ࢿࣝࢠ࣮ኚ໬ࢆDFT,
MP2 to MP4(SDQ), CCSD(T)ἲ᳨࡛ウࡋࡓࠋDFTィ⟬࡟ࡣB3PW91-D3࠶ࡿ࠸ࡣZB97XD஺᥮┦㛵ỗ㛵ᩘࢆ⏝- 64 -

࠸ࡓࠋ㑄⛣㔠ᒓඖ⣲ࡢෆẆ㟁Ꮚࡣ Hay-Wadt ࡶࡋࡃࡣ Stuttgart-Dresden-Bonn ࡢ᭷ຠෆẆ࣏ࢸࣥࢩࣕࣝ(ECP)࡛
⨨ࡁ᥮࠼ࠊཎᏊ౯㟁Ꮚࡣ split-valence ᆺࡶࡋࡃࡣ triple-zeta ᆺᇶᗏ㛵ᩘ࡛⾲ࡋࡓࠋࡲࡓࠊ㓄఩Ꮚ࡟ࡣᵓ㐀᭱㐺໬ィ⟬࡟ 6-31G(d)ࠊ࢚ࢿࣝࢠ࣮ኚ໬ࡸ㟁Ꮚ≧ែࡢホ౯࡟ࡣ 6-311G(d), cc-pVDZ, cc-pVTZ ᇶᗏ࡞࡝ࢆ౑⏝ࡋࡓࠋ཯ᛂ࡟┤᥋㛵ಀࡍࡿཎᏊ࡟ࡣ d ศᴟ㛵ᩘࢆຍ࠼ࡓࠋᵓ㐀᭱㐺໬࡜ DFT ィ⟬࡟ࡣࠊ୺࡟ࠊGaussian09 ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࡓࠋ㔠ᒓࢡࣛࢫࢱ࣮/ᚤ⢏Ꮚࡢ⌮ㄽ◊✲࡛ࡣᖹ㠃Ἴᇶᗏ࡟ࡼࡿ࿘ᮇቃ⏺᮲௳ DFT ἲ࡜ᖹ㠃Ἴᇶᗏࢆ⏝࠸ࠊVASP ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࡓࠋศᏊᛶ⤖ᬗࡢ㟁Ꮚ≧ែィ⟬࡟ࡣࠊ࿘ᮇቃ⏺᮲௳ QM/MM ἲࢆ⏝࠸ࡓࠋࡇࡢ᪉ἲࡣᡃࠎࡀ㛤ⓎࡋࠊGAMESS ࡟ᐇ⿦ࡋࡓࠋQM ศᏊ࡜ MM ศᏊࡢᵓ㐀ࠊ㟁Ⲵศᕸࢆ self-consistent ࡟ồࡵࠊMM ศᏊࡣቃ⏺᮲௳ࢆ౑⏝ࡋࠊ↓㝈⣔ࢆ෌⌧ࡍࡿࡼ࠺࡟⨨࠸ࡓࠋ

3

◊✲ᡂᯝ

3.1 Ir(III)ࠊRu(II)ࠊ࠾ࡼࡧ Rh(III)㘒య࡟ࡼࡿ࣓ࢱࣥࡢ࣎ࣜࣝ໬཯ᛂࡢ⌮ㄽⓗ◊✲㸸࣓ࢱࣥࡣ⌧ᅾࠊ⇞ᩱ࡜ࡋ࡚ࡋ࠿౑⏝ࡉࢀ࡚࠸࡞࠸ࠋ࣓ࢱࣥࢆ࣓࣎ࣜࣝࢱࣥ࡟ኚ᥮࡛ࡁࢀࡤࠊྜᡂ཯ᛂࡢཎᩱ࡜ࡋ࡚౑⏝ྍ⬟࡛࠶ࡿࠋ᭱
㏆ࠊ(phen)Ir(Bpin)3ࠊ[Cp*RuCl2]2, Cp*Rh(Bpin)2 㘒యࢆゐ፹࡜ࡋ࡚ࠊࢪ࣎ࣛࣥ࡟ࡼࡿ࣓ࢱࣥࡢ࣎ࣜࣝ໬཯ᛂࡀ
ᐇ㦂ศ㔝࡛ሗ࿌ࡉࢀࡓࠋάᛶࠊ㑅ᢥᛶ㸦࣓ࢱࣥ࡜⁐፹ࡢࢩࢡࣟ࣊࢟ࢧࣥ࡜ࡢ㑅ᢥᛶ㸧ඹ࡟ Cp*Rh(Bpin)2 ࡀ᭱ࡶ㧗࠸ࠋRu 㘒యࡣࠊ㑅ᢥᛶࡣⰋ࠸ࡀάᛶࡀ Rh 㘒యࡼࡾຎࡿࠊIr 㘒యࡣάᛶࡶ㑅ᢥᛶࡶຎࡿࠊ࡜㔠ᒓ࡟ࡼࡾ኱ࡁ࡞┦㐪ࡀࡳࡽࢀࡿࠋIr 㘒యࡣ sp2-C-H ⤖ྜࡢ࣎ࣜࣝ໬࡛ࡣάᛶࡀ㧗࠸ࡇ࡜ࡀྂࡃ࠿ࡽࡼࡃ▱ࡽࢀ࡚࠸ࡿࠋࡑࡇ࡛ࠊάᛶࠊ㑅ᢥไࡢ┦㐪ࡢ⌮⏤ࠊ࠾ࡼࡧࠊIr 㘒యࡢάᛶࠊ㑅ᢥᛶࢆྥୖࡉࡏࡿ⌮ㄽⓗணࢆ ┠ ⓗ ࡟ ⌮ ㄽ ⓗ ◊ ✲ ࢆ ⾜ ࡗ ࡓ ࠋ Cp*Rh(Bpin)2 ࡜(Phen)Ir(Bpin)3 ࡟ࡼࡿ࣎ࣜࣝ໬཯ᛂࡢ཯ᛂᶵᵓࡣࡍ࡛࡟᫂ࡽ
࠿࡟࡞ࡗ࡚࠸ࡿࡀࠊ[Cp*RuCl2]2 ࡢሙྜࠊάᛶ✀ࡶ཯ᛂᶵᵓ

Scheme 1. Cp*Ru(Bpin)n ࡟ࡼࡿ࣓ࢱࣥࡢ࣎ࣜࣝ ໬ ཯ ᛂ ࡢ ゐ ፹ ࢧ ࢖ ࢡ ࣝ 㸹 ᕥ ࡣ
Ru(II)/Ru(IV)ࢧ࢖ࢡࣝࠊྑࡣ Ru(IV)/Ru(VI)ࢧ࢖ࢡࣝࡶ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋ[Cp*RuCl2]2 ࡣࢪ࣎ࣛࣥ࡜཯ᛂࡋࠊCp*Ru(Bpin)2 ࡀ⏕ᡂࡍ ࡿ ࡜ ⪃ ࠼ ࡽ ࢀ ࡿ ࡀ ࠊ Cp*Ru(Bpin)2 ࡣRu(III)㘒య࡞ࡢ࡛ࠊ࣓ࢱࣥࡢ C-H ⤖ྜάᛶ໬ࡀ㓟໬ⓗ௜ຍ࡛㐍⾜ࡍࡿ࡞ࡽࠊRu(V)㘒యࡀ⏕ᡂࡋ࡞ࡃ࡚ࡣ࡞ࡽ࡞࠸ࠋRu(V)㘒యࡣ㠀ᖖ࡟㧗ཎᏊ౯࡛ࠊᏑᅾྍ⬟࡜ࡣ

Scheme 2. Cp*Ru(Bpin)3, Cp*Rh(Bpin)2 ࠾ࡼࡧ(Phen)Ir(Bpin)2⪃࠼ࡽࢀ࡞࠸ࠋࡑࡇ࡛ࠊScheme 1 ࡟♧ࡍ࡟ࡼࡿ࣓ࢱࣥࡢ࣎ࣜࣝ໬ࡢẚ㍑

㸰✀㢮ࡢྍ⬟࡞άᛶ✀࡜཯ᛂᶵᵓࢆ⌮ㄽⓗ࡟᳨ウࡋࡓࠋࡑࡢ⤖ᯝࠊ
Cp*Ru(Bpin) ࡬ ࡢ ࣓ ࢱ ࣥ ࡢ 㓟 ໬ ⓗ ௜ ຍ ࡣ ᐜ ᫆ ࡟ 㐍 ⾜ ࡍ ࡿ ࡀ ࠊ
Cp*Ru(Bpin)3 㘒య࠿ࡽ B2pin2 ࡀ㑏ඖ⬺㞳ࡋ Cp*Ru(Bpin)ࡀ⏕ᡂࡍࡿ㐣⛬ࡣ㠀ᖖ࡟྾⇕࡛࠶ࡾࠊCp*Ru(Bpin)㘒యࡣ࣓ࢱࣥࡢ࣎ࣜࣝ໬
཯ᛂࡢάᛶ✀࡟ࡣ࡞ࡾ࠼࡞࠸ࡇ࡜ࠊCp*Ru(Bpin)3 ࡣᙧᘧⓗ࡟ࡣ

Scheme 3. ᳨ウࡋࡓ㓄఩Ꮚ

Ru(IV)㘒య࡛࠶ࡿࡀࠊ࣓ࢱࣥࡢ C-H ⤖ྜࡢάᛶ໬ࡣẚ㍑ⓗᐜ᫆࡟㐍⾜ࡍࡿࡇ࡜ࠊ⏕ᡂࡍࡿ୰㛫య࡛ࠊࣄࢻࣜࢻᛶࡢ H ࡣ Bpin ࡢ✵ࡢ 2p ㌶㐨࡜┦஫స⏝ࡋ࡚࠾ࡾࠊRu ࡣ VI ౯࡛࡞ࡃ IV ౯ⓗ࡛࠶ࡿࡇ࡜࡞࡝ࡀ♧ࡉࢀࡓࠋ㓟໬ⓗ௜ຍࡢᚋࠊ཯ᛂࡣ CH3 ᇶ࡜ Bpin ࡢ㑏ඖ⬺㞳࡛㐍⾜ࡍࡿࠋ- 65 -

࣓ࢱࣥࡢ࣎ࣜࣝ໬࡜⁐፹࡛࠶ࡿࢩࢡࣟ࣊࢟ࢧࣥࡢ࣎ࣜࣝ໬ࢆẚ㍑ࡋࠊScheme 2 ࡟ᐃᛶⓗ࡟♧ࡍࡼ࠺࡟ࠊ
Cp*Ru(Bpin)2 ࡀάᛶࠊ㑅ᢥᛶ࡜ࡶ࡟ඃࢀ࡚࠾ࡾࠊCp*Ru(Bpin)3 ࡣάᛶࡀຎࡾࠊ(Phen)Ir(Bpibn)2 ࡣάᛶ࡜㑅ᢥᛶ࡜ࡶ࡟ຎࡿ⤖ᯝࡀᚓࡽࢀࠊᐇ㦂⤖ᯝ࡜୍⮴ࡋ࡚࠸ࡓࠋIr 㘒యࡢάᛶྥୖࡢࡓࡵྛ✀㓄఩Ꮚ(Scheme 3)ࢆẚ㍑
ࡋࠊphen ࡟ NHC ࢆᑟධࡋࡓ L3, L12, L13 ࢆ౑⏝ࡍࡿ࡜άᛶࠊ㑅ᢥᛶ࡜ࡶ࡟ࠊࡇࢀࡲ࡛ඃࢀ࡚࠸ࡿ࡜࠸ࢃࢀ࡚
࠸ࡿ Cp*Rh(Bpin)2 ࢆୖᅇࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ
㸦R. Zhong, S.Sakaki, J. Am. Chem. Soc. 2020, 142, 39, 16732–16747㸧
3.2 Rh(I)-Aluminyl 㘒య࡬ࡢᇶ㉁㓄఩ࡢከᵝᛶࡢ⌮ㄽⓗ◊✲㸸 Al ࢆ㓄఩ཎᏊ࡜ࡍ
ࡿࣆࣥࢧ࣮ᆺ㸱ᗙ㓄఩Ꮚ(PAlP)ࡀ᭱㏆ྜᡂࡉࢀࠊRh(I)㘒య㸦௨ୗࠊRh(PAlP)࡜␎ࡍ;Rh

Scheme 3㸧ࡣ C-F ⤖ྜάᛶ໬ࡸ C-H ⤖ྜάᛶ໬ࢆ⤒⏤ࡍࡿゐ፹཯ᛂࢆ⾜࠺ࡇ࡜ࡀ♧ࡉࢀࠊ⯆࿡ࢆ㞟ࡵ࡚࠸ࡿࠋࡇࡢ㘒యࡣ Al ࡀࣝ࢖ࢫ㓟ᛶࢆᣢࡘࡇ࡜࠿ࡽࠊRh ୖ
ࡢ Axial(Ax)఩ࠊEquatorial(Eq)఩࠾ࡼࡧ Al ఩ࡢ㸱࠿ᡤ࡛ᇶ㉁࡜┦஫స⏝ࡀྍ⬟࡜⪃

Scheme 4. PAlP ࡢ
Rh 㘒య࠼ࡽࢀࡿࠋ඾ᆺⓗ࡞㓄఩Ꮚ࡛࠶ࡿ NH3, CO, C2H4 ࢆྲྀࡾୖࡆࠊ
Rh(PAlP)㘒య࡬ࡢ㓄఩఩⨨ࡢ⌮ㄽⓗ᳨ウࢆ⾜ࡗࡓࠋNH3 ࡣ Al ఩࠾ࡼࡧ Rh-Ax ఩࡟ྠ⛬ᗘࡢᏳᐃᛶ࡛㓄఩ࡍࡿࠋCO, C2H4 ࡣ Al ࡟ࡣ㓄఩࡛ࡁࡎࠊRh ࡜ Al ࡟ᯫᶫ㓄఩ࡍࡿࡀࠊࡇࡢᵓ㐀ࡼࡾࡶ CO
ࡣ Rh ࡢ Ax ఩࡟ࠊC2H4 ࡣ Rh ࡢ Eq ఩࡟㓄఩ࡍࡿᵓ㐀ࡀᏳᐃ࡛࠶
ࡗࡓࠋ┦஫స⏝࢚ࢿࣝࢠ࣮ศ๭࠿ࡽ NH3 ࡢ Al ఩࡬ࡢ㓄఩࡟ࡣ㟼㟁┦஫స⏝ࡢᐤ୚ࡀ኱ࡁ࠸ࡇ࡜ࠊCO ࡸ C2H4 ࡛ࡣ Al ࡜ࡢ㛫࡛㟼㟁┦஫స⏝ࡀ ᑠࡉࡃࠊAl ࡟㓄఩࡛ࡁ࡞࠸ࡇ࡜ࠊC2H4 ࡣ Rh ࡜ࡢ
ȧ㏫౪୚┦஫స⏝ࡀᙉࡃࠊEq ఩࡟㓄఩ࡍࡿࡇ࡜ࠊCO ࡣȧ㏫౪୚
Fig. 1. Rh(PAlP)࡜ NH3, CO, C2H4 㘒యࡀࡑࢀ࡯࡝ᙉࡃ࡞࠸ࡇ࡜࠿ࡽࠊRh ࡢ Ax ఩࡟㓄఩ࡍࡿࡇ࡜ࡀ♧ࡉࡢᵓ㐀

ࢀࡓࠋ㏻ᖖࡢ㘒యࡣࠊ」ᩘࡢ㓄఩఩⨨ࢆᣢࡘࡶࡢࡣࡲࢀ࡛࠶ࡿࡀࠊ

Rh(PAlP)ࡣ㸱✀㢮ࡢ㓄఩఩⨨ࢆᣢࡕࠊࡑࡢ⤖ᯝࠊC-F ⤖ྜࠊC-H ⤖ྜࡢάᛶ໬ࢆຓࡅ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ(Q. Li, S. Sakaki, et al. Inorg. Chem., 59, 15862-15876 (2020)).
3.3 Pt(II)㘒యࡢศᏊᛶ⤖ᬗෆ࡛ࡢⓎගࢫ࣌ࢡࢺࣝ࡜ບ㉳≧ែᵓ㐀ࡢ⌮ㄽⓗ◊✲㸸[Pt(bpy)(CN)2]㘒యࡣ⁐ᾮෆ
࡛ࡣⓎගࡣᙅ࠸࠿ࠊ࠶ࡿ࠸ࡣࠊ඲ࡃⓎගࡋ࡞࠸ࡀࠊ⤖ᬗෆ࡛ᙉࡃⓎගࡍࡿࠋࡇࢀࡣ⤖ᬗෆ࡛ࡣ㞄᥋ࡍࡿ Pt(II)㘒యྠኈࡀࠊPt-Pt 㛫ࡢ dV-dV⤖ྜࢆᙧᡂࡋࠊࡑࡢ dV-dV⤖ྜ࠿ࡽ㓄఩Ꮚࡢȧ*㌶㐨࡬ࡢ MMLCT ບ㉳ࡀ㉳ࡁࡿࡓࡵ࡛࠶ࡿ࡜ㄝ᫂ࡉࢀ࡚ࡁࡓࠋࡇࡢⓎගࡣᗘ࡟ࡼࡾኚ໬ࡋࠊప

ᐃ࡛ࡣࢩ࣮ࣕࣉ࡞Ⓨගࡀప࢚ࢿࣝࢠ࣮ഃ࡟ࡳࡽࢀࡿࡀࠊᐊ

࡛ࡣ㧗࢚ࢿࣝࢠ࣮

ഃ࡟ࢩࣇࢺࡋࠊࣈ࣮ࣟࢻ࡞Ⓨග࡜࡞ࡿࠋᐇ㝿࡟
MMLCT ບ㉳≧ែࡀ⏕ᡂࡍࡿࡢ࠿ࠊࡲࡓࠊ࡞ࡐࠊ
ᐃᗘ࡛྾཰఩⨨࠾ࡼࡧ྾཰ࢫ࣌ࢡࢺࣝࡀኚ໬ࡍ

ࡿࡢ࠿ࠊྂࡃ࠿ࡽ▱ࡽࢀ࡚࠸ࡿ⌧㇟࡛࠶ࡿࡀࠊ⌮ㄽⓗ࡞ㄝ᫂ࡣ඲ࡃ⾜ࢃࢀ࡚࠸࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊ
periodic-QM/MM ἲࢆ౑⏝ࡋࠊPt 㘒యࢆ㸰ศᏊ࠿ࡽ㸲ศᏊࢆ QM 㡿ᇦ࡟࡜ࡾࠊࡑࢀ௨እࡣ MM ࡛⾲ࡋ࡚ࠊບ㉳≧ែࡢᵓ㐀ࢆ᭱㐺໬ࡋࠊⓎගࢫ࣌ࢡࢺࣝ
ࢆồࡵࡓࠋⓎගࢫ࣌ࢡࢺࣝࡢᙧ≧ࡣࠊບ㉳≧ែ࡛

Fig. 2 ⤖ᬗෆ࡛ࡢ[Pt(bpy)(CN)2]ࡢィ⟬࡛ồࡵࡓⓎගࢫ࣌ࢡࢺࣝ- 66 -

ࡢ Pt-Pt 㛫㊥㞳࡟ἢࡗࡓ potential 㠃࠿ࡽ᣺ືࡢ Schrödinger ᪉⛬ᘧࢆゎࡁࠊ᣺ືἼື㛵ᩘࡢᗘ࡟ࡼࡿ Boltzmannศᕸࢆ⪃࠼ࡿࡇ࡜࡛ồࡵࡓࠋບ㉳≧ែࡀ Pt(II)㘒య㸰ศᏊ࡛ᙧᡂࡉࢀࡿ࡜ࡋࡓࣔࢹ࡛ࣝࡣࠊప

࡟ẚ࡭࡚ࠊᐊ

࡛ࡣⓎගࢫ࣌ࢡࢺࣝࡣࣈ࣮ࣟࢻ࡟࡞ࡿࡀࠊⓎගࢫ࣌ࢡࢺࣝࡢࢩࣇࢺࡣぢࡽࢀ࡞࠸(Fig. 2a ཧ↷)ࠋບ㉳≧ែࡀ Pt(II)㘒య㸱ศᏊ࠾ࡼࡧ㸲ศᏊ࠿ࡽᙧᡂࡉࢀࡿ࡜ࡋࡓࣔࢹ࡛ࣝࡶྠᵝ࡛࠶ࡾ(Fig. 2b, 2c)ࠊࢫ࣌ࢡࢺࣝࡢᙧ≧ࡢࣈ࣮ࣟࢻ໬ࡣ෌⌧࡛ࡁࡿࡀࠊⓎගࢫ࣌ࢡࢺࣝࡢ

ᗘ࡟ࡼࡿࢩࣇࢺࡣ෌⌧ࡉࢀ࡞࠿ࡗࡓࠋPt(II)㘒య㸰ศᏊ࠿ࡽ࡞ࡿບ㉳≧ែࠊ㸱ศᏊ࠿ࡽ࡞ࡿບ㉳≧ែࠊ㸲ศᏊ࠿ࡽ࡞ࡿບ㉳≧ែࡣࠊ㟁Ꮚ≧ែࡀ㠀ᒁᅾ໬ࡋ࡚࠸ࡿࡇ࡜
࠿ࡽࠊ㸲ศᏊ࠿ࡽ࡞ࡿບ㉳≧ែࡢ᪉ࡀ࢚ࢿࣝࢠ࣮ⓗ࡟Ᏻᐃ࡛࠶ࡿࠋࡑࡇ࡛ࠊ

ᗘ࡟ࡼࡿ Boltzmann ศᕸࢆ⪃៖ࡋࡓ࡜ࡇࢁࠊFig.2d ࡟♧ࡍࡼ࠺࡟ࠊ྾཰఩⨨ࡢࢩࣇࢺ࠾ࡼࡧ྾཰ࢫ࣌ࢡࢺࣝࡢࣈ࣮ࣟࢻ໬ࢆ෌⌧ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ௨ୖࠊศᏊᛶ⤖ᬗෆ࡛ࡢ MMLCT ບ㉳≧ែࡣ」ᩘศᏊ࡟㠀ᒁᅾ໬ࡋ࡚࠸ࡿࡇ࡜ࠊ
ᅾ໬≧ែࡢศᕸࡀኚ໬ࡍࡿࡇ࡜ࠊࡑࡢࡓࡵࠊⓎගࢫ࣌ࢡࢺࣝࡀ

ᗘ࡟ࡼࡾࢩࣇࢺࡍࡿࡇ࡜ࠊప

ᗘ࡟ࡼࡾ㠀ᒁ
࠿ࡽᐊ࡟࡞ࡿ࡜ࠊ᣺ືບ㉳≧ែࡢ㧗ບ㉳≧ែࡀቑຍࡋࠊࡑࡢ⤖ᯝࠊ᣺ືἼື㛵ᩘࡢศᕸࡀᗈࡀࡾࠊࣈ࣮ࣟࢻ໬ࡀ㉳ࡇࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ(Nakagaki, Aono, Kato, S. Sakaki, J. Phys. Chem. C, 2020, 124, 19, 10453–10461).
3.4 Pd55 ࠾ࡼࡧ Rh55 ᚤ⢏Ꮚୖ࡛ࡢࣉࣟ࣌ࣥࡢ㓟໬཯ᛂࡢ⌮ㄽⓗ◊✲㸸⮬ື㌴᤼Ẽ࢞ࢫί໬ゐ፹(3 ඖゐ፹)࡛ࡣ
࢞ࢯࣜࣥṧᕪࢆ᏶඲࡟⇞↝ࡉࡏ࡚࠸ࡿࡀࠊࡑࢀ࡟ࡣ୺࡟ࠊPd, Pt ᚤ⢏Ꮚࡀ౑⏝ࡉࢀ࡚࠸ࡿࠋRh ࡣ㓟໬཯ᛂ࡟ࡣ㐺ࡋ࡚࠸࡞࠸ࡓࡵ࡛࠶ࡿࠋ࡞ࡐࠊ
Rh 㔠ᒓࡣⅣ໬Ỉ⣲ࡢ㓟໬࡟άᛶ
ࡀ࡞ࡃࠊPd, Pt ᚤ⢏Ꮚࡣάᛶࡀ࠶
ࡿࡢ࠿ࠊࣉࣟ࣌ࣥ(Ⅳ໬Ỉ⣲ࡢࣔࢹࣝ࡜ࡋ࡚ᐇ㦂࡛౑⏝ࡉࢀ࡚࠸ࡿ)ࡢ㓟໬཯ᛂࡣ࡝ࡢࡼ࠺࡞཯ᛂ⤒㊰࡛㐍⾜ࡍࡿࡢ࠿ࠊヲ⣽ࡣ඲ࡃ୙࡛᫂࠶ࡗࡓࠋࡑࡇ࡛ࠊPd ࠾ࡼࡧRh ᚤ⢏Ꮚࢆྲྀࡾୖࡆࠊࣉࣟ࣌ࣥ
ࡢ㓟໬཯ᛂࡢ཯ᛂ⤒㊰ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ➨㸯ẁ㝵ࡣ C-H ⤖ྜࡢษ

Fig. 3. Pd55 ࡛ࡢࣉࣟ࣌ࣥࡢ࢔ࢡࣟࣞ࢖ࣥ࡬ࡢ㓟໬཯ᛂ᩿࡛࠶ࡾࠊḟ࡟྾╔ゎ㞳ࡋࡓ O ཎᏊࡀȧ-࢔ࣜࣝ୰㛫య࡟཯ᛂࡋ࡚ࠊ࢔ࢡࣟࣞ࢖ࣥࡀ⏕ᡂࡍࡿࡇ࡜ࠊRh ࡛ࡣゎ㞳྾╔ࡋࡓ O ཎᏊࡀ Rh ⾲㠃࡜ᙉࡃ⤖ྜࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊȧ࢔ࣜࣝ࡜ࡢ཯ᛂࡀ୙฼࡟࡞ࡿࡓࡵ࡛࠶ࡿࡇ
࡜ࡀ♧ࡉࢀࡓࠋ(B.Zu, M. Ehara, S. Sakaki, Phys. Chem. Chem. Phys. 2020, 22, 11783—11796 (inside cover page)).

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ཎⴭㄽᩥ‫ۻ‬B. Zhu, M. Ehara, S. Sakaki, Phys. Chem. Chem. Phys., 2020, 22, 11783—11796. ‫ۻ‬M. Nakagaki, S.

Aono, M. Kato, S. Sakaki, J. Phys. Chem. C 2020, 124, 10453−10461. H. Kameo, Y. Baba, S. Sakaki, Y. Tanaka, H.
Matsuzaka, Inorg. Chem., 59, 4282-4291 (2020). ‫ ۻ‬R.-L. Zhong, S. Sakaki, J. Am. Chem. Soc. 2020, 142,
16732−16747. ‫ۻ‬Q.Z. Li, N. Hara, Y. Nakao, S. Sakaki, Inorg. Chem. 2020, 59, 21, 15862–15876. ‫ۻ‬J. Lu, B. Zhu, S.
Sakaki, RSC Adv., 2020, 10, 36090-36100. I. Fujii, K. Semba, Q.-Z. Li, S. Sakaki, Y. Nakao, J. Am. Chem. Soc., 2020,
142, 11647−11652. K. Sasakura, K. Okamoto, S. Sakaki, K. Ohe, Bull. Chem. Soc. Jpn. 2020, 93, 794–798. H. Kameo,
Y. Baba, S. Sakaki, Y. Tanaka, H. Matsuzaka, Inorg. Chem., 59, 4282-4291 (2020). S. Suzuki,. Y. Ishida, H. Kameo, S.
Sakaki, H. Kawaguchi, Angew. Chem. Int. Ed. 2020, 59, 13444– 13450. A. Matsumoto, B.-N. Nguyen, T. Honda, R.
Sakamoto, X. Huang, S. Sakaki, K. Maruoka, Chemistry–An Asian Journal, 2020, 16, 282-286. ‫ۻ‬P. Zhao, M. Ehara, A.
Satsuma, S. Sakaki, J. Cat., 393, 30–41 (2021). ‫ۻ‬N. Takagi, M. Ehara, S. Sakaki, ACS Omega, 2021, 6, 7, 4888–4898.
Ꮫ఍Ⓨ⾲㸸ゐ፹ウㄽ఍㸹ཱྀ㢌Ⓨ⾲  ௳- 67 -











Theoretical study on dynamical properties of materialsby quantum
dynamics
JO8.#N ",3HG91-,*7 /'2
7C6+  DI4+M ')&PKL>!=@?Q
1 =@<;{q_s¶#_s×iX¶Øs¤Ã´Ðs9+=E06Ó§(½xÁ#ÙxÁw½`Ðs9+=E06"Ù·]t ³\4EIMQ4JO(½ $¬²&ÓRÏÛÙ·]t_s¶xÇ(Ù}Ú¶µm( G.>7F"À£ÈÅÃÑ(&$Ë~ ©(× &RÏÛ_¾ÞSinglet Fission, SFß#&rÖØÓ
"_sÔ«TY¦Ø«TY¦o ÅÃÑ(&Ò#Ó_s/_s×l¶ &2AQMO<+O2AQMO<bÉ PØs®dG.>7FÂ(ÐsD68Q¯¸kÌ¯¥Æo *CNQ:#%v½&'$Ðs£4EIMQ4JOÃ´ÂÓ§Î¦#&¼j¡¶Â CN5,0<©¨&

2 =@%0FA%0Va¬²Ó& y  S0-T1 -?L/Q| ǻ(67 " S0-S1 -?L/Q| ǻ(66 Õ[2 3+<H;Lo Â(y^&Õ[zne»¢ÊÍÞLNOß 2 3
+<Þa, bßÔc0QNOf§ U (= Uaa – Uab)<KO6B)Q±_ tabªU±_ Kab o Âgº&LNO (x­Îi_sÊÍÞSAMOßp&SÄ±_\( HOMO " LUMO
u¹'&_s±_p&  &'$@KGQ8Â(ÝZ ǻ(67 B)+O:
IQ>O1Õ&_sÅÃ( $SF Ï¿ S1  T1 -?L/QiW
!SÄH;Lo Â(&'$ 2 3+<H;Lovalence CI #&Â¿h°±_\Ã´ÜW_?@KGQ8(:IQ>O1 LC-RBLYP Õ#%p
Kohn-Sham ÊÍ CASCI (­ iÞtuned-LC CASCIß({¦GAMESS CN1KF@
Q5(<¦v½
Ó± _s¶Ó]¥ ³£«ÕÕ["=q¤©'¬²(É  
~!h ¯ vÝ`CA± pe RÏÛ-ÏÛ-?L/Q| &l×Â
B)+O:IQ>O1I%­ÓRÏÛ_s¶ÈÎe6O=ÒwÕÞDFTß#%5K5.LSs y 6Obl(P)UHF "6OÙ=ÒÐÂÕ¸ DFT ÞLC-UBLYPß#%Gaussian 09/16 " GAMESS @Q5(<¦½µÜ½1¥Y¾yØ
Þ0,&ßw( JDXJHLQFOXGLQJ0,&Þ*,0,&ß#%´^RÓ_s×i¶Ós(×i¶ &_sÔ«TY¦ixj_sÔ«TY¦iÙ·]£«ÕÕ["=q#Â¤Ó_s×i¶.
:O¤(xÇ×i¶6OÙ=Ò SRVW+) ½HDQ(R5¨Î`È¼_sÔ«TY¦i«k&}5K5.LSs \6  38+) #%_sMLÙ·- 68 -

]t£(r &¨&Á_ Ȗ x & SRVW+) #%*DXVVLDQ " *$0(66 @Q5(<¦Ã´Rp$'«ÕÕ[Â  3+<VS3+<H;L(¦½
SF ¬²ÐsD68Q¯#&bÉs9+=E06Ã´|dÆ#&Â!(ÝZ'$Ã´PÂ¿Øs¤"Øs.CO1Ã´h°Ðset
Ã´#% Gaussian 09 " GAMESS (¦½VÑ¬²v (XN&

3

=@$(

3.1 +O;BLMOÞ(L =L<¶ÓµÜ«ÕÕ[Â[B1]a~¬²*#$#%iv'.QO=L<>@&1% È(! 'P 8P

UT± >@,)&1% (¥Æ¨ÅÃ_s "ÔÓ(¦(

$>1@,)&1% ʌ Øs 1 3%1     &  Q  ʌØs¢iµÜ¨ØsÈ(y 1  >@,)&1%  Qʌ   Qʌ ¶&ØsÏe¤ Qʌ

 3pe&¬² >1@,)&1% ²%ÅÞ1 ß
#Ø¶¤pe ÈµÜÓ &l×¼ÈÎe®"¤>@,)&1% _>@,)
s I%&!ßx­& 'G È 
&1% !ßx­& 'G $d' È !_uÈ& _h¶ÊÍ-?L/Q-È" 0,& wÃ´$>@,)&1% µÜ¨>@,)&1% fµÜT  h¶ 0,& wÃ´®¨ØsÈ(y® p$'R>@,)&1%(&ØsÏe Qʌ  >@,)&1%x­ß 'G È !_u%ÊÍ-?L/QÈ" 0,& wÃ´®$µÜ¨ØsÈ(y® p$'ÞT ß\L Ã´$'$¶7"ÔÓDL:K5.L¨È(¦® p$'VS®#%>1@,)&1%
"ÔÓØsÈ(&1 "Ø¶¤pe#%µÜ"] ³£ q
& $'$v\Í>#%È"£(qpepe&Ó=L<ÀÅÃfÓ & n'&
3.3 1 QLQC5K5.N+Ù·]t¥Æ¬²[B2]ß« ab initio MO D¬R5 3 3+< 2 ØsH;L(¦ 1 
QLQC5K5.N+ &Ó¨&Á_ γ Õ[¼1 QLQC'5K5.N+/H3+
(CH3)3 (SiH3)3 DTDA3 ¿H3 7 yS 
+

+

+

+

X

X

X

(CH3)3+, (SiH3)3+,
DTDA3+
H3 +

H

H

H

À γ (¦yS [B+ γ q  D¿[BR
(CH3)3+(SiH3)3+DTDA3+ yS
&´(¦RyS"Ô¨ÜW H3+# ,q ÜW γÀq\(%γ q  doγ §J À$fÃoyS ! γ

T 2. 1 QLQC5K
5.N+ yS-γ «Õ@¨[q& $ÞT 2ß(R5 3 3+< 2 ØsH;L#%Â&
1ØsÔ1Øs-:ØsÔ1Øs-Ô 3 °Ú0QNO«TY¦|ÉS& $'$®QLQCÓ_s×i¶ & γ q §JÕ&À=qÑ- 69 -

ªa & n'&
3.3 RÏÛ_¾9+=E06x&\ÍÖØYEBcÕ&¥Æ¬²[B3]ßc SF (v& D_sMLb
É-?L/Q"_sÔØs.CO1£=q Ø%'et2Û#& SF _sP_
s×i¶ÅÃ ¥ÆPvÝ!Ú$£½'
.@:JML862G&*-A4K?95

:J>4.



FML862 SF K0 3I&*-B/L;$')+!95  ML

T 3. \ÍÖØYEB#&ßÇ TT ¡v

8 SF #%( "CDE,4E1<7H=¬²SF 9+=E06x&ÖØYEBc( DFT #Ðs9+=E06#%Â&(©SF _s&O8O(¦¹&ÐXH;L(ªSF 9+=E06x&ÖØYEBc
¼SF (~Î&Ss&bÉ-?L/Q"Øs.CO1(ÖØYÃ´ SF )tÌ®¤&Ø¶®dÞCTß¤bÉ-?L/Q q+=E06 q[& ;SF 9pe&gº ¦Q'vÓp$'®(¦Ðs9+=E064EI

MQ4JO(½ &ÐXÚÔKÖØY(EBYiSF Ç [q& º^'ÞT 3ß«x¸kSsÞRRFß"|dÆ(¦Â#%ÖØY SF
%\ÍÖØYEB

BÇFS $

SF =qc&gº ¦Q'  π 9m_sÓRÏÛ_¾-?L/QiW[A1]MOPNMOÞT 4aß_sÞeÓ"bÉ-?L/QÕ[(¥Æ¨Â
WG

SF -?L/Qic¼(½MO#NMOÓbÉ¤Ã´$!M¨Ä¨c Þy0 = 0.201, 0.237ß
 SF W& %'&eVH;LÞT 4bß¼(½MO θ [q y0[B&4K(º$'E(S1) E(T1) .& $ÞT 4cß
NMOÞ y0 (.E(S1) E(T1)([B& ¶ &'$ y0 "bÉ-?L/Qpe$ HOMO-LUMO /Cpex &³$' ș 0^Ë_sÊÍ-«_gË(f&_sÞ

(¡



et2Û

Øs¤Gl×Õ(i) bay area  stitching(ii) π-bridge y6 &Æ%Õ
¼®(i) O " NH (y6YiÊÍ«TY¦#& HOMO-LUMO /Cpe Ù·%M T 4. (a) MONMOÈ(b) VMOH;L(c)OPNMOÓ''.P[B& $ bÉ-?L/Q θ 0^'#%¹LVNMOÚ°X©¨
 SF WÊvn'&'$®$ÓRÏÛ_s¶w% #& SF -?L/QiWB)+O:IQ>O1gºn'&

- 70 -

3.5 O8O®"Ø¶®d¤_ue SF 9+=E06G l×[B4]vnUX®"»'& SF ®" Zc 9+=E06l×(&³$'&¬²¤©&&ÐXOm_s«TY¦CT ¤-?L/Q&l×(_gºAYH;L(!³uHzd(¿ p$'®"c CT ¤SF 9+=E064EIMQ4JO(®"&ÐX

-?L/Q(¦ÐsD68Q¯o]ÐX!½®]ÐXFE bÉs CT bÉs×l Ô3+<ÔR
d(É $TT bÉs< 100 fs ÁßÇ¡v'  RRF o Â$®Yc#& CT ¤-?L/Q_ue#%7 ¤ CT Îa''( SF!$c¨BÇ'& $'$v Zc#& CT ¤

-?L/Q=qo ßc SF ¶ÅÃ & n'&¤O8O×i¶  9+=E06x&_sÎ0^[B5, B6]

SF _s&O8O#v'&(i)&ÎKx­¤_s×i¶H;LÞJ

J-aggregate
Ring

H-aggregate
Ring

V, H Vß &×i¶ SF 9+=E06v

SF rate k
TT yield a_s N 0^(Ä[B5](ii) SÄ
H VÈ(oÞĮ Ûßh_s( Į[˚]T 5. hH;L SF Ç TT H N 0^RÃ Slip-stack V ¤×i¶ SF 9+=
E06 N G Į 0^!¼[B6](i)H V  & SF Ç%· q

J V G H V  & SF Ç#%SF c · q

Singlet Fission (SF)S1 + S0  1(TT)& º^'ÞT 5ßR(ii) Slip-stack V ¤×i¶SF Ç · [q& Į " N ÜW ^n& $ÞT 6ß
RRF
Â"|dÆ(¦³#%¶È(BC&# YxÙx­& SF Ç [q&G.

T 6. Slip-stack VH;LÞN = 8ß
SF Ç TT H Į 0^

>7F $%ÈÞÙßx­¤© SF _s×i¶=qSF ÅÃc&gº ¦Q'

4:EB

[A1] 5( et¨  R~ OK+O$DP ( 41 W

5B

7 28 WÞ: 18 W $O8Q(<¦ß.
>%@5.LVKL0<DPDQH56XJLXUD:<RVKLGD<6KLPL]X01DNDQR56&$GYDQFHV   
>%@: <RVKLGD+ 0DWVXL+0L\DPRWR77RQDPL56XJLPRUL.<RQHGD5.LVKL01DNDQR$&62PHJD
   >%@77RQDPL56XJLPRUL56DNDL.7RNX\DPD+0L\DPRWR01DNDQR3K\V&KHP
&KHP3K\V'2,GFSF    >%@ 7 1DJDPL+0L\DPRWR56DNDL01DNDQR -3K\V&KHP
&    >%@+0L\DPRWR01DNDQR&KHP3KRWR&KHP    >%@+
0L\DPRWR.2NDGD.7RNX\DPD01DNDQRVXEPLWWHG

- 71 -

࢝࢖ࣛࣝศᏊࡀసࡾฟࡍ㟁Ꮚ࢝࢖ࣛࣜࢸ࢕ࡢ⏕ᡂᶵᵓ࡜ሙࡢ㔞Ꮚㄽ࡟ᇶ࡙ࡃ
ᒁᡤ≀⌮㔞࡟ࡼࡿ㔞Ꮚ≀ᛶࡢ◊✲
Study of the mechanism of the electron chirality generation in chiralmolecules and condensed matter physics research by local quantities
based on quantum field theory‫℩ۑ‬Ἴ ኱ᅵ, 㯮⏣ ┤ஓ, 㧗ᯇ ுኴᮁ, ᓥ⏣ 㝯ྐ, ྜྷ⏣ ዴᐶ,㸦ி㒔኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧1◊✲┠ⓗࠊෆᐜ
◊✲௦⾲⪅ࡢ㐣ཤࡢ◊✲࡛ࠊ࢝࢖ࣛࣝ࡞ᵓ㐀ࢆᣢࡘศᏊ୰࡟ࡣ㟁Ꮚࡢ࢝࢖ࣛࣜࢸ࢕࡟㠀ᑐ⛠ᛶࡀ࠶ࡿࡇ࡜ࢆⓎぢࡋࡓ(ECCM, Electron Chirality in Chiral Molecule)ࠋࡇࡢ㟁Ꮚࡢ࢝࢖ࣛࣜࢸ࢕ࡀศᏊෆࡢ࡝ࡢࡼ࠺࡞ᛶ㉁࠿ࡽసࡾࡔࡉࢀࠊ࡝ࡢࡼ࠺࡞໬Ꮫ࣭≀⌮ࡢ⌧㇟࡟ᙳ㡪ࢆཬࡰࡍ࠿ࡢ◊✲ࡋ࡚࠸ࡿࠋ≉࡟ࠊࡇࡢ ECCM ࡀ⮬↛⏺ࡢ Homochirality ࡢ㉳※࡜࡞ࡗ࡚࠸ࡿ࠿࡝࠺࠿ࡢ◊✲ࢆ୰ᚰ࡟⾜ࡗ࡚࠸ࡿࠋࡲࡓࠊሙࡢ㔞Ꮚㄽ࡟ᇶ࡙࠸ࡓ㔞Ꮚ໬ᏛࡢᴫᛕࡀཎᏊ࣭ศᏊࡢ⌧㇟ࢆ࡝ࡢࡼ࠺࡟グ㏙ࡋࠊ࡝ࡢࡼ࠺࡟ᙺ❧࡚ࡽࢀࡿ࠿ࡢ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋሙ
ࡢ㔞Ꮚㄽࡣ┦ᑐᛶ⌮ㄽ࡜ᩚྜࡍࡿ㔞Ꮚㄽࡢᯟ⤌ࡳ࡛࠶ࡾࠊ⌧ᅾᐃᘧ໬ࡉࢀࡓ≀⌮ࡢᇶ♏⌮ㄽࡣ㔞ᏊຊᏛ࡛ࡣ
࡞ࡃሙࡢ㔞Ꮚㄽࡢᯟෆ࡛ᵓ⠏ࡉࢀ࡚࠸ࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊ㐣ཤ࡟㔞ᏊຊᏛ࡟ᇶ࡙ࡁゎᯒࡀ⾜ࢃࢀⓎᒎࡋ࡚ࡁࡓ஦㇟ࡢ⌮ゎࢆࠊሙࡢ㔞Ꮚㄽ࡟ᇶ࡙࠸࡚ᐃ⩏ࡉࢀࡓᒁᡤ≀⌮㔞࡟ࡼࡾ෌ゎ㔘ࡍࡿ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ㟁Ꮚ࢝࢖ࣛࣜࢸ࢕ࡢィ⟬ࡣ┦ᑐㄽຠᯝࡀ㔜せ࡜࡞ࡿࡓࡵࠊDirac ᪉⛬ᘧࢆゎ࠸࡚ 4 ᡂศἼື㛵ᩘࡀィ⟬࡛ࡁࡿ DIRAC ࢆ౑⏝ࡋࡓࠋィ⟬ᑐ㇟࡜ࡋ࡚ࡣ H2X2 (X=O, S, Se, Te) ࢆ⏝࠸ࡓࠋOpenMX ࢆ⏝࠸࡚ࠊ㟁Ẽఏᑟࢆక࠺㟁Ꮚ≧ែࡢ◊✲ࡶ⾜ࡗࡓࠋᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡁ㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲ(NEGF)࡟ࡼࡾ㟁Ẽఏᑟ㔞Ꮚ≧ែィ⟬ࢆ⾜࠸ࠊࡽࡏࢇⅣ⣲ࢼࣀ࣡࢖࣮ࣖࣔࢹࣝࡢ◊✲ࢆ⾜ࡗࡓࠋ㡿ᇦ໬Ꮫ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸ࡓࣜࢳ࣒࢘࢖࢜
ࣥఏᑟ⤒㊰ࡢ᥈⣴ᡭἲࡢ◊✲࡟࠾࠸࡚ࡣࠊGaussian ࢆ౑⏝ࡋࡓࠋィ⟬ࡋ࡚ᚓࡓἼື㛵ᩘ࡟ᑐࡋ࡚, ࢫࢺࣞࢫࢸ
ࣥࢯࣝࡸ㡿ᇦ໬Ꮫ࣏ࢸࣥࢩࣕࣝ࡞࡝ࡢ✀ࠎࡢᒁᡤ≀⌮㔞ࡣ QEDynamics ࢆ⏝࠸࡚ィ⟬ࡋࡓࠋ

3◊✲ᡂᯝ
H2X2 (X=O, S, Se, Te) ศᏊࡣ୍⯡࡟㙾ീ␗ᛶయࢆᣢࡕࠊ㙾ീ␗ᛶయ㛫࡟ࡣᙅ࠸┦஫స⏝ࡢຠᯝ࡟ࡼࡾ࢚ࢿࣝ

ࢠ࣮ᕪࡀ⏕ࡌࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ◊✲௦⾲⪅ࡣࡇࡢ㙾ീ␗ᛶయ㛫ࡢ࢚ࢿࣝࢠ࣮ᕪࡀࠊศᏊ୰ࡢ㟁Ꮚບ㉳࡟ࡼࡾ኱ᖜ࡟ቑ኱ࡍࡿࡇ࡜ࢆணゝࡋ࡚࠸ࡓࠋࡑࡇ࡛ࠊEquation-of-Motion Coupled-Cluster (EOM-CC) ⌮ㄽ࡟ᇶ࡙ࡁ H2X2 ศᏊࡢບ㉳≧ែࢆㄪ࡭ࠊ඲࡚ࡢບ㉳≧ែ࡛ࡣ࡞࠸ࡀ࠸ࡃࡘ࠿ࡢບ㉳≧ែ࡛ࠊࡇࡢ㙾ീ␗ᛶయ㛫ࡢ࢚ࢿࣝࢠ࣮ᕪࡢ 1~3 ᱆⛬ᗘࡶࡢቑ኱ࡀ㉳ࡇࡿࡇ࡜ࢆⓎぢࡋࡓࠋࡇࡢィ⟬ࡣ┦ᑐㄽⓗ㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗ࡚࠾ࡾࠊ
≉࡟㧗࠸⢭ᗘࢆせồࡍࡿࠋィ⟬᮲௳࡟ࡼࡿ⤖ᯝࡢ୙ᐃᛶ࡟ࡘ࠸࡚ࡶὀព῝ࡃホ౯ࢆ⾜ࡗࡓࠋࡽࡏࢇᵓ㐀ࡢ᭷ᶵศᏊෆࢆ㟁Ꮚࡀ㏻㐣ࡍࡿ㝿࡟ࢫࣆࣥࡀศᴟࡍࡿ࡜࠸࠺࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶ(CISS)࡜࠸࠺⌧㇟ࡀ㏆ᖺⓎぢࡉࢀࡓࠋCISS ࡀ࡝ࡢࡼ࠺࡞࣓࢝ࢽࢬ࣒࡟ࡼࡗ࡚࠾ࡇࡿࡢ࠿ࡣᮍゎ࡛᫂࠶ࡿࠋᐇ㦂࡛ࡢ◊✲ࡀ୰ᚰ࡟㐍ࡵࡽࢀ࡚࠸ࡿࡀࠊ࣓࢝ࢽࢬ࣒ࡢゎ᫂࡟ࡣࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㏻ࡌࡓ⌮ㄽ◊✲ࡀ㔜せ࡛࠶ࡿ- 72 -

࡜⪃࠼࡚࠸ࡿࠋࡋ࠿ࡋࠊ⌧≧࡛ࡣࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ CISS ࡢ◊✲ࡣ㠀ᖖ࡟㝈ᐃࡉࢀ࡚࠸ࡿࠋᡃࠎࡣ㠀ᖹ
⾮ࢢ࣮ࣜࣥ㛵ᩘἲ࡟ࡼࡾࡽࡏࢇศᏊࢆ㏻㐣ࡍࡿ㟁Ẽఏᑟ㔞Ꮚ≧ែࢆ◊✲ࡋࠊCISS ࡀ㟁Ẽఏᑟࡢࢩ࣑࣮ࣗࣞࢩ
ࣙࣥ࡟࡛ࡶ㉳ࡇࡿࡇ࡜ࢆᐇドࡍࡿ◊✲ࢆ⾜ࡗࡓࠋࡽࡏࢇⅣ⣲ࢼࣀ࣡࢖࣮ࣖࣔࢹࣝࢆ౛࡜ࡋ࡚࡜ࡾ࠶ࡆࠊࣂ࢖
࢔ࢫ㟁ᅽ࡟ࡼࡿ㟁ὶࡢቑຍ࡟క࠸ࢫࣆࣥศᴟࡀቑຍࡍࡿ⤖ᯝࢆᚓࡓࠋࡲࡔ CISS ࢆᘬࡁ㉳ࡇࡍ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࡣ࡛ࡁ࡚࠸࡞࠸ࡀࠊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ CISS ࡢ◊✲ᡭἲࢆ☜❧ࡍࡿࡇ࡜ࡀ࡛ࡁࠊ௒ᚋࡢ◊✲ࡢᒎ㛤࡟ࡼࡾከࡃࡢࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ࡚࠸ࡁࡓ࠸ࠋ
ࣜࢳ࣒࢘࢖࢜ࣥ㟁ụࡢ඲ᅛయ㟁ụ࡛ࡣࠊࣜࢳ࣒࢘࢖࢜ࣥࡢ⛣ື≉ᛶࡀ㔜せ࡛࠶ࡿࠋࣜࢳ࣒࢘࢖࢜ࣥࡢ⛣ື⌧㇟ࡢ≀⌮ⓗ⌮ゎ࡟ࡣ㟁ゎ㉁ෆࡢ࢖࢜ࣥࡢ⛣ື⤒㊰᥎ᐃࡀ㔜せ࡛࠶ࡿࠋ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮㠃ࢆㄪ࡭ࡿࡇ࡜࡛⛣ື⤒㊰᥎ᐃࡀ⾜࠼ࡿࡀࠊ඲ᅛయ㟁ụࡢ㟁ゎ㉁ࡣィ⟬ᑐ㇟࡜࡞ࡿᵓ㐀ࡀ኱ࡁ࠸ࡓࡵィ⟬㔞ࡀ⭾኱࡜࡞ࡾࠊࣜࢳ࣒࢘࢖࢜ࣥࡢ఩⨨ࢆኚ࠼࡞ࡀࡽఱᗘࡶィ⟬ࡍࡿ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮㠃ࡢィ⟬ࡣ㠀ᖖ࡟㞴ࡋ࠸ࠋࡑࡇ࡛ᡃࠎࡣࠊࣜࢳ࣒࢘࢖࢜ࣥࡀ㟁ゎ㉁ෆ࡛㟁Ꮚࡢࢻࢼ࣮࡛࠶ࡿࡇ࡜࡟ὀ┠ࡋࠊ㟁Ꮚࡢቑῶ࡟ᑐࡍࡿ࢚ࢿࣝ
ࢠ࣮ኚ໬࡛࠶ࡿ໬Ꮫ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸ࡓ࢖࢜ࣥ⛣ື⤒㊰᥎ᐃᡭἲࢆᥦ᱌ࡋࡓࠋሙࡢ㔞Ꮚㄽ࡟࠾࠸࡚໬Ꮫ࣏
ࢸࣥࢩࣕࣝࢆᒁᡤ໬ࡋࡓ㡿ᇦ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡀᐃ⩏ࡉࢀ࡚࠸ࡿࠋ㡿ᇦ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢ್ࡀ㈇࡟኱ࡁ࠸
ᆅⅬࡣࠊࣜࢳ࣒࢘࢖࢜ࣥࡀᏳᐃ໬ࡋࡸࡍࡃࠊ࢖࢜ࣥ࡜ࡋ࡚⛣ືࡍࡿ㝿࡟㏻ࡾࡸࡍ࠸ࠋࡇࡢ᪉ἲࡢ฼Ⅼࡣࠊࣜࢳ࣒࢘࢖࢜ࣥࢆᑟධࡋ࡚࠸࡞࠸㟁ゎ㉁ࡢィ⟬ࣔࢹࣝࢆ୍ᗘィ⟬ࡍࢀࡤ㟁ゎ㉁ෆ඲㡿ᇦ࡛ࡢ㡿ᇦ໬Ꮫ࣏ࢸࣥࢩ
ࣕࣝࡀィ⟬࡛ࡁࠊ⛣ື⤒㊰᥎ᐃࡢィ⟬㔞ࢆ᱆㐪࠸࡟ᑠࡉࡃࡍࡿࡇ࡜ࡀ࡛ࡁࡿࡇ࡜࡛࠶ࡿࠋLaLiTiO ࡢ㟁ゎ㉁ࣔࢹࣝ࡟ᑐࡋ࡚ᐇ㝿࡟㡿ᇦ໬Ꮫ࣏ࢸࣥࢩࣕࣝࡢィ⟬࡜࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮㠃ࡢィ⟬ࢆ⾜࠸ࠊ୧⪅ࡀྠࡌ࢖࢜ࣥ⛣ື⤒㊰ࢆ♧ࡍࡇ࡜ࢆ☜ㄆࡋࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] Masato Senami, (Oral, Invited), “Electron Chirality in Amino Acid and Homochirality”, The 6th Quantum
Science (QS) symposium -The Main Symposium of International Conference of Computational Methods in Sciencesand Engineering (ICCMSE) 2020, April 2020, Video Conference (Heraklion), Greece.
[2] 㯮⏣ ┤ஓ㸪℩Ἴ ኱ᅵ, ͆ከཎᏊᴟᛶศᏊࢆ⏝࠸ࡓ㟁Ꮚ㟁Ẽ཮ᴟᏊ⬟⋡᥈⣴࡟࠾࠸࡚ศᏊᵓ㐀ࡀ᭷ຠ㟁ሙ࡜ࢫࣆࣥ࡟ཬࡰࡍᙳ㡪͇(ཱྀ㢌), ศᏊ⛉Ꮫ࢜ࣥࣛ࢖ࣥウㄽ఍, 2020/9/14-17, ࢜ࣥࣛ࢖ࣥ.
[3] Naoya Kuroda㸪Masato Senami, ͆Electron chirality of amino acid molecules and the origin of homochirality innature͇(࣏ࢫࢱ࣮), ᪂Ꮫ⾡㡿ᇦࠕࢽ࣮ࣗࢺࣜࣀ࡛ᣅࡃ⣲⢏Ꮚ࡜Ᏹᐂࠖ◊✲఍, 2020/12/21-22, ࢜ࣥࣛ࢖ࣥ.
[4] ྜྷ⏣ ዴᐶ, ℩Ἴ ኱ᅵ͆ศᏊࡢ㟁Ẽఏᑟ⌧㇟࡟࠾ࡅࡿ㟁Ꮚࢸࣥࢩࣙࣥᐦᗘࡢࢫࣆࣥ౫Ꮡᡂศ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲͇(࣏ࢫࢱ࣮), ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࣭ࢼࣀࢸࢡࣀࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗྜྠ࣮࣡ࢡࢩࣙࢵࣉ 㸫ࢹ࣮ࢱ⛉Ꮫ࡟ᇶ࡙ࡃ⌮ㄽ࣭ィ⟬⛉Ꮫ࡜ᐇ㦂⛉Ꮫࡢ༠ാࢆ┠ᣦࡋ࡚㸫, 2021/1/12-13, ࢜ࣥࣛ࢖ࣥ
[5] ྜྷ⏣ ዴᐶ㸪℩Ἴ ኱ᅵ, ͆ศᏊࡢ㟁Ẽఏᑟ⌧㇟࡟࠾ࡅࡿ㟁Ꮚࢸࣥࢩࣙࣥᐦᗘࡢࢫࣆࣥ౫Ꮡᡂศ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲͇(࣏ࢫࢱ࣮), ி㒔኱Ꮫ⚟஭ㅬ୍グᛕ◊✲ࢭࣥࢱ࣮࢜ࣥࣛ࢖ࣥࢩ࣏ࣥࢪ࣒࢘, 2021/1/25, ࢜ࣥࣛ࢖ࣥ
[6] ᓥ⏣ 㝯ྐ㸪℩Ἴ ኱ᅵ, ͆㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲࢆ⏝࠸ࡓ㟁ὶ࡟ࡼࡿ࢝࢖ࣛࣝㄏ㉳ࢫࣆࣥ㑅ᢥᛶࡢ㉳※ࡢ◊✲͇(࣏ࢫࢱ࣮), ி㒔኱Ꮫ⚟஭ㅬ୍グᛕ◊✲ࢭࣥࢱ࣮࢜ࣥࣛ࢖ࣥࢩ࣏ࣥࢪ࣒࢘, 2021/1/25, ࢜ࣥࣛ࢖ࣥ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

>@0DVDWR6HQDPL7RPRNL6KLPL]X³(OHFWURQFKLUDOLW\LQDPLQRDFLGPROHFXOHV´3K\V/HWW$   ★>@06HQDPL1.XURGD77DNDKDVKL³(൵HFWVRIH[WHUQDOHOHFWULF¿HOGDQGLQWHUQXFOHDUOHQJWKRQH൵HFWLYHHOHFWULF
¿HOGIRUPHDVXUHPHQWRIHOHFWURQHOHFWULFGLSROHPRPHQW´-&RPSXW0HWWKRGV6FL(QJ  - 73 -

$


(4)Al 

# C-H 

"!

Elucidating properties of reactive diborane(4)s and Al-anions,and design of homogeneous catalyst toward C-H activation of methane "$



#

%

1 ¢Ä´) ÀÕv$`Y]Ù.» 
U>@O(o-@PQ)9LOT(4)n(*9LPQM=T qoµ*, Ñ}ßHS@T.+&¶HS@Tloµ² K1®l(*@PLPQM=T.[+
U9/Q5Q³ Al /A3T IT;T'@Q2Tn C-H ±qi .[+ZÜtl®Û_jln.È
U,$e®ÓZÜt±q.+HQTDIT;Tm× oµUbÑlK1®lqLPRT£ "rNC/A3TF:357<PTÐaxÁ¿
U/Q4T¶®l"r¼ØxÆ{^~Ðax¿­ly¤hxÁ¿U¿­ly.d¡¼GT7VIr Ôc¾wÁ¿M=Tl¢Ä `Y 6 ÃÚ.¦«¥¤ª :JV:ÏqX(2)%§(1) @PLPQM=T/A3TUO94Q£ Øx¤Ç½(£¹Å 1)(2) 9/Q5Q Al /A3Tn½(£¹Å 2)(3) s 14 f®IT;TÛÇ½(£¹)(4) LPRTØx½(£¹)(5) ^~Ðax.+Ò|Ôc.¡/Q4T¶®lÂ¯n½(£¹)(6) M=Tloµ Ir Ôc¾w³ukÐax?80T(£¹)2 !
±Ë?V=.fGaussian 16 (* Al /A3T 1 (!@Q2TM=an  2 ËÌl.¸gEOa(!IT9Qan ËÌl.¸q-,) . \Öc(!Í¨ËÌl.¸,,n°É2BQ6V.
& (M06/def2-TZVP//PBE/def2-SVP RIQ, PCM(SMD, toluene), DFT-D3BJ º)3 
Ê q Al /A3T 1

p©·Ýlqn Al–C ±q.lq 2-

6 .[+.zÞ¤»(Scheme 1)¬# @Q2TnM=a C–H ±q Î ¤i,mW  2 .[+ - nM=aÎÈ.) +& DFT ¿­.¡n½.À+8

- 74 -

 +nEOa C–H ±q

6FKHPH
Si Si

nIT9Qa C–H ±qnq-À.¸
3 ©Ûn6),2B

Al

Q2Thx

a³.¨

H

K
(tol)

Si Si

63% (99%)

Q6V. Scheme 2(a), ! I
Ë 1  K+03TÐa@OMe
Toluener.t., 12 h

Al K(tol)2

r.t., 5 hMeK(tol)2Si Si
, 90%

OPh

Si Si

Si = SiMe3O

Alr.t., 5 h

Si Si

F

r.t., 5 h
I
2) I2

F
+
 (25%)

1)

Si Si

Si Si

Ph OPh2
Si Si
O
Al
K H
H K
Al
O
Si Si
Ph2O PhSi Si
, 69%

r.t., 5 h(28%))n
6FKHPH3  *+Í¨.» (a)‡H

+ \ M=a C–H ±q i4)+ - $Al /A3T

H

@Q2Thx"_j+ Meisenheimer \Öc meta-INT .[² Al ±q+®xX®x

P

 Al x".a+ - 

energy (kcal/mol),+Í¨ b 2}Å¤K(tol)
Alpara76-n Al /A3T #.oµ+W  2 $7n  Al /A3T_j 2$7*n
0\

Ë

$*lH

K(tol)
para76
Al




H

≈

Al

K(tol)meta,17K(tol)
para,17K(tol)±

1.416
1.107 1.446
H C1
C4
1.447
1.419
2.346 C6 C5
1.386
Al

1.381
C2 C3

H

Al

±
±

1.379
C2 C3

H

Al

≈
≈


Al

K(tol)meta76



H

‡

H





K(tol)
Almeta76

Al

K(tol)

benzyl76‡ ,+ 2 $7n.1
Al  (b)3¸»

Al K(tol)Al x Q0:ÑP.

xXÑl¤_jn

Al

meta
para
benzyl‡H‡

K(tol)Al

H K(tol)

1.383
C2 C3

H
H
1.419 1.839 1.328
1.412
1.479
1.142 C1 1.516
C4
C1
C4
Al
1.962
1.514
1.480
1.927
1.424
1.418
C6
C5
C6
C5
Al
1.386
1.389

C

meta-76

C

meta-LQW

C

meta-76- [Scheme 2(b)]meta-TS1  para-TS1 Øx.%/+&hx-5&¥+Al /A3T
#,+®

)»3Q@a(!EOa®X

-5    - +(Figure 1) NBO ½".¸Øx [MQu ³®x NPAØ+&¥´ –0.06´ –0.17 *Al /A
3T M=a.#+8MQuØx [Zlk.  Î È+) 

4





y£¹ ('


$NL\DPD6<DPDVKLWD0&KHP/HWW .XUXPDGD66XJLWD.1DNDQR5<DPDVKLWD0$QJHZ&KHP,QW(G 

6XJLWD.<DPDVKLWD02UJDQRPHWDOOLFV 



7DQLJXFKL:,WR-L<DPDVKLWD0-2UJDQRPHW&KHP 



.LVX+.RVDL7,ZDPRWR7<DPDVKLWD0&KHP/HWW 



6X]XNL$*XR;/LQ=<DPDVKLWD0&KHP6FL 

- 75 -





Theoretical study of the electronic structures of metalloproteinŪŘzūĶÇŌĶµ¯æsŬ¿¹¼ĝ­±bĽºì­±ŭ1ĔěĎč´Ś¸-Ćt ¯Đjuć#ľÞ$Ćăņ#Ąľ4ø*0!ÚS`cR,ĵ#ıË4g
0#ľÞ"$÷ËhÈ#Ļš!Ţ¯ĂÌ#(3/"Ŗq0ķČň45»­!Ġ4ß"/Ï3!1%!.ũËı!@aP[cF4Éļ0ĿğĖ±ĔěEaFc#ĿğŇú4ć/#ķČň#è4/ŋ5Ś¸ķČň#Ţ¯ĂÌĿğĿğ"-/Ś¸Ćt
ć#

¯#Đju

¯_U^#ľÞ4ĎÓtč"$lf#4ĸ

1.1

TXFaN>ň"0íŐïıĐŝ#ľç

TXFaN>ň$TX4ĺ¢¯"+FaN>ň#ĩĘ/d#§åŨé4Ò"+

3.

Ļt4ÂÎ0FaN>ň"-/ĉ!0ïı4Ċă0#-!TX#¬ïıË#ŉú$äÞ.
"!!Ō¾TX#ð)

FaN>ňïı"ŝg0 ĕ10åĔě$TX#ð)"¶0FaN>ňV?HJ#Ãţ4Ń'04ĎčĝtíŐÜē#}#TXFa
N>ň4¶ņ"TX#ð)TX ħ0FaN>ňV?HJ#7WMŗĥÎ4Ĩĭč"ľç   3QRU #Ê÷Ë#ľç
3QRU $dŗĜġ 12 4 12 "Ŕ{0TXFaN>ň0#ÊA8>^ŒĚ"Ŝt#íŐ$ô²1

.OK]KŔ{1ďÆ# +12±1

1#ĂÌ°¥0 äľÞ0Ō¾ßŜ
t#ħàíŐľç

ő*.1

h

S`Ja1 +12+ #ľėħàíŐľç 756); "-0 3QRU #hŜ/Ąńľç#y"-/ 3QRU #hŜtÆ#ÊA8>^"

0łģ!ïí#ľÞ"! 0ãÄ10ř¯±Ŀğ4ć 3QRU ÊhŜt#÷Ë4Ąńč"Łw0hŜt . 12 ĆÎ"0(#ÊŒĚ#2

¯ïÀ4ľçĔěÛõĿğÛõ
2.1

TXFaN>ň"0íŐïıĐŝ#ľç

3'% "ċś10TXFaN>ň#ĝtíŐ#h .ŖŦpË
#h7WMŗñ§l«#r
û7WMŗl«#7WMŗ

¯!

TX"Ŗq0+#lf#KY8a4Ð -&FaN>ňV?HJ"î(10+#4şFaN>ňV?HJ$TX#§åŨé#¯.c l"  le#¯ |07WMŗñ§#ĥ1."¶ïê±Į#  0\aGXQ;_DJõ4ćFaN>ňV?HJ#7WMŗĥÎ .TX#ð)#­·#iù4ĸ
FaN>ňą©TX#ð)#Đŝ4ľç  3QRU #Ê÷Ë#ľç~Ĕěİ-/×v1 3QRU hŜt#ħàíŐ4+"21,20 õ4ć +12±1 S`Ja1 +12+ #Ôľç440 Ť¦FaN>ň#á·Ş#÷Ëŕq4/+#4ć

- 76 -

40 Ť¦$ %/<3 óŝØ/Ï§ÁŝØĠ$ )H 1 2 6 &§ňe#òġ¯"$ * GS 1l«#¯"$ GHIVYS 4ć÷Ëŕql«$ $PEHU II ¨/Ï40Ť¦#)íŐáœ4ĸ00 Ť¦$ħàíŐ"¤²ÊĦŊÕĢ"$÷Ëŕq4/ZI^"ĸ!

3

ĔěÎè
3.1

TXFaN>ň"0íŐïıĐŝ#ľç

hkNRN/MO QRUPDOFRRUGLQDWHVWUXFWXUDOGHFRPSRVLWLRQq16'rZ";Es16' JUXE lpdN<F9+#L  lpdZ,2KBE:@XUNRK`of]3i^bcN[je5)N$6Z1QWES
M9moakg\n_cMTV[je5)>UhkNRNN Z0RE:NAZ  KB9N.>U(N Z-'BEK@Y9VDGGOLQJ9UXIIOLQJ9=TP GRPLQJ M6BIO9(?CXDX 89
898 K4#7;?UXEsCXN lpdMH;IO9(O  >U  &N
;KLGEs@XUN*>U9UXIIOLQJ =TP GRPLQJ M6BIO`of]3! KhkNRNN$6?
%

AXWs
  3QRU #Ê÷Ë#ľç
1+2± 1+2+ hŜt11# 12 oīöØ4Łw211  FP± ³ŧxŬFP±ŭ-/hŜt$ 1+2±0½¸1£" 3QRU #hŜt1+2±"ŮĎ# 12¯

ÊáĤĆÎā# 12 4ĆÎ

0ŒĚ#Ê#:L^=cS`Q68^4ĕÅŏ!0Ê
Šª$ NFDOPRO /³ŧxŬNFDOPROŭĒđS`JaÿÊőĸ0ĕ1# £. NHO–hŜt+NOŬRŭ .áĤĆÎā
Ŀğ$dŕ#ÊŒĚ$ŎS`Jaę#®tò ¯ N2O+OH–ŬPŭ"Ĳ0(#:L^=cS`Q68^ [kcal/mol]
4ZI^"ōĿğŬ£h<_aCĴŭ4ĸ!(á# 11 ħĆÎŒĚŬ76ŭ"$Ů#ĦŊ °¥ďÖ 11 ħ4ÂÎ0ĦŊòġę4ĦĈ
0ĦŊŬýĴþĪŭ °¥İ 3 ":L^=cč"â0

3 kÆ 21,20 õ

4ćFaN>ň&FaN>ň#ò ¯4įÍZI^ÊĦŊ4ëŀ0i²0

4ĊĹ³Ĭ($i²
4.1

ťĊĹŬEaFcć"-0+#} 2 mÑÄŅü 1 mŭŌĶ.Ğ 58 ¡ÝåĆāāĄ±n¾nBaVC9X ÑÄŅü!
4.2

VDFcĊĹŬEaFcć"-0+#} 2 mŭŪŘ.Ğ 58 ¡ÝåĆāāĄ±n¾n VDFcĊĹ !

5Ā³ĬŬńÙ} 3 mŭŌĶæĳåŪŘ" PyDISH: Database and analysis tools for heme porphyrin distortion in heme proteins"
Database. 2020, 2020, baaa066- 77 -

⏕యศᏊࡢᵓ㐀࡜ᶵ⬟࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Studies on Structures and Functionsof Biological Molecules‫ۑ‬㉥℩ ኱㸪┦⏣ ⨾◁Ꮚ㸪ᆏ᐀ ࿴᫂㸪⋢㔝 ᬛ❶㸦ᗈᓥ኱Ꮫ㸧1◊✲┠ⓗ⏕⌮άᛶศᏊࡸ⏕యศᏊࡢᵓ㐀ࡢ≉ᚩࡸ཯ᛂࡢ࣓࢝ࢽࢬ࣒㸪ࡲࡓ㸪ࡑࢀࡽ࡬ࡢ⁐፹ࡸ࿘ࡾࡢศᏊ࠿ࡽࡢᙳ

㡪ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚㸪୺࡟㠀⤒㦂ⓗศᏊ㌶㐨ἲ㸪ᐦᗘỗ㛵ᩘ⌮ㄽ㸪ศᏊືຊᏛἲ㸪ࣔࣥࢸ࢝ࣝࣟἲࢆ⏝࠸ࡓ◊✲ࢆ㐍ࡵࡓ㸬ᮏᖺᗘࡢ୺࡞◊✲ෆᐜࡣ㸪   ⁐፹ศᏊࢆ࠶ࡽࢃ࡟࡜ࡾධࢀࡓ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ⁐ᾮ୰ࡢ⁐㉁ศᏊࡢ 105 㐽ⶸᐃᩘࡢィ⟬࡜ࡑࢀ࡟ᇶ࡙ࡃ⁐፹ຠᯝࡢゎᯒ㸪   ⏕⌮άᛶศᏊࡸ⏕య㧗ศᏊࡢ≉␗ⓗ┦஫స⏝ࡢゎ᫂㸪࡛࠶ࡿ㸬

2◊✲᪉ἲ㸪ィ⟬᪉ἲ㠀⤒㦂ⓗศᏊ㌶㐨ἲ㸪ᐦᗘỗ㛵ᩘ⌮ㄽࡢィ⟬࡟ࡣ *DXVVLDQ 㸪ศᏊຊሙࢆ⏝࠸ࡓศᏊືຊᏛィ⟬࡟ࡣ

$PEHU ࡢࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࢆ౑⏝ࡋࡓ㸬105 㐽ⶸᐃᩘࡣ *,$2 ἲࢆ⏝࠸࡚ィ⟬ࡋࡓ㸬ゎᯒࡸᶵᲔᏛ
⩦࡟ࡣ⊂⮬ࡢࣉࣟࢢ࣒ࣛࢆసᡂࡋ࡚౑⏝ࡋࡓ㸬

3◊✲ᡂᯝ
3.1 Ỉ⁐ᾮ୰ࡢ⁐㉁ศᏊࡢ NMR 㐽ⶸᐃᩘࡢィ⟬࡜ᶵᲔᏛ⩦࡟ࡼࡿゎᯒ㹙Ⓨ⾲ࣜࢫࢺ(1)㹛
105 ໬ᏛࢩࣇࢺࡣཎᏊ᰾ࡢ࿘ࡾࡢ㟁Ꮚⓗ࡞⎔ቃ࡟㗦ᩄ࡛࠶ࡿࡓࡵ㸪⁐ᾮ୰࡛ࡣࡑࡢ

ᐃ್ࡀ⁐㉁ศᏊࡢᵓ

㐀ኚ໬ࡸ⁐፹ศᏊ࡟ࡼࡿᙳ㡪ࢆཷࡅࡿ㸬㔞Ꮚ໬Ꮫィ⟬࡛ࡣ㸪┤᥋ⓗ࡟ࡣ 105 㐽ⶸᐃᩘࢆィ⟬ࡋ࡚໬Ꮫࢩࣇ
ࢺ࡟ኚ᥮ࡍࡿ㸬105 㐽ⶸᐃᩘ࡬ࡢ⁐፹ຠᯝࢆྲྀࡾ㎸ࡴࡓࡵ࡟ࡣ㸪⁐፹ศᏊࢆ࠶ࡽࢃ࡟⪃៖ࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ㸬ࡑࡢࡓࡵ㸪⁐ᾮ୰ࡢ 105 ໬Ꮫࢩࣇࢺࡢᐇ㦂್࡜ᐃ㔞ⓗ࡟ẚ㍑࡛ࡁࡿ⢭ᗘ࡛㸪105
㐽ⶸᐃᩘࢆィ⟬ࡍࡿࡓࡵ࡟ࡣ㸪⁐፹ศᏊࢆ࠶ࡽࢃ࡟⪃៖ࡋ࡚⁐ᾮ୰࡛ࡢከࡃࡢᵓ㐀ࢆィ⟬ࡋ࡚࢔ࣥࢧࣥࣈࣝ
ᖹᆒࢆ࡜ࡿᚲせࡀ࠶ࡾ㸪ィ⟬ࢥࢫࢺࡀ࠿࠿ࡿ㸬ࡑࡇ࡛㸪105 㐽ⶸᐃᩘࢆィ⟬ࡋ㸪ᶵᲔᏛ⩦ࢆ⏝࠸࡚ᵓ㐀࠿ࡽ
105 㐽ⶸᐃᩘࢆண

ࡍࡿࣔࢹࣝࡢᵓ⠏ࢆヨࡳࡓ㸬ࡲࡓ㸪ᵓ⠏ࡋࡓࣔࢹࣝ࠿ࡽ㐽ⶸᐃᩘ࡬ࡢ⁐፹ຠᯝ࡟ࡘ࠸࡚

ࡢ᪂ࡓ࡞▱ぢࢆᚓࡿࡇ࡜ࢆ┠ᣦࡋࡓ㸬࣓ࢱࣀ࣮ࣝỈ⁐ᾮࡢᵓ㐀ࢆࢧࣥࣉࣜࣥࢢࡍࡿࡓࡵ࡟ *$)) ศᏊຊሙࢆ⏝࠸ࡓศᏊືຊᏛ㸦0'㸧ィ⟬ࢆᐇ⾜ࡋࡓ㸬0' ࡢࢺࣛࢪ࢙ࢡࢺ࣮ࣜ࠿ࡽ⁐㉁ศᏊ࡜ࡑࡢ㏆ഐࡢ⁐፹ỈศᏊࢆ  ࢫࢼࢵࣉࢩࣙࢵࢺ࠿ࡽᢤࡁฟࡋ㸪ᢤࡁฟࡋࡓࢡࣛࢫࢱ࣮ᵓ㐀ࡑࢀࡒࢀ࡟ࡘ࠸࡚㸪%/<3DXJFFS9'= ࡛ࣞ࣋ࣝ 105 㐽ⶸᐃᩘࢆィ⟬ࡋࡓ㸬2+
ᇶࡢ + ࡢ㐽ⶸᐃᩘࡢィ⟬್ࡣ㸪⁐፹ỈศᏊࡀ࡞࠸⁐㉁ศᏊࡔࡅࡢሙྜࡢィ⟬࡜ẚ࡭࡚íSSP ࠿ࡽ SSP
ࢩࣇࢺࡋ㸪ᵓ㐀࡟ࡼࡗ࡚ࡑࡢ್ࡀ࠾ࡼࡑ SSP ࡢ⠊ᅖ࡟ࡤࡽࡘࡃ⤖ᯝࢆᚓࡓ㸦ᅗ 㸧㸬ࡘࡲࡾ㸪㐽ⶸᐃᩘࡣ⁐፹ỈศᏊ࠿ࡽࡢᙳ㡪ࢆཷࡅ࡚ኚ໬ࡋ㸪ࡑࡢ኱ࡁࡉࡣᵓ㐀࡟౫Ꮡࡋ࡚࠸ࡿ㸬105 㐽ⶸᐃᩘࡢィ⟬್ࢆ┠ⓗኚᩘ࡟㸪ᵝࠎ࡞ᵓ㐀ࣃ࣓࣮ࣛࢱࢆㄝ᫂ኚᩘ࡜ࡋ࡚㔜ᅇᖐࣔࢹࣝࢆసᡂࡋࡓ㸬᭱ึ࡟ከᩘࡢᵓ㐀ࣃ࣓࣮ࣛࢱࢆㄝ᫂
ኚᩘ࡜ࡋ࡚ࢆ㑅ࡧ㸪ࡑࡇ࠿ࡽኚᩘࢆ୍ࡘࡎࡘῶࡽࡋ࡚࠸ࡃࡇ࡜࡛  ಶࡢኚᩘࢆࡶࡘ㔜ᅇᖐࣔࢹࣝࢆᚓࡓ㸬᭱⤊ⓗ࡞ࣔࢹࣝࡢㄝ᫂ኚᩘ࡟ࡣ㸪࣓ࢱࣀ࣮ࣝศᏊෆࡢᵓ㐀ࣃ࣓࣮ࣛࢱ࡜࣓ࢱࣀ࣮ࣝ̽ỈศᏊ㛫ࡢᵓ㐀ࣃ࣓࣮ࣛࢱ
ࡀ࠶ࡗࡓࡀ㸪᭱ࡶᐤ୚ࡀ኱ࡁ࠸ㄝ᫂ኚᩘࡣ࣓ࢱࣀ࣮ࣝࡢ 2+ ࡜⁐፹ỈศᏊࡢ 2 ࡢỈ⣲⤖ྜ㊥㞳 U 2+͐2 ࡛࠶ࡗࡓ㸬ࣔࢹࣝ࡟ࡼࡿண

್࡜ィ⟬್࡜ࡢ 506( ࡣ SSP ࡛࠶ࡾ㸪ࣔࢹࣝࡢண

- 78 -⢭ᗘྥୖࡢࡓࡵ࡟㸪ࡼࡾ」㞧࡞ᶵᲔᏛ⩦ࣔࢹࣝࡢ㐺⏝ࢆ᳨ウࡋ࡚࠸ࡿ㸬
ᅗ 1.

105 㐽ⶸᐃᩘࡢィ⟬್ࡢศᕸ㸦&+2+㸧㸬 D  ࢡࣛࢫࢱ࣮ィ⟬㸪 E  ⁐㉁ศᏊࡢࡳࡢィ⟬

3.2 ⏕⌮άᛶศᏊࡸ⏕య㧗ศᏊࡢ≉␗ⓗ┦஫స⏝ࡢゎ᫂
51$ LQWHUIHUHQFH㸦51$L㸧ࡣ㸪VPDOO LQWHUIHULQJ 51$㸦VL51$㸧࡜࠸࠺▷࠸஧ᮏ㙐 51$ ࡀ㑇ఏᏊⓎ⌧ᢚไຠᯝࢆ♧ࡍ⌧㇟࡛࠶ࡿ㸬VL51$ ࡣ $UJRQDXWH ࡜࠸࠺ࢱࣥࣃࢡ㉁࡟ྲྀࡾ㎸ࡲࢀ㸪୍ᮏ㙐࡟ศ࠿ࢀ࡚」ྜయࢆᙧᡂ
ࡋ㸪ࡑࡢ」ྜయࡀ VL51$ ࡜┦⿵ⓗ࡞㓄ิࢆࡶࡘᶆⓗࡢ P51$ ࡢษ᩿ࢆ㉳ࡇࡍࡇ࡜࡛స⏝ࡍࡿ㸬51$L ࡛ࡣ㸪ᶆⓗ௨እࡢ㒊ศⓗ࡟ VL51$ ࡜┦⿵ⓗ࡞㓄ิࢆࡶࡘ P51$ ࡟ᑐࡋ࡚ࡶ㑇ఏᏊⓎ⌧ࡢᢚไࢆ⏕ࡌࡿ࢜ࣇࢱ࣮ࢤࢵ
ࢺຠᯝࢆ♧ࡍࡇ࡜ࡶ࠶ࡿ㸬ᶆⓗ P51$ ࡜ᑐྜࡍࡿ VL51$ ࡢ୍ᮏ㙐 51$ ࡛࠶ࡿ࢞࢖ࢻ㙐ࡢ≉ᐃࡢ఩⨨ࡢࢾࢡࣞ࢜ࢳࢻࡢ࣮ࣜ࣎ࢫࡢ ¶఩ࢆಟ㣭ࡍࡿࡇ࡜࡛㸪࢜ࣇࢱ࣮ࢤࢵࢺຠᯝࢆᢚไ࡛ࡁࡿࡇ࡜ࡀᐇ㦂ⓗ࡟᫂ࡽ࠿࡟࡞
ࡗ࡚࠸ࡿ㸬ࡑࡇ࡛㸪ࡇࡢ໬Ꮫಟ㣭ࡢຠᯝࢆศᏊ࡛ࣞ࣋ࣝゎ᫂࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡟㸪VL51$ ࡢ㒊ศᵓ㐀࡛࠶ࡿ࢜ࣜࢦࢾࢡࣞ࢜ࢳࢻࡢࣔࢹࣝ⣔ࢆᵓ⠏ࡋ㸪Ȧ%;'* G ࡛ࣞ࣋ࣝᵓ㐀᭱㐺໬ࢆ⾜࡞ࡗࡓ㸬ࡑࡢ⤖ᯝ㸪໬Ꮫಟ㣭࡟ࡼࡗ࡚㞄᥋ࡍࡿࢾࢡࣞ࢜ࢳࢻ࡜ࡢศᏊ㛫┦஫స⏝ࡀኚ໬ࡋ㸪ࢥࣥࣇ࢛࣓࣮ࢩࣙࣥኚ໬ࡀ㉳ࡇࡾ᰾㓟ሷᇶࡢ㓄ྥࡀኚࢃࡾ࠺ࡿࡇ࡜㸪ࡲࡓࡑࢀࡀ໬Ꮫಟ㣭ࡍࡿࢾࢡࣞ࢜ࢳࢻࡢ఩⨨࡟౫Ꮡࡍࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬ࡇࡢ఩⨨౫Ꮡᛶࡣᐇ㦂⤖ᯝࢆ▩┪࡞ࡃㄝ࡛᫂ࡁࡿ㸬㹙Ⓨ⾲ࣜࢫࢺ  㹛ぶỈᛶ࡜␯Ỉᛶࡢࣈࣟࢵࢡࢆ୍ᮏ㙐ෆ࡟஺஫࡟ࡶࡘ୧ぶ፹ᛶ࣐ࣝࢳࣈࣟࢵࢡඹ㔜ྜయࢆᵝࠎ࡞ศᏊ㔞࡛ྜᡂࡋ㸪ࡑࡢỈ⁐ᾮࡢ᭎ⅬࡢศᏊ㔞౫Ꮡᛶࢆᐇ㦂ⓗ࡟᫂ࡽ࠿࡟ࡋࡓ㸬ࡑࡢࡼ࠺࡞౫Ꮡᛶࡀ୧ぶ፹ᛶ࣐ࣝࢳࣈࣟ
ࢵࢡඹ㔜ྜయ࡛⌧ࢀࡿཎᅉࢆ⌮ㄽⓗ࡟᫂ࡽ࠿࡟ࡍࡿ◊✲ࢆ㛤ጞࡋ࡚࠸ࡿ㸬㹙ฟ∧ࣜࢫࢺ>@㹛

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫⋢   ۻ‬㔝㸪┦⏣㸪㉥℩ࠕ㔜ᅇᖐࣔࢹࣝ࡟ࡼࡿ 105 㐽ⶸᐃᩘࡢண

࡟ࡘ࠸࡚ࡢ⌮ㄽ໬Ꮫⓗ◊✲ࠖ ᖺ᪥ᮏ໬Ꮫ఍୰ᅜᅄᅜᨭ㒊኱఍㸦 ᖺ  ᭶ ̽ ᪥㸪࢜ࣥࣛ࢖ࣥ㸧‫   ۻ‬ᑠᯘ㸪⚟ཎ㸪㉥℩㸪┦⏣㸪⛬ࠕ̓20H ಟ㣭࡟ࡼࡿ VL51$ ࢞࢖ࢻ㙐ࡢ VHHG 㡿ᇦ࡟࠾ࡅࡿ  ࡘࡢᶵ⬟ࢻ࣓࢖ࣥࡢྠᐃࠖ➨  ᅇ᪥ᮏศᏊ⏕≀Ꮫ఍㸦 ᖺ  ᭶ ̽ ᪥㸪࢜ࣥࣛ࢖ࣥ㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ @>ۻ‬7DVXNX +RULXFKL .D]XDNL 5LNL\DPD .HQML 6DNDQD\D <XVXNH 6DQDGD .HLVXNH :DWDQDEH 0LVDNR $LGD<XNLWHUX .DWVXPRWR (IIHFW RI 0ROHFXODU :HLJKW RQ &ORXG 3RLQW RI $TXHRXV 6ROXWLRQ RI 3RO\ HWK\OHQH
R[LGH ±3RO\ SURS\OHQH R[LGH  $OWHUQDWLQJ 0XOWLEORFN &RSRO\PHU -RXUQDO RI 2OHR 6FLHQFH 69 ± '2,MRVHVV

- 79 -

㔞Ꮚከᡂศ⣔ศᏊ⌮ㄽࢆ⏝࠸ࡓỈ⣲ࢲ࢖ࢼ࣑ࢡࢫ࡜ྠ఩యຠᯝࡢ⌮ㄽⓗ◊✲Theoretical and computational study on hydrogen dynamics and its
isotope effect by using quantum multi-component molecular theories‫❧ۑ‬ᕝ ோ඾ࠊ▼ඖ Ꮥెࠊ໭ ᖾᾏࠊἙὠ ບࠊᑠᯘ ⌮ࠊ኱ሙ ඃ⏕ࠊྂᓥ ᘺ᮶ࠊ▼஭ ᱒Ꮚࠊᆏୖ ᘯ㍤ࠊụ⏣ ༟ᘺࠊྡᇛ Ⴙᩄࠊᒸ㔝 ࡉࡃࡽࠊᑿᓮ ┿ᳰ㸦ᶓ὾ᕷ
❧኱Ꮫ㸧
1

◊✲┠ⓗ
ᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣࠊᚑ᮶ࡢ➨୍ཎ⌮ィ⟬ࡔࡅ࡛ࡣᢅ࠼࡞࠸ࡼ࠺࡞⣔ࢆ◊✲ᑐ㇟࡜ࡍࡿࡓࡵ࡟ࠊỈ⣲ཎᏊ᰾ࡢ㔞Ꮚᦂࡽࡂࡸࠊ࣑࣮ࣗ࢜ࢽ࣒࢘໬ྜ≀ࠊ㝧㟁Ꮚ໬ྜ≀࡟ࡶ㐺⏝ྍ⬟࡞㔞Ꮚከᡂศ⣔ศᏊ⌮ㄽࢆ㛤Ⓨ࣭ᐇ⿦ࡋ࡚࠸ࡿࠋ≉࡟Ỉ⣲⤖ྜࡣࠊ⮬↛⏺࡛᭱ࡶ༢⣧࡞⤖ྜᵝᘧ࡛࠶ࡿ࡟ࡶ࠿࠿ࢃࡽࡎࠊ⏕య≀㉁ࡸỈ࡞࡝ᡃࠎࡢᏑᅾ࡜῝ࡃ㛵ࢃࡗ࡚࠸ࡿࠋ࡜ࡇࢁࡀࡇࡢỈ⣲⤖ྜࡢ⤖ྜཎ⌮ࡣᮍࡔ࡟୙᫂࡞㒊ศࡀከࡃࠊࡇࢀࡲ࡛࡟ࡶ୙
ྍᛮ㆟࡞⌧㇟ࡀᩘከࡃⓎぢࡉࢀ࡚࠸ࡿࠋศᏊᛶ⤖ᬗ୰ࡢỈ⣲࣭㔜Ỉ⣲⨨᥮࡟ࡼࡿᵓ㐀┦㌿⛣ᗘࡢⴭࡋ࠸ኚ

໬ࡸỈ⣲⤖ྜᵓ㐀ࡢኚ໬࡟࠾ࡅࡿ H/D ྠ఩యຠᯝࡢゎ㔘࡟ࡣࠊࣉࣟࢺࣥࡢ㔞ᏊຊᏛⓗྲྀࡾᢅ࠸ࡀ㔜せ࡜࡞ࡿࠋ౛࠼ࡤᅄゅ㓟(H2SQ: C4H2O4)⤖ᬗ࡛ࡣᖖ᫬࡟ࡣᙉㄏ㟁య࡛࠶ࡿࡀࠊ

ᗘୖ᪼࡟ࡼࡾ཯ᙉㄏ㟁య࡬࡜┦㌿⛣ࡍࡿࡇࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋH2SQ ࡢ஧ḟඖỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡ୰ࡢỈ⣲ཎᏊࡣࠊ∦᪉ࡢ㓟⣲ཎᏊ࡟⤖ྜࡋࡓᵓ㐀࠿ࡽ┦㌿⛣࡟కࡗ࡚஧ࡘࡢ㓟⣲ཎᏊࡢ୰ኸ࡟఩⨨ࡋࡓᵓ㐀࡟ኚ໬ࡍࡿࡇ࡜ࡀᐇ㦂࠿ࡽぢฟࡉࢀ࡚࠸
ࡿࠋࡲࡓࠊ⤖ᬗࢆᵓᡂࡍࡿỈ⣲ࢆ㔜Ỉ⣲࡟⨨᥮ࡋࡓ D2SQ ࡛ࡣࠊ┦㌿⛣ᗘࡀ⣙ 150K ࡶୖ᪼ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊᐇ㦂ࡢࡳ࡛ࡣỈ⣲ཎᏊࡢ᣺ࡿ⯙࠸ࢆ┤᥋ゎᯒࡍࡿࡇ࡜ࡀᅔ㞴࡛࠶ࡿࠋࡑࡢࡓࡵࠊࡇࡢ┦㌿⛣ᗘ࡟ᑐࡍࡿ H/D ྠ఩యຠᯝࡢᶵᵓゎ᫂࡟⮳ࡗ࡚࠾ࡽࡎࠊ⌮ㄽィ⟬ࢆ⏝࠸ࡓゎᯒࡀᮃࡲࢀ࡚࠸ࡿࠋ

ࡑࡇ࡛ᮏᖺᗘࡣࠊỈ⣲ࡢ㔞Ꮚຠᯝࢆྵࡵࡓ⤒㊰✚ศἲࢆ⏝࠸࡚ࠊᅄゅ㓟ࡢィ⟬ࢆᐇ᪋ࡋࡓࠋ
ࡲࡓࠊᡃࠎࡢࢢ࣮ࣝࣉࡣᛂ⏝ⓗ࡞◊✲࡜ࡋ࡚ࠊᐇ㦂ࡢࢢ࣮ࣝࣉ࡜ඹྠࡋ࡚ṑ㌴≧୧ぶ፹ᛶศᏊࡢືⓗᦂࡽࡂ࡟㛵 ࡍࡿ◊✲ ࢆ⾜ ࡗ ࡚࠸ ࡿ ࠋ ᮾ ி ኱Ꮫ ࡢ ᖹ ᒸࡽ ࡟ࡼ ࡾ ྜ ᡂࡉ ࢀࡓ ṑ ㌴ ≧୧ ぶ፹ ᛶ ศ Ꮚ (Gear-Shaped
Amphiphiles, GSA)ࡣ⁐፹ෆ࡛఍ྜࡋ⮬ᕫ⤌⧊໬ࡍࡿࡇ࡜࡛ෆ㒊࡟✵Ὕࢆᣢࡘ㉸ศᏊⓗ࡞ᵓ㐀ࢆᙧᡂࡍࡿࠋᙧ
ᡂࡉࢀࡿ㉸ศᏊⓗᵓ㐀ࡢ❧యᵓ㐀ࡣࠊཎᩱ࡜࡞ࡿࣔࣀ࣐࣮ࡢᵓ㐀ࡸ⁐፹࡟ࡼࡾ␗࡞ࡾࠊ4 㠃యࡸ 6 㠃యࡢᵓ㐀ࢆྲྀࡾ࠺ࡿࡀࠊᮏ࣏࣮ࣞࢺ࡛㏙࡭ࡿ⣔࡛ࡣࣔࣀ࣐࣮6 ศᏊ࠿ࡽ࡞ࡿ 6 㠃య࡛࠶ࡿ㸦ࡑࡢࡓࡵࠊ௨㝆ࢼࣀ࣮࢟ࣗࣈ࡜࿧⛠ࡍࡿ㸧ࠋᖹᒸࡽࡣඛ⾜◊✲࡟࠾ࡅࡿᐇ㦂࠿ࡽࠊࡑࡢ✵㛫ࡢ኱ࡁࡉࡀෆໟศᏊ࡟ࡼࡾኚ໬ࡍࡿࡇ
࡜ࢆሗ࿌ࡋ࡚࠸ࡿࠋ౛࠼ࡤ 1,3,5-ࢸࢺࣛࣈࢳ࣓ࣝࢩࢳࣞࣥ(TBM)2 ศᏊࢆෆໟࡋࡓ࡜ࡁࡣ⁐፹ࡢࡳࢆෆໟࡍࡿ
࡜ࡁ࡟ẚ࡭య✚ࡀ⭾ᙇࡋࠊ1,2,3,4,5-࣌ࣥࢱࢩ࢔ࣀࢩࢡࣟࣉࣟࣆࣝ࢔ࢽ࢜ࣥ(PCCP) 2 ศᏊࢆෆໟࡋࡓ࡜ࡁࡣ཰
⦰ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࠋయ✚ࡢኚ໬ࡣᴟࡢ࣓ࢳࣝᇶࡢ 1H NMR ࢫ࣌ࢡࢺࣝࡢኚ໬࠿ࡽᐃᛶⓗ࡟☜ㄆࡉࢀࠊ1H DOSY ゎᯒ࡟ࡼࡾᚓࡽࢀࡓᣑᩓಀᩘࢆࠊࢼࣀ࣮࢟ࣗࣈࢆఱࡽ࠿ࡢ༙ᚄࢆᣢࡘ⌫య࡜ࡋ࡚㏆ఝࡋ࢔࢖ࣥࢩࣗࢱ࢖ࣥ-ࢫࢺ࣮ࢡࢫࡢᘧࢆ㐺⏝ࡋ࡚ᚓࡽࢀࡓࠕὶయຊᏛⓗ༙ᚄࠖࡼࡾᐃ㔞ⓗ࡟⟬ฟࡉࢀࡿࠋࡑࡇ
࡛ᮏ◊✲࡟࠾࠸࡚ࡣࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸࡚య✚ኚ໬ࡢศᏊㄽⓗ࡞⌮ゎࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋලయⓗ࡟ࡣࠊෆໟศᏊࡢ␗࡞ࡿࢼࣀ࣮࢟ࣗࣈ࡟ࡘ࠸࡚ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊࡑࡢࢺࣛ
ࢪ࢙ࢡࢺࣜࢆゎᯒࡍࡿࡇ࡜࡟ࡼࡾయ✚ኚ໬ࢆィ⟬ࡋࡓࠋ- 80 -

2◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 ⤒㊰✚ศἲ࡟ࡼࡾᅄゅ㓟⤖ᬗࡢィ⟬ᙜ◊✲ᐊ࡛㛤Ⓨࡋࡓ⤒㊰✚ศศᏊືຊᏛ(PIMD)ࣉࣟࢢ࣒ࣛ࡜ࠊ➨୍ཎ⌮ィ⟬ࣉࣟࢢ࣒࡛ࣛ࠶ࡿ VASP ࢆ⏝࠸࡚ on-the-fly ࡛ィ⟬ࢆᐇ᪋ࡋࡓࠋon-the-fly PIMD ἲ࡛ࡣࠊ㸯㸬᰾ࡢ㔞Ꮚᛶࢆྂ඾⢏Ꮚࡢ㞟ࡲࡾ(ࣅ࣮ࢬ)࡜ࡋ
࡚⾲⌧ࡋࠊ㸰㸬ྂ඾⢏Ꮚ࠿ࡽ࡞ࡿศᏊ⣔ࡢィ⟬࡟ࡣ➨୍ཎ⌮ィ⟬ࢆ⏝࠸ࡿࠋึᮇᵓ㐀ࡣඛ⾜◊✲࡟࠾࠸࡚ᚓ
ࡽࢀࡓࠊTBM 2 ศᏊࢆෆໟࡋࡓࢼࣀ࣮࢟ࣗࣈࡢ X ⥺ᅇᢡࡼࡾసᡂࡋࡓࠋᐇ㦂࡜⤖ᯝࢆẚ㍑ࡍࡿࡓࡵ࡟ 1H
NMR ࢫ࣌ࢡࢺࣝࡢィ⟬࡜ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ2.2. ṑ㌴≧୧ぶ፹ᛶศᏊ࡟࠾ࡅࡿ NMR ࢫ࣌ࢡࢺࣝࡢኚ໬
య✚ኚ໬࡟ࡼࡾ 1H NMR ࢫ࣌ࢡࢺࣝࡀࢩࣇࢺࡍࡿ⌮⏤ࡣࢼࣀ࣮࢟ࣗࣈࢆᵓᡂࡍࡿࣔࣀ࣐࣮ࡢ㠃㛫㊥㞳ࡀኚ໬ࡍࡿࡇ࡜࡟ࡼࡾ࣓ࢳࣝᇶࡢ 1H ࡢ⎔ቃࡀኚ໬ࡍࡿࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࢼࣀ࢟
࣮ࣗࣈࡢ㠃㛫㊥㞳ࢆேᕤⓗ࡟ኚ໬ࡉࡏࡓ࡜ࡁࡢ 1H NMR ࡢࢫ࣌ࢡࢺࣝࡢኚ໬ࢆィ⟬ࡋࠊࢼࣀ࣮࢟ࣗࣈࡢ㠃㛫㊥㞳ࡢ㛵ಀࢆㄪ࡭ࡓࠋ1H NMR ࢫ࣌ࢡࢺࣝࡢィ⟬ࡣ Gaussian 09 D01 ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࢆ⏝࠸ࡓ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾ⾜ࡗࡓࠋ 1H NMR ࡢィ⟬࡟࠾࠸࡚ࡣࢼࣀ࣮࢟ࣗࣈ඲య࡟ᑐࡋ࡚㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗࡓࠋィ⟬ࡣHartree-Fock ἲ࡟ࡼࡾ⾜࠸ࠊᇶᗏ㛵ᩘ࡟ࡣ 6-31G(d,p)ࢆ⏝࠸ࡓࠋỈ⁐፹ࡣ㐃⥆ㄏ㟁యࣔࢹࣝࢆ⏝࠸࡚⪃៖ࡋ
ࡓࠋNMR ࢫ࣌ࢡࢺࣝࡢィ⟬ࡣ Gauge-Independent Atomic Orbital (GIAO) ἲ࡟ࡼࡾ⾜ࡗࡓࠋ
2.3 ṑ㌴≧୧ぶ፹ᛶศᏊ࡟ࡼࡾᙧᡂࡉࢀࡿࢼࣀ࣮࢟ࣗࣈࡢࢤࢫࢺศᏊ࡟ࡼࡿయ✚ኚ໬ලయⓗ࡞య✚࡟ࡘ࠸࡚ࡣศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸࡚ィ⟬ࢆ⾜ࡗࡓࠋ⣔ࡣࢼࣀ࣮࢟ࣗࣈ 1 ࡘ(ࣔࣀ࣐࣮6 ศᏊ)ࡢ࿘㎶࡟ỈศᏊࢆ㓄⨨ࡋࠊ⣔඲యࡢ㟁Ⲵࡀ୰ᛶ࡟࡞ࡿࡼ࠺࡟ሷ໬≀࢖࢜ࣥࢆ㓄⨨ࡋࡓࠋࢼࣀ࢟
࣮ࣗࣈࡢศᏊຊሙ࡟ࡘ࠸࡚ࡣ General AMBER Force Field (GAFF)ࢆ⏝࠸ࠊ㟁Ⲵࡣ Restrained ElectroStatic
Potential (RESP) charges ࢆ⏝࠸ࡓࠋỈศᏊ࡜ሷ໬≀࢖࢜ࣥࡢຊሙ࡟ࡣࡑࢀࡒࢀ SPC/E ࣔࢹࣝ࡜ AMBER
ff14SB ࢆ౑⏝ࡋࡓࠋࡑࡢᚋࠊ࢚ࢿࣝࢠ࣮Ᏻᐃ໬ࢆ⾜࠸ࠊ୍⯡໬ Langevin ᪉⛬ᘧ࡟ᇶ࡙ࡃ⇕ᾎ࡜ Berendsen ࡢᅽຊᾎࢆ⏝࠸࡚ 300 K, 1 atm NPT ࡛ࡢ NPT ࢔ࣥࢧࣥࣈࣝ࡟ᚑ࠺ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡍࡿࡇ࡜࡛ 300 K ࡛ࡢึᮇᵓ㐀ࢆᚓࡓࠋᮏィ⟬ࡣ TBM 2 ศᏊࠊ⁐፹ࠊPCCP 2 ศᏊࢆෆໟࡋࡓࢼࣀ࣮࢟ࣗࣈ࡟ࡘ࠸࡚ NVT ࢔ࣥࢧࣥࣈࣝ࡟ᚑ࠺ศ
ᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࠾࠸࡚Ỉ⣲ཎᏊࢆྵࡴ໬Ꮫ⤖ྜࡣ
SHAKE ࢔ࣝࢦࣜࢬ࣒࡟ࡼࡾ⤖ྜ㛗ࢆᅛᐃࡋࡓࠋ᫬㛫Ⓨᒎࡣ 2.0 fs ࡢ้ࡳᖜ࡛ 3.0 ns ࡟ࢃࡓࡗ࡚⾜࠸ࠊࡑࢀࡒ
ࢀࡢศᏊ࡟ࡘ࠸࡚ 20 ྂ඾㌶㐨ࡎࡘࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࠾ࡅࡿ

ᗘࡣ୍⯡໬

-1

Langevin ᪉⛬ᘧ࡟ᇶ࡙ࡃ⇕ᾎࢆ⏝࠸┠ᶆ್ࢆ 300 K ࡟タᐃࡋࡓࠋ⇕ᾎࡢ⾪✺㢖ᗘࡣ 1.0 ps ࡜ࡋࡓࠋ

3

◊✲ᡂᯝ

3.1 ⤒㊰✚ศἲ࡟ࡼࡾᅄゅ㓟⤖ᬗࡢィ⟬
ᅄゅ㓟⤖ᬗࡣᅗ 1 ࡟♧ࡍࡼ࠺࡞᭷ᶵᛶ⤖ᬗ࡛࠶ࡾࠊ஧ḟඖࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࢆᙧᡂࡋ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ≉࡟
H2SQ ࡟࠾ࡅࡿ㓟⣲࣭㓟⣲㛫㊥㞳ࠊ㓟⣲࣭Ỉ⣲㛫㊥㞳࡜࠸ࡗࡓỈ⣲⤖ྜᵓ㐀࡟╔┠ࡋࠊH2SQ ࡜ D2SQ ࡟࠾ࡅࡿྠ఩యຠᯝ࡟
ࡘ࠸࡚ゎᯒࡋࡓࠋ
ᅗ㸯㸬ᅄゅ㓟⤖ᬗ࡜Ỉ⣲⤖ྜ㒊ศࣃ࣓࣮ࣛࢱ

- 81 -

PIMD ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡓ㓟⣲࣭㓟⣲㛫㊥㞳ࠊ㓟⣲࣭Ỉ⣲㛫㊥㞳ࡢ஧ḟඖศᕸࢆᅗ 2 ࡟♧ࡍࠋࡇࡢ⤖ᯝ࠿ࡽࠊỈ⣲⤖ྜ㛗ࡣ D2SQ ࡢ࡯࠺ࡀࡼࡾ኱ࡁࡃኚ໬ࡍࡿഴྥ࡟࠶ࡿࡇ࡜ࡀ
ศ࠿ࡗࡓࠋࡲࡓࠊỈ⣲࣭㔜Ỉ⣲ཎᏊ࡟ࡘ࠸࡚ࡣࠊỈ⣲⤖ྜࡢ୰ኸ㒊ศ࡟࠾࠸࡚㐪࠸ࡀࡳࡽࢀࡿࡶࡢࡢࠊࡑࡢヲ⣽࡟ࡘ࠸࡚ࡣᘬࡁ⥆ࡁࠊ኱つᶍ࠿ࡘ㛗᫬㛫࡞ PIMD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ
ᐇ⾜ࡀ୙ྍḞ࡛࠶ࡿࠋᅗ 2㸬H2SQ(ᕥ)࡜ D2SQ(ྑ)ࡢỈ⣲⤖ྜ㊥㞳(ROO)࡜Ỉ⣲఩⨨(GH/D)࡟࠾ࡅࡿ஧ḟඖศᕸ

3.2. ṑ㌴≧୧ぶ፹ᛶศᏊ࡟࠾ࡅࡿ NMR ࢫ࣌ࢡࢺࣝࡢኚ໬
య✚ࢆኚ໬ࡉࡏࡓ࡜ࡁࡢ 3 ࡘࡢ࣓ࢳࣝᇶࡢ 1H NMR ࢫ࣌ࢡࢺࣝ
ࡢኚ໬ࢆᅗ 3 ࡟♧ࡋࡓࠋᶓ㍈ࡣᐇ㦂࡟࠾ࡅࡿయ✚ࢆ 1 ࡜ࡋࡓ࡜ࡁ
ࡢ┦ᑐⓗ࡞య✚࡛࠶ࡿࠋ3 ࡘࡢ࣓ࢳࣝᇶࡢỈ⣲ࡢ໬Ꮫࢩࣇࢺࡣᖹ
ᆒࡋ࡚♧ࡋ࡚࠸ࡿࠋయ✚ࡀ኱ࡁࡃ࡞ࡿ࡟క࠸໬Ꮫࢩࣇࢺࡣ୍ᐃࡢ
್࡟཰᮰ࡍࡿ୍᪉ࠊయ✚ࡀ 1.0 ࡢ࠶ࡓࡾ࡛໬Ꮫࢩࣇࢺࡀ኱ࡁࡃኚ
໬ࡋ࡚࠸ࡿࠋ໬Ꮫࢩࣇࢺࡢᐇ㦂್࡟┦ᙜࡍࡿ┦ᑐయ✚ࢆᅗ 1 ࡢࢢࣛࣇࢆ⏝࠸࡚ồࡵࡓ࡜ࡇࢁࠊᮍෆໟࣔࢹ࡛ࣝࡣ 1.5ࠊTBM ෆໟࣔᅗ 3. NMR ࢫ࣌ࢡࢺࣝࡢయ✚౫Ꮡᛶࢹ࡛ࣝࡣ 1.6 ࡛࠶ࡗࡓࠋ

3.3. ṑ㌴≧୧ぶ፹ᛶศᏊ࡟ࡼࡾᙧᡂࡉࢀࡿࢼࣀ࣮࢟ࣗࣈࡢࢤࢫࢺศᏊ࡟ࡼࡿయ✚ኚ໬ᣑᩓಀᩘ࠿ࡽ⟬ฟࡋࡓయ✚ࢆ⾲ 1 ࡟♧ࡍࠋᣑᩓಀᩘ࠿ࡽ⟬ฟࡋࡓయ✚ࡣᐇ㦂್࡜ྠࡌ࣮࢜ࢲ࣮࡛࠶ࡾࠊᐇ
㦂್ࢆᐃᛶⓗ࡟ࡣ෌⌧࡛ࡁࡓ࡜⪃࠼ࡽࢀࡿࡶࡢࡢࠊᐇ㦂್ࡢయ✚ࡢᐃ㔞ⓗ࡞㐪࠸ࢆ෌⌧ࡍࡿࡇ࡜ࡣ࡛ࡁ࡞࠿
ࡗࡓࠋࡑࡢ⌮⏤ࡢ 1 ࡘ࡜ࡋ࡚ᐦᗘࡢ㐪࠸ࡀ⪃࠼ࡽࢀࡿࠋᮏ◊✲࡟࠾࠸࡚ࡣ TBM ෆໟࢼࣀ࣮࢟ࣗࣈࡢࢩ࣑ࣗ
࣮ࣞࢩࣙࣥ࡟࠾ࡅࡿᐦᗘࡣ 1.00 g cm-3ࠊࡑࢀ௨እ࡛ࡣ 1.01 g cm-3 ࡛࠶ࡾࠊࢩ࣑࣮ࣗࣞࢩࣙࣥୖࡢᐦᗘ࡟ࡣ࡯
࡜ࢇ࡝ኚ໬ࡀฟ࡚࠸࡞࠸ࠋィ⟬࡟౑⏝ࡋࡓࢫࢼࢵࣉࢩࣙࢵࢺࡢ㑅ࡧ᪉࡟ࡼࡾᣑᩓಀᩘࡢ┦ᑐⓗ࡞㛵ಀࡢ෌⌧࡟༑ศ࡞⢭ᗘࡀᚓࡽࢀ࡞࠿ࡗࡓ࡜⪃࠼ࡽࢀࡿࠋࡲࡓ⾲ 1 ࡟࠾࠸࡚ᐇ㦂್ࡣయ✚࡛⾲グࡋ࡚࠾ࡾࠊࡑࡢ᭱኱್
ࡣ 24,000 Å3ࠊ᭱ᑠ್ࡣ 11,500 Å3 ࡛࠶ࡿࠋࡇࢀࡽࡢẚࡣ 2.09 ࡛࠶ࡿࠋࡋ࠿ࡋࠊࡇࢀࢆὶయຊᏛ༙ᚄ࡛᭩ࡁ┤ࡍ࡜ࡑࢀࡒࢀ 17.9 Å ࡜ 14.0 Å ࡛࠶ࡾࠊࡑࢀࡽࡢẚࡣ 1.28 ࡛࠶ࡿࠋࡘࡲࡾࠊ༙ᚄࡢẚࡢෆໟศᏊ࡟ᑐࡍࡿ౫
Ꮡᛶࡣయ✚ࡼࡾࡶᑠࡉࡃࠊィ⟬ࡢㄗᕪࡢ࡯࠺ࡀ኱ࡁࡃ࡞ࡗ࡚ࡋࡲࡗࡓ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࠊศᏊືຊᏛ࡟
࠾ࡅࡿ⤒㦂ⓗ࡞ࣃ࣓࣮ࣛࢱ࡟ࡼࡗ࡚ࠊศᏊ㛫ࡢ┦஫స⏝ࡀᐇ㦂࡜ࡣ␗࡞ࡿഴྥࢆᣢࡕࠊᐇ㦂ࡢయ✚ࢆ෌⌧࡛ࡁ࡞࠿ࡗࡓྍ⬟ᛶࡶ࠶ࡿࠋࡲࡓᖹ⾜භ㠃య㏆ఝ࡛ࡣᐇ㦂್࡟ẚ࡭య✚ࡀ 1 ᱆ᑠࡉࡃ࡞ࡗ࡚࠸ࡿࠋ୍᪉⌫య㏆ఝ࡛ࡣᣑᩓಀᩘ࠿ࡽ⟬ฟࡋࡓయ✚ࡸᐇ㦂್࡟㏆࠸್࡜࡞ࡗ࡚࠾ࡾࠊὶయຊᏛ༙ᚄ࡟ࡼࡾồࡵࡽࢀࡓయ✚ࡣእ᥋⌫ࡢయ✚࡟┦ᙜࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ⌫య㏆ఝ࡛ᚓࡽࢀࡓయ✚࡟ὀ┠ࡍࡿ࡜ࠊෆໟศᏊ࡟ࡼࡿయ✚ኚ໬ࡀ࡯࡜ࢇ࡝ぢࡽࢀ࡞࠸ࠋࡇࡢࡇ࡜࠿ࡽὶయຊᏛ༙ᚄࡣእ᥋⌫ࡢ༙ᚄ࡜ࡣ㐪࠺ᴫᛕ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋ
௒ᚋࡢㄢ㢟࡜ࡋ࡚ࡣࠊึᮇᵓ㐀ࡢ㑅ᢥࡸศᏊຊሙࡢࣃ࣓࣮ࣛࢱࢆኚ᭦ࡋ࡚ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
ࡢᐇ⾜ࡀᣲࡆࡽࢀࡿࠋ

⾲ 1. ᣑᩓಀᩘ࠿ࡽ⟬ฟࡋࡓయ✚

TBM
ᮍෆໟ
PCCP

ᣑᩓಀᩘ࠿ࡽ⟬ฟࡋࡓయ✚(Å3)
20,29433,343
26,249ᖹ⾜භ㠃య㏆ఝ࠿ࡽ⟬ฟࡋࡓయ✚(Å3)
2,955
3,002
3,010

- 82 -⌫య㏆ఝ࠿ࡽ⟬ฟࡋࡓయ✚(Å3)
17,833
18,564
18,164ᐇຠయ✚ࡢᐇ㦂್(Å3)
24,00014,00011,5004ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] Nuttapon Yodsin, Hiroki Sakagami, Taro Udagawa, Takayoshi Ishimoto, Siriporn Jungsuttiwong, and Masanori
Tachikawa, "Metal-doped carbon nanocones as highly efficient catalysts for hydrogen storage: Nuclear quantum
effect on hydrogen spillover mechanism", Molecular Catalysis, 504, 111486 (10 pages) (2021). DOI:
doi.org/10.1016/j.mcat.2021.111486[2] ‫ۻ‬Hiroki Sakagami, Masanori Tachikawa, and Takayoshi Ishimoto, "Theoretical study of the H/D isotope effect of
CH4/CD4 adsorption on a Rh(111) surface using a combined plane wave and localized basis sets method", RSC
Advances, 11, 10253-10257 (2021). DOI: 10.1039/D0RA10796D[3] Kazuaki Kuwahata and Masanori Tachikawa, "Nuclear quantum effect on the geometry of NH4+(H2O)", Bull.
Chem. Soc. Jap., 93, 1558-1563 (2020). DOI: doi.org/10.1246/bcsj.20200120[4] ‫ۻ‬Shumpei Ito, Daisuke Yoshida, Yukiumi Kita, and Masanori Tachikawa, "First-Principles Quantum Monte Carlo
Studies for Prediction of Double Minima for Positronic Hydrogen Molecular Dianion", J. Chem. Phys., 153,
224305 (6 pages) (2020). DOI: doi.org/10.1063/5.0022673[5] Haruya Suzuki, Takuma Otomo, Ryusei Iida, Yutaro Sugiura, Toshiyuki Takayanagi, and Masanori Tachikawa,"Positron binding in chloroethenes: Modeling positron-electron correlation-polarization potentials for molecular
calculations", Phys. Rev. A, 102, 052830 (9 pages) (2020). DOI: doi.org/10.1103/PhysRevA.102.052830[6] Yutaro Sugiura, Toshiyuki Takayanagi, Masanori Tachikawa, "Theoretical calculation of positron annihilation
spectrum using positron-electron correlation-polarization potential", Int. J. Quant. Chem., 120, e26376 (5 pages)(2020). DOI: doi.org/10.1002/qua.26376[7] ‫ ۻ‬Haruki Funahashi, Masanori Tachikawa, and Taro Udagawa, "Determining if reaction selectivity can becontrolled by the H/D isotope effect in CH...O interactions", Org. Lett., 22, 9439-9443 (2020). DOI:
doi.org/10.1021/acs.orglett.0c03351[8] ‫ ۻ‬Hiroki Sakagami, Masanori Tachikawa, and Takayoshi Ishimoto, "Hydrogen/deuterium adsorption andabsorption properties on and in palladium using a combined plane wave and localized basis set method", Int. J.
Quant. Chem., 120, e26275 (5 pages) (2020). DOI: doi.org/10.1002/qua.26275[9] Yutaro Sugiura, Haruya Suzuki, Takuma Otomo, Takaaki Miyazaki, Toshiyuki Takayanagi, and Masanori
Tachikawa, "Positron-electron correlation ̺ polarization potential model for positron binding in polyatomic
molecules", J. Comput. Chem., 41, 1576-1585 (2020). DOI: doi.org/10.1002/jcc.26200[10] ‫ۻ‬Osamu Kobayashi, Kunihiro Noda, Naohiko Ikuma, Dai Shiota, Takayoshi Ishimoto, and Masanori Tachikawa,"Experimental and Computational Analyses of the Oxidation Mechanism of the Poly (arylsilane) Family as theSide Reaction During the Baking Process", J. Phys. Chem. C, 124, 16149-16158 (2020). (Cover Image) DOI:
doi.org/10.1021/acs.jpcc.0c02416[11] ‫ۻ‬Yusuke Ishida, Haruki Funahashi, Masanori Tachikawa, and Taro Udagawa, "Geometrical H/D Isotope Effect ofBlue-shifting Dihydrogen-bonded Clusters", Chem. Lett., 49, 745-748 (2020). DOI: doi.org/10.1246/cl.200198[12] Rathawat Daengngern, Osamu Kobayashi, Nawee Kungwan, Chanisorn Ngaojampa, and Masanori Tachikawa,"Nuclear quantum and H/D isotope effects on three-centered bonding diborane: Path integral molecular dynamics
simulations", Int. J. Quant. Chem., e26179 (2020). DOI: doi.org/10.1002/qua.26179[13] ‫ۻ‬Kuniaki Ono, Takayuki Oyamada, Yukiumi Kita, and Masanori Tachikawa, "Theoretical analysis of the bindingof a positron and pair-annihilation in fluorinated benzene molecules", Eur. Phys. J. D, 74, 1-8 (2020). DOI:
doi.org/10.1140/epjd/e2020-100538-3[14] Yusuke Kanematsu, Hiroyuki S Kato, Shinya Yoshimoto, Akira Ueda, Susumu Yamamoto, Hatsumi Mori, Jun
Yoshinobu, Iwao Matsuda, and Masanori Tachikawa, "A computational examination of the electric-field-induced
proton transfer along the interface hydrogen bond between proton donating and accepting self-assembled
monolayers", Chem. Phys. Lett., 741, 137091 (4 pages) (2020). DOI: doi.org/10.1016/j.cplett.2020.137091- 83 -



Simulation of chemical reactions of complex molecular system) $,

Akilesh Sharma *

(

'!

+

1 !w/AE9 ( Õ ^t¨Ã®Y|§:GRRM(Global Reaction Route Mapping)x)Uh·g^t#O­uUhOZi^tt^tHÖM#Î¢vÍ#-7A.
E %^t#ÏyuÂ)¿%'"·g#­uUh»¸{Ó)´T )'ÈSÙ¼ÂO)¡Uh £W)P('SÙ¼ÂO(Aggregation induce emission: AIE)p°ÛOu¯¦ SÙ$&Ou)z$'Á' Á)¶'!p°HÛOu'SÙ$&O)¡$')¾($ ( QÐÅ} SÙ$¤MØk ('AIE \c¬%('+=A8*2;@<E HGµVÍ"O'Uh e %" (z ('L² AIE Uh'45?8,6A-3BD(TPE)_8,6AdbÅ

AIE Â'½ ( FÈIÒ©`bÅÒ³'{ ('[1](%)Ä IÒ©`bÅ)0D5CEAµ23A:D¼
nMUh»¸)± XÂv9C5D¢YÞESIPTß)Â rÆbÅ)Â Çmf)Â Uh' K\GUR[\SKHQ\OEHQ]RWKLD]ROH +%7  ¹"±2 !&"XÂvla)j 'ÇmfRÔJoÈNÂ &# RÔJoªÊv&[Ñ«Y×ºÉ%Spin-Flip TDDFT #e]~Y)XÂv;4D1>A-7A.EÜ)¸¥¸¥ (;4D1>A-7A.EÜ%ÇmfÂ &#juÀ¿'RÔJo®MÝ #^t¨ÃËH'Î¢v ÇmfÌq)sK 'Úhv
¸¥ GAMESS US )

3 ! SÙ¼ÂO)¡mr23A:DUhÇmf¨Ã¶kw&0$&SÙ¼ÂO(AIE)\ £)  (  £$&Çmf HÂ &# SÙfÂ &(($Uh»¸{Ó

'$
D BW)(RÔJo GÇmf¨Ã

c|'23

A:D)" AIE ¯¦)Õ' ){&";¡$23A:DÇmfIÒ©`bÅ$& twisted pyramid =RÔJo.' $&Â ' BW:DDx

D¢Y'!UhIÒ©`bÅ)

/Z'SÙ'vEÇmfÂ- 84 -%(#¬%('!

&#

)»¸'





'¬%

('&!¬I) IÒ©`bÅq)
mr$&¾b'++y(mr23A:DÇmf¨Ã)¾'µ AIE ¯¦ »¸ 'QRQUDGLDWLYHGHFD\¬IÒ©`8)mr BST[n]Uh)¬o

DEV IOXRUHVFHQFH

Çmf¨Ã)¾Uh V<'$[ (' BST[5]IÒ©` bÅ% 
Ç

 1 

mf Â & [j (s8B"  $#

1A BST[7]3Y> R!mr ('Çmf3­'$[GBST[5]RÔJo8?D0DDvÞUh

O72Í)BÚhXÂvßs 40kJ/mol "Ý $;4
D1>A-7A.EÜ?`ÇmfÌqjOÌqj$&"&K[j(' &ÝOh2w hY ('FBST[6]RÔJo&) XÂv

 2 !

FjÍ$& 43kJ/mol "Ý"8?D
0DDv$&" 11kJ/mol )-7A.E
&Çmf'q}wÂ¡:'s BST[7]

BST[6]$&")%RÔJo

'

)





BST[5],BST[6]s8?D0DDv Ý-7A.E'  9x ÚhPÜu)"

'i'¬'Ý8?D0DDv)RÔJo
%"Çmf)Â

#

BST[7]Hh2w

'!

)[j

 3 

   (' :DDx¢YSÙfÂ &
% '$[ (   AIE u)¡:'&!¸¥©l)*&0$&+5 £)±'jMDK %/AE9$&`\uj±(G BST[7]} AIE u)¡BST[6]"HT O'"SÙfO@V ´%(BST[5] SÙf#E2 VO)¡ (%Uh"OGC>&¯¦]%
'O

3O>

+X)R'$C29@D/)¨'!+X

^U  !'©lBPST[7]µ AIE ¯¦)`o«}d)nP'  %'vuaB 3­& (" £)!'- 85 - XÂv9C5D¢Y$&IÒO)¡ HBT Uh¶k
K\GUR[\SKHQ\OEHQ]RWKLD]ROH +%7  XÂv9C5D¢YÞ(6,37ß)Â UhF'(6,37)Â OUh25E2185ÞÍBZ$'OBZß D !%Uh$',72)Â %  Oh2w)6!'!-'È+%7 n«}d)('7<3'£±(7<3{{sDOOh2w!d } ( ("SÙ¼ÂO   '+%7$¼nMÇmf¨Ã)¾Uh»¸{Ó)}¤+%7 -36A«} +%7 -7A.E9C8*A";$'«} +%7 p°HT O Oh2w &" © V O' Oh2w &! (" NHWR =%ONL ('¸¥ (^t9C8*A)´'(6,37 A )NHWR =Í&#  %r && ÆbÅA")!Çmf&#½ 'F`\ (-36A«} +%7 «} +%7 s' && ÆbÅA Ý 'Þ(" N-PRO qHe%('ß-36A«} +%7H aqOh2wO)¡«}dt  && ÆbÅA B
ZÇmfÌqj)j'  
S

S
N

N
OH

6

回転障壁小




無輻射失活




6



6

回転障壁大





 




OH

無輻射失活



6

keto 発光



 

 

keto 発光 4. HBT    

3K&&+%7 J"5qÀ¿)±-36A«} +%7  +X^U O'v)FjZ{JbÅA) 
'  ¡: (! %+X)^U 3K&&+%7  -36A«} +%7$&"ÝOh2w hY ('G
H aq-36A«} +%7 $&"%D'¸¥ (-7A.E9C8*A && ÆbÅrpKÍ  z_RÔJo- 86 -

   

  

.' ?`ÇmfÌqRÔJoÝ $ '3K&&+%7  +X^U$&8?D0DDv «} +%7 #-36A«} +%7 s" &©l{JRÔJo ! '¶'%«}d)z«} +%7 " £)! &&& bÅA«}dÚhtSuÖ{×#4Ag1l)¾'4 %#

 15 bUh~i¹¿'(2021 Q 9 g)²$j

5 #

([WHQGHGFRQMXJDWLRQRI(6,37W\SHGRSDQWVLQQHPDWLFOLTXLGFU\VWDOOLQHSKDVHIRUHQKDQFLQJIOXRUHVFHQFH
HIILFLHQF\DQGDQLVRWURS\Wanying Zhang, Satoshi Suzuki, Tsuneaki Sakurai, Hiroyuki Yoshida, Yusuke Tsutsui, Masanori Ozaki and Shu Seki
Phys. Chem. Chem. Phys., 2020, 22, 28393-28400
Principles of Aggregation-Induced Emission: Design of Deactivation Pathways for Advanced AIEgens andApplications
Satoshi Suzuki, Shunsuke Sasaki, Amir Sharidan Sairi, Riki Iwai, Ben Zhong Tang, Gen-ichi Konishi
Angew.Chem. Int. Ed. 2020, 59,9856–9867
Bridged Stilbenes: AIEgens Designed via a Simple Strategy to Control the Non-radiative Decay Pathway
Riki Iwai, Dr. Satoshi Suzuki, Dr. Shunsuke Sasaki, Amir Sharidan Sairi, Prof.Dr. Kazunobu Igawa, Prof.Dr.
Tomoyoshi Suenobu, Prof.Dr. Keiji Morokuma, Prof.Dr. Gen-ichi Konishi
Angew.Chem. Int. Ed. 2020, 59,10566-10573
A DFT Study on FeI/FeII/FeIII Mechanism of the Cross-Coupling between Haloalkane and Aryl Grignard Reagent
Catalyzed by Iron-SciOPP Complexes.
Sharma, A.K.; Nakamura, M. Molecules 2020, 25, 3612

- 87 -

」㞧ศᏊ⣔࡟࠾ࡅࡿࢸࣛ࣊ࣝࢶᖏ࠿ࡽ㉥እ㡿ᇦ࡟࠾ࡅࡿࢫ࣌ࢡࢺࣝゎᯒ
6SHFWUDO$QDO\VLVIURP7HUDKHUW]WR0LG,QIUDUHG5HJLRQRQ&RPSOH[6\VWHPVᐩỌ ᆂ௓㸦⚄ᡞ኱ᏛศᏊࣇ࢛ࢺࢧ࢖࢚ࣥࢫ◊✲ࢭࣥࢱ࣮㸧 ◊✲┠ⓗࢸࣛ࣊ࣝࢶᖏ㸦7+] FP㸧࠿ࡽ㉥እ㡿ᇦ㸦FPaFP㸧࡟࠾ࡅࡿ࿘ἼᩘᖏࡣࠊศᏊ⣔ࡢศᏊෆ࠾ࡼࡧศᏊ㛫᣺ື࣮ࣔࢻ࡟┦ᙜࡋࠊỈ⣲⤖ྜᛶᾮయࡸ⁐ᾮࠊࡲࡓࢱࣥࣃࢡ㉁ࠊᑟ㟁ᛶ㧗ศᏊ➼ࡢ」㞧ศᏊ⣔࡟࠾ࡅࡿືⓗᣲືࡸᒁᡤᵓ㐀ࠊศᏊ㛫ࡢ┦஫స⏝➼ࢆ⌮ゎࡍࡿ࠺࠼࡛㔜せ࡞࿘Ἴᩘᖏ࡛࠶ࡿࠋ⏦ㄳ⪅ࡢࢢ࣮ࣝࣉ࡛ࡣࠊ᫬㛫㡿ᇦࢸࣛ࣊ࣝࢶศගࡸ᫬㛫ศゎࢸࣛ࣊ࣝࢶศගࠊࡲࡓ  ḟඖ᣺ືศගࠊ࣓࢞࣊ࣝࢶ࠿ࡽ㐲㉥እ㡿ᇦ࡟ࢃࡓࡿᗈᖏᇦㄏ㟁ศග➼ࢆ⏝࠸࡚ࠊࡇࢀࡽࡢ」㞧ศᏊ⣔࡟㛵ࡍࡿศගᏛⓗ࡞◊✲ࢆ᥎㐍ࡋ࡚࠸ࡿࠋ
ᮏ◊✲ㄢ㢟࡛ࡣࠊࡇࢀࡽࡢᐇ㦂⤖ᯝ࠿ࡽᐃ㔞ⓗ࡞᝟ሗࢆᚓࡿࡓࡵ࡟ࠊ኱ᆺィ⟬ᶵࢆ⏝࠸ࡓ⢭ᐦィ⟬ࢆ⾜࠺ࠋලయⓗ࡟ࡣ௨ୗࡢࢸ࣮࣐ࢆ⾜ࡗࡓࠋ㸬 ஧ḟඖ᣺ືศගࢫ࣌ࢡࢺࣝࡢゎᯒ㸹Ỉ⁐ᾮ୰࡟࠾ࡅࡿ࢝ࣝ࣎ࢽࣝ໬ྜ≀ࡢ &2 ఙ⦰᣺ືࡢ㑄⛣᣺ືᩘࡢᦂࡽࡂࢆホ౯ࡋࡓࠋᅗ  ࡟♧ࡋࡓ⁐㉁ศᏊ࡟

ࡘ࠸࡚ࠊィ⟬ࢆ⾜ࡗࡓࠋ㸬 ⬡㉁஧㔜⭷ࡢࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࡢゎᯒࠋ
'03*

'LP\ULVWR\OVQJO\FHURSKRVSKRUDFᅗ 㸬࢝ࣝ࣎ࢽࣝ໬ྜ≀ࡢศᏊᵓ㐀ࠋ

JO\FHURO  6RGLXP 6DOWࠊᅗ 㸧ࡢࢸࣛ࣊ࣝࢶࢫ
࣌ࢡࢺࣝࡢィ⟬ࢆ⾜ࡗࡓࠋ௨ୖ࡟ࡘ࠸࡚ࠊྛ㡯┠࡟ࡘ࠸࡚㏙࡭ࡿࠋ ◊✲᪉ἲࠊィ⟬᪉ἲᅗ 㸬'03* ࡢศᏊᵓ㐀ࠋ஧ḟඖ᣺ືศගࢫ࣌ࢡࢺࣝࡢゎᯒ㸹ᮏ◊✲࡛ࡣࠊᅗ  ࡟♧ࡋࡓ⁐㉁ศᏊ࡟ࡘ࠸࡚ࠊ%/<3* GISG࡛ࣞ࣋ࣝ *DXVVLDQ ࡟ࡼࡿᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ⣙  ಶࡢ 7,33 ỈศᏊࢆ⏝࠸࡚Ỉ࿴ࡋࡓ⣔ࢆ෌⌧ࡍࡿࡇ
࡜࡛ࠊ$0%(5 ࡟ࡼࡿศᏊືຊᏛィ⟬ࢆ⾜ࡗࡓࠋ ᮏ◊✲࡛ࡣࠊ⁐㉁ࡢ㑄⛣᣺ືᩘࢆ㔞ᏊຊᏛⓗ࡟ồࡵࡿࡓࡵࠊ&KR ࡽࡀ♧ࡋࡓ 9LEUDWLRQDO6WDUNVKLIW ἲࢆ㐺⏝
ࡋࡓ>@ࠋᮏᡭἲ࡛ࡣࠊ*DXVVLDQ ࡟ࡼࡿᇶ‽᣺ືゎᯒ࠿ࡽᚓࡽࢀࡓ᣺ືᩘZ I ࡜ࠊࢺࣛࢪ࢙ࢡࢺ࣮ࣜ୰࡟࠾
ࡅࡿ⁐፹ศᏊ࡟ࡼࡾㄏ㉳ࡉࢀࡓ⁐㉁ࡢ M ␒┠ࡢ┦஫స⏝Ⅼ࡛ࡢ㟁఩࣏ࢸࣥࢩࣕࣝIM ࢆ⤖ࡧ௜ࡅࡿ OM ࣃ࣓࣮ࣛࢱ
ࢆ௨ୗࡢᘧ  ࡼࡾỴᐃࡍࡿࠋ



'Z Z I  Z I



1VROX

¦ O MI M
M 

ZLWK

1VROX

¦O

M





M 

ࡇࡇ࡛ࠊZ I  ࡣ⁐㉁༢య࡛ࠊ┿✵୰࡛ DELQLWLR ィ⟬ࢆ⾜ࡗࡓ㝿ࡢ್࡛࠶ࡿࠋᮏ◊✲࡛ࡣ┦஫స⏝Ⅼࡣ + ཎᏊࢆ㝖ࡃ඲࡚ࡢཎᏊࡢ୰ᚰ࡜ࡋࡓࠋࡲࡓࠊ㑄⛣᣺ືᩘ࡟ᙳ㡪ࢆཬࡰࡍỈศᏊࡢᣲື࡟ࡘ࠸᳨࡚ウࢆ⾜࠺ࡓࡵࠊỈศᏊࡢỌஂ཮ᴟᏊ࡜⁐㉁ࡢ㑄⛣཮ᴟᏊࡢ㓄ྥࡢ┦㛵ࢆ௨ୗࡢᘧ  ࠿ࡽồࡵࡓࠋ- 88 -



J U

1U

PM

M

1U

PVROX  ¦J M UM U

ࡇࡇ࡛ࠊPVROX ࡜PM ࡣつ᱁໬ࡉࢀࡓ㑄⛣཮ᴟᏊ࠾ࡼࡧỈࡢỌஂ཮ᴟᏊ࡛࠶ࡾࠊ«!ࡣ࢔ࣥࢧࣥࣈࣝᖹᆒࢆ⾲
ࡍࠋJM UMU ࡣỈศᏊ M ࡢ㓟⣲ཎᏊ࡜⁐㉁ࡢ &2 ᇶࡢ୰Ⅼ࡜ࡢ㊥㞳 UM ࡀ UíႲUMUႲ ࡢ࡜ࡁ  ࡜ࡋࠊࡑࢀ௨እ࡛ࡣ  ࡜ࡍࡿ㛵ᩘ࡛࠶ࡿࠋ1U ࡣྛ U ࡟ࡘ࠸࡚ JM UMU   ࢆ‶ࡓࡍࠊཌࡉ Ⴒ ࡢ༙ᚄ U ࡢ⌫Ẇෆ࡟Ꮡᅾࡍ
ࡿỈศᏊࡢಶᩘ࡛࠶ࡿࠋ
ࢸࣛ࣊ࣝࢶศග㸸ࢸࣛ࣊ࣝࢶᖏࡢ᣺ືࢫ࣌ࢡࢺࣝࡢィ⟬࡛ࡣࠊᅛయᐦᗘỗ㛵ᩘἲࢆ⏝࠸ࡓࡀࠊ&5<67$/ࢆ౑⏝ࡋࡓࠋ⤖ᬗࡢ୪㐍ᑐ⛠ᛶࢆ⪃៖ࡍࡿࡓࡵ࡟࿘ᮇቃ⏺᮲௳ࢆ᥇⏝ࡋࡓࠋỗ㛵ᩘ࡜ࡋ࡚ࠊ*ULPPH ࡢศᩓຊࢆ⪃៖ࡋࠊ3%(' ࢆ⏝࠸ࡓࠋᇶᗏ㛵ᩘ࡜ࡋ࡚ * GS  ࢆ⏝࠸ࡓࠋᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ᣺ືᩘィ⟬ࢆ⾜ࡗࡓࠋ ◊✲ᡂᯝ ஧ḟඖ᣺ືศගࢫ࣌ࢡࢺࣝࡢゎᯒ㸹ᮏ◊✲࡛ᚓࡽࢀࡓ OM ࣃ࣓࣮ࣛࢱࢆ⾲  ࡟♧ࡍࠋࡇࡇ࡛ࡣࠊ&2 ᇶ࿘㎶ࡢ ␒㸦ᅗ 㸧ࡢ್ࢆ♧ࡍࠋ࡞࠾ࠊ໬ྜ≀ D ࡜ G ࡣ &2 ᇶ࡟ᑐࡋ࡚࡯ࡰᑐ⛠࡞ᵓ㐀ࢆࡋ࡚࠸ࡿࡓࡵࠊ ࡜  ␒ࡢ್ࡣྠࡌ࡛࠶ࡿ࡜ࡋࡓࠋ
⾲ ࢝ࣝ࣎ࢽࣝ໬ྜ≀ D  G ࡢ OM ࣃ࣓࣮ࣛࢱ㸦íH㸧,QGH[ DWRPLFW\SH 

D

E

F

G

 & 









 & 

í

í

í

í

 2 

í

í

í

í

 & 









⁐㉁ࡢศᏊࢧ࢖ࢬࡀ኱ࡁࡃ࡞ࡿ࡟ࡘࢀࠊ&2 ᇶ࡟࠾ࡅࡿ್࡛࠶ࡿ  ␒ࡢ⤯ᑐ್ࡀቑຍࡋࠊ ␒ࡢ⤯ᑐ್ࡀῶᑡࡋࡓࠋࡇࢀࡣࠊ␯Ỉᛶᇶୖ࡟ᏑᅾࡍࡿỈศᏊࡀ᣺ືᩘࢩࣇࢺ࡟ᙉ࠸ᙳ㡪ࢆཬࡰࡍࡇ࡜ࢆ♧၀ࡍࡿࠋ␯Ỉᛶ
ᇶ࿘㎶࡟ᏑᅾࡍࡿỈศᏊࡣࠊ❧య㞀ᐖ࡟ࡼࡾࡑࡢᅇ㌿㐠ືࡀᢚไࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ>@ࠋ≉࡟ࠊ໬ྜ≀ G ࡣᮏ◊✲࡛ᢅࡗࡓ⁐㉁ࡢ୰࡛᭱ࡶ␯Ỉᛶᇶࡀ኱ࡁࡃࠊⰾ㤶⎔ࡢS㟁Ꮚ࡟ࡼࡗ࡚ືࡁࡀᢚไࡉࢀࡓỈศᏊࡀ᭱ࡶከࡃᏑᅾࡍࡿ࡜⪃࠼ࡽࢀࡿࠋࡼࡗ࡚ࠊ⁐㉁ࡢศᏊࢧ࢖ࢬ࡟క࠺ OM ࣃ࣓࣮ࣛࢱࡢኚ㑄࡟ࡣࠊⰾ㤶⎔ୖ࡟ᏑᅾࡍࡿᢚไࡉࢀࡓỈศᏊࡢᣲືࡀ཯ᫎࡉࢀ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡓࠋࡲࡓࠊᮏ◊✲࠿ࡽᚓࡽࢀࡓ OM ࣃ࣓࣮ࣛࢱ
ࢆ⏝࠸࡚㑄⛣᣺ືᩘࡢ᣺ືᩘᦂࡽࡂࡢ᫬㛫┦㛵㛵ᩘ㸦))7&)㸧ࢆィ⟬ࡋࡓ⤖ᯝࠊ඲࡚ࡢ⁐㉁࡟ࡘ࠸࡚aSV ࡢ
ῶ⾶ࡢ᫬ᐃᩘࡀᚓࡽࢀࡓࠋࡋ࠿ࡋࠊ஧ḟඖ᣺ືศග ᐃࡼࡾࠊ໬ྜ≀ G ࡛ࡣ㔜Ỉ୰࡟࠾࠸࡚aSV ࡜࡞ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࡢ஋㞳ࡢཎᅉ࡜ࡋ࡚ࠊᇶ‽᣺ືゎᯒࡢࢧࣥࣉࣜࣥࢢᩘࡀ㊊ࡾ࡞࠸ࡇ࡜࡟ࡼࡿ OM ࣃ࣓࣮ࣛࢱࡢ⢭ᗘࡢపࡉࠊཬࡧỈศᏊࡢศᴟ⋡➼ࡢᙳ㡪ࢆṇ☜࡟ホ౯࡛ࡁ࡞࠿ࡗࡓࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋ ḟ࡟ࠊᘧ  ࢆ⏝࠸࡚㑄⛣཮ᴟᏊ࡜ỈศᏊࡢỌஂ཮ᴟᏊ㛫ࡢ㓄ྥ┦㛵ࢆィ⟬ࡋࡓ⤖ᯝࢆᅗ D ࡟♧ࡍࠋᅗ D࡟ࡘ࠸࡚ࠊ▷࠸㊥㞳࡛ࡣ J U ࡣ㈇ࡢ್ࢆ࡜ࡿࠋࡇࢀࡣࠊỈศᏊࡀ &2 ᇶ᪉ྥࢆྥ࠸࡚ศᏊ㛫Ỉ⣲⤖ྜࡋࠊ㐲㊥㞳ࡢ⁐㉁̿⁐፹㛫┦஫స⏝ࢆ┦ẅࡍࡿࡼ࠺࡟ỈศᏊࡀ㓄ྥࡍࡿࡇ࡜࡟㉳ᅉࡍࡿࠋᅗ D ࠿ࡽࠊ㑄⛣᣺ື㍈࡟ᑐࡍࡿỈศᏊࡢ㓄ྥࡣ໬ྜ≀ D ࢆ㝖࠸࡚⣙  Ⴒ ⛬ᗘಖࡓࢀࡿࡇ࡜ࡀศ࠿ࡾࠊ⁐㉁ศᏊࡀᕧ኱࡟࡞ࡿ࡯࡝ࠊࡼ

- 89 -

ࡾ㐲᪉ࡢỈศᏊࡢᙳ㡪ࢆཷࡅࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
⥆࠸࡚ࠊࡇࡢ㓄ྥ┦㛵ࢆヲ⣽࡟᳨ウࡍࡿࡓࡵ࡟ࠊᘧ  ୰ࡢ㛵ᩘ JM UMU ࡟ሙྜศࡅࢆ㏣ຍࡍࡿࠋ&2 ᇶࡢ㍈࡟ᑐࡋ࡚ᆶ┤࡞᪉ྥ࡟⌫Ẇࢆศ๭ࡋࠊୖഃ㸦2 ཎᏊഃ㸧࡜ୗഃ㸦ⰾ㤶⎔ഃ㸧ࡢୖୗ༙⌫ࡢ⌫Ẇ࡟࠾ࡅࡿ㓄ྥ┦㛵ࢆィ⟬ࡋࡓ㸦ᅗ E㸧ࠋᅗ E ࡼࡾࠊୖ༙⌫࡛ࡣ඲᪉ྥ࡛⪃៖ࡋࡓ᫬࡜࡯ࡰྠࡌ⤖ᯝࢆ୚࠼ࡿࡀࠊୗ༙⌫࡛ࡣୖ༙⌫࡜ྠࡌ㓄ྥ᪉ྥࢆྥ࠸ࡓỈศᏊࡀᑡᩘᏑᅾࡍࡿࡇ࡜ࡀศ࠿ࡿࠋୗ༙⌫ࡢỈศᏊࡣⰾ㤶⎔ୖ࡟Ꮡᅾࡍࡿࡶࡢ࡟ᑐᛂࡋࠊS㟁Ꮚ࡟ࡼࡿᙳ㡪࡛ỈศᏊࡢᣲືࡀኚ໬ࡍࡿࡓࡵ࡟ୖ༙⌫ࡢࡶࡢ࡜㓄ྥࡢ┦ẅࡀ⏕ࡌ࡞࠸ࠋࡑࡢࡓࡵࠊᙉ࠸ㄏ㟁㐽ⶸࡀⓎ⏕ࡏࡎࠊ㐲㊥㞳ࡢ⁐㉁̿

⁐፹㛫┦஫స⏝ࡢᐤ୚ࡀቑ኱ࡍࡿ࡜⪃࠼ࡽࢀࡓࠋ໬ྜ≀D  G ࡛ẚ㍑ࡍࡿ࡜ࠊศᏊࢧ࢖ࢬࡢቑຍ࡜㓄ྥ┦㛵ࡀಖࡓ
ࢀࡿ㊥㞳ࡀቑຍࡋࠊᐇ㦂ⓗ࡟ࡶࠊ))7&) ࡢῶ⾶ࡢ᫬ᐃᩘࡣ
ศᏊࢧ࢖ࢬ࡜ඹ࡟ቑຍࡍࡿࠋࡋࡓࡀࡗ࡚ࠊㄏ㟁ⓗ⎔ቃࡢኚ໬࡟క࠺ỈศᏊࡢ㞟ᅋᛶࡢኚ໬ࡀ᣺ືᩘᦂࡽࡂ࡟࠾࠸࡚㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋ
>@-+&KRLDQG0&KR-&KHP3K\V  ᅗ 㸬㑄⛣཮ᴟᏊ࡜ỈศᏊࡢỌஂ཮ᴟᏊࡢ
㓄ྥ┦㛵㛵ᩘࡢ㊥㞳౫Ꮡᛶࠋᅗ  ୰ࡢ
D  G ࡣᅗ  ࡢ໬ྜ≀✀࡟ᑐᛂࡍࡿࠋD  ඲᪉఩ࡢ⌫Ẇ࡛⪃࠼ࡓሙྜࠊ E &2 ᇶ࡟ᑐࡋ࡚ᆶ┤࡞᪉ྥ࡛ୖ༙⌫㸦ᐇ⥺㸧࡜ୗ༙⌫㸦◚⥺㸧࡟ศࡅࡓሙྜࡢ⤖ᯝࠋ>@</$5H]XVDQG+-%DNNHU3K\V5HY/HWW  ࢸࣛ࣊ࣝࢶศග㸸ᅗ  ࡟⢊ᮎࡢ⬡㉁஧㔜⭷ '03* ࢆ࣌ࣞࢵࢺ≧࡟ࡋ࡚  . ࡛ᐃࡋࡓࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺ

ࣝࢆ♧ࡍࠋFP ࠾ࡼࡧ FP ௜㏆࡟ࣂࣥࢻࡀほ ࡉࢀࡿࠋࡇࡢࢫ࣌ࢡࢺࣝࡢ⌮ㄽィ⟬ࢆ⾜ࡗ࡚ࡁࡓࡀࠊᖖ
࡟㈇ࡢ᣺ືᩘࡢᇶ‽᣺ືࡀồࡲࡗ࡚࠸ࡓࠋࡘࡲࡾࠊ᭱㐺໬ࡉࢀࡓᵓ㐀ࡣ᭱ࡶᏳᐃ࡞ࡶࡢ࡛ࡣ࡞ࡃࠊ࠶ࡿᇶ‽᣺ື࡟ἢࡗ࡚ࡣ୙Ᏻᐃ࡞‽Ᏻᐃ≧ែ࡜࠸࠼ࡿࠋᮏᖺᗘࠊึࡵ࡚㈇ࡢ᣺ືᩘࢆᣢࡓ࡞࠸ᵓ㐀ࢆᚓࡿࡇ࡜ࡀ࡛ࡁ
ࡓࠋࡇࡢࢫ࣌ࢡࢺࣝࢆᅗ  ࡟♧ࡍࠋ ੉ၱ ௜㏆࡟ᙅ࠸ࡀ᫂☜࡞ࣆ࣮ࢡࠊ ੉ၱ ௜㏆࡟㠀ᖖ࡟ᙉ࠸ࣂࣥࢻࡀほࡉࢀࡿࠋࡲࡓࠊᚓࡽࢀࡓᇶ‽᣺ືࢆࠊᡃࠎࡀ㛤Ⓨࡋࡓࠊ୕ࡘࡢᐤ୚ࠊศᏊ㛫ࡢ୪㐍㐠ືࠊศᏊ㛫ࡢࣛ࢖ࣈ࣮ࣞࢩࣙࣥࠊศᏊෆ᣺ືࠊ࡟ศࡅࡿ᪉ἲ࡛ྛᐤ୚ࢆᐃ㔞໬ࡋࡓࠋࡑࡢ⤖ᯝࢆᅗ  ྑ࡟♧ࡍࠋ᭱ࡶప࠸᣺ືᩘ
ࡢᇶ‽᣺ືࡣ FP ࡟࠶ࡿࡀࠊࡇࢀࡣ࣐ࣛࣥάᛶ࡞ศᏊ㛫ࡢ୪㐍㐠ື࡛࠶ࡾࠊ㉥እ୙άᛶ࡛࠶ࡿࠋࡑࢀࡼ
ࡾࡶ㧗࠸᣺ືᩘࡢࣂࣥࢻ࡟ࡣࣛ࢖ࣈ࣮ࣞࢩࣙࣥࡸศᏊෆ᣺ືࡢᐤ୚ࡀྵࡲࢀ࡚࠾ࡾࠊ≉࡟  ੉ၱ ࡼࡾ㧗࠸᣺ືᩘࡢࣂࣥࢻ࡛ࡣࠊศᏊෆ᣺ືࡢᐤ୚ࡀ኱ࡁ࠸ࠋ ੉ၱ ௜㏆࡟ほ ࡉࢀࡿࣂࣥࢻࡣࠊࢼࢺ࣒ࣜ࢘࢖࢜ࣥ࡜ࣜ
ࣥ㓟ᇶࡢ㛫ࡢ᣺ື࡛࠶ࡾࠊ㟁Ⲵࢆࡶࡗ࡚࠸ࡿࡓࡵࠊ㠀ᖖ࡟ᙉ࠸㉥እάᛶᗘࢆᣢࡘࡇ࡜ࡀࢃ࠿ࡗࡓࠋᐇ㦂࡛ࡣࠊFP ௜㏆࡟ࣂࣥࢻࡀほ ࡉࢀ࡚࠸ࡿࡀࠊ࠾ࡑࡽࡃࡇࡢࣂࣥࢻࡀࡑࢀ࡟ᑐᛂࡋ࡚࠸ࡿ࡜⌧ᅾࡢ࡜ࡇࢁࠊ⪃࠼࡚࠸ࡿࠋ Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬³,QWHUSUHWDWLRQ RI 7+] ,QWHQVLWLHV RI 0ROHFXODU &U\VWDOV WKH 5ROH RI 0L[LQJ EHWZHHQ ,QWHUPROHFXODU DQG,QWUDPROHFXODU9LEUDWLRQV LQYLWH ´)=KDQJ+::DQJ.7RPLQDJD0+D\DVKL0DVDKLNR7DQL63,($VLDQ - 90 -ᅗ 㸬ᕥୖࠋ⢊ᮎࡢ⬡㉁஧㔜⭷ '03* ࢆ࣌ࣞࢵࢺ≧࡟ࡋ࡚ . ࡛ᐃࡋࡓࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࠋᕥୗࠋ

ィ⟬࠿ࡽồࡲࡗࡓࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࠋྑ㸸ᚓࡽࢀࡓᇶ‽᣺ືࢆࠊ୕ࡘࡢᐤ୚ࠊศᏊ㛫ࡢ୪㐍㐠ືࠊศᏊ㛫ࡢࣛ࢖ࣈ࣮ࣞࢩࣙࣥࠊศᏊෆ᣺ືࠊ࡟ศࡅࡿ᪉ἲ࡛ྛᐤ୚ࢆᐃ㔞໬ࡋࡓࠋ  
3KRWRQLFV%HLMLQJ RQOLQH 
‫ۻ‬³7RZDUGV (VWDEOLVKLQJ 7+] 9LEUDWLRQDO 6SHFWURVFRS\ LQ 0ROHFXODU &U\VWDOOLQH 6\VWHPV )HQJ =KDQJ .HLVXNH
7RPLQDJD0LFKLWRVKL+D\DVKL7HWVXR6DVDNL0DVDKLNR7DQLLQYLWH,&&$(6.RONDWD,QGLD RQOLQH 
 ‫ ۻ‬,QWHUSUHWDWLRQ RI 7+] ,QWHQVLWLHV RI 0ROHFXODU &U\VWDOV WKH 5ROH RI 0L[LQJ EHWZHHQ ,QWHUPROHFXODU DQG,QWUDPROHFXODU 9LEUDWLRQ´ )HQJ =KDQJ +RXQJ:HL :DQJ .HLVXNH 7RPLQDJD 0LFKLWRVKL +D\DVKL 0DVDKLNR 7DQL
,500:7+]%XIIDOR86$ RQOLQH  ‫ۻ‬³'HWHUPLQDWLRQ RI WKH )LQH 6WUXFWXUH RI D +DOLGH 3HURYVNLWH XVLQJ +LJKUHVROXWLRQ 7+] 6SHFWURVFRS\ DQG6ROLGVWDWH'HQVLW\)XQFWLRQDO7KHRU\´)HQJ=KDQJ,]XUX.DULPDWD+RXQJ:HL:DQJ7DNDVKL7DFKLNDZD.HLVXNH
7RPLQDJD0LFKLWRVKL+D\DVKL,500:7+]%XIIDOR86$ RQOLQH  ‫ۻ‬³'HWHUPLQDWLRQ RI WKH )LQH 6WUXFWXUH RI D +DOLGH 3HURYVNLWH XVLQJ 7+] 6SHFWURVFRS\´ )HQJ =KDQJ ,]XUX.DULPDWD +RXQJ:HL :DQJ 7DNDVKL 7DFKLNDZD .HLVXNH 7RPLQDJD 0LFKLWRVKL +D\DVKL 7HWVXR 6DVDNL $VLD
6SHFWURVFRS\&RQIHUHQFH6LQJDSRUH RQOLQH  ‫ ۻ‬³+\GURJHQ %RQG '\QDPLFV RI )OXRUHQRQH 'HULYDWLYHV LQ :DWHU 6WXGLHG E\ 7ZR'LPHQVLRQDO ,QIUDUHG
6SHFWURVFRS\´ <XNL )XMLL .DRUX 2KWD DQG .HLVXNH 7RPLQDJD $VLD 6SHFWURVFRS\ &RQIHUHQFH 6LQJDSRUH RQOLQH  ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬7KHRUHWLFDO 0RGHOLQJ IRU (OHFWURQLF 6WUXFWXUH RI 3RO\LRGLGH 6SHFLHV ,QFOXGHG LQ Į&\FORGH[WULQ 0DVDNL 2NXGD7DNDWR +LUDPDWVX 0LWVXUX <DVXGD 0LND ,VKLJDNL <XNLKLUR 2]DNL 0LFKLWRVKL +D\DVKL .HLVXNH 7RPLQDJD DQG (UL&KDWDQL-3K\V&KHP%   ³'\QDPLF %HKDYLRU RI 3KRWRJHQHUDWHG &KDUJH &DUULHUV LQ 'LNHWRS\UURORS\UUROH/LQNHG 7HWUDEHQ]RSRUSK\ULQ%DVHG
%XON+HWHURMXQFWLRQ7KLQ)LOPV3UREHGZLWK7LPH5HVROYHG7HUDKHUW]6SHFWURVFRS\´.DRUX2KWD<XLFKL+LUDPDWVX.RKWDUR 7DNDKDVKL 0LWVXKDUX 6X]XNL +LURNR <DPDGD DQG .HLVXNH 7RPLQDJD -RXUQDO RI 3KRWRFKHPLVWU\ DQG3KRWRELRORJ\$&KHPLVWU\   ‫ۻ‬³0ROHFXODU0HFKDQLVPRI$FFHOHUDWLRQDQG5HWDUGDWLRQRI&ROOHFWLYH2ULHQWDWLRQ5HOD[DWLRQRI:DWHU0ROHFXOHVLQ
$TXHRXV6ROXWLRQV´1RULIXPL0RULWVXJX7DNDIXPL1DUD6KLQLFKL.RGD.HLVXNH7RPLQDJDDQG6KLQML6DLWR-3K\V&KHP%     

- 91 -

ᐦᗘỗ㛵ᩘἲィ⟬ࡢ᪂ࡓ࡞ᒎ㛤࡜ࢼࣀ⾲㠃࣭⏺㠃ᡂ㛗ᶵᵓࡢゎ᫂
'HYHORSPHQWRI')7VFKHPHDQGLWVDSSOLFDWLRQWRQDQRVFDOH
VXUIDFHLQWHUIDFHIRUPDWLRQ‫ۑ‬ᢲᒣ ῟ࠊࣈ࢖ ࢩ࢚࢟࢘ ࣑ࠊไ㔝࠿࠾ࡾࠊ஭ᮏ ᩥ⿱ࠊ㛗ᕝ೺ኴࠊཎᔱᗤ௓
㸦ྡྂᒇ኱Ꮫ ᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒◊✲ᡤ㸧




◊✲┠ⓗ
ࢼࣀࢫࢣ࣮ࣝ⾲㠃࣭⏺㠃ࡣ≀㉁ࡀᙧᡂࡉࢀࡿ⯙ྎ࡛࠶ࡾࠊࡲࡓ㟁Ꮚࢹࣂ࢖ࢫ࡟࠾࠸࡚ࡣ⏺㠃ࢆ㏻ࡋ࡚ࢺࣛ

ࣥࢪࢫࢱస⏝࡞࡝ࡢࢹࣂ࢖ࢫస⏝ࡀྍ⬟࡜࡞ࡗ࡚࠸ࡿࠋࡋࡓࡀࡗ࡚ࠊ⾲㠃࣭⏺㠃ᡂ㛗⌧㇟ࡢ㔜せᛶࡣᇶ♏⛉Ꮫࡢ⠊␪࡟࡜࡝ࡲࡽࡎࠊᗈ⠊࡞ᛂ⏝ศ㔝࡛ࡢ㔜せᛶࢆ᭷ࡋ࡚࠸ࡿࠋᮏㄢ㢟࡛ࡣࠊᡃࠎࡀ㛤Ⓨࡋࡓࠊ኱つᶍ㧗㏿࣭㧗⢭ᗘィ⟬ࢆྍ⬟࡟ࡍࡿᐇ✵㛫ᐦᗘỗ㛵ᩘἲ㸦56')7㸧ࢥ࣮ࢻࠊࡑࡢⓎᒎᙧ࡛࠶ࡿᐇ✵㛫 &DU3DUULQHOORศᏊືຊᏛ㸦56&30'㸧ࢥ࣮ࢻࢆ㍈࡟ࡍ࠼ࠊ῝ᒙᏛ⩦࡟ࡼࡿ࣮࢜ࢲ࣮㸦1㸧RUELWDOIUHH ')7 ࡢ㛤Ⓨࢆ᪉ἲㄽⓗࢱ࣮ࢤࢵࢺ࡜ࡋࠊࡑࢀࡽࡢ⊂⮬㛤Ⓨࢥ࣮ࢻࢆ⏝࠸࡚ࠊࢼࣀ࣓࣮ࢺࣝࢫࢣ࣮ࣝ⌧㇟࡛࠶ࡿ⾲㠃⏺㠃ᡂ㛗ࡢᶵᵓゎ᫂ࢆ┠ᣦࡍࡶࡢ࡛࠶ࡿࠋලయⓗ࡞≀㉁⛉Ꮫࡢࢱ࣮ࢤࢵࢺ࡜ࡋ࡚ࡣࠊࣃ࣮࢚࣡ࣞࢡࢺࣟࢽࢡࢫࡢᇶᖿᮦᩱ
࡜ࡋ࡚ὀ┠ࢆ㞟ࡵ࡚࠸ࡿⅣ໬ࢣ࢖⣲ 6L& ࠊ❅໬࣒࢞ࣜ࢘ *D1 ࠊ࠾ࡼࡧࡑࡢࢤ࣮ࢺ⤯⦕⭷ 6L2ࠊ$O2ࠊ࠾ࡼࡧࡑࢀࡽࡢΰᬗ ࡟ࣇ࢛࣮࢝ࢫࡋࠊ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗⾲㠃ࡢᵓ㐀ゎ᫂ࠊᡂ㛗ࡢ⣲㐣⛬ゎ᫂ࠊ࢔ࣔࣝࣇ࢓ࢫ࣭
ࢤ࣮ࢺ⤯⦕⭷ࡢ≀ᛶゎ᫂ࠊ༙ᑟయ୰㌿఩ࡢ㟁Ꮚⓗ≉ᛶゎ᫂ࠊࢆ⾜࠺ࠋ◊✲᪉ἲࠊィ⟬᪉ἲᮏᖺᗘࡢ◊✲ᡂᯝࡢ୺࡞ࡿࡶࡢࡣࠊᐦᗘỗ㛵ᩘ⌮ㄽ㸦')7'HQVLW\)XQFWLRQDO7KHRU\㸧࡟ᇶ࡙ࡃ .RKQ6KDP᪉⛬ᘧࢆᐇ✵㛫ࡢ࣓ࢵࢩࣗୖ࡛ゎࡃᐇ✵㛫ᐦᗘỗ㛵ᩘἲ㸦ࢥ࣮ࢻྡ㸻56')7ࠊ5HDO6SDFH 'HQVLW\)XQFWLRQDO
7KHRU\㸧࠾ࡼࡧࣛࢢࣛࣥࢪ࢙ᙧᘧࡢ᫬㛫౫Ꮡ᪉⛬ᘧࢆゎࡃᐇ✵㛫 &DU3DUULQHOOR ศᏊືຊᏛἲ㸦ࢥ࣮ࢻྡ㸻
56&30'ࠊ5HDO6SDFH&DU3DUULQHOOR0ROHFXODU'\QDPLFV㸧࡟ࡼࡗ࡚ᚓࡽࢀ࡚࠸ࡿࠋࡇࢀࡽࡢࢥ࣮ࢻࡣ⊂⮬㛤Ⓨࡢࡶࡢ࡛࠶ࡾࠊ
ࠕிࠖࠊࠕᐩᓅࠖ࡟࠾࠸࡚ࡶ㧗㏿኱つᶍィ⟬ࡀྍ⬟࡟࡞ࡗ࡚࠸ࡿࠋ࠸ࡎࢀࡢࢥ࣮ࢻ࡛ࡶࠊཎᏊ᰾
࡜Ẇ㟁Ꮚࡣ➨୍ཎ⌮ⓗ࡟ᵓᡂࡉࢀࡿᨃ࣏ࢸࣥࢩ࡛ࣕࣝࢩ࣑࣮ࣗࣞࢺࡉࢀࠊ౯㟁Ꮚྠኈࡢ┦஫స⏝ࡣᐦᗘỗ㛵ᩘ⌮ㄽࡢࠊᒁᡤᐦᗘ㏆ఝ㸦/'$㸧ࠊᒁᡤࢫࣆࣥᐦᗘ㏆ఝ㸦/6'$㸧ࠊ୍⯡໬㸦ࢫࣆࣥ㸧ᐦᗘ໙㓄㏆ఝ㸦**$㸧ࠊࡉࡽ࡟ࡣࣁ࢖ࣈࣜࢵࢻ㏆ఝ࡛グ㏙ࡉࢀ࡚࠸ࡿࠋ
ࡲࡓࠊ௒ᖺᗘ࡟ࡣࠊ῝ᒙᏛ⩦࡟ࡼࡿ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘ .(') ࡢ㛤Ⓨࠊࡑࢀ࡟⥆ࡃ RUELWDOIUHH ࡢ ')7
ィ⟬ 2)')7 ࢫ࣮࣒࢟ࢆ㛤Ⓨࡋࡓࡀࠊࡑࡢࢥ࣮ࢻࡢࢥ࢔࡜࡞ࡿ㒊ศࡣ 56')7 ࢥ࣮ࢻࢆά⏝ࡋ࡚࠸ࡿࠋ㛤Ⓨࡋࡓ 2)')7 ࢫ࣮࣒࢟ࡢ㦵Ꮚࡣࠊձ ከ㔜ࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ࡟ࡼࡿ .(') ࡢ᪂ࡓ࡞㛤ⓎࠊղRUELWDOIUHH ࡟ᑐᛂࡍࡿ➨୍ཎ⌮ᒁᡤ ORFDO ᨃ࣏ࢸࣥࢩࣕࣝࡢ㛤Ⓨࠊճ .(') ࡢỗ㛵ᩘᚤศࢆྵࡴ (XOHU ᪉⛬ᘧࡢゎἲࠊࡢ 
Ⅼ࠿ࡽᡂࡗ࡚࠸ࡿࠋ㛤Ⓨࡉࢀࡓ .(') ࡣ㧗࠸⢭ᗘ࡜ỗ⏝ᛶࢆ᭷ࡋ࡚࠾ࡾࠊࢲ࢖ࣖࣔࣥࢻ⤖ᬗ࡛ࡢࢺ࣮ࣞࢽࣥ
ࢢ࡟ࡶ㛵ࢃࡽࡎࠊཎᏊࠊศᏊࠊᵝࠎ࡞ᅛయ࡛ࡢᵓ㐀ⓗᛶ㉁ࢆ㧗⢭ᗘ࡛෌⌧ࡍࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋ
- 92 -

◊✲ᡂᯝࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ࡟ࡼࡿ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘࡢ㛤Ⓨ࡜࣮࢜ࢲ࣮1 ᐦᗘỗ㛵ᩘἲィ⟬
')7 ࡛ࡣࠊ⣔ࡢ඲࢚ࢿࣝࢠ࣮ࡣ㟁Ꮚᐦᗘ U U ࡢỗ㛵ᩘ࡛࠶ࡾࠊࡑࡢỗ㛵ᩘࡢᙧࡀࢃ࠿ࢀࡤࠊ඲࢚ࢿࣝ
ࢠ࣮ࡢ㟁Ꮚᐦᗘ࡟ᑐࡍࡿኚศࢆྲྀࡗࡓ (XOHU ᪉⛬ᘧࢆゎࡃࡇ࡜࡟ࡼࡾࠊ⣔ࡢ㟁Ꮚᐦᗘࠊࡦ࠸࡚ࡣ඲࢚ࢿࣝ
ࢠ࣮ࡉࡽ࡟ࡣ≀⌮㔞ࡀィ⟬࡛ࡁࡿࠋ㏻ᖖࡢ .RKQ6KDP .6 ࡟ࡼࡿࢫ࣮࣒࡛࢟ࡣࠊࡇࡢỗ㛵ᩘࡢෆࠊ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘ 7 > U @  ࢆ୍㟁Ꮚ㌶㐨㸦.6 ㌶㐨㸧ࢆᑟධࡋ࡚⾲⌧ࡍࡿࡢ࡛ࠊ(XOHU ᪉⛬ᘧࡣ㌶㐨ࡢᩘࡢศ㸦ࢩࢫࢸ࣒ࢧ࢖ࢫ 1 ࡢ࣮࢜ࢲ࣮㸧ࡔࡅࡢ᭷ຠ୍㟁Ꮚ᪉⛬ᘧࡢᙧ࡜࡞ࡾࠊࡑࢀࢆゎࡃࡢ࡟ࡣ࣮࢜ࢲ࣮1 ࡢィ⟬᫬㛫ࡀ࠿࠿ࡿࠋࡋ࠿ࡋ ')7 ࡢ࠾࠾ࡶ࡜࡟❧ࡕ㏉ࢀࡤࠊ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘࡢᙧࡀ⢭ᗘࡼࡃồࡲࢀࡤࠊ(XOHU᪉⛬ᘧࡣ༢୍ࡢ᪉⛬ᘧ࡛࠶ࡾࠊ࣮࢜ࢲ࣮1 ィ⟬ࡀྍ⬟࡜࡞ࡿ>2UELWDO)UHH 2)  ')7@ࠋࡇࡢ㐠ື࢚ࢿࣝࢠ࣮
ỗ㛵ᩘ࡟ᑐࡋ࡚ࡣࠊྂࡃࡣ୍ᵝ⣔࡟ᑐࡍࡿ 7KRPDV)HUPL 7)  ㏆ఝࠊ୍㌶㐨࡟ᑐࡋ࡚ṇ☜࡞ YRQ:HL]VDFNHU㏆ఝࠊࡉࡽ࡟ࡣ㏆ᖺ࡛ࡣࡉࡲࡊࡲ࡞ ORFDO ࠶ࡿ࠸ࡣ QRQORFDO ࡞㏆ఝࡀᑟධࡉࢀ࡚࠸ࡿࠋ௒ᅇᡃࠎࡣࡇࡢ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘ .(') ࢆ

7>U @


ࡢᙧࡢ⠊ᅖ࡛ồࡵࡓࠋࡇࡇ࡛ W

7)

³W

7)

> U @ U ) 11 V   T^: ` GU  ࡣ 7KRPDV)HUPL ࡢ㐠ື࢚ࢿࣝࢠʊᐦᗘࠊ) ࡀ࠸ࢃࡺࡿ HQKDQFHPHQWIDFWRU

࡛࠶ࡿࠋࡇࢀࡣᐦᗘ໙㓄ᒎ㛤࡜ࡳ࡞ࡍࡇ࡜ࡀ࡛ࡁࠊVU  > S   U  @ ࠊT

  U  > S   U  @࡞ࡢ࡛ ᐦᗘ໙㓄ࡢ  ḟࡲ࡛ࡢ㏆ఝ࡛࠶ࡿࠋ) ࢆࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ㸦ࡑࡢ㔜ࡳࣃ࣓࣮ࣛࢱ㞟ྜ ^: `  㸧࡛ồࡵࡿࢃࡅࡔࡀࠊᏛ⩦ࡉࡏࡿ㔞࡜ࡋ࡚ࡣࠊ 7 > U @ ࡛ࡣ࡞ࡃࡑࡢỗ㛵ᩘᚤศ G 7 > U @  GU U  ࡢᐇ✵㛫࣓ࢵࢩࣗୖ࡛ࡢ್ࢆ᥇⏝ࡋࡓࠋ.RKQ6KDP ࢫ࣮࣒࡛࢟ࡢࡇࡢỗ㛵ᩘᚤศࡢ್࡜ࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ 11 ࡛సᡂࡉࢀࡓỗ㛵ᩘᚤศࡢ್ࡢ஧஌࣮ࣝࢺㄗᕪ㸦506(㸧ࢆࢥࢫࢺ㛵ᩘ࡜ࡋ࡚ࠊ ^: ` ࢆỴᐃࡋࡓࠋࢲ࢖ࣖࣔ
ࣥࢻ⤖ᬗ࡛ࡢỗ㛵ᩘᚤศ್ࢆᏛࡤࡏ࡚㸦WUDLQLQJGDWD㸧Ỵᐃࡋࡓ G 7 > U @  GU U ࢆ⏝࠸࡚ (XOHU ᪉⛬ᘧࢆゎࡁࠊ௚ࡢ≀㉁⩌࡟ᑐࡋ࡚ࡢ᭷ຠᛶࢆ᳨ドࡋࡓࠋᅗ  ࡣࢲ࢖ࣖࣔࣥࢻᵓ㐀ࡢ 6L ⤖ᬗࡢᚓࡽࢀࡓ㟁Ꮚᐦᗘ࡛࠶ࡿࠋᚑ᮶ࡢ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘࢆ⏝࠸ࡓ 2)')7 ࡟ẚ࡭ࠊ௒ᅇࡢ 11.(') ࡣࡼࡾ⢭ᗘࡼࡃ .6 ᐦᗘࢆ෌⌧ࡋ࡚࠸ࡿࡇ
࡜ࡀࢃ࠿ࡿࠋࡉࡽ࡟඲㒊࡛  ✀㢮ࡢ␗࡞ࡿ⣔㸦GLDPRQG&JUDSKHQHGLDPRQG6LIFF6LEHWDWLQ6L&6L&EFF/LIFF$O
IFF&XEFF1D1D&O ࡘࡢ␗࡞ࡿཎᏊࠊ ࡘࡢ␗࡞ࡿ஧ཎᏊ
ศᏊ㸧ࡢ㟁Ꮚᐦᗘࡶ⢭ᗘࡼࡃ෌⌧ࡍࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋᅛయ
ࡢ᱁Ꮚᐃᩘࠊయ✚ᙎᛶ⋡ࠊ஧ཎᏊศᏊࡢศᏊ㛫㊥㞳ࡢ࠸ࡎࢀࡶࠊᚑ᮶ࡢ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘࢆ෽㥙ࡋ࡚ࠊ.6 ࢫ࣮࣒࢟ࡢ⤖ᯝࢆ෌⌧ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࢲ࢖ࣖࣔࣥࢻᵓ㐀ࡢⅣ⣲࡛ࢺ࣮ࣞࢽࣥࢢࡋࡓࡔࡅ࡛ࠊࡇࢀࡔࡅࡢࣃࣇ࢛࣮࣐ࣥࢫࡀฟ
ࡿࡇ࡜ࡣࠊ11 ࢆ⏝࠸ࡓỗ㛵ᩘ㛤Ⓨࡢྍ⬟ᛶࢆឤࡌࡉࡏࡿ
㸦,PRWRHWDO3K\VLFDO5HYLHZ5HVHDUFK ࡟ᢞ✏୰㸧

- 93 -

ᅗ㸯㸸ࢲ࢖ࣖࣔࣥࢻᵓ㐀ࡢ 6L ࡟ᑐࡋ࡚ᚓࡽࢀࡓ㟁Ꮚᐦᗘࠋ㉥⥺ࡀ௒ᅇࡢࢽ࣮ࣗ
ࣛࣝࢿࢵࢺ࣮࣡ࢡ࡛సᡂࡋࡓ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘࢆ౑ࡗࡓ⤖ᯝࠋ E ࡣ.RKQ6KDP ᐦᗘ࡜ࡢᕪࠋ

ࢫࢸࢵࣉࣇ࣮ࣟGaN-MOVPE ᡂ㛗ᶵᵓࡢ⣲㐣⛬ゎ᫂
GaN ࡢ ࢚ ࣆ ࢱ ࢟ ࢩ ࣕ ࣝ ᡂ 㛗 ࡛ ࡣ ࠊ MOVPE
㸦MetalOrganic Vapor Phase Epitaxy㸧ἲࡀ᭱ࡶࡼࡃ⏝࠸ࡽࢀࡿࠋࡑࡇ࡛ࡣࠊᡂ㛗࡛ࡢ Ga ࢯ࣮ࢫ࡛࠶ࡿ TMG ࡣ GaH3 ࡲ࡛ศゎࡋࠊᡂ㛗⾲㠃ࡣ Ga
ࣜࢵࢳ࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࡀᡃࠎࡢ BLIP ィ⟬࡛ࢃ࠿ࡗ࡚࠸ࡿࠋ୍᪉ N ࢯ࣮ࢫ࡛࠶ࡿ NH3 ࡣẼ┦࡛ศゎࡏࡎ࡟⾲㠃࡟฿㐩ࡍࡿࡇ࡜ࡀࡢ㉁㔞ศᯒᐇ㦂࠿ࡽ᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࠋࡋࡓࡀࡗ࡚⾲㠃ᡂ㛗ᶵᵓゎ᫂࡟ࡣࠊGa ࣜࢵࢳ⾲㠃࡛ࡢ NH3 ࡢ᣺⯙ࢆㄪ࡭ࡿ࡭ࡁ࡛࠶ࡿࠋ2018 ᖺ࡟Ⓨ⾲ࡋࡓ(J. Phys.
Chem. C)ᡃࠎࡢ DFT ィ⟬࡟ࡼࢀࡤࠊGaN(0001)
⾲㠃࡛ࡢ NH3 ࡣ Ga ࢔ࢻ࢔ࢺ࣒ୖ࡟྾╔ࡋࠊNHᅗ  *D1  ᚤഴᩳ㠃࡛ࡢᏳᐃཎᏊࢫࢸࢵࣉᵓ㐀ࠋ
D *1 ࢫࢸࢵࣉࠊ E *D ࢫࢸࢵࣉࠋ኱ࡁ࠸⌫ࠊᑠࡉ࠸⌫ࡀ
*Dࠊ1 ཎᏊࢆ⾲ࡋ࡚࠸ࡿࠋ㯤Ⰽ࠸㞼ࡣィ⟬ࡉࢀࡓ㟁Ꮚᐦᗘࡢ➼್㠃ࠋᑠࡉ࡞➼್㠃ࡣ㟁Ꮚᐦᗘࡀప࠸ࡇ࡜࡟ᑐᛂ
ࡋ࡚࠾ࡾࠊࢫࢸࢵࣉ➃࡛ࡢᙅ࠸ *D*D ࣎ࣥࢻࡢᏑᅾࡀぢ࡚ྲྀࢀࡿࠋ࡜ H2 ࡟ศゎࡋࠊNH ࡣᙅ࠸ Ga-Ga ࣎ࣥࢻ࡟౵ධ
ࡍࡿࠋ௒ᅇࡇࡢ NH ࡢ⾲㠃ࢸࣛࢫୖ࡛ࡢᣑᩓ⤒㊰ࡢỴᐃ࡜ᣑᩓ࢚ࢿࣝࢠ࣮㞀ቨࡢィ⟬ࢆ⾜࠸ࠊNHࡣ➼౯࡞Ᏻᐃ఩⨨ࢆẚ㍑ⓗ࡟ప࠸࢚ࢿࣝࢠ࣮㞀ቨࢆ㉺࠼࡚⤒ࡵࡄࡿࡇ࡜ࡀุ᫂ࡋࡓࠋࡑࡢᣑᩓ㞀ቨࡢ㧗ࡉࡣ 0.6 eV ࡜ィ⟬ࡉࢀࡓࠋ୍᪉ᡂ㛗⾲㠃࡛ࡣཎᏊࢫࢸࢵࣉࡀᏑᅾࡋࠊࡑࡢ
ࢫࢸࢵࣉࡀᡂ㛗ࡍࡿࡇ࡜࡟ࡼࡾ࢚ࣆࢱ࢟ࢩࣕࣝᡂ
㛗ࡀ㉳ࡇࡿࠋࢫࢸࢵࣉᵓ㐀࡟ࡣ඲㒊࡛ 5 ࡘࡢྍ⬟ᛶࡀ࠶ࡿࠋ[11-20]᪉ྥ࡟ᚤഴᩳࡋࡓ㠃࡛ࡣ Ga ࡜
N ࡢ཮᪉ࡀࢫࢸࢵࣉ➃࡟⌧ࢀࡿ GN ࢫࢸࢵࣉ➃ࠊ
[1-100]᪉ྥ࡟ᚤഴᩳࡋࡓ㠃࡛ࡣࠊGa ࡀࢫࢸࢵࣉ➃࡟⌧ࢀࠊᵓ㐀᭱㐺໬๓࡟ࡣ 2 ᮏ࠶ࡿ࠸ࡣ 3 ᮏࡢࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࡀⓏሙࡍࡿ Ga2 ࠾ࡼࡧ Ga3 ࢫࢸࢵࣉ➃ࠊN ࡀࢫࢸࢵࣉ➃࡟⌧ࢀࡿሙྜࡣྠᵝ࡟ N2࠾ࡼࡧ N1 ࢫࢸࢵࣉ➃ࡀࡑࢀ࡛࠶ࡿࠋ௒ᅇᡃࠎࡣ
ࡑࡢࡍ࡭࡚ࡢࢫࢸࢵࣉᵓ㐀ࢆ඲࢚ࢿࣝࢠ࣮ィ⟬ࡼࡾ᭱㐺໬ࡋࠊࡑࡢ⏕ᡂ࢚ࢿࣝࢠ࣮ࢆồࡵࡓࠋ୍౛
ࡀᅗ 2 ࡟♧ࡋࡓ[11-20]࡟ᚤഴᩳࡋࡓ GaN(0001)⾲

ᅗ ࢫࢸࢵࣉࣇ࣮࣭࢚ࣟࣆࢱ࢟ࢩࣕࣝᡂ㛗ࡢ⣲㐣⛬ࠋ
D *1 ࢫࢸࢵࣉ࡟ྲྀࡾ㎸ࡲࢀࡓ  ࡘࡢ 1+ ࣘࢽࢵࢺࠋ E
᪂ࡓ࡞ *D ࡀࢫࢸࢵࣉ࡟ྲྀࡾ㎸ࡲࢀࡿ࡜࡜ࡶ࡟ࠊ1+ ࣘࢽࢵࢺࡢ + ࡀ⬺㞳ࡋࡓᵓ㐀ࠋ F  ᵓ㐀 E ࢆ>@᪉ྥ࠿ࡽぢࡓᅗࠋ㟷ࡀ❅⣲ཎᏊࠊᶳࡀ + ཎᏊࠊ⥳ࠊ㉥⣸ࠊ㉥࣡࢖ࣥⰍࡣ *D ཎᏊࠋ㠃࡟≉ᚩⓗ࡞ GN ࢫࢸࢵࣉᵓ㐀ࠊ࠾ࡼࡧ[1-100]᪉
ྥ࡟ᚤഴᩳࡋࡓ(0001)⾲㠃࡟≉ᚩⓗ࡞ Ga2 ࢫࢸࢵࣉᵓ㐀࡛࠶ࡿࠋ࠸ࡎࢀࡢሙྜ࡟ࡶࠊࢫࢸࢵࣉ➃࡛ࡣୖࢸࣛࢫࡢ Ga ࡜ୗࢸࣛࢫࡢ Ga ࡀ᪂ࡓ࡞࣎ࣥࢻࢆᙧᡂࡋ࡚࠸ࡿࠋࡇࡢࣜ࣎ࣥࢻࡀ༙ᑟయ⾲㠃ࢫࢸࢵࣉ࡛ࡢᵓ㐀ⓗ≉ᚩ࡛࠶ࡿࠋࡋ࠿ࡋࡇࡢ࣎ࣥࢻࡣ Ga-N ࡢ࣎ࣥࢻ࡟ẚ࡭࡚ᙅ࠸ࠋࡑࢀࡣ⾲♧ࡋࡓ㟁Ꮚᐦᗘ࠿ࡽࡶ᫂ࡽ࠿
࡛࠶ࡿࠋࡇࡢࢫࢸࢵࣉ➃࡟ࢸࣛࢫୖࢆᣑᩓࡋ࡚ࡁࡓ NH ࡀྲྀࡾ㎸ࡲࢀࡿࣉࣟࢭࢫࢆ⪃࠼ࡿࠋࢸࣛࢫୖࡢ㸰ࡘࡢ⊂❧࡞ NH ࡀࢫࢸࢵࣉ➃࡟ྲྀࡾ㎸ࡲࢀࡓሙྜࡢᏳᐃᵓ㐀ࡀᅗ 3(a)࡛࠶ࡿࠋࡇࡢᵓ㐀ࡣࢸࣛࢫୖ࡟ NH ࡀ࠸ࡿ- 94 -

ሙྜ࡟ẚ࡭࡚ 0.45 eV ࢚ࢿࣝࢠ࣮ࢆᚓࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡘࡲࡾ NH ࡣࢫࢸࢵࣉ➃࡟ᘬࡁᐤࡏࡽࢀࡿࠋ
ࡇࡇ࡛⾲㠃࡟ࣜࢵࢳ࡟Ꮡᅾࡍࡿ Ga ཎᏊࡀ᪂ࡓ࡟ࡇࡢࢫࢸࢵࣉ➃࡟㏆࡙ࡁࠊ஧ࡘࡢ NH ࡢ H ࡀ H2 ࡜ࡋ࡚⬺㞳ࡋࠊ௦ࢃࡾ࡟᪂ࡓ࡞ Ga ࡀ N ࡢࢲࣥࢢࣜࣥࢢ࣎ࣥࢻࢆಟ᚟ࡍࡿ㐣⛬ࢆ⪃࠼ࡿ࡜ࠊࡑࡢ᭱⤊ᵓ㐀ࡣᅗ 3(b)ࡢࡼ࠺࡟࡞ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋィ⟬ࡢ⤖ᯝࠊࡇࡢ㐣⛬ࡣᡂ㛗ᗘࠊᡂ㛗⅔ෆࡢẼᅽୗ࡛ࡢ⮬⏤࢚ࢿࣝࢠ࣮

ኚ໬ࢆィ⟬ࡍࡿ࡜ࠊ༑ศ㉳ࡇࡾᚓࡿ㐣⛬࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢ᭱⤊ᵓ㐀ࢆ[0001]᪉ྥ࠿ࡽぢࡓࡢࡀᅗ 3(c)࡛࠶ࡿࠋ཯ᛂ๓ࡢ GN ࢫࢸࢵࣉ➃ࡀ 1 ࣘࢽࢵࢺ㐍ࢇࡔࡇ࡜ࡀ᫂ࡽ࠿࡛࠶ࡿࠋࡇࢀࡀࢫࢸࢵࣉࣇ࣮࣭ࣟ
࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ࡢ⣲㐣⛬࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ㸦ฟ∧ᐇ⦼[1]㸧
ࠋ௨ୖㄝ᫂ࡋࡓ 2 ௳ࡢ௚࡟ࡶࠊ⣬㠃ࡢ㒔ྜୖ᭩ࡁࡁࢀ࡞࠸ࡀࠊGaN ࢹࣂ࢖ࢫ࡛ࡢࢤ࣮ࢺ⤯⦕⭷ࡢ≉ᛶ[2]ࠊ
GaN ୰ࡢ㌿఩ᵓ㐀ࡢゎ᫂࡜࢔ࢡࢭࣉࢱ࣮ࡢ୙άᛶ໬[3]ࠊSiC ࢚ࣆᡂ㛗୰ࡢ⾲㠃ཎᏊᣑᩓ⤒㊰ࡢゎ᫂[4]࡞
࡝ࡢᡂᯝࡀᚓࡽࢀࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᣍᚅㅮ₇
1.

A. Oshiyama, ``Computics Approach toward Clarification of Atomic Reactions during Epitaxial
Growth of GaN" Int. Conf. Simulation of Semiconductor Processes and Devices (SISPAD)(September 23 - October 6, 2020, All-Virtual Conf)2.

ᢲᒣ῟ࠊ``኱つᶍ➨୍ཎ⌮ィ⟬࡜ࢹࣂ࢖ࢫ࣭ࣉࣟࢭࢫࢩ࣑࣮ࣗࣞࢱ⤫ྜ࡟ྥࡅ࡚㸫ࣃ࣮༙࣡ᑟయࢆ୰
ᚰ࡟㸫" 㟁Ꮚ᝟ሗ㏻ಙᏛ఍ ࢩࣜࢥࣥᮦᩱ࣭ࢹࣂ࢖ࢫ◊✲఍㸦SDM㸧
㸦2021 ᖺ 11 ᭶ 19-20 ᪥ࠊ࢜ࣥࣛ
࢖ࣥ㸧

3.

(Plenary) A. Oshiyama, ``Structures, electron states and reactions on growing surfaces and atdevice interfaces of SiC and GaN" International Symposium on Wide Gap Semiconductor Growth,
Process and Device Simulation 2021 (ISWGPDs2021) (January 19-21, 2021, on line).

4.

ᢲᒣ῟ࠊ``ࣃ࣮༙࣡ᑟయ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ᶵᵓゎ᫂࡜ࢹࣂ࢖ࢫ⏺㠃ไᚚ࡟ྥࡅࡓࢥࣥࣆࣗ̿ࢸ࢕ࢡ
ࢫ࣭࢔ࣉ࣮ࣟࢳ" ィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔࣒㸦PCoMS㸧ࢩ࣏ࣥࢪ࣒࢘ 㸦2021 ᖺ 2 ᭶ 15-16
᪥ࠊ࢜ࣥࣛ࢖ࣥ㸧5.

㛗ᕝ ೺ኴ, ``SiC ࡜ GaN ࡢ MOS ⏺㠃‽఩:⌮ㄽィ⟬࡟ࡼࡿ⪃ᐹ, ᛂ⏝≀⌮Ꮫ఍ ඛ㐍ࣃ࣮༙࣡ᑟయศ
⛉఍ 㸦2020 ᖺ 9 ᭶ 14 ᪥ࠊ࢜ࣥࣛ࢖ࣥ㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1.

K. M. Bui, K. Shiraishi and A. Oshiyama, ``Gallium-gallium weak bond that incorporates nitrogenat atomic steps during GaN epitaxial growth" Appl. Surf. Sci. 557, 149542 (2021).

2.

K. Chokawa, T. Narita, D. Kikuta, T. Kachi, K. Shiozaki, A. Oshiyama and K. Shiraishi, ``Absenceof oxygen-vacancy-related deep levels in amorphous (Al2O3)1-x(SiO2)x: First-principles explorationof gate oxides in GaN-based devices" Phys. Rev. Applied 14, 014034 (2020).

3.

T. Nakano, Y. Harashima, K. Chokawa, K. Shiraishi, A. Oshiyama, Y. Kangawa, S. Usami, N.
Mayama, K. Toda, A. Tanaka, Y. Honda, and H. Amano, ``Screw dislocation that converts p-type
GaN to n-type: Microscopic study on Mg condensation and leakagae current in p-n diodes" Appl.
Phys. Lett. 117, 012105 (2020).

4.

K. Seino and A. Oshiyama ``Microscopic mechanism of adatom diffusion on stepped SiC surfaces
revealed by first-principles calculations" Appl. Surf. Sci. 561, 149927 (2021).

- 95 -

㔞ᏊຊᏛ㸦40㸧ศᏊຊᏛ㸦00㸧ἲ࡟ࡼࡿࣁࣟ㓟⬺ࣁࣟࢤࣥ໬㓝⣲ࡢ཯ᛂᶵᵓ
ゎᯒ
Analysis of reaction mechanism of haloacid dehalogenase
by Quantum mechanics (QM) / Molecular mechanics (MM) method‫ ۑ‬୰ᮧ ༟㸦㛗὾ࣂ࢖࢜኱Ꮫ㸧㸯 ◊✲┠ⓗࠊෆᐜᡃࠎࡢ◊✲ᐊ࡛ࡣ⌧ᅾࠊ᭷ᶵࣁࣟࢤࣥ໬ྜ≀ࡢศゎ㓝⣲࡜ࡋ࡚᭷ᐖ≀㉁ศゎ࡬ࡢᛂ⏝ࡀᮇᚅࡉࢀࡿ L-2-ࣁࣟ㓟⬺ࣁࣟࢤࣥ໬㓝⣲㸦L-DEX㸧࡜ࠊ་⸆ရࡢࣅࣝࢹ࢕ࣥࢢࣈࣟࢵࢡ࡜࡞ࡾᚓࡿ㠀ኳ↛࢔࣑ࣀ㓟ࢆྜᡂ࡛ࡁ
ࡿࠊ኱⭠⳦ࡸ㉸ዲ⇕ᛶྂ⣽⳦⏤᮶ࡢࢩࢫࢸ࢖ࣥྜᡂ㓝⣲㸦OPSS㸧ࢆࢱ࣮ࢤࢵࢺ㓝⣲࡜ࡋ࡚ࠊᐇ㦂࡜ィ⟬࡟ࡼࡾ㓝⣲཯ᛂᶵᵓࢆศᏊ࡛ࣞ࣋ࣝゎ᫂ࡋࠊࡑࡢ▱ぢࢆ⏝࠸࡚㔝⏕ᆺࡢ㓝⣲ࡼࡾࡶ㧗ᶵ⬟࡞ᨵኚ㓝⣲ࢆࢹࢨ࢖ࣥࡋ࡚ᐇ㝿࡟๰ࡾฟࡍࡇ࡜ࢆ┠ᣦࡋ࡚࠸ࡿࠋ
L-DEX ࡛ࡣࠊάᛶ࡟㔜せ࡞࠸ࡃࡘ࠿ࡢṧᇶࡀᐇ㦂࡛ࡍ࡛࡟᫂ࡽ࠿࡟࡞ࡗ࡚࠾ࡾࠊࡑࡢᙺ๭࡟ࡘ࠸࡚⌧ᅾศᏊືຊᏛ㸦MD㸧ィ⟬ࡸ㔞ᏊຊᏛ㸦QM㸧ィ⟬ࢆ⏝࠸࡚ゎᯒ୰࡛࠶ࡿࠋ2017 ᖺᗘࡲ࡛ࡣࠊ㔝⏕ᆺ L-DEX ࡛ࡣ࡯࡜ࢇ࡝ศゎ࡛ࡁ࡞࠸Ⅳ⣲㸫ࣇࢵ⣲⤖ྜࢆ᭷ࡍࡿࣇࣝ࢜ࣟ㓑㓟㸦MFA㸧ࡢศゎ⬟ຊࢆࠊL-DEX ࡢᶵ⬟ᨵⰋ࡟ࡼࡾྥୖ࡛ࡁࡿ࠿࡟ࡘ࠸᳨࡚ウࡋ࡚ࡁࡓࡶࡢࡢࠊQM 㡿ᇦࡀ Parameterized Model number 3 (PM3) ἲࡢࡼ࠺࡞༙⤒㦂ⓗᡭἲ࡛ࡋ࠿཯ᛂ⤒㊰ࢆ≉ᐃ࡛ࡁࡎࠊࡑࡢ⤖ᯝ࡛ࢹࢨ࢖ࣥࡋࡓ㓝⣲ࡣ㔝⏕ᆺࡼࡾࡶ MFA ࡟ᑐࡍࡿά
ᛶࡀྥୖࡍࡿࡇ࡜ࡣ࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊ2018 ᖺᗘ࠿ࡽᮏ᮶ࡢᇶ㉁࡛࠶ࡿ L-2-ࢡࣟࣟࣉࣟࣆ࢜ࣥ㓟㸦L-2-CPA㸧ࢆ⏝࠸࡚ࠊL-DEX ࡢ㓝⣲཯ᛂ⤒㊰ࢆ㧗⢭ᗘ࡞㠀⤒㦂ⓗᡭἲࡢ୍ࡘ࡛࠶ࡿ B3LYP ࡸ M06-2X ࡜࠸ࡗࡓỗ㛵ᩘࢆ฼⏝ࡋࡓᐦᗘ༙㛵ᩘἲ㸦DFT㸧࡟ࡼࡾィ⟬ࡋࠊᐇ㦂⤖ᯝ࡜ᑐᛂࡍࡿ཯ᛂ⤒㊰ࢆỴᐃࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋOPSS ࡣࠊL-DEX ࡜␗࡞ࡾ⿵ᅉᏊࢆᚲせ࡜ࡋࠊ཯ᛂᶵᵓࡀ L-DEX ࡼࡾࡶ」㞧࡛࠶ࡿࡓࡵࠊࡲࡎࡣ L-DEXࡢィ⟬ࢆ㔜Ⅼⓗ࡟⾜࠺ࡇ࡜࡟ࡋࡓࠋ௨ୗ࡟ࠊ2020 ᖺᗘࡢ◊✲⤖ᯝ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ㸰 ◊✲᪉ἲࠊィ⟬᪉ἲ
L-DEX ࡜ L-2-CPA ࡜ࡢ」ྜయࡢ QM/ศᏊຊᏛ㸦MM㸧ィ⟬࡟ࡘ࠸࡚ࠊ2018 ᗘࡣࡇࢀࡲ࡛ࡢᐇ㦂ࡸィ⟬⤖ᯝ࡛άᛶ࡟㔜せࡔ࡜᥎ᐃࡉࢀ࡚࠸ࡿṧᇶࡢ୰࠿ࡽࠊAsp10ࠊArg41ࠊLys151ࠊAsp180 ࡢഃ㙐㒊ศ࡜ᇶ㉁࡛࠶ࡿ
L-2-CPA ࡸ཯ᛂ࡟㛵୚ࡍࡿゐ፹Ỉࡢྜィ 59 ཎᏊࡢ⣔ࠊ59 ཎᏊࡢ⣔࡟ Thr14ࠊAsn177 ࡢഃ㙐㒊ศࢆ㏣ຍࡋࡓ

75 ཎᏊࡢ⣔ࠊ75 ཎᏊࡢ⣔࡟ࡉࡽ࡟ Ser118 ࡢഃ㙐㒊ศࢆ㏣ຍࡋࡓ 80 ཎᏊࡢ⣔ࢆ QM 㡿ᇦ࡟ᣦᐃࡋࠊ2019 ᖺᗘࡣࠊ80 ཎᏊࡢ⣔࡟ᚋ༙ࡢຍỈศゎ཯ᛂ࡟㛵ࢃࡿ࡜ᛮࢃࢀࡿṧᇶ㸦Ser175㸧ࡢഃ㙐㒊ศࢆࡉࡽ࡟ຍ࠼ࡓ 85
ཎᏊࢆ QM 㡿ᇦ࡟ᣦᐃࡋࠊ
ࡑࢀ௨እࢆ MM 㡿ᇦ࡜ࡋ࡚ Gaussian09 ࡢ Our own N-layered Integrated molecularOrbital and Molecular mechanics (ONIOM)ἲ࡟ࡼࡾ㑄⛣≧ែ㸦TS㸧ᵓ㐀᥈⣴ࠊ᣺ືᩘゎᯒࠊ཯ᛂ⤒㊰㏣㊧㸦IRC㸧ࡢィ⟬ࢆ⾜ࡗ࡚ࠊTS ᵓ㐀ࠊ཯ᛂ๓ᵓ㐀ࠊ཯ᛂᚋᵓ㐀ࢆỴᐃࡋࠊάᛶ໬࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࡓࠋQM 㡿ᇦࡣࠊ㠀⤒㦂ⓗ࡞ᡭἲࡢ୍✀࡛࠶ࡿ DFT ࡢ࠺ࡕࠊB3LYP/6-31G (d)ࢆ౑⏝ࡋࡓࠋMM 㡿ᇦ࡟ࡣ AMBER ຊሙࢆ⏝࠸ࡓࠋࡋ࠿ࡋࠊ2 ẁ㝵┠ࡢຍỈศゎ཯ᛂࡢィ⟬࡛ᚓࡽࢀࡓάᛶ໬࢚ࢿࣝࢠ࣮ࡀୖ㏙ࡢ QM 㡿ᇦࢆ PM3 ࡛ィ⟬ࡋࡓ⤖ᯝ㸦34 kcal/mol㸧ࡼࡾࡶ኱ࡁࡃ࡞ࡗ࡚ࡋࡲࡗࡓࠋࡑࡇ࡛ࠊ2020 ᖺᗘࡣ QM 㡿ᇦ࡟ᇶ㉁௜㏆࡟Ꮡᅾࡍࡿ
Phe60 ࡢഃ㙐㒊ศࢆ㏣ຍࡋࡓ 99 ཎᏊࡢ⣔ࠊ99 ཎᏊࡢ⣔࡟ゐ፹Ỉ௜㏆ࡢṧᇶ㸦Phe173 ࡜ Ser176㸧ࡢഃ㙐ࢆ
㏣ຍࡋࡓ 118 ཎᏊࡢ⣔ࢆ౑⏝ࡋ࡚ྠᵝ࡟ィ⟬ࡋࡓࠋ- 96 -

཯ᛂ⤒㊰᥈⣴࡟ࡘ࠸࡚ࡣࠊࡇࢀࡲ࡛⾜ࡗ࡚ࡁࡓ≉ᐃࡢ཯ᛂᗙᶆ࡟ὀ┠ࡋ࡚ࠊࡑࡢཎᏊ㛫㊥㞳ࢆᡭ᧯స࡛ 0.1
Å ࡎࡘ⦰ࡵࠊྛⅬ࡛ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓᚋࡢ⤖ᯝ࠿ࡽ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢕࣮ࣝࢆᥥࡁࠊTS ᵓ㐀ࢆ᥎ࡍ

ࡿ SCAN ィ⟬࡛Ỵᐃࡉࢀࡓ PM3/amber ࣞ࣋ࣝࡢᵓ㐀ࢆึᮇᵓ㐀࡜ࡋ࡚⏝࠸ࠊNudged Elastic Band㸦NEB㸧
ἲ࡟ࡼࡾ TS ᵓ㐀ࡸ཯ᛂ⤒㊰ࢆ⮬ື᥈⣴ࡍࡿࢯࣇࢺ࢙࢘࢔ Reaction Plus Pro2㸦HPC ࢩࢫࢸ࣒ࢬ㸧ࢆ౑⏝ࡋࡓࠋᚓࡽࢀࡓ TS ೃ⿵ᵓ㐀ࢆᇶ࡟ TS ᵓ㐀᭱㐺໬ࠊ᣺ືᩘゎᯒࠊIRC ィ⟬ࢆ⾜ࡗ࡚άᛶ໬࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࡓࠋ㸱 ◊✲ᡂᯝ
2018 ᖺᗘ࡟⾜ࢃࢀࡓࠊL-DEX ࡟ࡼࡿ L-2-CPA ࡢ 2 ẁ㝵┠ࡢຍỈศゎ཯ᛂࡢ QM/MM ィ⟬࡟ࡘ࠸࡚ࡣࠊ80ཎᏊࡢ⣔࡛ QM 㡿ᇦࢆ B3LYP/6-31G (d)࡛ࣞ࣋ࣝィ⟬ࡋ࡚ᚓࡽࢀࡓάᛶ໬࢚ࢿࣝࢠ࣮ࡀࠊ40.4 kcal/mol ࡜࡞ࡾࠊQM 㡿ᇦࢆ PM3 ࡛ࣞ࣋ࣝィ⟬ࡋ࡚ᚓࡽࢀࡓάᛶ໬࢚ࢿࣝࢠ࣮(34.4 kcal/mol)ࡼࡾࡶ኱ࡁࡃࠊᐇ㦂⤖ᯝ࡜ࡶᑐᛂࡋ࡞࠸⤖ᯝ࡜࡞ࡗࡓࠋࡲࡓࠊ2019 ᖺᗘࡣຍỈศゎ཯ᛂ࡟㛵ࢃࡿ࡜ᛮࢃࢀࡿṧᇶ㸦Ser175㸧ࡢഃ㙐㒊ศࢆࡉࡽ࡟ຍ࠼ࡓ 85 ཎᏊࢆ QM 㡿ᇦ࡜ࡋ࡚ࠊSCAN ィ⟬ࡸ NEB ἲ࡟ࡼࡾ཯ᛂ⤒㊰ࢆ᥈⣴ࡋࡓࡶࡢࡢࠊScanィ⟬࡛ࡣ TS ೃ⿵ᵓ㐀ࢆぢࡘࡅࡿࡇ࡜ࡀ࡛ࡁࡎࠊNEB ἲ࡛ࡣࠊIRC ィ⟬࡛ TS ᵓ㐀࠿ࡽ཯ᛂ๓ࡢᵓ㐀㸦࢚ࢫࢸࣝ୰㛫యᵓ㐀㸧࡟ᡠࡽ࡞࠿ࡗࡓࡓࡵࠊάᛶ໬࢚ࢿࣝࢠ࣮ࢆィ⟬࡛ࡁ࡞࠿ࡗࡓࠋ
2020 ᖺᗘࡣ QM 㡿ᇦࢆ 99 ཎᏊ࡜ 118 ཎᏊ࡟ᣑᙇࡋ࡚ࠊࡇࢀࡲ࡛࡜ྠᵝ࡟ B3LYP/6-31G (d)࡛ࣞ࣋ࣝィ⟬ࡋࡓ࡜ࡇࢁࠊ1 ẁ㝵┠ࡢ⬺ࣁࣟࢤࣥ໬཯ᛂ࡟ࡘ࠸࡚ࡣࠊάᛶ໬࢚ࢿࣝࢠ࣮ࡀ 4.28 kcal/mol ࡜࡞ࡾࠊ80 ཎᏊࡢ⣔ࡢ 3.29 kcal/mol ࡼࡾᑡࡋ㧗࠸⤖ᯝ࡜࡞ࡗࡓࠋ2 ẁ㝵┠ࡢຍỈศゎ཯ᛂ࡟ࡘ࠸࡚ࡣࠊゐ፹Ỉࡀ࢚ࢫࢸࣝ⤖ྜࡋ࡚࠸ࡿ ASP10 ࡢⅣ⣲࡟ᨷᧁࡋ࡚⏕ᡂࡍࡿࢸࢺࣛ࣊ࢻࣛࣝ୰㛫యࡢᙧᡂ཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀ 30.87
kcal/mol ࡜࡞ࡾࠊࢸࢺࣛ࣊ࢻࣛࣝ୰㛫య࠿ࡽ⏕ᡂ≀ࡢ D-ங㓟ࡀ⏕ᡂࡍࡿ཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀ 10.31
kca/mol ࡜࡞ࡗࡓࠋࡇࡢ⤖ᯝࡣࠊ80 ཎᏊࡢ⣔ࡼࡾࡶᚊ㏿ẁ㝵ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀ⣙ 10 kcal/mol పୗࡋࡓࡶ
ࡢࡢࠊࡲࡔᐇ㦂⤖ᯝ࡜ᑐᛂࡋ࡞࠸άᛶ໬࢚ࢿࣝࢠ࣮ࡢ್࡛࠶ࡗࡓࠋ୍᪉࡛ࠊ2 ẁ㝵┠ࡢຍỈศゎ཯ᛂ࡟㛵ࢃࡿ࡜᥎ᐃࡉࢀ࡚࠸ࡓ Ser175 ࡸ Asn177 ࡢഃ㙐ࡢࣄࢻࣟ࢟ࢩᇶࡸ࢔࣑ࢻᇶࡀࠊゐ፹Ỉࡢ㓟⣲࡜Ỉ⣲⤖ྜ࡛ࡁࡿ఩⨨㛵ಀ࡟࠶ࡾࠊ཯ᛂࡢ㏵୰࡛⏕ᡂࡍࡿ࡜ᛮࢃࢀࡿࣄࢻࣟ࢟ࢩ࢖࢜ࣥࢆᏳᐃ໬ࡋ࡚࠸ࡿࡢ࡛ࡣ࡞࠸࠿࡜࠸࠺
ࡇ࡜ࡀ♧၀ࡉࢀࠊᐇ㦂⤖ᯝ࡜ᑐᛂࡋࡓࠋ
118 ཎᏊࡢ⣔࡟㛵ࡋ࡚ࡣࠊศᩓຊࢆ⪃៖ࡋࡓỗ㛵ᩘ㸦wB97X-D㸧ࢆ౑⏝ࡋ࡚ 2 ẁ㝵┠ࡢຍỈศゎ཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡢィ⟬ࢆヨࡳࡓࡶࡢࡢࠊ཯ᛂ⤒㊰඲యࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡍࡿ࡟⮳ࡽ࡞࠿ࡗࡓࠋ⌧ᅾࠊィ⟬ࢆᘬࡁ⥆ࡁ㐍ࡵ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ

㸲 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ  ࡞ࡋ㸳 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ  ࡞ࡋ

- 97 -

㠉᪂ⓗ㔞Ꮚ⛉Ꮫ࡜኱つᶍࢩ࣑࣮ࣗࣞࢩࣙࣥ⛉Ꮫࡢ๰㐀Innovations in computational quantum science and large-scale simulation science‫ۑ‬୰㎷ ༤ࠊ୰ᔱ ᾈஅࠊ㯮ᕝ ᝆ⣴㸦㔞Ꮚ໬Ꮫ◊✲༠఍㸧ᮏ◊✲ㄢ㢟࡛ࡣࠊ
ࠕ㠉᪂ⓗ㔞Ꮚ⛉Ꮫ࡜኱つᶍࢩ࣑࣮ࣗࣞࢩࣙࣥ⛉Ꮫࡢ๰㐀ࠖࡢࢸ࣮࣐ࡢࡶ࡜ࠊࠕṇ☜࡞ணゝⓗ㔞Ꮚ໬Ꮫ⌮ㄽࡢᵓ⠏࡜ᒎ㛤ࠖ࡜ࠕSAC-CI ἲࡢ⌮ㄽⓗᒎ㛤࡜ග⏕≀Ꮫࡸගᮦᩱ⛉Ꮫ࡬ࡢᛂ⏝ࠖࡢ◊✲ࢆᒎ㛤ࡋ࡚࠸ࡿࠋᮏሗ࿌᭩࡛ࡣࠊ๓⪅ࡢ◊✲ㄢ㢟ࡢ㐍ᒎ࡟ࡘ࠸࡚୺࡟ሗ࿌ࡍࡿࡀࠊᚋ⪅ࡢㄢ㢟࡛⾜ࡗࡓ㔞Ꮚ⛉Ꮫᢏ⾡◊✲㛤Ⓨᶵᵓࡢᶓ㇂᫂ᚨඛ⏕ࡢࢢ࣮ࣝࣉ࡜ඹྠ◊✲࡟ࡘ࠸࡚ࡶሗ࿌ࡍࡿࠋ

1 ◊✲┠ⓗ໬Ꮫࡣࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ࡟ࡼࡗ࡚ᨭ㓄ࡉࢀ࡚࠸ࡿࠋࡑࡢࡓࡵࠊࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࢆṇ☜࠿ࡘᐜ᫆࡟ゎࡃ⌮ㄽࡀᏑᅾࡋࠊࡑࢀࢆㄡࡶࡀ౑࠼ࡿィ⟬ࣉࣟࢢ࣒ࣛࡀ᏶ᡂࡍࢀࡤࠊ໬Ꮫ⌧㇟ࢆᐇ㦂ࡢࡳ࡛࡞ࡃ⌮ㄽ࡜ィ⟬࡟ࡼࡗ࡚ࡶṇ☜࡟ணゝࡍࡿ㐨ࡀ㛤ࡅࡿࠋᮏ◊✲ㄢ㢟ࡢ௦⾲⪅ࡣࠊ2000-2005 ᖺ࡟Ⓨ⾲ࡋࡓ exact
wave function ࡢᵓ㐀࡜ explicit ࡞⾲⌧࡟㛵ࡍࡿ◊✲ࠊࣁ࣑ࣝࢺࢽ࢔ࣥࡀࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࢆྵࡴ㝿ࡢⓎᩓࡢᅔ㞴ࡢඞ᭹࡞࡝ࢆ⤒࡚ࠊཎᏊ࣭ศᏊࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࢆṇ☜࡟ゎࡃࡇ࡜ࡢ࡛ࡁࡿ୍⯡⌮ㄽ:Free-Complement (FC) theory (⮬⏤᏶ဨ㛵ᩘ⌮ㄽ)ࢆⓎ⾲ࡋࡓ(H. Nakatsuji, J. Chem. Phys., Phys. Rev. Lett, Phys.
Rev. A,. www.qcri.or.jp.))ࠋᮏ◊✲ㄢ㢟ࡢ┠ⓗࡢ୍ࡘࡣࠊࡇࡢ⌮ㄽ࡟ᇶ࡙ࡁࠊࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢṇ☜࡞ゎࢆᐜ᫆࠿ࡘᏳᐃ࡟ィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ⌮ㄽ࡜᪉ἲࢆ๰ࡾୖࡆࠊࡑࡢゎࡢᣢࡘṇ☜࡞ணゝ⬟ࢆ᭱኱㝈ᘬࡁฟࡏࡿࡼ࠺࡟ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊ໬Ꮫ⪅ࡢࡓࡵࡢṇ☜࡞ணゝⓗ㔞Ꮚ໬Ꮫࢆᵓ⠏ࡍࡿࡇ࡜࡛࠶ࡿࠋࡲࡓࠊ௒
ᖺᗘࡢ◊✲ࡢࡶ࠺୍ࡘࡢ┠ⓗࡣࠊSAC-CI ⌮ㄽࢆෆẆ࢖࢜ࣥ໬ࡢ⌧㇟࡟ᛂ⏝ࡋࠊᐇ㦂ᐙ࡜ࡢඹྠ◊✲ࢆ᥎ࡋ㐍ࡵࡿࡇ࡜࡛࠶ࡿࠋ

2 ◊✲᪉ἲࠊィ⟬᪉ἲࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࢆṇ☜࡟ゎࡃࡓࡵ࡟ࠊᮏሗ࿌࡛୺࡟⏝࠸ࡓ᏶ဨ㛵ᩘ⌮ㄽ(FC ⌮ㄽ)࡜ィ⟬ἲࡢὶࢀࢆᅗ 1 ࡟ࡲ࡜ᅗ1. 䝅䝳䝺䞊䝕䜱䞁䜺䞊᪉⛬ᘧ䜢ṇ☜䛻ゎ䛟⌮ㄽ⮬⏤᏶ဨ㛵ᩘ⌮ㄽ(ṇ☜䛺䝅䝳䝺䞊䝕䜱䞁䜺䞊ゎ䜈䛾཰᮰)\\ Q 

ࡵࡓࠋ᏶ဨ㛵ᩘ⌮ㄽࡣࠊscaled ࢩ࣮ࣗࣞࢹ
࢕࣮ࣥ࢞᪉⛬ᘧ࡜ exact ࡞Ἴື㛵ᩘࢆ⾲⌧
ࡍࡿ SICI ⌮ㄽࢆ⤌ࡳྜࢃࡏ࡚ᚓࡽࢀࠊࡑ
ࡢἼື㛵ᩘࢆᵓᡂࡍࡿゎᯒ㛵ᩘࢆ⮬⏤࣭⊂

^IL `

FC⌮ㄽ

䠄Free Complement ⌮ㄽ䠅䠄ึᮇ㛵ᩘ䠅ª¬  &Q J +  (Q º¼\ Q䠄᏶ဨ㛵ᩘ䠅

¦ FI
0

\

,

, ,

໬Ꮫ䝣䜷䞊䝭䝳䝷⌮ㄽ䚸ᒁᡤⓗ䛺Ἴື㛵ᩘ⌮ㄽ
From Atomic States to Molecular States (FASTMS) 䝁䞁䝉䝥䝖཯ᑐ⛠໬䛾㧗㏿໬❧࡟ᢅ࠸(free complement function, ⮬⏤᏶ Nk⌮ㄽ: ⾜ิᘧ䝧䞊䝇䛾㧗㏿཯ᑐ⛠໬ Inter-exchange (iExg) ⌮ㄽ: ኱䛝䛺ศᏊ䛷O(N)ィ⟬䛾ᐇ⌧ဨ㛵ᩘ)ࠊࡑࡢ⥺ᙧ࿴࡛ exact Ἴື㛵ᩘࢆ⾲ኚศἲ(✚ศἲ)䝃䞁䝥䝸䞁䜾ἲ⌧ࡍࡿࠋࡉࡽ࡟ࠊ໬Ꮫ⪅ࡢ໬Ꮫᴫᛕ(ศᏊFC sij ⌮ㄽ

FC-LSE⌮ㄽᵓ㐀ᘧࡸ໬Ꮫ཯ᛂᘧ)࡟ᑐᛂࡍࡿἼື㛵ᩘኚศཎ⌮䜢‶䛯䛩㧗⢭ᗘィ⟬䛜
1,2㟁Ꮚ✚ศ䛾䜏䛷ྍ⬟✚ศ䞉ィ⟬䛾ไ⣙䛜䛺䛟䚸୍⯡ⓗ䛺ཎᏊ䞉ศᏊ䛷exactゎ䛾㏣ồ䛜ྍ⬟ࢆᵓ⠏ࡍࡿ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ(J. Chem.
Phys. 149, 114105 (2018))ࢆ౑࠺࡜ࠊṇ☜ࡉ࡜ྠ᫬࡟໬Ꮫⓗ⌮ゎ࡟ࡶ࡜⧅ࡀࡿࠋ኱ࡁ࡞ศᏊࡢィ⟬࡟ࡣࠊィ⟬㈇Ⲵࡢ኱ࡁ࡞㟁Ꮚࡢ཯ᑐ⛠໬ࢆ኱ࡁࡃῶࡽࡍࡇ࡜ࡢ࡛ࡁࡿ Nk ⌮ㄽࡸ Inter Exchange (iExg) ⌮ㄽࡀ᭷⏝࡛࠶ࡿࠋ- 98 -

FC Ἴື㛵ᩘ࡟ྵࡲࢀࡿኚศᮍ▱ಀᩘࡣࠊኚศἲ(✚ศἲ)ࡲࡓࡣ Local Schrödinger Equation (LSE) ἲ࡟ࡼࡗ࡚
Ỵᐃࡍࡿࠋ᏶ဨ㛵ᩘࡢ✚ศࡀྍ⬟࡛࠶ࡿሙྜࡣኚศἲࡀ᭷฼ࡔࡀࠊࡑ࠺࡛࡞࠸ሙྜࡣ LSE ἲࢆ౑࠺ࠋᮏᖺᗘ
ࡣ⮬⏤᏶ဨ㛵ᩘἲࢆࠊLSE ἲࠊ✚ศἲࡢ 2 ࡘࡢ❧ሙ࡛ᒎ㛤ࡋࡓࠋ⮬⏤᏶ဨ㛵ᩘἲ࡛ࡣࠊ2 㟁Ꮚ㛵ᩘ㡯࡟㧗⢭ᗘ࡞㛵ᩘࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊFC ⌮ㄽࡢἼື㛵ᩘࢆࠊ㛵ᩘᮏ᮶ࡢṇ☜ࡉ࡛グ㏙ࡋࠊexact ゎࢆ㏣ồࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࠋࡇࡢ᪉ἲ࡟ࡘ࠸࡚ࡣࠊ๓ᖺᗘࡢ࣏࣮ࣞࢺ࡛ሗ࿌ࡋ
ࡓࡀࠊࡇࡇ࡛ࡣࡲࡎࠊ㧗⢭ᗘ࡞㛵ᩘࢆ⏝࠸ࡿ㝿ࡢ᏶ဨ㛵ᩘࡢసᡂἲ࡟ࡘ࠸࡚ᖖ㐨࡟ࡢࡗ࡜ࡗࡓ᪉ἲࡢ⤖ᯝࡶ
㏣ຍⓗ࡟ሗ࿌ࡋ࡚࠾ࡃࠋࡇࡢ᪉ἲࡶ๓ࡢ᪉ἲࡶ exact Ἴື㛵ᩘࢆ୚࠼ࡿⅬ࡛ࡣྠࡌ࡛࠶ࡿࡀࠊィ⟬⬟⋡ࡢⅬ࡛ࡣ๓ࡢ᪉ἲࡢ᪉ࡀඃࢀ࡚࠸ࡿࠋ௒ᖺᗘࡣ LSE ἲࡢᨵⰋࢆ୺࡟⾜ࡗࡓࠋ௒ࡲ࡛ࡢ LSE ἲࡢࢧࣥࣉࣜࣥࢢἲ࡛
ࡣࠊ࣓ࢺ࣏ࣟࣜࢫἲࢆ⏝࠸ࡓࡀࠊࡇࡢ᪉ἲࡣྂ඾⤫ィᏛ࡟ᇶ࡙ࡃ᪉ἲ࡛ࠊࣛࣥࢲ࣒ࢿࢫ࡟ࡼࡿ᪂ࡓ࡞᭕᫕ᛶ
ࢆྵࢇ࡛ࡋࡲ࠺࡜ࡇࢁࡶ࠶ࡾࠊ௒ᖺᗘࡣ┤᥋ἲࠊᡈ࠸ࡣࠊ㏫ኚ᥮ἲ࡜࿧ࡤࢀࡿࡼࡾ rational ࡞ࢧࣥࣉࣜࣥࢢἲ
ࢆ㛤Ⓨࡍࡿࡇ࡜࡟୺ຊࢆ⨨࠸ࡓࠋࡲࡔࠊ୙᏶඲࡛࠶ࡿࡀࠊࣉࣟࢢࣞࢫ࣭࣏࣮ࣞࢺ࡜ࡋࡓ࠸ࠋ
ࡲࡎࠊ⮬⏤᏶ဨ㛵ᩘἲࢆ✚ศἲ࡟ࡼࡗ୍࡚⯡໬ࡍࡿࡓࡵ࡟ FC-sij ⌮ㄽࢆᥦၐࡋࡓ(Phys. Rev. A 101, 062508(2020)ࠋࡇࢀ࡟ࡘ࠸࡚ࡣ᪤࡟᫖ᖺࡢሗ࿌᭩࡟㏙࡭࡚࠸ࡿࡢ࡛ࠊヲ⣽ࡣ┬ࡃࡀࠊせࡣࠊ2 㟁Ꮚ㛵ᩘ rij 㡯ࡢ௦ࢃࡾ࡟ sij㸻rij2 = (xi-xj)2 + (yi-yj)2 + (zi-zj)2 㸻ri2 + rj2 - 2(xixj +yiyj +zizj)ࢆ⏝࠸ࡿࠋࡇࢀ࡟ࡼࡾࠊཎᏊ࣭ศᏊࡢィ⟬ࡣࠊ
ᬑ㏻ࡢ㔞Ꮚ໬Ꮫィ⟬࡜ྠᵝࠊ1࣭2 㟁Ꮚ✚ศࡢィ⟬ࡢࡳ࡛ྍ⬟࡟࡞ࡿࠋsij ࡣ rij ࡼࡾ⬟⋡ࡣᝏ࠸ࡀࠊⓎᩓࡢᅔ㞴ࡣⴠ࡜ࡍࡇ࡜ࡀ࡛ࡁࡿࠋ௒ᖺᗘࡢ୺࡞┠ⓗࡣࠊࡇࡢ FC sij ⌮ㄽࡢయ⣔ⓗࣉࣟࢢ࣒ࣛࢆసᡂࡋ࡚ࠊⰍࠎ࡞໬Ꮫ࡟
ᛂ⏝࡛ࡁࡿࡼ࠺࡟ࡍࡿࡇ࡜࡛࠶ࡿࠋ
ࡇࢀࡽࡢᡂᯝ࡟ࡘ࠸࡚ࠊ௨ୗ࡛ヲ⣽ࢆ㏙࡭ࡿࠋ

3 ◊✲ᡂᯝ
3.1 㧗⢭ᗘ࡞ࢫࢣ࣮ࣜࣥࢢ㛵ᩘࡢ⏕ᡂ
2004 ᖺ࡟Ⓨ⾲ࡋࡓ Schrödinger equation ࡢ୍⯡ゎἲࡢ᰿ᖿࡣࠊscaled Schrödinger equation J +  ( \ࡢᑟධ࡟࠶ࡿࠋࢫࢣ࣮ࣜࣥࢢ㛵ᩘ(g 㛵ᩘ)ࡣࠊ⢏Ꮚ⾪✺࡛ࡢࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝ࡟⏤᮶ࡍࡿⓎᩓࢆ㝖ཤࡍࡿാࡁࢆࡋࠊscaled ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ࡟ࡼࡗ࡚⾪✺ࡀ࠶ࡗ࡚ࡶṇࡋ࠸Ἴື㛵ᩘ࡟ᑟࡃࠋࡑࡇ࡛ g 㛵ᩘࡣ⾪✺㛵ᩘ࡜ࡶ࿧ࡤࢀࠊ᰾㟁Ꮚ㡯 JL$ ࡜ 2 㟁Ꮚ㡯 JLM ࠿ࡽ࡞ࡿࠋ᫖ᖺࡢሗ࿌᭩࡟ࡶ㏙࡭ࡓࡼ࠺࡟ࠊձ ⾪✺఩⨨࡛ࡢⓎᩓࢆ㜵ࡄ࡜ྠ᫬࡟⾪✺఩⨨࡛ࡢ᝟ሗࢆᾘࡉ࡞࠸(࢝ࢫࣉ᮲௳ࢆ‶ࡓࡍ)ࡇ࡜ࠊղ ⾪✺ࡢ࡞࠸㡿ᇦ࡛ࡣscaled ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡀඖࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ࡟₞㏆ࡍࡿࡇ࡜ࠊ࡜࠸࠺ 2 ᮲௳ࢆ‶ࡓࡍ࡭ࡁ࡛࠶ࡿࠋࡑࡢࡼ࠺࡞㛵ᩘࢆ correctࠊձࡢࡳࢆ‶ࡓࡍ㛵ᩘࢆ reasonableࠊձࢆ‶ࡓࡉ࡞࠸㛵ᩘࢆ approximate࡜࿧ࢇࡔࠋ⾲㸯࡟ࡑࡢᵝ࡞ 2 㟁Ꮚ㛵ᩘࡢ౛ࢆ࠶ࡆࡓ(ǻ( ࡣ⤯ᑐ࢚ࢿࣝࢠ࣮ࡢ exact ್࡜ࡢᕪࢆ♧ࡍ)ࠋࡑࡢࡼ
࠺࡞㛵ᩘ࠿ࡽసࡽࢀࡿ᏶ဨ㛵ᩘࡣࠊ1. 㛵ᩘ ULM ࢆ౑ࡗ࡚ྛ࣮࢜ࢲ࣮ࡢ cf ࢆᐃ⩏ࡋࠊࡑࡇ࡟ JLM ࢆ௦ධࡋࡓࡶࡢࠊ
2. ࡇࢀ࡟㐠ື₇⟬Ꮚࡢຠᯝࡶ㏣ຍࡋࡓฎ᪉⟢㏻ࡾࡢ᪉ἲ࡛సࡗࡓࡶࡢࠊࡢ஧㏻ࡾ࡛ィ⟬ࡋࡓ⤖ᯝࢆẚ㍑ࡋࡓࠋ
࣮࢜ࢲ࣮ࢆୖࡆ࡚࠸ࡃ࡜ࠊ࠸ࡎࢀࡢሙྜࡶ exact Ἴື㛵ᩘ࡟཰᮰ࡍࡿ࠿ࡽ࠸ࡎࢀ࡛ࡶࡼ࠸ࠋ1 ḟࡲ࡛ࡣ୧⪅୍⮴ࡍࡿࡀࠊ2 ḟ࠿ࡽࡣ␗࡞ࡿࠋ2.࡛ࡘࡃࡗࡓ cf ࡢᩘࡣ 1.ࡢࡑࢀࡼࡾ࠿࡞ࡾከ࠸ࡀࠊྠࡌಶᩘ࡛ぢࡿ࡜ 1. ࡢ᪉ἲࡢ᪉ࡀ཰᮰ࡀ㏿࠸ࠋ௨๓࡟ Gauss 㛵ᩘࡢ᫬ྠࡌࡼ࠺࡞⤒㦂ࢆࡋ࡚࠾ࡾࠊࡸࡣࡾ㐠ື₇⟬Ꮚ࠿ࡽసࡽࢀࡓ cfࡣ࣏ࢸࣥࢩࣕࣝ₇⟬Ꮚ࠿ࡽసࡽࢀࡓࡶࡢࡼࡾ less effective ࡛࠶ࡿ࠿ࠊ࠶ࡿ࠸ࡣࠊredundant ࡛࠶ࡗࡓࠋ⾪✺ࡀ࣏ࢸࣥࢩࣕࣝ₇⟬Ꮚ࡟⏤᮶ࡍࡿࡇ࡜࠿ࡽࠊࡇࢀࡣᙜ↛࡜ゝ࠼ࡿࠋ1. ࡢ᪉ἲࡣࠊྛḟᩘ࡛㛵ᩘ࡟ࡼࡽࡎ cf ࡢᩘࡀ୍ᐃࡋ࡚࠸ࡿࡇ࡜ࡶ࣓ࣜࢵࢺ࡛࠶ࡿࠋ
᫖ᖺࡢሗ࿌࡛ࡶ᭩࠸ࡓࡼ࠺࡟ࠊ௨๓࠿ࡽ⏝࠸࡚ࡁࡓࢫࢣ࣮ࣜࣥࢢ㛵ᩘ rij ࡣ”reasonable”㛵ᩘ࡛ࠊࡑࡢ௚ࡢ࡝
ࡢ”correct”ࠊ ”reasonable”㛵ᩘࡼࡾࡶ཰᮰ࡀ㐜࠸ࠋLSE ἲࢆ⏝࠸ࢀࡤ࡝ࡢࡼ࠺࡞ g 㛵ᩘࡶᐜ᫆࡟ᢅ࠺ࡇ࡜ࡀ࡛

- 99 -

ࡁࡿࡢ࡛ࠊ㧗ᛶ⬟ࡢ”correct”㛵ᩘ࡟ศࡀ࠶ࡿࠋ୍⯡ࡢཎᏊ࣭ศᏊ࡛ࡶࠊFC-LSE ἲ࡟ࡼࡗ࡚ࠊṇࡋ࠸ᣲືࢆᣢ
ࡘ”Correct” g 㛵ᩘࢆ⏝࠸ࡿࡇ࡜࡛ࠊ௒㎾ࡼࡾṇ☜࠿ࡘᐜ᫆࡟ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢゎࡀᚓࡽࢀࡿࡇ࡜
ࡀᮇᚅࡉࢀࡿࠋ⾲ +H ཎᏊ࡟࠾ࡅࡿ gij 㛵ᩘࡢ᳨ド
g

᪉ἲ

M

n 
ǻE
NFDOPROMn 
ǻE
NFDOPROMn 
ǻE
NFDOPROMn 
ǻE
NFDOPRO&RUUHFWU  E U  E U


 



 

 U  E U  E U  D

(L J  U  J   (L J U  U  D
DUFWDQ J  U  H[S J  U








































































































































5HDVRQDEOH
U H[S J  U
VLQ J  U
U

3.2 FC-LSE ⌮ㄽࡢ㧗⢭ᗘ໬Ἴື㛵ᩘࡢ㧗⢭ᗘ໬: FC-LSE ⌮ㄽࡣࠊἼື㛵ᩘࡀ potentially exact ࡛࠶ࡿ࡯࡝ࠊࡑࡢ㛵ᩘᮏ᮶ࡢṇ☜ࡉࢆ཯ᫎࡋᏳᐃ࡟ゎࢆồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡑࡢࡓࡵࠊ⣔࡟㐺ࡋࡓึᮇ㛵ᩘ࡜ g 㛵ᩘࡢ㑅ᢥࡣࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞
ࣞ࣋ࣝࡢゎࢆຠ⋡ⓗ࡟ィ⟬ࡍࡿࡓࡵ࡟㔜せ࡛࠶ࡿࠋᡃࠎࡣࠊึᮇ㛵ᩘࡢᵓ⠏ࡢࡓࡵࠊ໬Ꮫ⪅ࡢ໬Ꮫᴫᛕ(ศᏊᵓ㐀ᘧࡸ໬Ꮫ཯ᛂᘧ)࡜ᑐᛂࡍࡿἼື㛵ᩘࢆᵓ⠏ࡍࡿ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽࢆᥦ᱌ࡋࡓ(J. Chem. Phys. 149,
114105 (2018).)ࠋࡇࡢ᪉ἲࡣࠊ໬Ꮫⓗ࡞ᮏ㉁ࢆἼື㛵ᩘ࡟཯ᫎࡍࡿࡓࡵṇ☜ࡉ࡜ྠ᫬࡟໬Ꮫⓗ⌮ゎ࡟ࡶ⧅ࡀࡾࠊ
ᒁᡤⓗ࡞Ἴື㛵ᩘ(㟁Ꮚ≧ែ)⌮ㄽ࡛࠶ࡿࡓࡵ iExg ⌮ㄽ࡞࡝࡜㐃ᦠࡋ኱ࡁ࡞⣔࡬ࡢᣑᙇ࡟ࡶ⧅ࡆࡽࢀࡿࠋࡲࡓࠊ
ྛ㟁Ꮚ࡟␗࡞ࡿ㌶㐨ࢆ඘࡚ࡿᴫᛕࢆᑟධࡋࠊ1 㟁Ꮚ㛵ᩘ࡛ࣞ࣋ࣝ㟁Ꮚ┦㛵ࢆᑟධࡍࡿ㓄⨨ࢆసࡿࠋࡇࢀࡣࠊ
ཎᏊෆࡢ㛢Ẇࢩ࢙࡛ࣝࡣ in-out ┦஫స⏝࡟ᑐᛂࡋࠊ໬Ꮫ⤖ྜࢆᙧᡂࡍࡿ singlet coupling ࡣ left-right ┦஫స⏝࡜ࡋ࡚グ㏙ࡍࡿࠋᚋ⪅ࡣࠊศᏊ㌶㐨(Hartree-Fock ㌶㐨)࡜ࡣ␗࡞ࡾᖹ⾮≧ែ࠿ࡽゎ㞳㐣⛬ࡲ࡛ṇࡋ࠸グ㏙ࢆ୚࠼ࡿࠋࡉࡽ࡟ࠊgij 㛵ᩘ࡟ᑐࡋ࡚ 3.1 ࡛ᥦ᱌ࡋࡓ”correct”ᆺࡢ୍⯡໬ࢫࢣ࣮ࣜࣥࢢ㛵ᩘࢆ⏝࠸ࡿࠋLSE ἲ࡛࠶ࡿࡓࡵࠊ࡝ࡢࡼ࠺࡞㛵ᩘ࡛ࡶᢅ࠺ࡇ࡜ࡀ࡛ࡁࠊ”reasonable”ࡸ” approximate”ࢆ⏝࠸ࡿᚲせࡣ࡞࠸ࠋࡲࡓࠊ」ᩘࡢ
gij 㛵ᩘࢆ⏝࠸ࡿࡇ࡜ࡶ᭷⏝࡛࠶ࡿࠋ␗࡞ࡿゎᯒ㛵ᩘࡀ஫࠸ࢆ⿵᏶ࡋ࡚඲యࡢ㟁Ꮚ┦㛵ࢆຠ⋡ⓗ࡟グ㏙࡛ࡁࡿࠋLSE ⌮ㄽࡢ㧗⢭ᗘ໬: ࢧࣥࣉࣜࣥࢢ⌮ㄽ࡛ࡣࠊࢧࣥࣉࣜࣥࢢⅬࡢᐦᗘࡀ඲Ἴື㛵ᩘ\ ࡢ 2 ஌( * \  )࡟ἢ
࠺ศᕸ࡛⏕ᡂࡉࢀ࡚࠸ࡿ࡜ࡁࠊimportance sampling ࡟ࡼࡗ࡚ࢧࣥࣉࣜࣥࢢ౫Ꮡᛶࢆ㍍ῶࡋṇ☜࡞ィ⟬⤖ᯝࢆᏳᐃ࡟ィ⟬࡛ࡁࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋ௨๓ࡢィ⟬࡛ࡣࠊࡇࢀࢆᐇ⌧ࡍࡿࡓࡵ࡟ྛ㟁Ꮚࡢ local sampling ࢆฟⓎศᕸ࡜ࡋ࡚࣓ࢺ࣏ࣟࣜࢫἲࢆ⏝࠸ࡿ LMn ἲࢆᥦ᱌ࡋࡓ(J. Chem. Phys. 149, 114106 (2018).)ࠋࡋ࠿ࡋࠊ࣓ࢺ࣏ࣟ
ࣜࢫἲࡣྂ඾ⓗ࡞᪉ἲ࡛࠶ࡾࠊࣃ࣓࣮ࣛࢱࡢ౫Ꮡᛶࡶ኱ࡁࡃࠊࡼࡾ☜ᐇ࡛Ᏻᐃ࡞ࢧࣥࣉࣜࣥࢢἲࡢ☜ಖࡀ㔜せ࡛࠶ࡿࠋࡑࡇ࡛ࠊᮏᖺᗘࡢ◊✲࡛ࡣࠊᡃࠎࡣࠊlocal sampling ࡢᴫᛕࢆᣑᙇࡋࠊ࣓ࢺ࣏ࣟࣜࢫἲࢆ౑ࢃࡎࠊ
N 㟁ᏊἼື㛵ᩘ\ V ࠿ࡽ┤᥋ࠊࢧࣥࣉࣜࣥࢢⅬࢆ㏫ኚ᥮ἲ(/'HYUR\H³1RQ8QLIRUP5DQGRP9DULDWH*HQHUDWLRQ´- 100 -

1HZ<RUN6SULQJHU9HUODJ  ࡟ࡼࡗ࡚⏕ᡂࡍࡿ”┤᥋ἲ”ࢆ⏝࠸ࡓࠋࡲࡎࠊከ㟁Ꮚ⣔࡟࠾࠸࡚㔜せ࡞Ἴື㛵ᩘࡢ཯ᑐ⛠໬ࢆࢧࣥࣉࣜࣥࢢⅬ⏕ᡂ࡟཯ᫎࡍࡿࡇ࡜ࢆ⪃࠼ࠊ⣔ࢆ௦⾲ࡍࡿ \  ࢆ\ V ࡜ࡋ࡚⏝࠸ࡿ཯ᑐ⛠໬ࢧࣥࣉࣜࣥࢢࡢᐃᘧ໬ࢆ⾜ࡗࡓࠋࡇࡢィ⟬࡛ᚲせ࡞཯ᑐ⛠ᛶࢆྵࡴ⦰⣙ᐦᗘ⾜ิࡣࠊ/|ZGLQ ࡢㄽᩥ 3 /|ZGLQ
3K\V5HY$  ࡟♧ࡉࢀ࡚࠸ࡿ IXQGDPHQWDOLQYDULDQW  㟁Ꮚᐦᗘ⾜ิࡑࡢࡶࡢ ࢆ⏝࠸ࡓ⾜ิᘧ⾲⌧࡛ィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁࠊ1 ࡢከ㡯ᘧ⛬ᗘࡢ RUGHU ࡛཯ᑐ⛠໬ࢧࣥࣉࣜࣥࢢⅬࡢ⏕ᡂࡀྍ⬟࡛࠶ࡿࠋࡉࡽ࡟\ V࡜ࡋ࡚ࠊ㟢ࢃ࡞㟁Ꮚ┦㛵(rij, gij)ࡶྵࡴ FC ⌮ㄽࡢἼື㛵ᩘ\ ⮬㌟ࢆ⏝࠸ࡿ᪉ἲࡶ⌧ᅾ㛤Ⓨ୰࡛࠶ࡿࠋࡲࡓࠊ඲
㟁ᏊἼື㛵ᩘ࡟ᑐࡍࡿ┤᥋ἲ࡛ࡣ࡞ࡃࠊ୰㎷ࡢᐦᗘ⾜ิࡢ┤᥋Ỵᐃἲࡢ◊✲(Phys. Rev. A 14, 41 (1976))➼࡛ࣇ࢓࣑ࣜ࢔̿࡞ 1 㟁Ꮚ, 2 㟁Ꮚ⦰⣙ᐦᗘ⾜ิ࡜ N-representability ࢆ⏝࠸ࡓࢧࣥࣉࣜࣥࢢⅬࡢ⏕ᡂἲࡶ㛤Ⓨ୰࡛࠶ࡿࠋࡇࢀ࡟ࡼࡗ࡚ࢧࣥࣉࣜࣥࢢⅬ⏕ᡂ࡟ಀࡿィ⟬㔞ࢆ኱ࡁࡃ๐ῶࡋ࡞ࡀࡽࠊ㧗⢭ᗘࡢ FC-LSE ἲࢆ㛤Ⓨ࡛ࡁࡿྍ⬟ᛶࡀ࠶ࡿࠋ ௨ୖࡢ◊✲㛤Ⓨࡢ⤖ᯝࢆ౑ࡗ࡚ᚓࡽࢀࡓᗄࡘ࠿ࡢᡂᯝࢆḟ࡟㏙࡭ࡿࠋ

3.3 ᪂ࡋ࠸ FC-LSE ⌮ㄽࡢᛂ⏝Be ཎᏊࡢィ⟬: ࡲࡎࠊୖࡢ⌮ㄽࠊィ⟬ἲࢆ Be ཎᏊ࡟ᛂ⏝ࡋࡓ⤖ᯝࢆ♧ࡍࠋึᮇ㛵ᩘࡣࠊ



\ 

VLQ VRXW DE  ED  VLQ V RXW DE  ED

\ 

VLQ VRXW DE  ED  ª¬  S[    S \    S]  º¼ DE࡛࠶ࡿࠋ2s,2p ㌶㐨ࡣ࢚ࢿࣝࢠ࣮‽఩ࡀ㏆ࡃᨃ⦰㏥࡛࠶ࡿࡢ࡛\  ࡜ࡋ࡚(2s)2Ѝ(2p)2 ࡢ 2 㟁Ꮚບ㉳㓄⨨ࡶྲྀࡾධࢀࡓࠋᵝࠎ࡞ࢫࢣ࣮ࣜࣥࢢ gij 㛵ᩘࢆ౑ࡗ᳨࡚ドࡋࡓ⤖ᯝࢆ⾲ 2 ࡟♧ࡍࠋᕥഃ࡟♧ࡍ 1 ✀ࡢ gij 㛵ᩘ(Single)
࡛ࡣࠊorder(n)=2 ࡛඲࡚ࡢ gij 㛵ᩘ࡛ ǻ( ࡀ 1 kcal/mol ௨ୗࡢゎࡀᚓࡽࢀࠊn=3 ࡟ୖࡆࡿ࡜ከࡃࡢ”Correct”ࡢ gij㛵ᩘ࡛ࡣࡉࡽ࡟ 1 ᱆⢭ᗘࡀୖࡀࡾ 0.1 kcal/mol ௨ୗࡢゎࡀᚓࡽࢀ࡚࠸ࡿࠋࡉࡽ࡟ྑഃ࡟♧ࡍ 2 ✀(Double), 3 ✀(Triple)࡛ྛ gij 㛵ᩘ࡟⊂❧࡟ኚศಀᩘࢆ assign ࡍࡿ࡜ࡉࡽ࡟㧗⢭ᗘ࡞⤖ᯝࡀᏳᐃ࡟ᚓࡽࢀ࡚࠸ࡿࠋ≉࡟ࠊn=3
࡛ࡣ 0.01 kcal/mol, 0.001 kcal/mol ௨ୗࡢゎࡶᚓࡽࢀ࡚࠾ࡾࠊgij=rij ࡛ィ⟬ࡋࡓኚศἲ(✚ศἲ)࡛ィ⟬ࡋࡓ⤖ᯝ(J.
Chem. Phys. 150, 044105 (2019))ࡼࡾࡶ㠀ᖖ࡟㧗⢭ᗘ࡞ゎࡀᚓࡽࢀࠊ୍⯡໬ gij 㛵ᩘࡢ᭷ຠᛶࢆ♧ࡋ࡚࠸ࡿࠋࡲ
ࡓࠊLSE ἲࡢィ⟬᫬㛫ࡣࠊ3,4 㟁Ꮚ✚ศࢆせࡍࡿ FC sij-assisted rij ἲࡢኚศἲ࡜ẚ࡭࡚ࡶ㠀ᖖ࡟㏿ࡃ(n=3 ࡛
LSE(Single):11.8 min, ኚศἲ:8.6 hour)ࠊexact ィ⟬࡜ࡣᛮ࠼࡞࠸㧗㏿࡞ィ⟬ࡀྍ⬟࡟࡞ࡗ࡚࠸ࡿࠋࡲࡓࠊ࣓ࢺ
࣏ࣟࣜࢫἲࢆ౑ࢃ࡞⾲ %H ཎᏊࡢィ⟬࠸┤᥋ἲ(㏫ኚ᥮)࡟ 1R

gij
n 
n 

gij
n 
n 

ǻE NFDOPRO   
ǻE NFDOPRO  ࡼࡿ཯ᑐ⛠໬ࢧࣥࣉ &RUUHFW 6LQJOH 
M  M   'RXEOH M  M 
U  E U  E U  U  E U  E U  D  
   
ࣜࣥࢢࡣࠊLMn ἲࡢU  E U  U  E U  D 
   
⧞ࡾ㏉ࡋࡶᚲせ࡜ࡏ (L J  U  J   (L J  
   
U  E U   E U  U  E U   E U  D  



ࡎࠊἼື㛵ᩘࡢ
U  E U  U  E U  D 
   
quality ࢆᚤ⣽࡞ࣞ࣋ U  U  D 
   
DUFWDQ J  U 

 
ࣝࡲ࡛⢭ᐦ࠿ࡘᏳᐃ
  H[S J  U 
   
࡟ィ⟬ࡍࡿࡇ࡜ࡀ࡛ 
WDQK J  U 
  7ULSOH M  M 
5HDVRQDEOH 6LQJOH 
M  M     
ࡁ࡚࠸ࡿࠋ
U H[S J  U 
    
U H[S J  V 
    VLQ J  U 
    
U 


    

- 101 -

B ཎᏊࡢィ⟬: ḟ࡟ࠊB ཎᏊࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ࣞ࣋ࣝࡢゎࡢィ⟬࡟ᛂ⏝ࡋࡓࠋB ཎᏊࡣ 5 㟁Ꮚࡢ༢⣧࡞⣔࡛࠶ࡿࡀࠊ2s ㌶㐨࡜ 2p ㌶㐨ࡢ࢚ࢿࣝࢠ࣮㡰఩ࡀ㏆᥋ࡋ࡚࠸ࡿࡓࡵࠊ2s ㌶㐨࡟ᑐࡍࡿ⮬⏤ᗘ࡜ 2s, 2p 㟁Ꮚࡢ㛵㐃ࡍࡿࢫࣆࣥ㛵ᩘࡸ 2sЍ2p ࡬ࡢ 2 㟁Ꮚບ㉳㓄⨨ࡀ㔜せ࡟ᐤ୚ࡍࡿྍ⬟ᛶࡀ࠶ࡿࠋࡇࢀࡽࡣࠊHartree-Fockࡸ CI ➼ࡢ㏆ఝⓗ࡞࡛ࣞ࣋ࣝࡣ࠶ࡲࡾຠ࠿࡞࠸ࡀࠊexact ࣞ࣋ࣝࡢゎࢆᚓࡿࡓࡵ࡟ࡣ㠀ᖖ࡟㔜せ࡛࠶ࡿሙྜࡀ
࠶ࡿࠋࡑࡇ࡛ࠊB ཎᏊ(2P ᇶᗏ≧ែ)ࡢึᮇ㛵ᩘ࡜ࡋ࡚ࠊ



\ 

U 
VLQ VRXW DE  ED  VLQU  V RXW
 S[ DE  ED D

\ 

U 
VLQ VRXW DE  ED  VLQU  V RXW
 S[

\ 

VLQ VRXW DE  ED  ¬ª  S[    S \    S]  ¼º DE   S[ D\ \  \ DE  ED D  DDE S[ o  S[ࢆ᥇⏝ࡋࡓࠋࡇࡇ࡛ࠊ\  ࡣ Aufbau principle ࡛⤌ࡳ❧࡚ࡽࢀࡿ୺㓄⨨࡛ࠊ\  ࡣ 2P ≧ែ࡛ 2s,2p 㟁Ꮚࡢ⤡ࡴ
ࡶ࠺ 1 ࡘࡢࢫࣆࣥ㛵ᩘࡢ㓄⨨࡛࠶ࡿࠋ\  ࡣ(2s)2Ѝ(2p)2 ࡢ 2 㟁Ꮚບ㉳㓄⨨࡛࠶ࡿࠋ\  ࡣ\  \   ࡢ 2px ㌶㐨
࡟ูࡢ㌶㐨ᣦᩘࢆ⏝࠸࡚ 2p ㌶㐨ࢆ double ࡟ࡋࡓ㓄⨨࡛࠶ࡿ(\  ࠿ࡽࡣ n=1 ࡢ cf ࡢࡳࢆ⏕ᡂ)ࠋ
U ࡲࡓࠊ VLQU   VRXW
ࡣ 2s ㌶㐨ࡢ୺࡛࠶ࡿ U H[S D UV U ࡜ 1s ࡜ࡢ┤஺໬㡯 H[S D UV U ࢆ⊂❧࡞ cf ࡜ࡋ࡚ᢅ࠺

ࡇ࡜ࢆ♧ࡍࠋgij 㛵ᩘࡣࠊ࣭ Single: No.1 ( (L J  U  J   (L J , No.3 (   H[S J  U

࣭ Double: No. 3 + No. 8
࣭ Triple: No. 3 + No. 6 + No. 8
࣭ Quadruple: No. 3 + No. 6 + No. 7 + No. 8
ࢆ᳨ドࡋࡓ(No.ࡣ⾲ 2 ཧ↷)ࠋ⾲ 3 ࡟ࠊ\  㹼\  ࠿ࡽࡢ cf ⏕ᡂࢆẁ㝵ⓗ࡟ྲྀࡾධࢀࡓ࡜ࡁࡢ n=2 ࡢィ⟬⤖ᯝࢆ♧ࡋࡓࠋձ: ୺㓄⨨࡛࠶ࡿ\  ࡢࡳ࠿ࡽ cf ࢆ⏕ᡂࡍࡿ࡜ࠊgij ࢆ Quadruple ࡲ࡛ᑟධࡋ࡚ࡶ ǻ( ࡣ NFDOPRO࡜໬Ꮫ⢭ᗘࡣᚓࡽࢀ࡞࠿ࡗࡓࠋḟ࡟ࠊղ \  ࡜ࡶ࠺  ࡘࡢ GRXEOHW ࢫࣆࣥ㛵ᩘࡢ㓄⨨࡛࠶ࡿ\  ࢆᑟධࡍࡿ
࡜ࠊǻ( ࡣ኱ࡁࡃᨵၿࡋ 'RXEOH ௨ୖࡢ JLM 㛵ᩘࡢሙྜ࡟໬Ꮫ⢭ᗘࡀᚓࡽࢀࡓࠋࡉࡽ࡟ࠊճ 2sЍ2p ࡬ࡢ 2 㟁Ꮚບ㉳㓄⨨, մS ㌶㐨ࢆ GRXEOH ࡜ࡋࡓ\  Q  ࢆᑟධࡋࡓ࡜ࡁࡣࠊղ࡜ẚ࡭ FI ࡢḟඖࡣࡑࢀ࡯࡝ቑຍࡋ࡚࠸࡞࠸ࡀ ǻ( ࡣ࠿࡞ࡾᨵၿࡋࡓࠋࡲࡓࠊH-square error(Ἴື㛵ᩘࡢ exactness ࢆ♧ࡍ 1 ࡘࡢ㔜せ࡞ᣦᶆ(exact ࡛࠶ࢀࡤ 0))ࡣࠊἼື㛵ᩘࡀⰋࡃ࡞ࡾࡉࡽ࡟ Double, Triple, Quadruple ࡟࡞ࡿ࡯࡝ 0 ࡟㏆࡙ࡁࠊἼື㛵ᩘࡶṇ☜࡟ィ⟬࡛ࡁ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋFC ⌮ㄽ࡛ࡣ\  ࡢࡳ࡛ࡶ RUGHU ࢆ㐍ࡵࢀࡤ H[DFW ࡬཰᮰ࡍࡿࡀࠊ໬Ꮫࣇ࢛࣮࣑ࣗ
ࣛ⌮ㄽ࡟ᚑ࠸≀⾲ % ཎᏊࡢィ⟬ ≀⌮ⓗ࡞ึᮇ㛵ᩘࡢ㑅ᢥࢆ᳨ド  n  ձ \  ղ \  \  gij 1R+VTXDUH (QHUJ\ǻE+VTXDUH (QHUJ\
ǻE
M
M
HUURU (H[DFW  DX 
NFDOPRO 
HUURU (H[DFW  DX 
NFDOPRO 
せ࡞㓄⨨ࢆ㐺ษ 6LQJOH             ࡟ྲྀࡾධࢀࡿࡇ
 6LQJOH             ࡜ࡀ࡛ࡁࢀࡤࠊᐇ
 'RXEOH              7ULSOH             ⏝ⓗ࡞ Q  ࣞ࣋ 4XDGUXSOH              ࡛ࣝࡶࢩ࣮ࣗࣞ
ճ \   \   \   մ \  , \  , \  , \  (n=1)
gij 1R+VTXDUH (QHUJ\ǻE+VTXDUH (QHUJ\ǻEࢹ࢕࣮ࣥ࢞ࣞ࣋M
M
HUURU (H[DFW  DX 
NFDOPRO 
HUURU (H[DFW  DX 
NFDOPRO ࣝࡢゎࢆຠ⋡ⓗ 6LQJOH             
6LQJOH            ࡟ィ⟬ࡍࡿࡇ࡜
 'RXEOH             ࡀ࡛ࡁࡓࠋ 7ULSOH              4XDGUXSOH        ⌮ⓗ࣭໬Ꮫⓗ࡟㔜- 102 -

C ཎᏊ(s2p2, 3P ≧ែࠊsp3, 5So ≧ែ)ࡢィ⟬: C ཎᏊ(s2p2, 3P ≧ែ)ࡶ㛢Ẇࡢ 2s ㌶㐨ࢆྵࡳࠊ2s ㌶㐨࡟ᑐࡍࡿ⮬⏤ᗘࡸ 2s, 2p 㟁Ꮚࡢ㛵㐃ࡍࡿࢫࣆࣥ㛵ᩘ, 2sЍ2p ࡬ࡢ 2 㟁Ꮚບ㉳㓄⨨࡞࡝ࡀ㔜せ࡟ᐤ୚ࡍࡿྍ⬟ᛶࡀ࠶ࡿࠋ
ࡑࡢࡓࡵࠊB ཎᏊ࡜ྠᵝ࡟௨ୗࡢึᮇ㛵ᩘࢆ᥇⏝ࡋࡓࠋ



\ 

U 
VLQ VRXW DE  ED  VLQU  V RXW
 S[  S \ DE  ED DD

\ 

U 
VLQ VRXW DE  ED  VLQU  V RXW
 S[  S \DE  ED D  DDE D

\ 

U 
VLQ VRXW DE  ED  VLQU  V RXW
 S[  S \DED  EDD  DDE D  DDDE\ 

VLQ VRXW DE  ED  ¬ª  S[    S \    S]  º¼ DE   S[  S \ DD\  ࡣ Aufbau principle ࡛⤌ࡳ❧࡚ࡽࢀࡿ୺㓄⨨࡛ࠊ\  ,\  ࡣ 3P ≧ែ࡛ 2s,2p 㟁Ꮚࡢ⤡ࡴูࡢࢫࣆࣥ㛵ᩘࡢ㓄⨨࡛࠶ࡾࠊ\  ࡣ(2s)2Ѝ(2p)2 ࡢ 2 㟁Ꮚບ㉳㓄⨨࡛࠶ࡿࠋ୍᪉ࠊC ཎᏊ(sp3, 5So ≧ែ)ࡣࠊ2s, 2px, 2py, 2pz 㟁Ꮚࡀ඲࡚㛤Ẇࡢ㧗ࢫࣆࣥ≧ែ࡜࡞ࡗ࡚࠾ࡾࠊࡇࢀࡽࡢ㟁Ꮚࡢ⤡ࡴࢫࣆࣥ㛵ᩘࡣ 1 ㏻ࡾࡋ࠿Ꮡᅾࡋ࡞࠸ࠋࡑࡢࡓ
ࡵࠊึᮇ㓄⨨ࡣ௨ୗࡢࡼ࠺࡟୺㓄⨨ࡢࡳ࡛᭩࠿ࢀࡿࠋ\

VLQ VRXW DE  ED  V U   S[  S \  S] DDDD ⾲  ࡟ィ⟬⤖ᯝࢆ♧ࡋࡓࠋC ཎᏊ(s2p2, 3P ≧ែ)ࡢィ⟬࡛ࡣࠊ6LQJOH ࡢ JLM 㛵ᩘ࡛ࡣ ǻ( ࡀ 㹼NFDOPRO ࡛ഹ࠿࡟໬Ꮫ⢭ᗘ࡟฿㐩ࡋ࡞࠿ࡗࡓࡀࠊ'RXEOH 7ULSOH ࡢ JLM 㛵ᩘ࡛ࡣ໬Ꮫ⢭ᗘࢆ㐩ᡂࡋࡓࠋ୍᪉ࠊC ཎᏊ(sp3, 5So≧ែ)ࡣࠊC ཎᏊ(s2p2, 3P ≧ែ)ࡼࡾࡶḟඖࡀᑠࡉ࠸࡟ࡶ㛵ࢃࡽࡎ ǻ(+VTXDUHHUURU ඹ࡟Ⰻ࠸⤖ᯝࡀᚓࡽࢀ࡚࠸
ࡿࠋ㧗ࢫࣆ࡛ࣥ࠶⾲ & VS & VS ཎᏊࡢィ⟬ n  & VS & VS gij 1R+VTXDUH (QHUJ\ǻE+VTXDUH (QHUJ\
ǻE
M
M
ࡢ㟁Ꮚࡀ㏆᥋ࡍ
HUURU (H[DFW  DX 
NFDOPRO 
HUURU (H[DFW  DX 
NFDOPRO  6LQJOH             ࡿࡇ࡜ࡀ࡞ࡃࠊ㧗 6LQJOH             ⢭ᗘἼື㛵ᩘࡢ
 'RXEOH              7ULSOH             
グ㏙ࡀᐜ࡛᫆࠶
 4XDGUXSOH        ࡿࡓࡵࠊ␗ࢫࣆࣥ

ࡿࡇ࡜ࡀศ࠿ࡿࠋ

N ཎᏊࡢィ⟬: N ཎᏊࡶ B ཎᏊࡸ C ཎᏊ(s2p2, 3P ≧ែ)࡜ྠᵝ࡟ࠊ2s ㌶㐨࡟ᑐࡍࡿ⮬⏤ᗘ, 2s, 2p 㟁Ꮚࡢ㛵㐃ࡍࡿࢫࣆࣥ㛵ᩘ(4 ࡘࡢ⊂❧࡞ࢫࣆࣥ㛵ᩘ)࠿ࡽึᮇ㛵ᩘࢆᵓ⠏ࡋࡓࠋ2px, 2py, 2pz ㌶㐨࡜ࡶ high spin ࡛༨᭷ࡉࢀ࡚࠸ࡿࡓࡵ(2s)2Ѝ(2p)2 ࡢ 2 㟁Ꮚບ㉳㓄⨨ࡣ࡞࠸ࠋ

\ 

U 
VLQ VRXW DE  ED  VLQU  V RXW
 S[  S \  S] DE  ED DDD

\ 

U 
VLQ VRXW DE  ED  VLQU  V RXW
 S[  S \  S]

DE  ED D  DDE DD\VLQ VRXW DE  ED  V

DED  EDD  DDE D  DDDE D



\ 

U 
LQ

V

U 
RXW

 S[  S \  S]

U 
VLQ VRXW DE  ED  VLQU  V RXW
 S[  S \  S]

DEDD  EDDD  DDED  DDDE D  DDDDE⾲  ࡟ィ⟬⤖ᯝࢆ♧ࡋࡓࠋC ཎᏊ(s2p2, 3P ≧ែ)࡜ྠᵝ࡟ 6LQJOH
ࡢ JLM 㛵ᩘ࡛ࡣ ǻ( ࡀ 㹼NFDOPRO ࡛ഹ࠿࡟໬Ꮫ⢭ᗘ࡟฿⾲ 1 ཎᏊࡢィ⟬ n  +VTXDUH (QHUJ\ǻE
HUURU
(DX
NFDOPRO
H[DFW 㐩ࡋ࡞࠿ࡗࡓࡀࠊ'RXEOH 7ULSOH ࡢ JLM 㛵ᩘ࡛ࡣ໬Ꮫ⢭ᗘࢆ㐩 6LQJOH       
ᡂࡋࡓࠋB ཎᏊ, C ཎᏊ, N ཎᏊࡣࠊ5㹼7 㟁Ꮚࡢᑠࡉ࡞⣔࡟  6LQJOH       ࡶ㛵ࢃࡽࡎࠊᪧ᮶ࡢ Hylleraas-CI ἲ࡛ࡣ⤯ᑐゎ࡛ࡢ໬Ꮫ⢭ᗘ  'RXEOH        7ULSOH       ࡀᮍࡔ࡟㐩ᡂࡉࢀ࡚࠸࡞࠸ࠋ㠀ᖖ࡟኱ࡁ࡞ᇶᗏ㛵ᩘࢆ⏝࠸

- 103 -

Mࡓ F12 ἲࡸ ECG ἲ➼ࡢ኱つᶍ࡞ィ⟬࡛⢭ᐦ࡞ゎࡀᚓࡽࢀ࡚࠸ࡿࡀࠊᮏ◊✲࡟ࡼࡗ࡚໬Ꮫⓗᛶ㉁ࢆ཯ᫎࡍࡿ⡆༢࡞Ἴື㛵ᩘࡢグ㏙࡜㠀ᖖ࡟ᑡ࡞࠸⮬⏤ᗘ࡛ࡶ໬Ꮫ⢭ᗘࡀᏳᐃ࡟㐩ᡂ࡛ࡁ࡚࠸ࡿࡇ࡜ࡣࠊ࢖ࣥࣃࢡࢺࡢ኱ࡁ
࡞ᡂᯝ࡜ゝ࠼ࡿࠋ
LiH ศᏊࡢィ⟬: ศᏊࡢィ⟬࡛ࡣࠊ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ࡟ᇶ࡙ࡁࠊཎᏊࡢ㔞Ꮚ≧ែ࠿ࡽึᮇ㛵ᩘࢆᵓᡂࡋࠊ໬Ꮫ⤖ྜࡢグ㏙࡟ left-right ┦஫స⏝ࢆᑟධࡍࡿࠋึᮇ㛵ᩘࡣࠊ\ ,

V/L V/L








DE  ED  D , E , DE  ED

/L 6 + 6  D G

/L 3 + 6  D 


 V/L

G

 V/L  G V +  E  S[ /L

 

,


+

G

 V/L  G + V +


 V/L

 S[ /L  G V +  E 

+

G


 S[ /L S[ /L  G



+



V +

ࢆ⏝࠸ࡓࠋࡇࡇ࡛ࠊศᏊ㍈ࡣ x ㍈࡜ࡋ࡚࠸ࡿࠋ\  ࡣ Li ཎᏊ(2S ≧ែ)࡜ H ཎᏊ(ᇶᗏ≧ែ): Li(2s)-H(1s)ࡢ⤖ྜ㓄⨨ࢆ♧ࡋ, \  ࡣ Li ཎᏊ(2P ≧ែ)࡜ H ཎᏊ(ᇶᗏ≧ែ): Li(2px)-H(1s)ࡢ⤖ྜ㓄⨨ࢆࡑࢀࡒࢀ left-right ┦஫స⏝࡛グ㏙ࡋ࡚࠸ࡿࠋಀᩘ d ࡣᖹ⾮఩⨨࡛᭱㐺໬ࡋ࡚࠸ࡿࡀࠊ᰾㛫㊥㞳ࡀᗈࡀࢀࡤ G +G V/L ࡜࡞ࡾࠊcovalentᆺࡢゎ㞳ࢆṇࡋࡃ⾲⌧ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋෆẆࡢ 1s 㟁ᏊࡣཎᏊྠᵝ in-out ┦஫స⏝ࢆᑟධࡋ࡚࠸ࡿࠋ⾲ 6 ࡟ᇶᗏ≧ែ Ȉ ࡜ྠᑐ⛠ᛶࡢ Ȉບ㉳≧ែ(ᆶ┤ບ㉳)ࡢ⤖ᯝࢆ♧ࡋࡓࠋࡇࡢບ㉳≧ែ࡟ᑐᛂࡍࡿึᮇ㛵ᩘࡣࠊLi ཎᏊࡢ 2P ≧ែ࠿ࡽᵓᡂࡉࢀࡿࡓࡵ(6)ᘧࡢ㓄⨨࡟ྵࡲࢀ࡚࠸ࡿࠋLiH ศᏊࡢᇶᗏ≧ែ Ȉ ࡣࠊSingle ࡢ No.
3 ࡢ gij 㛵ᩘ࡛ࡣ 0.1 kcal/mol ௨ୗࡢゎࡀᚓࡽࢀࠊDouble, Triple ࡢ gij 㛵ᩘ࡛ࡶᏳᐃ࡟ 0.1 kcal/mol ௨ୗࡢゎࡀồࡲࡗ࡚࠸ࡿࠋH-square error ࡶᑠࡉࡃࠊἼື㛵ᩘࡶ⢭ᐦ࡟ồࡵࡽࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋࡲࡓࠊບ㉳≧ែ Ȉ
ࡢ H-square error ࡶᇶᗏ≧ែ࡜ྠࣞ࣋ࣝ࡟ᑠࡉࡃ(6)ᘧࡢ\  ࡟ࡼࡗ࡚ຠ⋡ⓗ࡟ṇࡋࡃゎࡀồࡵࡽࢀ࡚࠸ࡿࠋບ
㉳࢚ࢿࣝࢠ࣮ࡣࠊ࡝ࡢ gij 㛵⾲ /L+ ศᏊࡢᇶᗏ࣭ບ㉳≧ែࡢィ⟬ n  ᇶᗏ≧ែ Ȉ ບ㉳≧ែ Ȉ ᩘࡢィ⟬࡛ࡶ࡯ࡰ୍ᐃࡢ್
ࡀᏳᐃ࡟ᚓࡽࢀࠊᩥ⊩್࡜ࡶࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋࡇࡢ
ࡼ࠺࡟ࠊ໬Ꮫࣇ࢛࣮࣑ࣗࣛ
⌮ㄽ࡟ࡼࡾࠊᇶᗏ≧ែࡔࡅ࡛࡞ࡃບ㉳≧ែࡶᐜ᫆࡟ィ

M+VTXDUH (QHUJ\ǻE+VTXDUH (QHUJ\ ([FLWDWLRQHUURU (H[DFW  DX 
NFDOPRO 
HUURU
DX  HQHUJ\ H9  6LQJOH        

 6LQJOH        

 'RXEOH        

 7ULSOH        


5HI )XOO&,= D 
D$%DQGH+1DNDVKLPDDQG+1DNDWVXML&KHP3K\V/HWW  ⟬ࡉࢀ࡚࠸ࡿࠋ

Li2 ศᏊࡢィ⟬: Li2 ศᏊࡢึᮇ㛵ᩘࡶྠᵝࡢ᪉ἲ࡛ᵓ⠏ࡋࠊ\ ,

V $V $DE  ED  V% V% DE  ED  D , E , DE  ED













/L $ 6 /L % 6  D 

/L $ 6 /L % 3  D 

G


 V$

G

V$  G


 V$


 V%

V$  G S[  % V%

V $  G

 S[  %  E  V$ V%  E  S[  % S[  $  G


 V$

G

 V%  E G/L $ 3 /L % 6  D GG

/L $  3 /L %  3  D 

G S[  $  S[  $  G S[ %  S[  %  E  S[ % V$,  

 V%

 V $  G S[ %  S[  % S[  $  G


 V$



 V%

G S[ %  S[  $  G S[  $  S[  %ࢆ⏝࠸ࡓࠋ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ࡟ᇶ࡙ࡁ Li ཎᏊࡢ 2S, 2P ≧ែ࠿ࡽ໬Ꮫ⤖ྜࢆグ㏙ࡋ࡚࠸ࡿࠋ⾲ 7 ࡟ࠊᇶᗏ≧ែ(1ȈJ)࡜ྠᑐ⛠ᛶࡢ ȈJບ㉳≧ែ(ᆶ┤ບ㉳)ࡢ⤖ᯝࢆ♧ࡋࡓࠋᇶᗏ≧ែ(ȈJ)ࡣࠊSingle ࡢ No. 3 ࡢ gij㛵ᩘཬࡧ Double, Triple ࡢ gij 㛵ᩘ࡛Ᏻᐃ࡟໬Ꮫ⢭ᗘࡀᚓࡽࢀࠊH-square error ࡢ್ࡶᑠࡉ࠿ࡗࡓࠋ୍᪉ࠊບ㉳≧ែ(2ȈJ)ࡢ H-square error ࡣᇶᗏ≧ែࡼࡾࡶ 1 ᱆⛬ᗘ኱ࡁ࠿ࡗࡓࡀࠊLi(2P)≧ែ࡟ᑐࡍࡿ flexible ࡞ cf ࢆᑟධ- 104 -

ࡍࡿࡇ࡜࡟ࡼࡗ࡚ᨵၿ࡛ࡁ⾲ /L ศᏊࡢᇶᗏ࣭ບ㉳≧ែࡢィ⟬ n  ᇶᗏ≧ែ ȈJ ບ㉳≧ែ ȈJ ࡿ࡜⪃࠼࡚࠸ࡿࠋࡑࢀ࡟ࡶ
㛵ࢃࡽࡎࠊບ㉳࢚ࢿࣝࢠ࣮

M+VTXDUH (QHUJ\ǻE+VTXDUH (QHUJ\ ([FLWDWLRQHUURU
(DX
NFDOPROHUURU
DX  HQHUJ\ H9 
H[DFWࡣࠊ࡝ࡢ gij 㛵ᩘࡢィ⟬࡛ࡶ 6LQJOH         
Ᏻᐃ࡟ồࡵࡽࢀࡓࠋບ㉳࢚
 6LQJOH         
ࢿࣝࢠ࣮ࡢࡼ࠺࡞┦ᑐゎࡣࠊ  'RXEOH         
 7ULSOH        
໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽ࡟ࡼ






5HI 6$&&, Dࡗ࡚ࠊẚ㍑ⓗᐜ᫆࡟ồࡵࡽD+1DNDWVXML-8VKLRDQG7<RQH]DZD&DQ-&KHP  ࢀࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ
ୖ㏙ࡢ඲࡚ࡢィ⟬ࡣࠊn=2 ࡢィ⟬㔞ࡢᑡ࡞࠸ᐇ⏝ࣞ࣋ࣝࡢィ⟬࡟ࡶ㛵ࢃࡽࡎࠊᏳᐃ࡟㧗⢭ᗘゎࡀồࡲࡗ࡚࠸ࡿࠋࡇࡢࡼ࠺࡟ࠊ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽࡸ⣔࡟㐺ࡋࡓึᮇ㛵ᩘࡢᵓ⠏࡜୍⯡໬ࢫࢣ࣮ࣜࣥࢢ㛵ᩘࡢᑟධ࡟
ࡼࡿἼື㛵ᩘࡢグ㏙࡜ࠊ࣓ࢺ࣏ࣟࣜࢫἲࢆ⏝࠸࡞࠸┤᥋ἲ(㏫ኚ᥮ἲ)ࡢ᪂ࡓ࡞ࢧࣥࣉࣜࣥࢢἲ࡟ࡼࡗ࡚ࠊṇ☜࡞ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ࣞ࣋ࣝࡢゎࢆࡇࢀࡲ࡛ࡼࡾ㐶࠿࡟Ᏻᐃ࠿ࡘᐜ᫆࡟ゎࡃ⌮ㄽయ⣔ࡀ☜❧ࡋࡘࡘ࠶ࡿࠋ
LSE ἲࡣ㉸୪ิィ⟬࡟ྥ࠸࡚࠾ࡾࠊ✚ศἲ࡜ẚ࡭࡚࣓ࣔࣜ✵㛫ࡶ㠀ᖖ࡟ᑡ࡞ࡃィ⟬᫬㛫ࡶ㏿ࡃࠊィ⟬ᶵୖ࡛ࡢ࣓ࣜࢵࢺࡶ኱ࡁ࠸ࠋఱࡼࡾࠊ✚ศ➼ࡢไ⣙࡟ᤕࡽࢃࢀࡎ࡝ࡢࡼ࠺࡞⣔ࡸἼື㛵ᩘ࡛ࡶᢅ࠺ࡇ࡜ࡀ࡛ࡁࡿ኱
ࡁ࡞ỗ⏝ᛶࡣࠊLSE ⌮ㄽࡢ᭱኱ࡢ࣓ࣜࢵࢺ࡛࠶ࡿࠋୖグ࡛♧ࡋࡓᛂ⏝౛ࡣ⡆༢࡞ཎᏊ࣭ศᏊ࡟ࡍࡂ࡞࠸ࡀࠊ
㛤Ⓨࡋࡓ⌮ㄽ࡜࢔ࣝࢦࣜࢬ࣒ࡢ☜࠿ࡉࢆ᳨ドࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ௒ᚋࡶ⌮ㄽ࡜ࣉࣟࢢ࣒ࣛ㛤Ⓨࢆ㐍ࡵࠊ໬Ꮫࣇ࢛࣮࣑ࣗࣛ⌮ㄽࡸ୍⯡໬ࢫࢣ࣮ࣜࣥࢢ㛵ᩘࡢ⌮ㄽࠊLSE ⌮ㄽࡢࢧࣥࣉࣜࣥࢢἲࡸィ⟬࢔ࣝࢦࣜࢬ࣒ࢆࡉࡽ
࡟Ⓨᒎࡉࡏ࡚ࠊ୍⯡ⓗ࡞኱ࡁ࡞ཎᏊ࣭ศᏊࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ࣞ࣋ࣝࡢィ⟬࡟ᛂ⏝ࡋ࡚࠸ࡃࠋ

3.4 ኚศ⌮ㄽ࣭FC sij ἲࡢᐇ⏝ࣉࣟࢢ࣒ࣛࡢ㛤Ⓨ ḟ࡟ࠊࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ゎࢆồࡵࡿ᏶ဨ㛵ᩘ⌮ㄽ(FC ⌮ㄽ)ࡢ୰࡛ࡶࣘࢽ࣮ࢡ࡞ࠊ1࣭2 㟁Ꮚ✚ศࡢࡳ࡛ኚ
ศἲ࡟ࡼࡾཎᏊ࣭ศᏊࡢ㟁Ꮚ≧ែࢆィ⟬࡛ࡁࡿ FC sij ἲࡢࣉࣟࢢ࣒ࣛ㛤Ⓨࢆ⾜ࡗࡓࠋࡲࡎࠊSlater ᆺᇶᗏ㛵ᩘ࡟ࡘ࠸࡚ࠊḟ࡟ Gauss ᆺᇶᗏ㛵ᩘ࡟ࡘ࠸࡚㏙࡭ࡿࠋ
3.4.1 Slater ᇶᗏ࡟ᑐࡍࡿࣉࣟࢢ࣒ࣛ ୍⯡ࡢศᏊ࡟ᑐࡍࡿࣁ࣑ࣝࢺࢽ࢔ࣥࡣࠊ +㹥㛵ᩘࡣࠊ J

¦ U ¦ V , V
L  $ L$L  M LMLM  ¦ L L  ¦ L  $ UL$$  ¦ L  $ ULM ࡜᭩ࡅࠊᮏ FC-sij ⌮ㄽ࡟࠾࠸࡚ࠊ
=ULM ࡜ࡍࡿࠋࡇࡇ࡛ࠊi,j ࡣ㟁Ꮚࡢ␒ྕࠊA ࡣཎᏊࡢ␒ྕࢆ⾲ࡍࠋࡇࢀࡽ

ࡢ g 㛵ᩘཬࡧࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸࡚ SICI ࡢᘧ࡟ᇶ࡙ࡁ cf ࢆ⏕ᡂࡍࡿ࡜ࠊࡑࡢ୰࡟ UL% H[S D UL$ ࡢࡼ࠺࡞㛵ᩘࡀ⏕ᡂࡉࢀࡿ(ึᮇ㛵ᩘ࡟ Gauss ᆺ㛵ᩘࢆ⏝࠸ࡓ᫬ࡣ UL% H[S D UL$ )ࠋࡇࡢ㛵ᩘࡣࠊ㟁Ꮚ i ࡢ୰ᚰࡣཎᏊ A࡛࠶ࡿࡀࠊࡑࢀ࡟ཎᏊ B ࡲ࡛ࡢ㊥㞳 UL% ࡀ࠿࠿ࡗ࡚࠾ࡾࠊ㸰୰ᚰ㛵ᩘ࡛࠶ࡿࠋᡃࠎࡣࡇࡢ㡯ࢆ U L$  % 㡯࡜࿧ࡪࠋ୍⯡࡟ࡇࢀࡽࡢከ୰ᚰ㛵ᩘࡢ✚ศࡣᅔ㞴࡛࠶ࡿࡀࠊSlater ᆺᇶᗏ㛵ᩘࢆ⏝࠸ࡓሙྜࡣ✚ศྍ⬟࡛࠶ࡿࡇ࡜
ࡀศ࠿ࡗࡓࡓࡵࠊᮏ◊✲࡛ࡣ U L$  % 㡯ࡶྵࡵࡓ✚ศἲࢆᑟฟࡋࠊࣉࣟࢢ࣒ࣛ㛤Ⓨࢆ⾜ࡗࡓࠋࡇࢀ௨እࡢ㛵ᩘࡣ඲࡚ᚑ᮶ἲ࡟ࡼࡾᐜ᫆࡟✚ศྍ⬟࡛࠶ࡿ࠿ࡽࠊࡇࢀ࡟ࡼࡾ FC ἲ࡟ࡼࡗ࡚⏕ᡂࡉࢀࡿ඲࡚ࡢ cf ࢆ⏝࠸࡚ኚศィ⟬ࡀྍ⬟࡜࡞ࡗࡓࠋࡇࡢ U L$  % 㡯ࡣࠊ㟁Ꮚࡢศᴟࡸ໬Ꮫ⤖ྜࢆグ㏙ࡍࡿຠᯝࡀᮇᚅࡉࢀࠊ⯆࿡῝࠸ࠋ

U L$  % 㡯ࡢ୍⯡ᙧࡣ F $[$D $ \ E$ $ ] $F $ U$Q $ UP$ %% H[S D $ U $ ࡜࠿ࡅࠊa,b,c,n,m ࡣ㠀㈇ᩚᩘ࡛࠶ࡿࠋU L$  % 㡯ࡀྵࡲࢀ࡚࠸ࡿࡓࡵከ୰ᚰ࡜࡞ࡾࠊᚑ᮶ࡢ LCAO(linear combination of atomic orbital)㏆ఝ࡟ᇶ࡙࠸ࡓศᏊ㌶㐨
ἲ࡟ࡣ⌧ࢀ࡞࠸ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ U L$  % 㡯ࢆྵࡴ Cartesian ᆺ Slater ᆺ㛵ᩘ࡟ࡘ࠸࡚ࡑࡢ✚ศἲࢆᑟฟࡋ
ࡓࠋ- 105 -

 U L$  % 㡯ࢆ⏝࠸ࡓ 1 㟁Ꮚ✚ศࡢ୍⯡ᙧࡣࠊ,

F D  2Ö F E , D $  D %  D $  E$  F $  Q$  D%  E%  F%  Q%

¦ ³ GW [ \ ] U [ \ ] U H[S D U  D U 
D$
$

E$
$

F$ Q$
$ $

D%
%

E%
%

F % Q%
% %

$ $

% %

࡜᭩ࡅࡿࠋࡇࡇ࡛ 2Ö ࡣ 1 㟁Ꮚ₇⟬Ꮚ࡛࠶ࡾࠊ㔜࡞ࡾ✚ศࠊ㐠ື࢚ࢿࣝࢠ࣮✚ศࠊ᰾ᘬຊ✚ศ࡟ᑐࡋࡑࢀࡒࢀࠊ

2Ö   U$  U% ࡜࡞ࡿࠋ࠸ࡎࢀࡢሙྜ࡛ࡶ୍⯡ᙧ࡜ࡋ࡚ࡣୖᘧࡢ 3 ⾜┠ࡢࡼ࠺࡟࡞ࡿࠋᘬᩘ࡜ࡋ࡚ࠊୖᘧࡢ
2 ⾜┠ࡢࣃ࣓࣮ࣛࢱࢆ୚࠼ࡿ࡜✚ศ್ࡀᡠࡗ࡚᮶ࡿ subroutine ࢆసᡂࡋࡓࠋྠᵝ࡟ࠊ U L$  % 㡯ࢆ⏝࠸ࡓ 2 㟁Ꮚ✚ศࡢ୍⯡ᙧࡣࠊḟᘧࡢࡼ࠺࡟᭩ࡅࡿࠋ
,

F D  FE  U F F  F G ³³,  D $  D%  D  $  D  %  D $  E $  F $  Q $  D%  E%  F%  Q%  D $  E $  F $  Q $  D %  E %  F %  Q %

GW U [D$ $ \E$$ ]F$$ UQ$ $ [D%% \E%% ]F%% UQ%% [D$$ \E$$ ]F$$ UQ$ $ [D%% \E%% ]F%% UQ% % H[S D $ U $  D% U%  D  $ U $  D  % U %✚ศィ⟬ἲࡢヲ⣽ࡣ๭ឡࡍࡿࡀࠊᇶᮏ᪉㔪ࡣࠊᅇ㌿ᴃ෇ᗙᶆ⣔{λ, μ, φ}ࢆ⏝࠸࡚⿕✚ศ㛵ᩘࢆኚ᥮ࡍࡿࠋ

U L$  % 㡯ࡣᅇ㌿ᴃ෇ᗙᶆࢆ⏝࠸ࡿ࡜ λ ࡜ μ ࡛⾲⌧࡛ࡁࡿࠋࡲࡓࠊ U 㡯ࡣࣀ࢖࣐ࣥᒎ㛤ࢆ⾜࠺ࡇ࡜࡟ࡼࡾኚ
ᩘศ㞳ࡉࢀࠊ඲య࡜ࡋ࡚✚ศྍ⬟࡜࡞ࡿࠋᮏ᪉ἲࢆ N2 ศᏊ࡟㐺⏝ࡋࡓ⤖ᯝࢆ⾲ 8 ࡟♧ࡍࠋึᮇ⾲ )&VLM ἲ࡟ࡼࡿ 1 ศᏊࡢ࢚ࢿࣝࢠ࣮
㛵ᩘࡣ Clementi ࡢ single zeta ࢆ⏝࠸ࡓ VB ᆺἼື㛵ᩘ 
U L$  % ࡞ࡋ࡜ࡋࡓࠋ UL % 㡯ࢆྵࡵ࡞࠸ᚑ᮶ࡢ᪉ἲ࡜ U L$  % 㡯ࢆྵ RUGHU 0 ǻ( NFDOPRO 
$

 

ࡵࡓᮏἲࢆẚ㍑ࡍࡿ࡜ࠊorder=2 ࡟࠾࠸࡚ 128kca/mol 
 


ࡶࡢᨵၿࡀᚓࡽࢀࡓࠋ

U L$  % ࠶ࡾ
0 ǻ( NFDOPRO   
 


3.4.2 Gauss ᇶᗏ࡟ᑐࡍࡿࣉࣟࢢ࣒ࣛ
 FC ἲࡢึᮇ㛵ᩘ࡟ Gauss ᆺ㛵ᩘࢆ⏝࠸ࡓ᫬ࠊcf ࡜ࡋ࡚ UL$ H[S D UL$ ࡀ⏕ᡂࡉࢀࡿࠋࡇࡢ㛵ᩘࢆࡇࡇ࡛ࡣ
rGauss (rG)࡜࿧ࡪࠋⰋࡃ▱ࡽࢀࡿࡼ࠺࡟ࠊGauss ᆺ㛵ᩘ H[S D UL$ ࡣ᰾-㟁Ꮚ࢝ࢫࣉ᮲௳ࢆ‶ࡓࡉ࡞࠸ࡀࠊFC
ἲࢆ౑࠺࡜ࡇࡢ rG 㛵ᩘࡀ⏕ᡂࡉࢀࡿࡓࡵ࢝ࢫࣉ್ࡣࢮ࡛ࣟࡣ࡞ࡃィ⟬ࡉࢀࡿࠋࡇࢀࡽࡢ rG 㛵ᩘࡢ 1 ୰ᚰ✚ศࡣᐜ᫆࡟ィ⟬࡛ࡁࠊ࢝ࢫࣉ್ࡣ୺࡟୍୰ᚰ✚ศࡀ㛵୚ࡍࡿࡓࡵ Gauss ᆺᇶᗏࡢሙྜ࡛ࡶ FC-sij ἲ࡟ࡼࡗ࡚
ṇࡋࡃィ⟬ࡉࢀࡿࠋࡋ࠿ࡋࠊࡑࡢከ୰ᚰ✚ศࡣ Gauss ᆺ㛵ᩘࡢሙྜࠊSlater 㛵ᩘࡢ᫬࡜␗࡞ࡾゎᯒⓗ࡞ィ⟬ࡣᅔ㞴࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊrGauss ᆺ㛵ᩘࢆ Gauss ᆺ㛵ᩘ࡛ᒎ㛤ࡍࡿࡇ࡜࡟ࡼࡾࡑࡢ✚ศ್ࢆồࡵࡿ᪉ἲࢆᥦ
᱌ࡋࣉࣟࢢ࣒ࣛ㛤Ⓨࢆ⾜ࡗ࡚࠸ࡿࠋ ࡲࡎࠊrGauss 㛵ᩘࢆ᭱ᑠ 2 ஌ࣇ࢕ࢵࢸ࢕ࣥࢢἲ࡟ࡼࡾ N ಶࡢ Gauss 㛵ᩘ࡛ᒎ㛤ࡋࠊࡑࡢᒎ㛤ಀᩘ࡜㌶㐨ᣦᩘࢆồࡵࡓࠋࡇ࠺ࡋ࡚ᒎ㛤ࡍࢀࡤ rGauss ࡣᚑ᮶ࡢ Gauss ⾲ U*DXVV 㛵ᩘࢆ⏝࠸ࡓ )&VLM ἲ࡟ࡼࡿ  ཎᏊศᏊ㛵ᩘ࡜ྠࡌᙧ࡟࡞ࡾࠊ1,2 㟁Ꮚ✚ศࢆồࡵࡿࡇ࡜ࡀྍ⬟࡜ ࡢᖹ⾮᰾㛫㊥㞳࡜ຊࡢᐃᩘ
ᖹ⾮᰾㛫㊥㞳 ύ ຊࡢᐃᩘ 1P ࡞ࡿࠋࡓࡔࡋࠊrGauss ࡢ U L$  % 㡯࡟ࡘ࠸࡚ࡣࡲࡔຠ⋡ⓗ)&VLM ἲ ᐇ㦂್ )&VLM ἲ ᐇ㦂್


࡞✚ศἲࡀᑟฟ࡛ࡁ࡚࠸࡞࠸ࡀࠊ௒ᚋ U L$  % 㡯ࡢ௦ࢃࡾ /L+/L



&+



࡟ศᴟ㛵ᩘࢆ⏝࠸ࡿࡇ࡜ࢆ᳨ウࡋ࡚࠸ࡿࠋ
1+

 ᮏ FC-sij ἲࢆ⏝࠸࡚ࠊ2 ཎᏊศᏊࡢᖹ⾮᰾㛫㊥㞳࡜ຊࡢ&


ᐃᩘࢆồࡵࡓࠋึᮇ㛵ᩘࡣ d95*ᇶᗏ࡟ࡼࡿ Hartree-Fock㌶㐨࡛࠶ࡿࠋ⾲ 9 ࡟ࡲࡔ⢒࠸ Order=1 ࡢ⤖ᯝ࡛࠶ࡿࡀ♧ࡋࡓࠋorder ࢆᣲࡆࡓィ⟬ࡶ⾜࠺ࠋ

㸲㸬 SAC-CI ἲ࡟ࡼࡿ᰾㓟ศᏊࡢෆẆ࢖࢜ࣥ໬ཬࡧບ㉳ࢫ࣌ࢡࢺࣝ
ᮏ 6$&&, ἲ࡟ࡼࡿ◊✲ࡣࠊ㔞Ꮚ⛉Ꮫᢏ⾡◊✲㛤Ⓨᶵᵓࡢᶓ㇂᫂ᚨඛ⏕ࡢᐇ㦂࡟ᇶ࡙ࡃඹྠ◊✲࡛࠶ࡿࠋ

- 106 -

ᨺᑕ⥺࡟ࡼࡿ '1$ ศᏊࡢᦆയࡣࠊࡲࡎ㟁Ꮚࡢບ㉳ཬࡧ࢖࢜ࣥ໬ࡀ㉳ࡁࡿ࡜ࡉࢀࡿࡀࠊࡑࡢヲ⣽࡞࣓࢝ࢽࢬ
࣒ࡣࡲࡔ᫂ࡽ࠿࡟ࡣ࡞ࡗ࡚࠸࡞࠸ࠋ≉࡟ࠊࣁࣟࢤࣥ໬ࣆ࣑ࣜࢪࣥࢆྵࡴࢾࢡࣞ࢜ࢳࢻࡢ
EURPR¶GHR[\XULGLQH¶PRQRSKRVSKDWH㸦%UG803㸧ࢆྵࡴ '1$ ࢆᣢࡘ⣽⬊ࡣࠊᨺᑕ⥺ឤཷᛶࢆ㧗ࡵࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊᨺᑕ⥺἞⒪࡬ࡢᛂ⏝ࡸࠊ࢔ࣥࢸࢼศᏊ࡜ࡋ࡚ࡢᛂ⏝ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋࡇࢀࡽࡢ⌧㇟࡟ࡘ࠸࡚ࠊ࠸ࡃࡘ࠿࣓࢝ࢽࢬ࣒ࡀᥦ᱌ࡉࢀ࡚࠸ࡿࡀࠊᮏ◊✲࡛ࡣࠊ'1$ ศᏊࡢෆẆ㟁Ꮚࡢ࢖࢜ࣥ໬ཬࡧບ㉳࡟ࡘ࠸࡚⌮ㄽⓗ࡟᳨ウࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋࡲࡎࡣࠊᇶᗏ࣭ບ㉳࣭࢖࢜ࣥ໬࣭࢔ࢽ࢜ࣥ໬࡞࡝௵ពࡢ㟁Ꮚ≧ែࢆᢅ࠺ࡇ࡜ࡀ࡛ࡁࠊ࠿ࡘಙ㢗ᛶࡢ㧗࠸㔞Ꮚ໬Ꮫ⌮ㄽ࡛࠶ࡿ 6$&6$&&, ἲࢆ⏝࠸࡚ࠊᨺᑕ⥺࡟ࡼࡿ '1$ ศᏊࡢບ㉳㐣⛬ཬࡧ࢖࢜ࣥ໬㐣⛬࡟ࡘ࠸࡚◊✲ࡋࡓࠋ ࡇࡇ࡛ࡣࣔࢹࣝศᏊ࡜ࡋ࡚ࠊ%URPRXUDFLO ࢆ⏝࠸ࡓࠋᇶᗏ㛵ᩘࡣ ' GS ࢆ⏝࠸ࡓࠋᐇ㦂ࢫ࣌ࢡࢺࣝࢆᅗ  ࡟ࠊ6$&&, ἲ࡟ࡼࡿ⤖ᯝࢆ⾲  ࡟♧ࡋࡓࠋᐇ㦂࡛ࡣࠊࢫ࣌ࢡࢺࣝࡢ
DVVLJQ ࡀ୍㒊ᅔ㞴࡞ᡤࡶ࠶ࡿࡀࠊ6$&&, ィ⟬ࢆ⾜࠺ࡇ࡜࡛ࠊ%U21& ࡢෆẆ㌶㐨࠿ࡽࡢ࢖࢜ࣥ໬≧ែࢆồࡵࡿࡇ࡜ࡀ࡛ࡁࠊᖜᗈ࠸࢚ࢿࣝࢠ࣮㡿ᇦࡢࢫ࣌ࢡࢺࣝࡢ QDWXUH ࡀ᫂ࡽ࠿5-Bromouracil࡜࡞ࡗࡓࠋ⾲ 6$&&, ἲ࡟ࡼࡿ %URPRXUDFLO ࡢ࢖࢜ࣥ໬ࢫ࣌ࢡࢺࣝ
H[SWO
6$&&,

H9  
H9 %UV
  
%US
    
%US
  
2V  
1V 
 
 &V
%UV
%US

%UG



 


     


 ᅗ %URPRXUDFLO ࡢ࢖࢜ࣥ໬ࢫ࣌ࢡࢺࣝ

࣏ࢫࢱ࣮ࠕᨺᑕ⥺ቑឤࢆㄏᑟࡍࡿࣁࣟࢤࣥ໬ '1$ ࡢ࢔ࣥࢸࢼ≉ᛶࡢ᥈⣴ࠖᖹᡞ ᮍᙬ⣖ 㤿ሙ ♸἞ ⸨஭ ೺ኴ㑻 ᶓ㇂ ᫂ᚨ ࡼࡾᘬ⏝

ࡉࡽ࡟ C ཎᏊ࠿ࡽࡢ࢖࢜ࣥ໬ࢫ࣌ࢡࢺࣝ࡟ࡘ࠸࡚ヲ⣽࡟᳨ウࡋࡓࠋᅗ 3 ࡟♧ࡋࡓࡢࡣࠊThymine ཬࡧ
5-Bromouracil ࡢ C ཎᏊࡢෆẆ࢖࢜ࣥ໬ࢫ࣌ࢡࢺ࡛ࣝ࠶ࡿࠋᐇ㦂࡛ࡣ 290~296eV ௜㏆࡟ 4 ࡘࡢࣆ࣮ࢡࡀᚓࡽࢀ
࡚࠸ࡿࡀࠊࡑࢀࡒࢀࡢࣆ࣮ࢡࡀ࡝ࡢ C ཎᏊ⏤᮶ࡢࣆ࣮ࢡࡀ assign ࡛ࡁࡓࠋࡓࡔࡋࠊᅗ 3 ࡟࠾࠸࡚ Thymine ࡣ
3.35eV, 5-Bromouracil ࡣ 3.48eV ప࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡋ࡚࠸ࡿࠋ

- 107 -ᅗ  %URPRXUDFLO ࡢ ;$1(6 ࢫ࣌ࢡࢺࣝ ୖ ཬࡧ
6$&&, ἲ࡟ࡼࡿࢫ࣌ࢡࢺࣝ ୗ ᅗ 7K\PLQH ཬࡧ %URPRXUDFLO ࡢ & ཎᏊࡢෆẆ࢖࢜ࣥ໬ࢫ࣌ࢡࢺࣝࠋ⥳⥺ཬࡧ㟷⥺ࡀ 6$&&, ἲ࡟ࡼࡾᚓࡽࢀࡓ࢖࢜ࣥ໬ࣆ࣮ࢡ࡛࠶ࡿࠋ

࣏ࢫࢱ࣮ࠕᨺᑕ⥺ቑឤࢆㄏᑟࡍࡿࣁࣟࢤࣥ໬ '1$ ࡢ࢔ࣥࢸࢼ≉ᛶࡢ᥈⣴ࠖᖹᡞ ᮍᙬ⣖㤿ሙ ♸἞ ⸨஭೺ኴ㑻 ᶓ㇂ ᫂ᚨ ࡼࡾᘬ⏝ ᐇ 㦂 ࢫ ࣌ ࢡ ࢺ ࣝ ࡣ ( ,WlOl ' 7 +D . .RRVHU (5DFKOHZ 0 $ +XHOV DQG( .XNN - &KHP 3K\V 
  ࡼࡾᘬ⏝  ḟ࡟ 5-Bromouracil ࡢ O ཎᏊࡢෆẆບ㉳ࢫ࣌ࢡࢺࣝࢆ SAC-CI ἲ࡟ࡼࡾồࡵࡓࠋ࡞࠾ࠊBr ࢆྵࡴศᏊ࡟ࡘ࠸
࡚ 6$&&, ἲ ࡟ ࡼ ࡿ ෆ Ẇ ບ ㉳ ࢫ ࣌ ࢡ ࢺ ࣝ ࡢ ィ ⟬ ࡣ ࡇ ࢀ ࡲ ࡛ ࡟ ሗ ࿌ ࡉ ࢀ ࡚ ࠸ ࡞ ࠸ ࠋ ᇶ ᗏ 㛵 ᩘ ࡣ ࠊ
DXJFFS&97='=SRO5\G ࡜ࡋࠊィ⟬ࣞ࣋ࣝࡣ /HYHO7KUHH ࡜ࡋࡓࠋᐇ㦂࡛ᚓࡽࢀࡓ ;$1(6 ࢫ࣌ࢡࢺࣝཬࡧ
6$&&, ἲ࡟ࡼࡾᚓࡽࢀࡓࢫ࣌ࢡࢺࣝࢆᅗ  ࡟♧ࡍࠋᐇ㦂ࡢ & ཬࡧ & ࡢࣆ࣮ࢡࡣࡑࢀࡒࢀ 2 V ࠿ࡽ ʌ ㌶㐨࡬ࡢບ㉳ࠊཬࡧ 2 V ㌶㐨࠿ࡽ ʌ ࡜ ı ㌶㐨࡬ࡢບ㉳࡜ DVVLJQ ࡉࢀࡓࠋᮏ◊✲࡛ࡣࠊ2 ཎᏊࡢෆẆບ㉳࡟ࡘ࠸࡚ồࡵࡓࡶࡢ࡛࠶ࡿࡀࠊ%U ཎᏊࡸࠊ1 ཎᏊࠊ& ཎᏊ࠿ࡽࡢෆẆບ㉳࡟ࡘ࠸࡚ࡶ௒ᚋィ⟬ࢆ⾜࠸ࠊ'1$ ศᏊࡢᨺᑕ⥺྾཰ࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚᫂ࡽ࠿࡟ࡋ࡚࠸ࡁࡓ࠸ࠋㅰ㎡ศᏊ◊ィ⟬ᶵࢭࣥࢱ࣮࡟ࡣࠊ ᖺᗘࡶᑓ᭷ࢡࣛࢫࢱ࣮ࡢ฼⏝ࢆㄆࡵ࡚㡬ࡁࠊࡑࡢィ⟬ᶵࣃ࣮࣡࡟ࡼࡗ࡚
◊✲ࡀ኱ࡁࡃ㐍ᒎࡋࡓࡇ࡜ࢆ῝ࡃឤㅰ⏦ࡋୖࡆࡿࠋ௒ᚋࡶࠊ㈗ࢭࣥࢱ࣮ࡢィ⟬ᶵ㈨※ࡢࡼࡾຠ⋡ⓗ࡞฼⏝࡟ࡼࡗ࡚ࠊᘬࡁ⥆ࡁ᪉ἲㄽ࡜ࣉࣟࢢ࣒ࣛࡢ㛤Ⓨ࣭ᨵⰋࢆ㐍ࡵࠊ㔞Ꮚ໬Ꮫࡢ◊✲ศ㔝ࢆඛᑟࡋ⥆ࡅࡽࢀࡿࡼ࠺࡞ࠊ
໬Ꮫⓗ౯್ࡢ㧗࠸ィ⟬ࢆᐇ⾜ࡋ࡚࠸ࡁࡓ࠸ࠋ

4 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ۻ‬1) Hiroshi Nakatsuji and Hiroyuki Nakashima, “Scaled Schr|dinger equation and the accurate and efficientmethodology for solving the Schr|dinger equation formulated therefrom”, L|wdin Lectures - a 60th Anniversary
Celebration, Uppsala, Sweden, (Online) Dec. 3-4 (2020) (Invited).

5 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ۻ‬1) Hiroyuki Nakashima and Hiroshi Nakatsuji, “Inverse Hamiltonian method assisted by the complex scaling
technique for solving the Dirac-Coulomb equation: Helium isoelectronic atoms”, Chem. Phys. Lett. 749,
137447-1-7 (2020).

- 108 -

‫ۻ‬2) Hiroshi Nakatsuji, Hiroyuki Nakashima, and Yusaku I. Kurokawa, “Solving the Schrödinger equation of atoms
and molecules using one- and two-electron integrals only”, Phys. Rev. A 101, 062508 (2020).
‫ۻ‬3) Yusaku I. Kurokawa, Hiroyuki Nakashima, and Hiroshi Nakatsuji, “Solving the Schrödinger Equation of
Hydrogen Molecule with the Free-Complement Variational Theory: Essentially Exact Potential Curves andVibrational Levels of the Ground and Excited States of Π symmetry”, Phys. Chem. Chem. Phys. 22, 13489 (2020)..
‫ۻ‬4) Hiroyuki Nakashima and Hiroshi Nakatsuji, “Free complement sij-assisted rij theory: Variational calculation of
the quintet state of a carbon atom”, Phys. Rev. A 102, 052835 (2020).

- 109 -

⏕యศᏊ」ྜయ⣔ࡢ඲ཎᏊ࣭⢒ど໬ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲
$OODWRPFRDUVHJUDLQHGPROHFXODUVLPXODWLRQVWXGLHVIRUELRPROHFXODUFRPSOH[HV‫⏣ۑ‬୰ ᡂ඾㸪᳃ ⩏἞㸪ᰩᓮ ௨ஂ⏨㸪ᒾᇛ 㞝┿㸦⚄ᡞ኱Ꮫ኱Ꮫ㝔ࢩࢫࢸ࣒᝟ሗᏛ◊✲⛉㸧




◊✲┠ⓗ
 ඲㌟㯞㓉⸆ࢱ࣮ࢤࢵࢺ࡛࠶ࡿ *$%$$ ཷᐜయࡢసືᶵᵓࡢゎ᫂*$%$$ ཷᐜయࡣ୰ᯡ⚄⤒⣔࡟࠾࠸࡚ᢚไᛶࡢാࡁࢆࡍࡿ &O࢖࢜ࣥࢳࣕࢿ࡛ࣝ࠶ࡾ㸪⚄⤒ఏ㐩≀㉁࡛࠶ࡿ

*$%$ ࡀ⤖ྜࡍࡿࡇ࡜࡟ࡼࡾ࢖࢜ࣥࢳࣕࢿࣝࡀ㛤ཱྀࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡲࡓ *$%$$ ཷᐜయࡣ඲㌟㯞㓉
࡟㛵ࢃࡿཷᐜయ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࡀ㸪඲㌟㯞㓉⸆స⏝ࡢศᏊᶵᵓࡣ୙᫂࡞Ⅼࡀከ࠸ࠋᮏ◊✲ㄢ㢟࡟࠾࠸࡚ࡣ㸪඲㌟㯞㓉⸆ศᏊࡢ⤖ྜ࡟క࠺ *$%$$ ཷᐜయࡢࢧࣈࣘࢽࢵࢺ㛫ࡢ༠ㄪⓗ࡞ᵓ㐀ኚ໬ࡸࣜ࢞ࣥࢻࡢస
⏝࡟㛵ࡍࡿศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ
 ࣜ࣎ࢯ࣮࣒⩻ヂ㛤ጞ」ྜయ࡟࠾ࡅࡿ㧗⢭ᗘ࡞ศᏊ㑅ᢥᛶࡢゎ᫂ࣜ࣎ࢯ࣮࣒ࡣ⣽⬊࡟࠾࠸࡚ࢱࣥࣃࢡ㉁ྜᡂࢆࡘ࠿ࡉ࡝ࡿᕧ኱࡞ࢱࣥࣃࢡ㉁࣭51$ 」ྜయ࡛࠶ࡿࠋࣜ࣎ࢯ࣮
࣒࡟࠾ࡅࡿࢱࣥࣃࢡ㉁ྜᡂࡢ㛤ጞ㐣⛬࡛ࡣ㸪ࣜ࣎ࢯ࣮࣒࡜㛤ጞẁ㝵≉᭷ࡢࢱࣥࣃࢡ㉁࠿ࡽᵓᡂࡉࢀࡿ⩻ヂ㛤ጞ」ྜయࡀᙧᡂࡉࢀࡿࠋࡇࡢ㛤ጞẁ㝵≉᭷ࡢࢱࣥࣃࢡ㉁ࡣ㛤ጞᅉᏊ ,),QLWLDWLRQIDFWRU ࡜࿧ࡤࢀ࡚࠾ࡾ㸪ࣂࢡࢸࣜ࢔ࡢሙྜࡣ ,),),) ࡀᏑᅾࡍࡿࠋࡇࡢࡼ࠺࡞㛤ጞᅉᏊࡢᙺ๭ࡢࡦ࡜ࡘ࡜ࡋ࡚ W51$ ࢆ㑅ᢥⓗ࡟ࣜ࣎ࢯ࣮࣒࡟⤖ྜ࡛ࡁࡿࡼ࠺࡟ࡍࡿࡇ࡜ࡀ࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋᮏ◊✲ㄢ㢟࡟࠾࠸࡚ࡣ㸪ࡇࢀࡽࡢㅖᅉᏊࡢᙺ๭
ࢆศᏊㄽⓗ࡟ゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ ඲㌟㯞㓉⸆ࢱ࣮ࢤࢵࢺ࡛࠶ࡿ *$%$$ ཷᐜయࡢసືᶵᵓࡢゎ᫂ࢡࣛ࢖࢜㟁Ꮚ㢧ᚤ㙾ἲ࡟ࡼࡾᚓࡽࢀࡓࣄࢺ *$%$$ ཷᐜయ࡟ࡘ࠸࡚⢒ど໬ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ

ᐇ⾜ࡋࡓࠋ*$%$$ ཷᐜయࡢ❧యᵓ㐀࡜ࡋ࡚㸪⚄⤒ఏ㐩≀㉁ *$%$ ࠾ࡼࡧ඲㌟㯞㓉⸆ศᏊࡀ⤖ྜࡋࡓࡶࡢࢆ
౑⏝ࡋࡓࠋࢱࣥࣃࢡ㉁ࣜ࢞ࣥࢻ」ྜయᵓ㐀࡟ࡘ࠸࡚⬡㉁஧㔜⭷࡜Ỉ⁐፹࡟ᇙࡵ㎸ࢇࡔ⣔ࢆ⏝ពࡋࡓࠋ*$%$$
ཷᐜయࢆྵࡴ⢏Ꮚᩘࡣ⣙  ࡜࡞ࡗࡓࠋ⢒ど໬ࣔࢹࣝ࡜ࡋ࡚ 0$57,1, ࢆ౑⏝ࡋ㸪ࡑࢀࡒࢀࡢࢱࣥࣃࢡ㉁ෆ࡟ࡣ (ODVWLF QHWZRUN ࡟ࡼࡿ᮰⦡ࢆㄢࡋࡓࠋࡲࡓ *$%$ ࡸ඲㌟㯞㓉⸆ศᏊ࡟ᑐࡋ࡚ࡢ⢒ど໬ຊሙࡣᏑᅾࡋ
࡞࠸ࡓࡵ㸪0$57,1, ຊሙ࡟ࡋࡓࡀ࠸඲ཎᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࡸᐇ㦂⤖ᯝ࡜ᩚྜࡍࡿࡼ࠺࡟ࣜ࢞ࣥࢻࡢ
⢒ど໬ࣔࢹࣝࢆసᡂࡋࡓࠋࡇࡢࡼ࠺࡟ࡋ࡚ᚓࡽࢀࡓ⣔࡟ᑐࡋ࡚ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ *520$&6 ࡟ࡼࡾᐇ⾜ࡋࡓࠋィ⟬⣔࡜ࡋ࡚  ࣜ࢞ࣥࢻࢆྵࡲ࡞࠸⣔㸪  *$%$ ࡢࡳྵࡴ⣔㸪  *$%$ ࡜඲㌟㯞㓉⸆ࢆྵࡴ⣔ࢆᵓ⠏ࡋ㸪ࡑࢀࡒࢀ࡟ᑐࡋ࡚ ȝV ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ  ᅇᐇ⾜ࡋࡓࠋ ࣜ࣎ࢯ࣮࣒⩻ヂ㛤ጞ」ྜయ࡟࠾ࡅࡿ㧗⢭ᗘ࡞ศᏊ㑅ᢥᛶࡢゎ᫂ࣂࢡࢸࣜ࢔࡟࠾ࡅࡿ⩻ヂ㛤ጞ」ྜయࢆィ⟬ᑐ㇟࡜ࡋࡓࠋࡇࡢ」ྜయࡣࣜ࣎ࢯ࣮࣒ᑠࢧࣈࣘࢽࢵࢺ㸪
PHVVHQJHU51$ P51$  ศᏊ㸪㛤ጞ WUDQVIHU51$ W51$  ศᏊ㸪㛤ጞᅉᏊ ,)࣭,)࣭,) ࠿ࡽᵓᡂࡉࢀ࡚࠸ࡿࠋ

- 110 -

」ྜయᵓ㐀ࡣࢡࣛ࢖࢜㟁Ꮚ㢧ᚤ㙾ἲ࡟ࡼࡾᚓࡽࢀ࡚࠸ࡿᵓ㐀ࢆ౑⏝ࡋ㸪ࡇࢀࡽࡢᵓ㐀ࢆ⢒ど໬ࣔࢹࣝ
0$57,1,  ࡛ᢅࡗࡓࠋ0$57,1, ࣔࢹࣝ࡟ࡼࡾ⢒ど໬ࡉࢀࡓ⩻ヂ㛤ጞ」ྜయࡣ⣙  ⢏Ꮚ࡛࠶ࡾ㸪⁐፹࡞࡝ࢆྵࡵࡓ඲⢏Ꮚᩘࡣ⣙  ࡜࡞ࡗࡓࠋ⩻ヂ㛤ጞ」ྜయࢆᵓᡂࡍࡿࢱࣥࣃࢡ㉁ࡸ 51$ ศᏊࡢࡑࢀࡒࢀ࡟
ᑐࡋ࡚ศᏊෆ࡟ (ODVWLFQHWZRUN ࡟ࡼࡿ᮰⦡ࢆㄢࡋࡓࠋศᏊືຊᏛィ⟬ࡣ *520$&6 ࡟ࡼࡾᐇ⾜ࡋࡓࠋィ⟬⣔࡜ࡋ࡚  ⩻ヂ㛤ጞẁ㝵ึᮇ㸦⤖ᯝ࡛ࡣ VWDWH $㸧㸪  ⩻ヂ㛤ጞ୰㛫ẁ㝵㸪࠾ࡼࡧ  ⩻ヂ㛤ጞẁ㝵ᚋᮇ㸦⤖ᯝ࡛ࡣ VWDWH %㸧ࡢ  ࡘࡢ≧ែࢆタᐃࡋࡓࠋࡑࢀࡒࢀࡢ≧ែ࡟࠾࠸࡚ࡣ W51$ ࡸ ,) ࡢ❧యⓗ࡞఩⨨㛵ಀࡀ␗࡞ࡿࠋ
ࡑࢀࡒࢀࡢ≧ែ࡟ᑐࡋ࡚ ȝV ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ  ᅇᐇ⾜ࡋࡓࠋ



◊✲ᡂᯝ


඲㌟㯞㓉⸆ࢱ࣮ࢤࢵࢺ࡛࠶ࡿ *$%$$ ཷᐜయࡢసືᶵᵓࡢゎ᫂*$%$$ ཷᐜయࡢ኱᣺ᖜ㐠ືࢆㄪ࡭ࡿࡓࡵ㸪ྛึᮇᵓ㐀࡟ࡘ࠸࡚ᚓࡽࢀࡓࢺࣛࢪ࢙ࢡࢺࣜࡢ୺㙐⢏Ꮚ࡟ᑐࡋ࡚୺ᡂศศᯒࢆᐇ⾜ࡋࡓ㸦ᅗ 㸧ࠋ୺ᡂศ࡟ྵࡲࢀࡿ㐠ືࡢ࡯࡜ࢇ࡝ࡀࢱࣥࣃࢡ㉁ࢧࣈࣘࢽࢵࢺ༢఩ࡢᅇ㌿㐠ື࡛࠶ࡿࡇ࡜ࡀศ࠿ࡾ㸪ࡇࢀࡣࣜ࢞ࣥࢻ⤖ྜ࡟ࡼࡿཷᐜయࡢ㛤㛢㐠ື࡜㛵㐃ࡍࡿ㐠ື࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ
ᮏ⤖ᯝࡣ඲㌟㯞㓉⸆ࡢ⤖ྜ࡟ࡼࡿࢱࣥࣃࢡ㉁ࡢᵓ㐀≧ែኚ໬࡟ࡘ࠸࡚ࡢศᏊᶵᵓゎ᫂࡟ᐤ୚ࡍࡿࡶࡢ࡛࠶ࡿࠋᅗ  *$%$$ ཷᐜయᵓ㐀ኚ໬ࡢ୺ᡂศ  ࡟ᑐࡍࡿཷᐜయṧᇶࡢᐤ୚㸪᫬㛫Ⓨᒎ࠾ࡼࡧࡑࡢศᕸ
ࣜ࣎ࢯ࣮࣒⩻ヂ㛤ጞ」ྜయ࡟࠾ࡅࡿ㧗⢭ᗘ࡞ศᏊ㑅ᢥᛶࡢゎ᫂ࣜ࣎ࢯ࣮࣒࡟࠾ࡅࡿ W51$ ࡜ྛ㛤ጞᅉᏊࡢ┦஫స⏝ࡣ⩻ヂ㛤ጞ」ྜయࡢ
≧ែ࡟ࡼࡾ␗࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋᅗ  ࡟ึᮇ㐣⛬ VWDWH $ ࡜ᚋᮇ㐣⛬VWDWH% ࡟࠾ࡅࡿ W51$ ࡜ ,) ࡢືᚄศᕸ㛵ᩘࢆ♧ࡍࠋᚋᮇ㐣⛬࡜ẚ㍑ࡍࡿ
࡜ึᮇ㐣⛬࡟࠾࠸࡚ࡣ W51$ ࡜ ,) ࡢ┦஫స⏝ࡀ㢧ⴭ࡛࠶ࡾ㸪W51$ ࡢࣜ࣎ࢯ࣮࣒࡟࠾ࡅࡿㄆ㆑࡟㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀ
ࡣ」㞧࡞ࢱࣥࣃࢡ㉁ࡢ⩻ヂ㐣⛬ࢆ⌮ゎࡍࡿࡇ࡜࡟㈉⊩ࡍࡿࡶࡢ࡛࠶ࡿࠋ

ᅗ  W51$$UJ ,) ࡢືᚄศᕸ㛵ᩘ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬᳃⩏἞㸪⏣୰ᡂ඾㸪➨  ᅇศᏊ⛉Ꮫウㄽ఍㸦Ⓨ⾲ணᐃ㸧  ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
,.XULVDNL DQG67DQDND5HDFWLRQ3DWKZD\6DPSOLQJDQG)UHH(QHUJ\$QDO\VHVIRU0XOWLPHULF3URWHLQ&RPSOH['LVDVVHPEO\E\(PSOR\LQJ+\EULG&RQILJXUDWLRQ%LDV0RQWH&DUOR0ROHFXODU'\QDPLFV6LPXODWLRQ$&62PHJD
 SS'2,DFVRPHJDF
< 2NL\DPD < 0RFKL]XNL 0 <DPDQDND DQG 6 7DQDND 'HQVLW\0DWUL[ %DVHG 6FKHPH RI %DVLV 6HOHFWLRQ IRU/LQHDU &RPELQDWLRQ RI )UDJPHQW 0ROHFXODU 2UELWDOV - 3K\V 6RF -SQ      SDJHV 
KWWSVGRLRUJ-36-

- 111 -

%#"*&%)$+'

(



!

,-

Cooperation of molecular simulation and machine learning for exploringnovel functional materials realized with specific mixing rates
 ( "1 

Fabian WEBER& %' )

*ĈŃōžƦ+8/%)ĈFnt_%Ů(!$Őu¬ĲĽ(£ÁƵĄ¥^lFgrVcTrKinƯx EFPưğ*ƙĻ9¿)û)ŏ w2*% 7ÌƩĽŃō9Ů³Ńōş5&)ƱEFP-MD/MCğ4,śŸſ9ƨ7&%ĘšèħĢ*ĲſźŸ9Ìý7&9ĿĽ&$ 7
2020 ÚÜ+ƱĽ(QtHSVŕ&$ƖÆ¨ÉŸŒ&ĘĒÉŝ9ķ ƂÞƓ*ƓèÜƆƈ{ĦƱ46ƫ

CO2 µ¯š92"ćł<ArĢôŘ*1*<ArĢz*ŎƞŌ*ż4,ƌ¢ī£

ÉĬè{Ħ*1*ĘĒÉŝƯ½ıĴÂĶĔîůŃōĘĕsÔĸňÑøó&*³Ńōư
Ł?ZnDt
Ļĭè9ñ"BMGtW¾īĠèƋÝŭĉú*ƙĻ*ƴTtd)ƛ7Ttd9õƊ%+Ŗƣ*Ƒ²wTtd)" $Ź

100% ńƓ462ÞƂÞƓ+©Ð¤Ø3¨ÉMhSFĲ%

ķ87ĘšĬƀ%7*çķ)46ÃĖ(Þ92"ƂÞƓźŸ)Ï7Ĩ¼Ľ(YtN 7°6í w*«Ɲè2 68/%)ƙĻ8ƂÞƓ*ƪđ+ cyanocarbon 3 disulfonamide ('(ŋƧ)Ɯ58$ 71
wƇ*Šā9±ĈŃō*ĂřĿĽ+ûŶƪđ9ñ"ƂÞƓÆ*źŸ% 7Ɠ*ƆƈźŸ)+
H+ ŷƠ¡* zèÆĕƉ*0 5H+ ŷƠŤĹ?ZnDt9{Ħ7ìğ*Ņŏą/ Ɠ*Ã
+Ģŀ%ķ87Ģŀz%+ƓÆ*2** H+ öš%(ħÅ·ƛ7ĈÀ¶%+ěŀz%*ƓèÜ9űěŀƓèÜƯGAư9ƫŔÜƖÆ¨ÉŸŒ)4!$ŒƆƈ{Ħ*1)
ĭäƖ9ôĐŚĎ9À¶7

2 $

1,67 &KHPLVWU\ :HE%RRN  *$ H6W{   dz* * &%60:%' (%'F;Gvh :F *$ jLvh

 /N_[Go~RLx3HeQ@ >(%'O -R:F]qc r+)* G  i4`*$ fu 


O
F3C

H
S N

O

CN

O
S
O

CH
CN H3Si SiH3

CF3
O2N

A   \w;?d2

- 112 -

3s  vh6Ha6mIyJKC^b7J vh",!Yg s *$ mIyJlv<0NFDOPRO

*



*



&%60



:%'



W1BD +ElMQtÒƙğ)¿#ơÆŀƛŸŒ)47ƫŔÜī£ÉĬèŸŒğ% 7*1M\Ir)47`rPr*ŸŒ)ƫƈ(ŸŒĘ%ùþ 10 þ9ŵ7Ŋ)ŸŒIMV+ƫ uü%ŔÜ+¹ƍķŸŒğ*z%Ă2ƫ &{Ħ8ű 1 46G2 *üƫŔÜ% !ãŕŴù
7:YAr9ĕƉĂƍ¨7&ãŕƚ*  Ś²*ƙŲƁ7& 7W1BD %+*ƙŲ46ƥŜ)Ɓ&%ŽÙÄ(!&Ş587
º 2 )Ţ_pVr¨J<V&* G2 %* GA ŸŒŚĎ& H+ *ŤĪơŧ*ƛ9Ź846 

H+ *ŤĪơŧ+ 8*ŗ5ŢƠ7)Ç7&7

A   *$ $)#*qc r5* (%'F;Gvh*$ k NFDOPRO jLvh A 
 qc r*$ jL.a$)#*X9 #}8MpT Pt:eBZ",!D:F]U =Fn+qc rSE *$ |~.a _[Go&"'1UVº 3 GA *ÌĦ&ŸŒŚĎ*ĚƄ- 113 -

4 #!

Ư ưGoto D.., Takashima K., Kanebako Y., Nahoko K., Mori H, to be submitted.
Ư ưOno T., Kimura K. , Ihara M., Yamanaka Y., Sasaki M., Mori H., Hisaeda Y.,
Room-temperature Phosphorescence Emitters Exhibiting Red to Near-infrared Emission Derived from Intermolecular
Charge-transfer Triplet States of Naphthalenediimide-Halobenzoate Triad Molecules,
Chem. Eur. J (2021) accepted. selected as Front Coverhttps://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202100906
Ư ưMiyake R., Suganuma E., Kimura S, Mori H., Okabayashi J., Kusamoto T.
Cyclic heterometallic interactions formed from a flexible tripeptide complex showing effective antiferromagnetic spin
coupling,
Angew. Chem. Intl. Ed., 60, 5179-5183 (2021). Communication
https://onlinelibrary.wiley.com/doi/10.1002/anie.202013373
Ư ưAbe K., Nakada A., Matsumoto T., Uchijyo D., Mori H., Chang, H-C.
Functional-Group-Directed Photochemical Reactions of Aromatic Alcohols, Amines, and Thiols Triggered by
Excited-State Hydrogen Detachment: Additive-Free Oligomerization, Disulfidation, and C(sp2)–H Carboxylation withCO2
J. Org. Chem. 86, 959–969 (2021). https://doi.org/10.1021/acs.joc.0c02456
Ư ưKuroki N.*, Maruyama S., Mori H.*, selected as Inside Cover
Theoretical Strategy for Improving CO2 Absorption of Mixed Ionic Liquids Focusing on the Anion Effect:
A Comprehensive COSMO-RS Study,
Ind. Eng. Chem. Res. 59, 8848-8854 (2020). https://doi.org/10.1021/acs.iecr.0c00488
Ư ưL>tfNsMslSOn ūz~× İÆ Żē Í÷ ľŻ
Elementary 118 ŗ ļŉ (2021)ƯYjtVr_oMưISBN978-4-315-52316-4
Ư ưMochizuki Y., Nakano T., Sakakura K., Okiyama Y., Watanabe H., Kato K., Akinaga Y., Sato S., Yamamoto J-I,
Yamashita K., Murase T., Ishikawa T., Komeiji Y., Kato Y., Watanabe N., Tsukamoto T., Mori H., Okuwaki K., Tanaka
S., Kato A., Watanabe C., Fukuzawa K., Chapter: ABINIT-MP Program, in Recent Advances of the Fragment MolecularOrbital Method, (2021) Splinger.
Ư ưē Í÷ƱƭĆ ŪÆ
dTm:nNs<r^@dT;EMƸƮƷƟ ƲŷČÌ§&çķ|Ʋ(2020)ƯéÀĘĕƶQ9.10 ðßưISBN 978-4-86502-204-9


Ư ư

Strategy to obtain better catalysts using subnanosized Pt-alloy clusters:

Origin of high oxygen reduction reaction activity of Pt12 and controlling electronic state fluctuation- 114 -

Catalysis & Chemical Engineering 2021 (CCE-2021) San Francisco, USA (Feb. 2021). ƯƯ ưē Í÷Ư

ư

ư

Őu¬ĲĄ¥^lFgrVÆ¦£Éğ&ơÆĮê<r^@dT;EM*ƙĻ&*çķCMµ¯Ģ4,Ƃţĺġ*ƂƫƈĬè{Ħ5²ësĬèŸĦÌƩ/%JACI ęy Computer Chemistry Working Group OeXtċƯArl<rưƱ2021 Ú 3 ăƳƯ ưē Í÷ƯươÆĮê<r^@dT;EM)47<ArĢ*CMƠ/µ¯ĭèĂƍ¨ÆŃŸŒŉÉŃōOrQt X[TE[pLt_lSV^@tf|Ĕ²³qtEKkS_ƲUtQŉÉ)¿#ĲſsŸŒŉÉ&ÌƩŉÉ*ª9Ŀò$ƲÕÖƯArl<rưƱ2021 Ú 1 ăƳƯ ưNahoko KUROKIƱHirotoshi MORI
Possibility of ab initio effective fragment potential molecular dynamics simulations for predicting thermodynamic
properties of the functional liquid materials
þĈ¨É

Ő 101 ÿÈÚ ƱArl<rƱ2021 Ú 3 ăƳ
ƯĻű{ËưƯ ưĥƐ ÑĝƏƱƭĆ ŪÆƱē Í÷ ƯưƖÆ¨É&śŸī£É)¿#<ArĢ&ƢĜħÅ*Ĥ²Ā*ƌ¢?rQn]tż¨ÉØÉ

Ő 23 ¹ ÉĵĻű Ʊ A04ƱArl<rƱ2021 Ú 3 ăƯ ưƭĆ ŪÆƱĥƐ ÑĝƏƱē Í÷CMƠèĢ9æ´<ArĢ/ÆèĢĤ²Ā*Æƚŀ}ķ)ƛ7ƖÆ¨ÉĽŞÎ¨ÉØÉŐ 86 ¹Ú ƱK123ƱArl<rƱ2020 Ú 3 ăƳƯ ưƭĆ ŪÆƱē Í÷<ArĢ*ơÆĮêUtQ`tMĕœ&CMµ¯šż-*çķ¨ÉØÉ

Ő 85 ¹Ú ƱY215ƱArl<rƱ2020 Ú 9 ăƳį ÄƅƱŨƕ ģƱƫė ÛÄƱƭĆ ŪÆƱē Í÷ƱChowdhury FirozƱÔĸ ňÑ
bMbY=fŕ<ArĢ*CMħŷÜ)­.:YAr*âƤ¨ÉØÉ

Ő 85 ¹Ú ƱY216ƱArl<rƱ2020 Ú 9 ăƳƘĆ ƔƬƱƭĆ ŪÆƱē Í÷
ƂÞƓ in silico źŸ)´ƫŔÜƖÆ¨ÉŸŒ&ĘĒÉŝ)47ěŀƓèÜ{ĦþĈ¨É

Ő 101 ÿÈÚ ƱArl<rƱ2021 Ú 3 ăƳũĞ ĳƔƱĆĊ ťƱē Í÷ƱÕč ĩƱŦĈ ¸ƏƱvÊ 
Vma_RWƒÆ9ķ  Cu(II)-Ni(II)ĴĮƒ*ƎïĽàë&*®Þņèŀ}ķþĈ¨ÉŐ 101 ÿÈÚ ƱArl<rƱ2021 Ú 3 ăƳvÊ ƱŬ ŰƱĜƕ ųáƱē Í÷ƱŇ¬ É
ďƃ(Vma_RW6ƗÓzå)7»£çőèþĈ¨É

Ő 101 ÿÈÚ ƱArl<rƱ2021 Ú 3 ăƳ

- 115 -

⁐ᾮ⏺㠃ࡢᵓ㐀࡜ᶵ⬟ࡢィ⟬໬Ꮫ
Computational Chemistry on Structures and Functionsof Liquid Interfaces‫ۑ‬᳃⏣ ᫂ᘯࠊ㧗ᶫ ⱥ᫂ࠊ⋤ ⍅ࠊᖹ㔝 ᬛ೔ࠊᑠἨ ឡࠊఀ⸨ Ꮧࠊబ⸨ ኱࿴ࠊᕷᕝ ⋹ዉࠊ⣽㇂ Ẏࠊ▮⃝ ᑦஓ㸦ᮾ໭኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧1◊✲┠ⓗᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊ୺࡟⁐ᾮ⏺㠃ࡢゎ᫂ࢆ┠ᣦࡋ࡚ᐇ㦂◊✲࡜ࡢඹྠࡢࡶ࡜࡟ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࡸ

㟁Ꮚ≧ែィ⟬࡟ࡼࡿ◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ⁐ᾮ⏺㠃ࡢ㛵ࢃࡿ⌧㇟ࡣࠊ⇕ຊᏛࠊ㟁Ẽ໬ᏛࡸศගᏛ࡟ᇶ࡙ࡃほࡀ࡞ࡉࢀ࡚ࡁࡓࡀࠊᐇ㦂࡛ࡣ⁐ᾮ⏺㠃ࡢศᏊࢆ㑅ᢥⓗ࡟࡜ࡽ࠼࡚ほࡍࡿࡇ࡜ࡀ㞴ࡋࡃࠊ࣑ࢡ࡛ࣟ⢭ᐦ࡞ゎ᫂࡟ࡣ⌮ㄽィ⟬࡜ࡢ༠ຊࡀ࡜ࡾࢃࡅᚲせ࡜ࡉࢀࡿࠋᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊ⁐ᾮ⏺㠃ࡢศᏊࢆᤊ࠼ࡿᩘᑡ࡞࠸
᭷ຊ࡞ᐇ㦂ᡭἲ࡛࠶ࡿ⏺㠃࿴࿘ἼⓎ⏕ศගࡢ⌮ㄽィ⟬ᡭἲࢆ⾜࠸ࠊࡑࢀ࡟ᇶ࡙ࡃࡑࡢᛂ⏝ࢆ㐍ࡵ࡚ࡁࡓࠋᮏ
ᖺᗘ࡟ࡣ⏺㠃ศගࡢᢅ࠸ࢆࣂࣝࢡࡢᅄ㔜ᴟᡂศࢆྵࡵ࡚ỗ⏝໬ࡍࡿ⌮ㄽ࡜ࡑࡢィ⟬ᡭἲࢆ㛤Ⓨࡋࡓࠋࡲࡓࠊ
ἜỈ⏺㠃࡛ࡢ࢖࢜ࣥ㍺㏦ࡸ㟁Ꮚ⛣ື཯ᛂࡢ◊✲ࢆ⾜࠸ࠊࡑࢀࡽࡢ཯ᛂᶵᵓࢆศᏊ࡛ࣞ࣋ࣝゎ᫂ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ⏺㠃㠀⥺ᙧศගࡢィ⟬ࡣࠊᡃࠎࡢ㛤Ⓨࡋࡓ㟁Ꮚศᴟࣔࢹࣝ࡟ᇶ࡙ࡃศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ࠶ࡾࠊ

᫬ࠎ้ࠎ࡛ࡢ⏺㠃⣔ࡢศᴟࢆィ⟬ࡍࡿࣉࣟࢢ࣒ࣛ Calnos ࡢ㛤Ⓨࢆ㐍ࡵ࡚ࡁࡓࠋ௒ᖺᗘ࡟ࡣࠊᅄ㔜ᴟᡂศࢆྲྀ
ࡾᢅ࠺ࡓࡵ࡟ࠊศᏊࡢ㟁Ꮚ≧ែィ⟬࡜ศᏊືຊᏛࢺࣛࢪ࢙ࢡࢺࣜ࡜ࡶ࡜࡟ࠊᵓᡂศᏊࡢ཮ᴟᏊᡂศ࡜ᅄ㔜ᴟᡂศࢆྠ᫬࡟ඹ㏻ࡢ⢭ᗘ࡛ホ౯ࡍࡿࢶ࣮ࣝ Qsac ࢆ㛤Ⓨࡋࡓࠋࡲࡓ࢖࢜ࣥ㍺㏦ࢆྲྀࡾᢅ࠺ࡓࡵ࡟ࠊࡉࡲࡊࡲ
࡞୍⯡໬ᗙᶆୖࡢࣂ࢖࢔ࢫࡸᣊ᮰࡞࡝ࢆᐇ⿦ࡋࠊࣞࣉࣜ࢝஺᥮࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢ࡞࡝ࡢᡭἲ࡟ࡼࡗ࡚
⮬⏤࢚ࢿࣝࢠ࣮㠃ࢆィ⟬ࡍࡿࣉࣟࢢ࣒ࣛ FreeFlex ࢆ㛤ⓎࡋࠊἜỈ⏺㠃ࡢᵓ㐀ࡺࡽࡂࡢ water finger ᗙᶆࠊ㟁Ꮚ⛣ືࡢ࢚ࢿࣝࢠ࣮ᗙᶆ࡞࡝ࡉࡲࡊࡲ࡞ᗙᶆ࡬ࡢᣑᙇࢆᐇ⿦ࡋ࡚౑⏝ࡋࡓࠋ

3

◊✲ᡂᯝ

3.1 ࿴࿘Ἴศග࡟࠾ࡅࡿࣂࣝࢡຠᯝ ࿴࿘Ἴศගࡀ⏺㠃㑅ᢥᛶࢆࡶࡘࡢࡣࠊ2 ḟࡢㄏ㉳཮ᴟᏊࡀ཯㌿ᑐ⛠ᛶࡢ࡞࠸፹య࡛ࡢࡳチᐜ࡜࡞ࡿࡇ࡜࡟
⏤᮶ࡍࡿࠋࡋ࠿ࡋㄏ㉳ᅄ㔜ᴟᏊࡣ཯㌿ᑐ⛠ᛶࡀ࠶ࡿࣂࣝࢡ፹య࡛ࡶチᐜ࡛࠶ࡾࠊ࿴࿘ἼⓎ⏕࡬ࡢᐤ୚ࡀ࠶ࡾ
࠺ࡿࡇ࡜ࡀྂࡃ࠿ࡽᣦ᦬ࡉࢀ࡚ࡁࡓࠋㄏ㉳ᅄ㔜ᴟᡂศࡣ୍⯡࡟ㄏ㉳཮ᴟᏊࡼࡾࡶ㧗ḟࡢຠᯝ࡛࠶ࡿࡀࠊࣂࣝ
ࢡ፹యࡢయ✚ࡣ⏺㠃ࡼࡾࡶ኱ࡁࡃࠊ඲య࡜ࡋ࡚ࡢຠᯝࡣྠ⛬ᗘ࡟ࡶ࡞ࡾ࠺ࡿࠋࡇࢀࡲ࡛ࡢ⏺㠃࿴࿘Ἴศගࡢ
ゎᯒ࡛ࡣࣂࣝࢡᅄ㔜ᴟࡢᐤ୚ࡣ࡯ࡰ↓どࡉࢀ࡚࠸ࡓࡀࠊࡑࡢᐤ୚ࡢ኱ࡁࡉࡣၥ㢟࡜ࡍࡿศᏊࡸ᣺ື࣮ࣔࢻ࡟
౫Ꮡࡍࡿ࡜᝿ᐃࡉࢀࡿࠋ௒ᚋࡢ⏺㠃ศගࡢᐃ㔞ⓗ࡞⌮ゎࡢࡓࡵ࡟ࡣࠊࡑࡢ▱ぢࢆ☜❧ࡍࡿࡇ࡜ࡀᮃࡲࢀࡿࠋ ᮏ◊✲࡛ࡣࠊලయⓗ࡟ほࡍࡿศᏊࡢ᣺ື࣮ࣔࢻ࡟ᑐࡋ࡚ࠊࣂࣝࢡᅄ㔜ᴟࡢ┦ᑐⓗ࡞㔜せᛶࢆぢ✚ࡶࡿࡇ࡜ࡀ࡛ࡁࡿ୍⯡ⓗ࡞ᡭἲࢆ㛤Ⓨࡋࡓࠋࣂࣝࢡᅄ㔜ᴟ࡟⏤᮶ࡍࡿ㠀⥺ᙧឤཷ⋡ࡢ⾲ᘧࡣࠊ௨๓࡟ᮏࢢ࣮ࣝࣉࡢ
௦⾲⪅ࡀᥦ᱌ࡋ࡚࠾ࡾ㸦A. Morita, Chem. Phys. Lett. 398 (2004) 361㸧ࠊࡑࢀࢆᐇ⿦ࡍࡿࣉࣟࢢ࣒ࣛࢶ࣮ࣝ Qsac
(quadrupole susceptibility automatic calculator) ࢆ㛤Ⓨࡋࡓࠋ፹యࢆᵓᡂࡍࡿศᏊ࡟ᑐࡍࡿ Gaussian ࡢࢪࣙࣈࢫ

- 116 -

ࢡࣜࣉࢺࢆ⏕ᡂࡋ࡚ Gaussian ࢆ࿧ࡧฟࡍࡇ࡜࡛ᚲせ࡞ㄏ㉳཮ᴟᏊ࣮࣓ࣔࣥࢺࡸㄏ㉳ᅄ㔜ᴟ࣮࣓ࣔࣥࢺࢆィ⟬ࡋࠊࡉࡽ࡟ࡑࡢゎᯒࢆ⾜࠺ࠋࡲࡓ Calnos ࢆ⏝࠸ࡓศᏊືຊᏛィ⟬ࢆ⾜࠸ࠊࡑࡢࣛࢪ࢙ࢡࢺ࣮ࣜࡢࢹ࣮ࢱࢆ
ㄞࡳ㎸ࢇ࡛ࠊ⏺㠃࡜ࣂࣝࢡࡢ୧ᡂศࢆ༙ᐃ㔞ⓗ࡟ホ౯ࡍࡿࡶࡢ࡛࠶ࡿࠋࡇࡢࣉࣟࢢ࣒ࣛࢶ࣮ࣝࡣࠊ௵ពࡢศ
Ꮚࡢ᣺ື࣮ࣔࢻ࡟ࡘ࠸࡚ࠊ࿴࿘Ἴศගࢫ࣌ࢡࢺࣝࡢ࡞࠿࡛ࡢ⏺㠃཮ᴟᏊ࡜ࣂࣝࢡᅄ㔜ᴟᏊࡢ┦ᑐⓗ࡞኱ࡁࡉࢆ୚࠼ࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡇࡢࣉࣟࢢ࣒ࣛࢆࡉࡲࡊࡲ࡞ศᏊࡢ᣺ື࣮ࣔࢻ࡟ᛂ⏝ࡋࠊ࠸ࡃࡘ࠿ࡢ᣺ື࣮ࣔࢻ࡛
ࡣࣂࣝࢡᅄ㔜ᴟࡢᙳ㡪ࡀ኱ࡁ࠸ࡇ࡜ࢆぢฟࡋࡓࠋࡓ࡜࠼ࡤࠊ୍⯡࡟ C=O ఙ⦰࣮ࣔࢻ࡟ࡣᅄ㔜ᴟࡢᐤ୚ࡀ኱
ࡁࡃྵࡲࢀࠊࡑࡢ᣺ືࢫ࣌ࢡࢺࣝࡢゎᯒ࡟ࡣᅄ㔜ᴟࢆ⪃៖ࡍࡿࡇ࡜ࡀᚲせ࡛࠶ࡿࠋࡲࡓࠊ࣓ࢳࣝᇶࡢ C-H ఙ⦰ࡢ࠺ࡕ཯ᑐ⛠࣮ࣔࢻࡣࣂࣝࢡᅄ㔜ᴟࡢᐤ୚ࡀ኱ࡁ࠸ࠋ࣓ࢳࣝᇶࡢ C-H ఙ⦰ࡣከࡃࡢ᭷ᶵศᏊ࡟ྵࡲࢀࠊࡑ
ࡢศᏊ㓄ྥࡢゎᯒ࡟ᗈࡃ⏝࠸ࡽࢀ࡚ࡁࡓࡀࠊࡑࡢᐃ㔞໬࡟ࡣࣂࣝࢡᅄ㔜ᴟࡢ⪃៖ࡀᚲせ࡛࠶ࡿࡇ࡜ࢆ♧ࡉࢀࡓࠋᅗ㸯. ⏺㠃཮ᴟᏊ࡜ࣂࣝࢡᅄ㔜ᴟࡢᐤ୚ࢆホ౯ࡍࡿࣉࣟࢢ࣒ࣛࢶ࣮ࣝ Qsac ࡢᴫせࠋ

3.2 ᾮᾮ⏺㠃ࡢ࢖࣭࢜ࣥ㟁Ⲵ⛣ືࡢᚤどⓗᶵᵓ ᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊ㏆ᖺᾮయ⏺㠃ࡢᵓ㐀ゎ᫂ࢆ㉸࠼࡚ࠊᾮయ⏺㠃ࡢᇶ♏ⓗ࡞ᶵ⬟࡛࠶ࡿ࢖࢜ࣥ㍺㏦ࡢᶵ
ᵓゎ᫂࡟ྲྀࡾ⤌ࢇ࡛ࡁࡓࠋᾮయࡢ⏺㠃ࡢ࡞࠿࡛ࡶᾮᾮ㸦Ỉ㸫Ἔ㸧⏺㠃ࡢศᏊࡣ࡜ࡾࢃࡅᐇ㦂ⓗ࡞ほࡀ㞴ࡋࡃࠊࡑࡢศᏊㄽࡣᮍ㛤ᣅ࡛࠶ࡿࠋᾮᾮ⏺㠃ࡢ࢖࢜ࣥ㍺㏦ࡣࠊᢳฟࡸࢭࣥࢧ࣮ࠊ⭷ศ㞳࡞࡝ࡢ⌧㇟ࡢᇶ♏㐣⛬࡛ࠊࡑࡢศᏊㄽࡢゎ᫂ࡣ⯆࿡῝࠸ࠋᮏᖺᗘ࡟ࡣࠊ࢖࢜ࣥ㍺㏦࡟㛵ࡋ࡚⏺㠃ᩘᒙ࡛㉳ࡇࡿ facilitated ion transport(FIT) ࡢ࣑ࢡࣟ࡞ゎ᫂ࠊ࠾ࡼࡧ⏺㠃㟁Ꮚ⛣ື཯ᛂࡢᶵᵓࡢ◊✲ᡂᯝࢆⓎ⾲ࡋࠊࡉࡽ࡟ࡑࢀࡽࢆໟᣓࡋࡓ⥲ㄝ㸦A.
Morita et al. J. Chem. Phys. 154 (2021), 080901㸧ࢆⓎ⾲ࡋࡓࠋ௨ୗࡑࡢෆᐜࢆ⤂௓ࡍࡿࠋ ࢖࢜ࣥࡀ⏺㠃ࢆ㏻㐣ࡍࡿ㝿࡟ูࡢ໬Ꮫ✀㸦ࣜ࢞ࣥࢻࠊionophore㸧ࡢᏑᅾ࡟ࡼࡗ࡚ಁ㐍ࡉࢀࡿຠᯝࡣࠊ1970
ᖺ௦࡟ぢ࠸ࡔࡉࢀ FIT ࡜࿧ࡤࢀ࡚࠸ࡿࠋࣜ࢞ࣥࢻࡢ࢖࢜ࣥ✀࡟ᑐࡍࡿ㑅ᢥᛶࡣ㘒ྜయᙧᡂ࡟⏤᮶ࡋࠊ⭷㏱㐣
ࡸࢭࣥࢧ࣮࡞࡝࡬ࡢ኱ࡁ࡞ᛂ⏝ࡀ࠶ࡿࠋ㏻ᖖࡇࢀࡲ࡛ࡢ⌮ㄽ࡛ࡣࠊ㘒ྜయᙧᡂ࡟ࡼࡗ࡚㏻㐣ᚋࡢࣂࣝࢡ┦࡛- 117 -

ࡢ⇕ຊᏛⓗ࡞Ᏻᐃᛶࡀ㧗ࡃ࡞ࡿࡓࡵ࡜⌮ゎࡉࢀࡿࠋࡋ࠿ࡋࠊ㏆ᖺࡢᐇ㦂࡛ࠊpmol/L ࡢᴟࡵ࡚ᚤ㔞ࡢࣜ࢞ࣥࢻ
✀ࡢᏑᅾ࡟ࡼࡗ࡚ࠊぶỈⓗ࡞◳࠸࢖࢜ࣥࡢ⏺㠃㏻㐣ࡀⴭࡋࡃಁ㐍ࡉࢀࡿࢣ࣮ࢫࡀᐇドࡉࢀࠊࡇࢀࡣ㏻ᖖࡢ㘒ྜయᙧᡂ࡛ࡣ࡞ࡃࠊ⏺㠃࡛ࡢゐ፹ⓗຠᯝ࡜ࡳ࡞ࡉࢀࡿࠋᮏ◊✲࡛ࡣࠊࡑࢀࡀぢฟࡉࢀࡿ඾ᆺⓗ࡞ሙྜ࡜ࡋ࡚ Fࡢ⏺㠃㏱㐣࡟ᑐࡍࡿ tetra-hexyl ammonium (THA+) ࢖࢜ࣥࢆ౛࡟࡜ࡗ࡚ࠊゐ፹ⓗ࡞ຠᯝࡀ㉳ࡇࡿ࣓࢝ࢽࢬ࣒ࢆ
⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࠿ࡽ᫂☜࡟ゎ᫂ࡋࡓࠋF- ࡜ THA+ ࡣᾮᾮ⏺㠃ࡢ nm ⛬ᗘࡢ⠊ᅖ࡛ࡢࡳ୍᫬ⓗ࡞㘒ྜయࢆᙧᡂࡋ࡚⏺㠃㏻㐣ࡢ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࢆୗࡆࡿ཯ᛂ⤒㊰ࡀ⾲ࢀࡿࠋ୍᪉ࠊ㢮ఝࡢ࢖࡛࢜ࣥ࠶ࡿ tetra-butyl
ammonium (TBA+) ࡛ࡣᐇ㦂ⓗ࡟ゐ፹ຠᯝࡀ࡞࠸ࡇ࡜ࡶ♧ࡉࢀ࡚࠸ࡿࡀࠊࡑࡢ㐪࠸ࡶ⮬⏤࢚ࢿࣝࢠ࣮㠃࡜཯ᛂ⤒㊰࠿ࡽ⌮ゎࡉࢀࡓࠋ࡝ࡕࡽࡢ⣔࡛ࡶࠊ୍᫬ⓗ࡞㘒ᙧᡂࢆ㏻ࡋ࡚ࣂࣜ࢔ࢆୗࡆࡿ⤒㊰࡜㉳ࡇࡉ࡞࠸⤒㊰ࡢ 2ࡘࡢ࣓࢝ࢽࢬ࣒ࡀᏑᅾࡋࠊࡑࢀࡀࢫ࢖ࢵࢳࡍࡿࡇ࡜࡛␗࡞ࡿ㏻㐣ᶵᵓ࡜࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ ࡲࡓࠊỈ㸫Ἔ஧┦ඹᏑୗ࡛ࡣぶỈⓗ࡞໬Ꮫ✀࡜␯Ỉⓗ㸦ぶἜⓗ㸧࡞໬Ꮫ✀ࡢ㛫࡛㟁Ꮚ⛣ື཯ᛂࡀほࡉࢀࡿࡇ࡜ࡀ࠶ࡿࠋᾮᾮ⏺㠃ࡢ㟁Ꮚ⛣ືࡣࣂࣝࢡᆒ୍┦࡛ࡢ㟁Ꮚ⛣ື࡜␗࡞ࡾࠊ㟁Ⲵ⛣ື≧ែࢆศ㞳ࡋ࡚ࢥࣥࢺ
࣮ࣟࣝࡍࡿ࠺࠼࡛᭷ຠᛶࢆࡶࡘࠋࡋ࠿ࡋࡑࡢᚤどⓗ࡞཯ᛂᶵᵓࢆㄪ࡭ࡿᡭἲࡣࠊᚑ᮶࡯ࡰ㟁Ẽ໬Ꮫᐃࡢ㏿ᗘㄽ࠿ࡽࡢ㢮᥎࡟ࡼࡗ࡚࠾ࡾࠊ⏺㠃࡛ࡢศᏊࢆࡳࡿ࠺࠼࡛኱ࡁ࡞᭕᫕ࡉࡀṧࡉࢀ࡚࠸ࡓࠋ᭱ࡶྂࡃ࠿ࡽ▱ࡽࢀࡓ඾ᆺⓗ࡞⏺㠃㟁Ꮚ⛣ື཯ᛂ࡛࠶ࡿࣇ࢙ࣟࢭࣥ࡜ࣇ࢙ࣜࢩ࢔࣭ࣥࣇ࢙ࣟࢩ࢔ࣥ໬≀࢖࢜ࣥࡢ཯ᛂ࡛ࡶࠊ㟁Ꮚ⛣ືࡀ⏺㠃ࢆࡲࡓ࠸࡛㉳ࡇࡿ୙ᆒ୍ᶵᵓ࠿ࠊࣇ࢙ࣟࢭࣥࡀỈ┦࡟ධࡗ࡚࠿ࡽ㟁Ꮚ⛣ືࢆ㉳ࡇࡍᆒ୍ᶵᵓ࠿
ࡣ㛗࠸㆟ㄽࡀ࠶ࡗࡓࠋࡑࡇ࡛ࠊࡑࡢ཯ᛂᶵᵓࡢ඲యࢆ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡟ᇶ࡙࠸࡚᫂ࡽ࠿࡟ࡋࡓࠋ ィ⟬ୖࡣࠊࢻࢼ࣮࡜࢔ࢡࢭࣉࢱ࣮ศᏊࡢ⏺㠃࡬ࡢ᥋㏆࡜ complex ⏕ᡂࢆ⾲ࡍᗙᶆ z, r ࡟ຍ࠼࡚ࠊ⁐፹࿴ࡺࡽࡂࢆ⾲ࡍ࢚ࢿࣝࢠ࣮ᗙᶆ X ࡢ 3 ࡇࡢᗙᶆୖ࡛ࡢ 3 ḟඖ⮬⏤࢚ࢿࣝࢠ࣮㠃ࢆࠊ኱つᶍ࡞ࣞࣉࣜ࢝஺᥮࢔ࣥ
ࣈࣞࣛࢧࣥࣉࣜࣥࢢἲࡢィ⟬࡟ᇶ࡙࠸࡚ồࡵࡓࠋࡑࡢ⤖ᯝࠊᮏ཯ᛂࡣ⁐㉁࡜⁐፹ศᏊࡀ⏺㠃ࢆࡲࡓ࠸࡛㟁Ꮚ⛣ືࢆ㉳ࡇࡍ୙ᆒ୍ᶵᵓ࡛࠶ࡿࡇ࡜ࢆᐇドࡋࡓࠋࡉࡽ࡟⏺㠃࡟㟁఩ࢆ༳ຍࡋࡓ᮲௳࡛ࡢィ⟬ࡶ⾜ࡗ࡚཯ᛂ㏿ᗘࡢኚ໬ࢆࡶ࡜ࡵࠊ㟁Ẽ໬Ꮫィࡢᐇ㦂ࢆ⮬↛࡟ㄝ᫂ࡍࡿࡇ࡜ࡶ♧ࡋࡓࠋ

ᅗ 2. ᾮᾮ⏺㠃࡛ࡢ 3 ḟඖ⮬⏤࢚ࢿࣝࢠ࣮㠃 G(3)(z, r, X) ࡜཯ᛂ⤒㊰ࡢᶍᘧᅗࠋ

- 118 -

4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬⣽㇂ Ẏࠊ⋤ ⍅ࠊ᳃⏣ ᫂ᘯࠊ㟁Ꮚඹ㬆࡟ࡼࡿ࢟ࣛࣝ SFG ࡢࣂࣝࢡ࣭⏺㠃ᡂศࡢ⌮ㄽゎᯒࠊศᏊ⛉Ꮫ఍࢜ࣥࣛ࢖ࣥウㄽ఍ࠊ2020. 9. 14-17.
‫ ۻ‬A. Morita, Development of Qsac Program to Evaluate Whole SFG Susceptibility, Telluride Science Research
Conference on "Nonlinear Optics at Interfaces", Web online (Telluride, CO, USA), Jun. 8-12, 2020.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫¨ ۻ‬5HFHQW3URJUHVVLQ6LPXODWLQJ0LFURVFRSLF,RQ7UDQVSRUW0HFKDQLVPVDW/LTXLG/LTXLG,QWHUIDFHV´$NLKLUR0RULWD$L.RL]XPL7RPRQRUL+LUDQR-&KHP3K\V 3HUVSHFWLYH   ³5HSO\WRµ&RPPHQWRQ%LOD\HULQJDWLRQLFOLTXLGVXUIDFHVDVXPIUHTXHQF\JHQHUDWLRQYLEUDWLRQDOVSHFWURVFRS\DQG
PROHFXODUG\QDPLFVVLPXODWLRQEDVHGVWXG\´¶E\0'HXWVFK200DJQXVVHQ-+DGGDG'3RQWRQL%00XUSK\DQG%02FNR´
7DNDVKL ,ZDKDVKL 7DWVX\D ,VKL\DPD <DVXQDUL 6DNDL $NLKLUR 0RULWD 'RVHRN .LP DQG <XNLR 2XFKL 3K\V &KHP
&KHP3K\V23  ‫&¨ ۻ‬RPPHQW RQ 7RZDUG 8QUDYHOLQJ WKH 3X]]OH RI 6XP )UHTXHQF\ *HQHUDWLRQ 6SHFWUD DW ,QWHUIDFH RI $TXHRXV
0HWKDQRO6ROXWLRQ(IIHFWVRI&RQFHQWUDWLRQ'HSHQGHQW+\SHUSRODUL]DELOLW\ ´
7DWVX\D,VKL\DPD6KLQ\D7DNDJL7RPRQRUL+LUDQR/LQ:DQJ$NLKLUR0RULWD -3K\V&KHP&124
 ‫'¨ ۻ‬HYHORSPHQWRI4XDGUXSROH6XVFHSWLELOLW\$XWRPDWLF&DOFXODWRULQ6XP)UHTXHQF\*HQHUDWLRQ6SHFWURVFRS\DQG
$SSOLFDWLRQWR0HWK\O&+9LEUDWLRQV´:DWDUX0RUL/LQ:DQJ<DPDWR6DWR$NLKLUR0RULWD-&KHP3K\V153 SDJHV   ‫¨ ۻ‬4XDGUXSROH&RQWULEXWLRQRI& 29LEUDWLRQDO%DQGLQ6XP)UHTXHQF\*HQHUDWLRQ6SHFWUDRI2UJDQLF&DUERQDWHV´/LQ :DQJ :DWDUX 0RUL $NLKLUR 0RULWD 0DVDWR .RQGRK 0DVDQDUL2NXQR DQG 7DNDDNL ,VKLEDVKL - 3K\V &KHP
/HWW11  ³,Q 6LWX 0RQLWRULQJ RI WKH 8QVDWXUDWHG 3KRVSKROLSLG 0RQROD\HU 2[LGDWLRQ LQ WKH $PELHQW $LU E\ +'6)*
6SHFWURVFRS\´.HQLFKL,QRXH&KXQML7DNDGD/LQ:DQJ$NLKLUR0RULWDDQG6KHQ<H-3K\V&KHP%124  ‫¨ ۻ‬%LOD\HULQJ DW ,RQLF /LTXLG 6XUIDFHV $ 6XP)UHTXHQF\ *HQHUDWLRQ 9LEUDWLRQDO 6SHFWURVFRS\ DQG 0ROHFXODU'\QDPLFV6LPXODWLRQEDVHG6WXG\´
7DNDVKL ,ZDKDVKL 7DWVX\D ,VKL\DPD <DVXQDUL 6DNDL $NLKLUR 0RULWD 'RVHRN .LP DQG <XNLR 2XFKL 3K\V &KHP
&KHP3K\V22  ³5HIUDFWLYH,QGH[RI1DQRFRQILQHG:DWHU5HYHDOV,WV$QRPDORXV3K\VLFDO3URSHUWLHV´
7KX++/H$NLKLUR0RULWDDQG7DNXR7DQDND1DQRVFDOH+RUL]5  - 119 -

᪘㔠ᒓ࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࡢタィ࡜ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࡢ㛤Ⓨ
0HFKDQLVWLFVWXGLHVRQWKHROHILQSRO\PHUL]DWLRQFDWDO\]HGE\JURXSPHWDOFDWDO\VWVDQGPHWDO±OLJDQGFRRSHUDWLYHERQGFOHDYDJHVZLWKF\FORSHQWDGLHQRQHPHWDOFRPSOH[HV‫ۑ‬㔝ᓮ ிᏊ㸦ᮾி኱Ꮫ኱Ꮫ㝔ᕤᏛ⣔◊✲⛉㸸໬Ꮫ⏕࿨ᕤᏛᑓᨷ㸧1 ◊✲┠ⓗ㸪ෆᐜᮏ◊✲࡛ࡣ“10 ᪘㔠ᒓ㘒య࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࡢタィ”࠾ࡼࡧ“ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࡢ㛤Ⓨ”ࢆ⾜࠸ࡲࡍࠋ᭱⤊ⓗ࡟ࡣ᪂つゐ፹タィ㸪࠾ࡼࡧ཯ᛂᶵᵓࡢゎ᫂࡬ࡢ▱ぢࢆᚓ࡚㸪ᐇ㝿ࡢゐ፹ྜᡂ࡟཯ᫎࡉࡏ㸪᪂つᶵ⬟ࢆᣢࡘ㑄⛣㔠ᒓゐ፹ࡢྜᡂࢆ┠ᣦࡋࡲࡍࠋ
  ᪘㔠ᒓ࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࡢタィ࣏࢚ࣜࢳࣞࣥࡸ࣏ࣜࣉࣟࣆࣞࣥࡣ᪥ᮏᅜෆ࡛ᖺ㛫 200 ୓ t ௨ୖ⏕⏘ࡉࢀࡿ㠀ᖖ࡟㔜せ࡞ᮦᩱ࡛ࡍࡀ㸪ࡑࡢᴟᛶࡢపࡉ࠿ࡽ┦⁐ᛶࡸ᥋╔ᛶ࡜࠸ࡗࡓᛶ㉁࡟ຎࡾࡲࡍࠋࡇࢀࡽࡢᛶ㉁ࡣᴟᛶᐁ⬟ᇶࢆᑟධࡍࡿࡇ࡜࡛ᨵၿࡀ
ྍ⬟࡛ࡍࠋࡇࡢࡓࡵ㸪ᴟᛶᐁ⬟ᇶᏑᅾୗ࡛ࡶάᛶࢆࡶࡘ 10 ᪘㑄⛣㔠ᒓゐ፹ࢆࡶࡕ࠸ࡓඹ㔜ྜ཯ᛂࡢ㛤Ⓨࡀ㏆ᖺὀ┠ࢆ㞟ࡵ࡚࠸ࡲࡍࠋᡃࠎࡣ 2015 ᖺᗘ࡟㸪10 ᪘㔠ᒓゐ፹ࢆ⏝࠸ࡓ࢔ࢱࢡࢳࢵࢡ࣏ࣜࣉࣟࣆࣞࣥࡢྜᡂ㸪࠾ࡼࡧࣉࣟࣆࣞࣥ࡜ᴟᛶࣔࣀ࣐࣮ࡢඹ㔜ྜࢆୡ⏺࡛ึࡵ࡚㐩ᡂࡋࡲࡋࡓࠋ(ᅗ 1; J. Am. Chem. Soc. 2015,
137,10934.; Angew. Chem. Int. Ed., 2016, 55, 7505̽7509.)

ᅗ 1. Pd/IzQO ゐ፹࡟ࡼࡿࣉࣟࣆࣞࣥ࡜ᴟᛶࣔࣀ࣐࣮࡜ࡢඹ㔜ྜࡋ࠿ࡋ㸪ࡑࡢ཯ᛂᶵᵓࡣᮍࡔ୙᫂࡞Ⅼࡀከࡃ㸪ᶵᵓゎᯒࡣゐ፹ᛶ⬟ࡢྥୖࡢࡓࡵ࡟㔜せ࡛ࡍࠋ2014 ᖺ࡟ᡃࠎࡣࣜࣥୖࡢ⨨᥮ᇶ࡜ࡋ࡚㣬࿴࢔ࣝ࢟ࣝᇶࢆᣢࡘࣃࣛࢪ࣒࣭࢘࣍ࢫࣇ࢕ࣥࢫࣝ࣍ࢼ࣮ࢺゐ፹(Pd/PS)ࡢ࠿ࡉ
㧗ࡉ࡛࠶ࡿ Sterimol ࡢ B5 ࣃ࣓࣮ࣛࢱࢆホ౯࡟⏝࠸ࡿࡇ࡜࡛ᚓࡽࢀࡿ࣏࣐࣮ࣜࡢศᏊ㔞ࢆㄝ᫂ࡍࡿࡇ࡜
࡟ᡂຌࡋࡲࡋࡓ(J. Am. Chem. Soc. 2014, 136, 11898̽11901.) ࡋ࠿ࡋ㸪ࡇࡢຠᯝࡣࡍ࡭࡚ࡢ Pd/ PS ゐ፹࡟㐺⏝࡛ࡁࡿࡶࡢ࡛ࡣ࠶ࡾࡲࡏࢇࠋ

- 120 -ᅗ ࣃࣛࢪ࣒࣭࢘࣍ࢫࣇ࢕ࣥࢫࣝ࣍ࢼ࣮ࢺゐ፹ࢆ⏝࠸ࡓ࢚ࢳࣞࣥ㔜ྜ࡟ᑐࡍࡿ
㓄఩Ꮚࡢ❧యⓗຠᯝࡑࡇ࡛㸪ᮏ◊✲࡛ࡣ࢜ࣞࣇ࢕ࣥ㔜ྜࡢᶵᵓࢆ㸪DFT ィ⟬ࢆ⏝࠸࡚ゎᯒࡋ㸪ゐ፹ᛶ⬟ྥୖࡢࡓࡵࡢᣦ㔪ࢆᚓࡿࡇ࡜ࢆ➨୍┠ᶆ࡜ࡋ㸪୍⯡ᛶࢆᣢࡘண

ἲࢆ┠ᣦࡋ࡚㸪ᶵᲔᏛ⩦ࢆ⏝࠸ࡓண ࢆ⾜࠸ࡲࡋࡓࠋ

 ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࡢ㛤Ⓨ㐣ཤ࡟ᡃࠎࡣ㸪㔠ᒓ㓄఩Ꮚ༠ാⓗ H–H ⤖ྜษ᩿ࢆ㘽࡜ࡋࡓ C–C ⤖ྜࡢ⬺Ỉ⣲໬཯ᛂ(ᅗ 3. ᕥ; J. Am. Chem. Soc.
2013, 135, 18726.) ࡸ㸪C–O ⤖ྜࡢຍỈ⣲ศゎ཯ᛂ(ᅗ 3. ྑ; Nat. Commun. 2015, 6, 6296.)ࢆሗ࿌ࡋࡲࡋࡓࠋࡲ
ࡓ୍᪉࡛㸪௒ᖺᗘᡃࠎࡣࣄࢻࣟ࢟ࢩࢩࢡࣟ࣌ࣥࢱࢪ࢚ࢽࣝⓑ㔠࣓ࢳࣝ㘒య࠿ࡽࡢ㔠ᒓ㓄఩Ꮚ༠ാⓗ C–H ⤖ྜᙧᡂ཯ᛂࢆሗ࿌ࡋ(ᅗ 4; J. Am. Chem. Soc. 2019, 141, 2247.)㸪ࡇࢀࡲ࡛ H–H ⤖ྜษ᩿࡟㝈ࡽࢀ࡚࠸ࡓ཯ᛂᛶࢆ
ᵝࠎ࡞⤖ྜษ᩿/ᙧᡂ➼࡟ᛂ⏝࡛ࡁࡿྍ⬟ᛶࢆ♧ࡋࡲࡋࡓࠋ

ਦ 3. ۜ଒ഓҒࢢ‫ڢ‬ಉద H–H ݃߻઀இΝ伶ͳͤΖৰഖൕԢ͹ྭ

ਦ 4. ϐχϫΫεεέϫϘϱνζΦωϩപۜϟοϩࡪର͖Δ͹ C–H ݃߻‫ܙ‬੔ᮏ◊✲࡛ࡣ㸪㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࢆ B–H ⤖ྜษ᩿࡬ᒎ㛤ࡋ㸪ࡑࢀࡽࡢゐ፹཯ᛂࡢ㛤Ⓨࢆ┠ᣦࡋࡲࡋࡓࠋࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㓄఩Ꮚୖࡢ⨨᥮ᇶ㸪㔠ᒓ㸪ᨭᣢ㓄఩Ꮚࡢ⤌ࡳྜࢃࡏࡀ⤖ྜษ᩿άᛶ࡟ᑐࡋ࡚࡝
ࡢࡼ࠺࡟ᙳ㡪ࢆ୚࠼ࡿ࠿㸪DFT ィ⟬࡟ᇶ࡙ࡃண

ࢆ⾜࠺ࡇ࡜࡛◊✲ࢆຍ㏿ࡉࡏࡲࡋࡓࠋ

- 121 - ◊✲᪉ἲࠊィ⟬᪉ἲ
10 ᪘㔠ᒓ࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࡢタィࡢ◊✲࡛ࡣ㸪Gaussian 09 ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚㸪ᵓ㐀᭱㐺໬࡟
B3LYP-D3/Lanl2dz(㔠ᒓ)㸪B3LYP-D3/6-31G(d)(ࡑࡢ௚ࡢඖ⣲)㸪࢚ࢿࣝࢠ࣮ィ⟬࡟ B3LYP-D3 (SCRF)/Lanl2dz(㔠ᒓ)㸪B3LYP-D3(SCRF)/6-31G(d)(ࡑࡢ௚ࡢඖ⣲)ࢆ⏝࠸ࡲࡋࡓࠋ⁐፹⿵ṇ࡟ࡣ SMD ࢆ⏝࠸ࡲࡋࡓࠋ

ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࡢ㛤Ⓨ ࡢ◊✲࡛ࡣ㸪Gaussian
16/M06/def2-TZVP ࢆ౑ࡗ࡚ᇶᗏ≧ែ㸪㑄⛣≧ែ㸪IRC ィ⟬ࢆ⾜࠸ࡲࡋࡓࠋ ◊✲ᡂᯝ
  ᪘㔠ᒓ࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࡢタィࡲࡎ㸪ࡑࢀࡒࢀࡢゐ፹ࡢᛶ㉁ࢆồࡵࡿࡓࡵ࡟ DFT ィ⟬ࢆ฼⏝ࡋࡲࡋࡓࠋᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓᚋ࡟ゐ፹ࡢ
Sterimol ࡢࣃ࣓࣮ࣛࢱ࡟௦⾲ࡉࢀࡿ❧యⓗᛶ㉁ࡸ NBO 㟁Ⲵ࡟௦⾲ࡉࢀࡿ㟁Ꮚⓗᛶ㉁࡞࡝ࢆィ⟬ࡋࡲࡋࡓࠋࡇ
ࢀࡽࡢᛶ㉁ࢆグ㏙Ꮚ࡜ࡋ࡚ Pd/PS ࢆ⏝࠸ࡓ࢚ࢳࣞࣥ࡜࢔ࢡࣜࣝ㓟࣓ࢳࣝࡢඹ㔜ྜࡢணࢆ㸪ᶵᲔᏛ⩦ࢆ⏝࠸࡚⾜࠸ࡲࡋࡓࠋࡑࡢ⤖ᯝ㸪ᅗ 5 ࡢ㏻ࡾ࡟࡞ࡾࡲࡋࡓࠋ

ᅗ 5. ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ Pd/PS ࡟ࡼࡿ࢚ࢳࣞࣥ/࢔ࢡࣜࣝ㓟࣓ࢳࣝඹ㔜ྜࡢ(ᕥ)ศᏊ㔞(ྑ)ゐ፹άᛶ࡟ᑐࡍࡿゎᯒࡢ⤖ᯝࡲࡓ㸪᭦࡞ࡿゎᯒࡢ⤖ᯝ㸪ࡇࢀࡲ࡛࡟ሗ࿌ࡉࢀࡓ Sterimol ࡢ B5 ࣃ࣓࣮ࣛࢱ࡞࡝࡟ຍ࠼࡚ PȂPdȂO ࡢࣂ࢖ࢺ࢔ࣥࢢࣝࡀ኱ࡁ࡞ᙳ㡪ࢆཬࡰࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡾࡲࡋࡓࠋ⌧ᅾࡇࡢண࡟ᇶ࡙࠸ࡓࡼࡾゐ፹ᛶ⬟ࡢ㧗࠸

Pd/PS ゐ፹ࡢྜᡂࢆ㐍ࡵ࡚࠾ࡾࠊゐ፹ᛶ⬟ࡢホ౯ࢆ⾜࠸ࠊࡉࡽ࡞ࡿᛶ⬟ྥୖ࡬ࡢ◊✲ࢆ㐍ࡵ࡚࠸ࡃணᐃ࡛ࡍࠋ ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ㓄఩Ꮚ༠ാⓗ⤖ྜษ᩿཯ᛂࡢ㛤Ⓨᡃࠎࡣ㸪ࡲࡎᐇ㦂ⓗ࡟ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ࢖ࣜࢪ࣒࢘㘒య࡜ࣄࢻࣟ࣎ࣛࣥ࡜ࡢ཯ᛂࢆヨࡳࡲࡋࡓ㸦ᅗ 3㸧ࠋᅗ࡟♧ࡍ㏻ࡾ㸪࢚ࢺ࢟ࢩ࢝ࣝ࣎ࢽࣝᇶ⨨᥮ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㓄఩Ꮚࢆᣢࡘ࢖ࣜࢪ࣒࢘ࣄࢻ
ࣜࢻ㘒య 1 ࡜ࣆࢼࢥ࣮ࣝ࣎ࣛࣥ(=HBpin)ࢆ཯ᛂࡉࡏࡓ࡜ࡇࢁ㸪ࣄࢻࣟ࢟ࢩࢩࢡࣟ࣌ࣥࢱࢪ࢚ࢽࣝ࣎ࣜࣝ
࢖ࣜࢪ࣒࢘㘒య 2 ࢆᚓࡿࡇ࡜࡟ᡂຌࡋࡲࡋࡓࠋࡇࡢ཯ᛂࡣ㸪H–࡜ B+࡬ศᴟࡋ࡚࠸ࡿ B–H ⤖ྜࢆ㓄఩Ꮚୖࡢ H+࡜㔠ᒓୖࡢ B–࡬ษ᩿ࡋࡓࡇ࡜㸪ࡍ࡞ࢃࡕ B–H ⤖ྜࡢᴟᛶ㌿᥮ࡀ㐍⾜ࡋࡓࡇ࡜ࢆ♧ࡋࡲࡍࠋᚓࡽࢀࡓᴟᛶ㌿᥮⏕ᡂ≀ 2 ࡀ࡝ࡢࡼ࠺࡟ࡋ࡚⏕ᡂࡋࡓࡢ࠿࡟㛵ࡍࡿ▱ぢࢆᚓࡿࡓࡵ࡟ DFT ィ⟬ࢆ฼⏝ࡋࡲࡋࡓࠋࡑࢀ࡟ࡼࡿ࡜㸪ࡲࡎ࢖ࣜࢪ࣒࢘୰ᚰ࡛ B–H ⤖ྜࡢ㓟໬ⓗ௜ຍࡀ㐍⾜ࡋ㸪ࡑࡢᚋࡶ࠺୍ศᏊࡢ
࢖ࣜࢪ࣒࢘㘒యୖࡢࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㓄఩Ꮚ࡟ࡼࡾ⬺ࣉࣟࢺࣥ໬ࡍࡿࡇ࡜࡛ 2 ࡀ⏕ࡌࡿࡇ࡜ࢆ᫂ࡽ

- 122 -

࠿࡟ࡋࡲࡋࡓࠋᅗ ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ࢖ࣜࢪ࣒࢘㘒య࡟ࡼࡿ %̽+ ⤖ྜࡢᴟᛶ㌿᥮཯ᛂ Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ྜ」ۻ‬㔠ᒓ㘒యࡢ≉ᛶ࡟❧⬮ࡋࡓゐ፹ⓗⅣ⣲㦵᱁ᵓ⠏཯ᛂࡢ㛤Ⓨ ᒾᓮ Ꮥ⣖ 㘒య໬Ꮫ఍➨ 70 ᅇウㄽ఍ ࢜ࣥࣛ࢖ࣥ 2020 ᖺ 9 ᭶ 28̽30 ᪥ Aw-02 (ཷ㈹ㅮ₇)‫ۻ‬Umpolung of B̽H Bonds by Metal̽Ligand Cooperation. ᮾ ᣅஓ࣭ᴋᮏ ࿘ᖹ࣭㔝ᓮ ிᏊ 㘒య໬Ꮫ఍➨ 70 ᅇウㄽ఍ ࢜ࣥࣛ࢖ࣥ 2020 ᖺ 9 ᭶ 28̽30 ᪥ 1C-07 (ཱྀ㢌)‫ۻ‬ᶵ⬟ᛶ᪂つȧඹᙺ⣔ศᏊࡢ๰ฟࢆᣦྥࡋࡓࣇࢵ⣲⣔ከ⨨᥮ⰾ㤶᪘ศᏊࡢྜᡂᡭἲࡢ㛤ᣅ ᒾᓮ Ꮥ⣖ ᚨᒣ⛉Ꮫᢏ⾡᣺⯆㈈ᅋ➨ 23 ᅇ◊✲ᡂᯝሗ࿌఍ ࢜ࣥࣛ࢖ࣥ 2020 ᖺ 11 ᭶ 26̽27 ᪥ (ཱྀ㢌)‫ࣝࢣࢵࢽۻ‬ゐ፹࡟ࡼࡿඹᙺࢪ࢚ࣥࡢከᡂศ㐃⤖཯ᛂ ᒾᓮ Ꮥ⣖ ௧࿴ 2 ᖺᗘ᭷ᶵྜᡂ໬Ꮫ༠఍ᮾᾏᨭ㒊⥲ྜ
ㅮ₇఍ ࢜ࣥࣛ࢖ࣥ 2020 ᖺ 12 ᭶ 3 ᪥ (౫㢗ㅮ₇)‫ۻ‬㑄⛣㔠ᒓ࢔ࢽ࢜ࣥ࡜඾ᆺ㔠ᒓ࢝ࢳ࢜ࣥࡀ࠾ࡾ࡞ࡍゐ፹స⏝−୙άᛶ⤖ྜࡢษ᩿ࢆక࠺Ⅳ⣲㦵᱁ᵓ⠏ᡭἲ−ᒾᓮ Ꮥ⣖ ୕஭໬Ꮫᰴᘧ఍♫⿇ࢣᾆࢭࣥࢱ࣮ ༓ⴥ 2020 ᖺ 12 ᭶ 8 ᪥ (౫㢗ㅮ₇)‫ۻ‬Metal-Ligand Cooperative Bond Cleavage/Formation and their Catalytic Applications with Cyclopentadienone Metal
Complexes. ᮾ ᣅஓ ➨ 11 ᅇ኱ὠ఍㆟ ⁠㈡ࣉࣜࣥࢫ࣍ࢸࣝ 2021 ᖺ 2 ᭶ 22̽23 ᪥ (ཱྀ㢌)‫ۻ‬Cleavage of C̽H Bonds by Cyclopentadienone Iridium Complex. ᮾ ᣅஓ࣭ᴋᮏ ࿘ᖹ࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍
➨ 101 ᫓Ꮨᖺ఍ ࢜ࣥࣛ࢖ࣥ 2021 ᖺ 3 ᭶ 19̽22 ᪥ A12-4am-08 (ཱྀ㢌)‫ۻ‬Synthesis and Structure of Hexaarylrhodate and -Iridate Complexes. ᘅᒸ భᏊ࣭ᒾ㷂 Ꮥ⣖࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍ ࢜ࣥࣛ࢖ࣥ 2021 ᖺ 3 ᭶ 19̽22 ᪥ A14-4pm-10 (ཱྀ㢌)‫ࣥ࢕ࣇࢫ࣍ۻ‬-࣍ࢫࣇ࢕ࢽࣥ-࣍ࢫࣇ࢕ࣥࣆࣥࢧ࣮࢖ࣜࢪ࣒࢘㘒యࡢྜᡂ࡜཯ᛂᛶ ṇ⏣ ᾈ୍ᮁ࣭ᴋᮏ ࿘ᖹ࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍ ࢜ࣥࣛ࢖ࣥ 2021 ᖺ 3 ᭶ 19̽22 ᪥ A14-4pm-11 (ཱྀ㢌)‫ۻ‬㟁Ꮚồᘬᇶ⨨᥮ࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥ㓄఩Ꮚࢆ᭷ࡍࡿࣟࢪ࣒࢘㘒యࡢྜᡂ࡜ࢽࢺࣜࣝ࡜ࡢ཯ᛂᛶ ᖹᑿ ᨻ⣖࣭ᴋᮏ ࿘ᖹ࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍ ࢜ࣥࣛ࢖ࣥ 2021 ᖺ 3 ᭶ 19̽22 ᪥ A12-3pm-03 (ཱྀ㢌)‫ۻ‬Heavy-Metal-Free Fischer−Tropsch Type Reaction. Shrinwantu Pal࣭Andreas Phanapoulos࣭ᕝୖ ㈗ྐ࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍ ࢜ࣥࣛ࢖ࣥ 2021 ᖺ 3 ᭶ 19–22 ᪥ A20-2am-03 (ཱྀ㢌)‫ࢆࣥ࢜ࢽ࢔ࣝࢳ࣓ࣝࣜ࣎ࢪۻ‬᭷ࡍࡿ PCP ࣆࣥࢧ࣮࢖ࣜࢪ࣒࢘㘒యࡢྜᡂ࡜཯ᛂᛶ ᓊ㔝 ┿㐨࣭㧗ᒸ ဏ㒔Ꮚ࣭ᴋᮏ ࿘ᖹ࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍ ࢜ࣥࣛ࢖ࣥ 2021 ᖺ 3 ᭶ 19̽22 ᪥ A12-3pm-09 (ཱྀ㢌)‫ۻ‬Synthesis and Properties of Spiro-double Sila[7]helicene: The LUMO Spiro-Conjugation. ᑎ⏣ ᮃ࣭᳜ᯇ ၨ㍜࣭ᵽཱྀ ுኴ࣭᫬୸ ♸㍤࣭బ⸨ 㝧௓࣭୰㔝 ᖾྖ࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍ ࢜ࣥࣛ࢖ࣥ 2021 ᖺ 3
᭶ 19̽22 ᪥ A17-1am-01 (ཱྀ㢌)‫ ۻ‬Analysis of Catalytic Performance by Machine Learning for Understanding of Ethylene/Methyl Acrylate
Copolymerization Catalyzed by Palladium/Phosphine̽Sulfonate Complexes. ⛅⏣ 㞙ᖹ࣭Jin-Yao Guo࣭Matthew- 123 -

Sigman࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍ ࢜ࣥࣛ࢖ࣥ 2021 ᖺ 3 ᭶ 19̽22 ᪥ A12-4am-07 (ཱྀ㢌) ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬+HDY\ 0HWDO)UHH )LVFKHU7URSVFK 7\SH 5HDFWLRQ 6HTXHQWLDO +RPRORJDWLRQ RI $ON\OERUDQH 8VLQJ D
&RPELQDWLRQRI&2DQG+\GULGHVDV0HWK\OHQH6RXUFH$3KDQRSRXORV63DO7.DZDNDPL.1R]DNL J.
Am. Chem. Soc.142±MDFVF.
‫ۻ‬6\QWKHVLVRIDQG6WUXFWXUDO,QVLJKWVLQWR&RQWDFW,RQ3DLUDQG6ROYHQW6HSDUDWHG,RQ3DLU'LSKHQ\OLULGDWH
&RPSOH[HV7,ZDVDNL7$NDLZD<+LURRND63DO.1R]DNL1.DPEHOrganometallics39±DFVRUJDQRPHWF
‫[(ۻ‬SHGLHQW 6\QWKHWLF ,GHQWLILFDWLRQ RI D 1RYHO 3VWHUHRJHQLF /LJDQG 0RWLI IRU WKH 3DOODGLXP&DWDO\]HG
3UHSDUDWLRQ RI ,VRWDFWLF 3RODU 3RO\SURS\OHQHV ) : 6HLGHO , 7RPL]DZD . 1R]DNLAngew. Chem. Int.
Ed.59±DQLH
‫ۻ‬8PSROXQJRI%±+%RQGVE\0HWDO±/LJDQG&RRSHUDWLRQZLWK&\FORSHQWDGLHQRQH,ULGLXP&RPSOH[HV7
+LJDVKL6.XVXPRWR.1R]DNLAngew. Chem. Int. Ed.60±DQLH
‫ۻ‬5HYHUVLEOH3W,,&+'HXWHUDWLRQZLWKRXW0HWKDQH/RVV0HWDO/LJDQG&RRSHUDWLRQYV/LJDQG$VVLVWHG
3W,,3URWRQDWLRQ63DO.1R]DNL$9HGHUQLNRY-/RYHChem. Sci.12±'6&+‫ۻ‬6\QWKHVLVDQG3URSHUWLHVRI6SLURGRXEOH6LOD>@KHOLFHQH7KH/8026SLURFRQMXJDWLRQ17HUDGD.
8HPDWVX5+LJXFKL<7RNLPDUX<6DWR.1DNDQR.1R]DNLChem. Eur. J.LQ
SUHVVFKHP
0HWDO6XSSRUW&RRSHUDWLRQLQ$O 32 6XSSRUWHG3W1DQRSDUWLFOHVIRUWKH6HOHFWLYH+\GURJHQRO\VLVRI
3KHQROVWR$UHQHV;-LQ57VXNLPXUD7$LKDUD+0LXUD76KLVKLGR.1R]DNLNat. Catal.4
±V[‫&ۻ‬RSRO\PHUL]DWLRQRI(WK\OHQHDQG0HWK\O$FU\ODWHE\3DOODGLXP&DWDO\VWV%HDULQJ,]42/LJDQG&RQWDLQLQJ
0HWKR[\HWK\O(WKHU0RLHW\DQG6DOW(IIHFWIRUWKH3RO\PHUL]DWLRQ6$NLWD.1R]DNLPolym. J.DFFHSWHG
0HWDO&RPSOH[HVIRU&DWDO\WLF3RO\PHUL]DWLRQV&:LOOLDPV.1R]DNLInorg. Chem.59±
&DWDO\WLF)XQFWLRQDOL]DWLRQRI%XWDGLHQHE\&DUERQ(OHFWURSKLOHV7,ZDVDNLJ. Jpn. Petrol. Inst.63
±2UJDQRFDWDO\VLV$3DUDGLJP6KLIWLQWKH6\QWKHVLVRI$OLSKDWLF3RO\HVWHUVDQG3RO\FDUERQDWHV.)XNXVKLPD.1R]DNLMacromolecules53±
7RZDUGVWKH&RSRO\PHUL]DWLRQRI3URS\OHQHZLWK3RODU&RPRQRPHUV6/XFNKDP.1R]DNLAcc. Chem.
Res.54± ࣉࣟࣆࣞࣥࡢ❧య≉␗ⓗ࢜ࣜࢦ࣐࣮໬࡟ࡼࡿࢹ࢜࢟ࢩࣉࣟࣆ࢜ࢼ࣮ࢺᵓ㐀ࡢ༢ẁ㝵ᵓ⠏ 70XUD\DPD.
1R]DNL ᭷ᶵྜᡂ໬Ꮫ༠఍ㄅ79±
1HZ3RO\PHUVPDGHIURP&DUERQ'LR[LGHDQG$ONHQHV.1R]DNLBull. Chem. Soc. Jpn.94
±

- 124 -

ⰾ㤶᪘⁐፹࿴ࢡࣛࢫࢱ࣮ࡢගㄏ㉳⁐፹෌㓄ྥࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࢃࡿ⁐፹࿴ᵓ㐀᥈⣴
'HWHUPLQDWLRQRIVROYDWLRQVWUXFWXUHVE\YLEUDWLRQDOVSHFWURVFRS\FRQFHUQLQJWRSKRWRLQGXFHGVROYDWLRQUHRUJDQL]DWLRQG\QDPLFVLQWKHJDVSKDVHVROYDWHG
FOXVWHUVżᐑ㷂 ඘ᙪࠊᯇ㔝 㔛᪩Ꮚ㸦࠾ⲔࡢỈዪᏊ኱Ꮫ㸧




◊✲┠ⓗ
ᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣࠊගບ㉳࡟క࠺⁐፹࿴ࡢ෌㓄ྥࢲ࢖ࢼ࣑ࢡࢫ࡟ࡘ࠸࡚ࠊẼ┦⁐፹࿴ࢡࣛࢫࢱ࣮࡟ᑐࡍࡿࣆࢥ⛊᫬㛫ศゎ㉥እศගࢆ⏝࠸࡚ᐇ᫬㛫ほࢆ⾜ࡗ࡚ࡁࡓࠋ≉࡟ࠊᇶ㉁㸦ⓎⰍᅋ㸧ࡢ཯ᛂ࡜୪⾜ࡋ࡚㐍⾜ࡍࡿ⁐፹ศᏊࡢ෌㓄ྥ㐠ື࡟ὀ┠ࡋ࡚࠸ࡿࠋࡇࢀࡲ࡛࡟ࠊ࠸ࡃࡘ࠿ࡢ⣔࡛Ẽ┦ࢡࣛࢫࢱ࣮࡟࠾࠸࡚ (6,&7཯ᛂࡀほࡉࢀࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࡀ >@ࠊẚ㍑ⓗ኱ࡁ࡞ศᏊ࡛࠶ࡿࡇ࡜

࠿ࡽࠊࡑࡢ⁐፹࿴ᵓ㐀ࡣ༑ศ࡟᫂ࡽ࠿࡟ࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊ⁐፹෌㓄ྥ㐠ືࡢᐇ᫬㛫ほ࡟ྥࡅ࡚ࠊƍELDQWKU\O 㸦%$㸧㸦)LJ㸧ࡢỈ࿴ᵓ㐀ࢆ᫂ࡽ࠿࡟

)LJ ƍࣅ࢔ࣥࢫࣜࣝ

ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ
%$± +2 Q ࢡࣛࢫࢱ࣮ࡣࠊʌʌ ≧ែ࡟ගບ㉳ࡍࡿ࡜࢔ࣥࢺࣛࢭࣥ⎔ࡢ㛫࡛ ,&7 ཯ᛂ࡜࢔ࣥࢺࣛࢭࣥ⎔ࡢ㛫ࡢ᤟ࡌࢀゅࡢኚ໬ࡀ⏕ࡌࡿ࡜ࡉࢀ࡚࠸ࡿ>@ࠋ୍᪉ࠊ➼౯࡞࢔ࣥࢺࣛࢭࣥ⎔ࡢ㛫࡛ࡣࠊᑐ⛠ᛶࡢせㄳ࠿ࡽ ,&7 ≧ែࢆᙧᡂࡍࡿࡇ࡜ࡣ࡛ࡁ࡞࠸ࠋᚑࡗ࡚ࠊ,&7 ≧ែࡢ⏕ᡂ࡟ࡣ⁐፹࿴࡟ࡼࡿ஧ࡘࡢ࢔ࣥࢺࣛࢭࣥ⎔ࡢ㠀ᑐ⛠໬ࡀ㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋᮏ◊✲࡛ࡣࠊࡇࢀࡽ %$ ⁐፹࿴ࢡࣛࢫࢱ࣮ࡢ㉥እࢫ࣌ࢡࢺࣝࢆ
ᐃࡋࠊ㔞Ꮚ໬Ꮫィ⟬࡜ࡢ⤖ᯝ࡜ẚ㍑ࡋ࡞ࡀࡽ⁐፹࿴ᵓ㐀ࡢỴᐃࢆ⾜ࡗࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ*DXVVLDQ㸦&$0%/<3* GS ZLWK*'%-㸧ࢆ⏝࠸࡚ %$±+2 ࢡࣛࢫࢱ࣮ࡢᵓ㐀᭱㐺໬ࠊ㉥እࢫ࣌ࢡࢺࣝࡢィ⟬ࢆ⾜ࡗࡓࠋ⤖ᯝࢆᐇ㦂㉥እࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡍࡿࡇ࡜࡛ࠊほࡉࢀࡓࢡࣛࢫࢱ࣮ࡢᵓ㐀ࢆỴ

ᐃࡋࡓࠋ



◊✲ᡂᯝ
)LJ $ ࡟ %$±+2 ࢡࣛࢫࢱ࣮ࡢ 6 ≧ែࡢ㉥እࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋFPí ࠾ࡼࡧ FPí ࡢ྾཰ࡣỈศᏊࡢ 2+ ఙ⦰᣺ື㸦Ȟ2+㸧ࠊ FPí ࡢࣂࣥࢻࡣ %$ ࡢ &+ ఙ⦰᣺ື㸦Ȟ&+㸧࡟ᖐᒓࡉࢀࡿࠋほࡉࢀࡓ Ȟ2+í᣺ືᩘࡣỈ༢㔞యࡢ Ȟ2+ ࡟ẚ࡭ FP ࡯࡝పἼᩘࢩࣇࢺࡋ࡚࠾ࡾࠊʌ Ỉ⣲⤖ྜࡢᏑᅾࡀண᝿ࡉࢀࡿࠋ
ᐦᗘỗ㛵ᩘィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊỈศᏊࡀ୍᪉ࡢ⎔࡜ࡔࡅ ʌ Ỉ⣲⤖ྜࡋࡶ࠺୍᪉ࡢ⎔ࡢ &+ ࡜ᙅࡃ┦஫స⏝ࡋ࡚࠸ࡿ ʌ&+ ᵓ㐀㸦)LJ  % 㸧࡜ࠊ୧⎔࡟ᶫ᥃ࡅࡋ࡚ ʌ Ỉ⣲⤖ྜࡋࡓ ʌEULGJH ᵓ㐀㸦)LJ  & 㸧ࡢ  ✀㢮ࡢᏳᐃᵓ㐀ࡀᚓࡽࢀࡓࠋ┦ᑐ࢚ࢿࣝࢠ࣮ࡣ ʌ&+ ᵓ㐀ࡀࢃࡎ࠿࡟ FP± ࡯࡝ప࠿ࡗࡓࠋ

- 125 -

ࡑࢀࡒࢀࡢ⌮ㄽ㉥እࢫ࣌ࢡࢺࣝࢆᐇ

ࡢࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡍࡿ࡜ࠊȞ2+ ࡢࢩࣇࢺ㔞ࠊȞ2+ ࡜ Ȟ&+ ࡜ࡢ┦ᑐᙉᗘ࡜ࡶ࡟ ʌ&+ ᵓ㐀㸦%㸧ࡀᐇࢆࡼࡃ෌⌧ࡋ࡚࠸ࡿࠋࡇࢀࡼࡾࠊ%$±+2 ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࡣࠊʌ&+ ᵓ㐀࡛࠶ࡿ࡜⤖ㄽࡋࡓࠋࡇࡢ ʌ&+ ᵓ㐀ࡣࠊ஧ࡘࡢ࢔ࣥࢺࣛࢭࣥ⎔ࡢᑐ⛠ᛶࡀỈ࿴࡟ࡼࡾᔂࢀ࡚࠸ࡿࡓࡵࠊࡇࡢࡲࡲ &7 ≧ែ࡟㑄⛣ྍ⬟࡛࠶ࡿࠋࡇࡢࡇ࡜ࡣࠊ%$±+2 ࢡࣛࢫࢱ࣮ࡢගບ㉳㟁Ⲵ⛣ືࡀaSV>@࡜ẚ㍑ⓗ㏿࠸ࡇ࡜࡜▩┪ࡋ࡞࠸ࠋ
୍᪉ࠊ㟁Ꮚບ㉳≧ែࡢ㉥እࢫ࣌ࢡࢺࣝࡣບ㉳≧ែ㛫ࡢ㑄⛣࡟ࡼࡿ࡜⪃࠼ࡽࢀࡿᙉ࠸྾཰ࡀ

ᐃ⠊ᅖ඲య࡟ࢃࡓࡗ࡚⌧ࢀࠊᵓ㐀᝟ሗࢆᚓࡿࡇ࡜ࡣ࡛
ࡁ࡞࠿ࡗࡓࠋບ㉳≧ែࡢ㟁Ꮚᵓ㐀ࢆ 7'')7 ィ⟬)LJ%$±+2 ࡢ 6 ≧ែ࡟࠾ࡅࡿ㉥እࢫ࣌ࢡࢺࣝí࡟ࡼࡾぢ✚ࡶࡗࡓ࡜ࡇࢁࠊFP ⛬ᗘࡢ㛫㝸࡛ບ㉳≧ែࡀ࠸ࡃࡘ࠿Ꮡᅾࡍࡿࡇ࡜ࡀணࡉࢀࡓࠋほࡉࢀࡓ㑄⛣ࡣࡇࢀࡽࡢ≧ែ㛫ࡢ㑄⛣࡟ࡼࡿ࡜⪃࠼ࡽࢀࡿࠋFPí 㡿ᇦࡢ ;+ ఙ⦰᣺ື࠿ࡽᵓ㐀᝟ሗࢆᚓࡿࡇ࡜ࡀᅔ㞴࡛࠶ࡿࡓࡵࠊaFPí 㡿ᇦࡢ㦵᱁᣺ື࡟ࡼࡿᵓ㐀ゎᯒࢆ⾜࠺ணᐃ࡛࠶ࡿࠋཧ⪃ᩥ⊩>@7,VKLGD<)XMLPXUD7)XMLZDUD2.DMLPRWR&KHP3K\V/HWW ±   [2] 0=DNKDURY2.UDXVV<1RVHQNR%%UXWVFK\DQG$'UHXZ, J. Am. Chem. Soc. 131(2), 461 (2009).

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
★ᯇ㔝 㔛᪩Ꮚࠊᐑ㷂 ඘ᙪࠊࠕ,5GLS ศගἲ࡟ࡼࡿ ࣓ࢳ࣒ࣝ࣍ࣝ࢔ࢽࣜࢻဨỈ  ࢡࣛࢫࢱ࣮࡟࠾ࡅࡿ࢖

࢜ࣥ໬ㄏ㉳ỈศᏊ࣐࢖ࢢ࣮ࣞࢩࣙࣥࡢほࠖࠊ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊ ᖺ  ᭶ࠊ໭ᾏ㐨኱Ꮫࠊ໭ᾏ㐨ࠊ

ᮐᖠᕷ



ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
★00L\D]DNL7.DPL\D0:RKOJHPXWK.&KDWWHUMHH50LWULü2'RSIHUDQG0)XMLL³5HDOWLPHREVHUYDWLRQRI SKRWRLRQL]DWLRQLQGXFHG ZDWHU PLJUDWLRQ G\QDPLFV LQ PHWK\OIRUPDQLOLGH±ZDWHU E\ SLFRVHFRQG WLPHUHVROYHGLQIUDUHGVSHFWURVFRS\DQGDELQLWLRPROHFXODUG\QDPLFVVLPXODWLRQV´LQSUHSDUDWLRQ- 126 -

➨୍ཎ⌮཯ᛂࢲ࢖ࢼ࣑ࢡࢫ࡜ඛ㐍ⓗ㟁Ꮚ≧ែ⌮ㄽࡢከゅⓗᒎ㛤'LYHUJHQWDSSOLFDWLRQVRIDELQLWLRUHDFWLRQG\QDPLFVDQG 
DGYDQFHGHOHFWURQLFVWUXFWXUHWKHRULHV‫ۑ‬Ṋḟ ᚭஓ㸪ᑠᯘ ṇே㸪/\DOLQ$QGUH\㸪ᒾబ ㇦㸪ᑠ㔝 ࡺࡾᏊ㸪ᩧ⏣ ㅬ୍㑻㸪ᖖ⏣ ㈗ኵ㸪㉥㛫 ▱Ꮚ㸪㏆⸨ ᭷㍜㸪.XPDU6RQX㸪➉୰ ᑗᩯ㸪ሐ ᣅᮁ㸪⸨᳃ ಇ࿴㸪⋤ ዑ㸪⧊⏣ ⪔ᖹ㸪ᾏ⪁⃝ ಟ୍㸪㧗ཎ 㔛ዉ㸪⏣௦ ၨ௓㸪ᐑ㉺ Ὧ஧㸪ẟ฼ ᗈ㔝㸪࿴⏣ ㄹ㸪ఀ⸨ ᑠኪᏊ㸪ᒾ⏣ ೺୍㑻㸪ᡞ⏣ ᩗ஧㑻㸪す⏣ ཿ೔㸪ᐑᮏ ┿ᕹ㸦໭ᾏ㐨኱Ꮫ㸧◊✲┠ⓗࠊෆᐜ
$E LQLWLR 㟁Ꮚ≧ែィ⟬࡛ᚓࡽࢀࡿ࣏ࢸࣥࢩࣕࣝ໙㓄࡟ᇶ࡙ࡃศᏊືຊᏛ㸦$,0'㸧ἲࡣࠊ࣏ࢸࣥࢩࣕࣝ㛵ᩘࢆ⏝࠸ࡿᚑ᮶ࡢศᏊືຊᏛィ⟬࡟ẚ࡭ࢥࢫࢺࡣ࠿࠿ࡿࡀ௵ពࡢ໬Ꮫ཯ᛂ࡟㐺⏝࡛ࡁࡿᙉࡳࢆᣢࡕࠊࡑࡢ㐺⏝ᑐ㇟ࡣࡲࡍࡲࡍᗈࡀࡗ࡚࠸ࡿࠋᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣࠊࣔࢹ࡛ࣝࡣ࡞ࡃᐇ㝿ࡢศᏊ⣔ࢆᑐ㇟࡜ࡋࡓ➨୍ཎ⌮཯ᛂࢲ࢖ࢼ࣑ࢡࢫࡢ㐺⏝⠊ᅖࢆᣑᙇࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚ࠊᛂ⏝ィ⟬ࡶ㐍ࡵ࡞ࡀࡽᐇ⏝ⓗ࡞ィ⟬ᡭἲࡢ㛤Ⓨࢆ⾜࠺ࡇ࡜࡟㔜Ⅼࢆ࠾ࡁࠊ◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋࡲࡓࠊඛ㐍ⓗ㟁Ꮚ≧ែ⌮ㄽ࡜ࡋ࡚ࠊ኱つᶍ⣔ࡢ㔞Ꮚ໬Ꮫィ⟬ࢆྍ⬟࡜ࡍࡿศ๭⤫἞㸦'&㸧ἲࡸࠊ཮ᴟᏊ㏆ఝࢆ㉸࠼ࡓගศᏊ┦஫స⏝ࡢィ⟬ἲ࡞࡝ࠊᵝࠎ࡞⌧㇟ࢆࢱ࣮ࢤࢵࢺ࡜ࡋࡓࢩ࣑࣮ࣗࣞࢩ࣭ࣙࣥࢶ࣮ࣝࢆ㛤Ⓨࡋ࡚࠸ࡿࠋᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊࡇࢀࡽࢆ⏝࠸࡚໬Ꮫ཯ᛂࡸ
ග໬Ꮫ㐣⛬ࡢཎ⌮࣭ࢲ࢖ࢼ࣑ࢡࢫࡢゎ᫂ࠊ≀ᛶࡢண ࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ◊✲ࢆᒎ㛤ࡋ࡚࠸ࡿࠋ௧࿴  ᖺᗘࡣ≉࡟ࠊ  ศ๭⤫἞ 03 ィ⟬࡟ᑐࡍࡿㄗᕪࡢ⮬ືไᚚᡭἲࡢ㛤Ⓨࠊ  ගච␿⒪ἲ⸆๣ ,5ࡢග໬Ꮫ཯ᛂ㐣⛬ࡢゎ᫂ࠊ  ྂ඾ⓗከḟඖᑻᗘᵓᡂἲ࡟ࡼࡿᅛ᭷཯ᛂ⤒㊰ࡢྍど໬࡜ 0' ࢺࣛࢪ࢙ࢡࢺࣜࡢ
࣐ࢵࣆࣥࢢ࡞࡝ࢆ⾜ࡗࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ ࡛ࡣ *$0(66 ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿศ๭⤫἞㸦'&㸧ἲࡢィ⟬ࣉࣟࢢ࣒ࣛࢆᣑᙇࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋỈ ศᏊࡢィ⟬ࡣࠊ* ᇶᗏ㛵ᩘ⣔ࢆ⏝࠸࡚ᐇ⾜ࡋࡓࠋ  ࡛ࡣࠊ*DXVVLDQ ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚㟁Ꮚ≧ែィ⟬ࢆ⾜ࡗࡓࠋィ⟬ᡭἲ࡟ࡣ 8/&%/<3 ࢆࠊᇶᗏ㛵ᩘ⣔ࡣ 1 ཬࡧ 2 ཎᏊ࡟ࡣ DXJFFS9'= ࢆࠊࡑࢀ௨እࡢཎᏊ
࡟ࡣ FFS9'= ࢆ⏝࠸ࡓࠋỈ⁐፹ࡢຠᯝࢆ ,()3&0 ἲ࡛ྲྀࡾ㎸ࡳࠊᇶᗏ≧ែ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝ
ࢠ࣮᭤⥺ࡸ࢚ࢿࣝࢠ࣮ࢲ࢖ࣖࢢ࣒ࣛࢆᵓ⠏ࡋࡓࠋ  ࡛ࡣࠊ*$0(66 ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ 03* ࡛ࣞ࣋ࣝ ,5& ィ⟬ࢆ⾜ࡗࡓࠋࡇࢀ࡟ἢࡗ࡚  ಶࡢཧ↷ᵓ㐀ࢆྲྀᚓࡋࠊ&0'6 ἲࢆ⏝࠸࡚཯ᛂ࡟㛵୚ࡍࡿ୺ᗙᶆࢆ
⋓ᚓࡋࡓࠋḟ࡟ࠊᙜ◊✲ᐊ࡛㛤Ⓨࡋ࡚࠸ࡿ 6335 ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ࠊ㑄⛣≧ែᵓ㐀㡿ᇦ࠿ࡽฟⓎࡍࡿ
RQWKHIO\ ศᏊືຊᏛィ⟬ࢆᐇ⾜ࡋࠊRXWRIVDPSOH ࡟ᣑᙇࡉࢀࡓ &0'6 ࢆ⏝࠸࡚ࡇࢀࡽࡢࢺࣛࢪ࢙ࢡࢺࣜࢆ୺
ᗙᶆ✵㛫࡟ᑕᙳࡋࡓࠋ




◊✲ᡂᯝ

 ศ๭⤫἞ 03 ィ⟬࡟ᑐࡍࡿㄗᕪࡢ⮬ືไᚚᡭἲࡢ㛤Ⓨ⏕యศᏊࢆྵࡴ኱つᶍ⣔ࡢ㟁Ꮚ≧ែ࡛ࡣࠊศᩓຊࢆࡣࡌࡵ࡜ࡍࡿᙅ࠸┦஫స⏝ࡀᮏ㉁ⓗ࡟㔜せ࡜࡞ࡿࢣ࣮

- 127 -

ࢫࡀከࡃぢཷࡅࡽࢀࡿࠋࡑࡢࡓࡵࠊ኱つᶍ⣔ࡢ཯ᛂゎᯒ࡟ࡣࠊ㟁Ꮚ┦㛵ࢆ⪃៖ࡋࡓ㧗⢭ᗘ㟁Ꮚ≧ែィ⟬ᡭἲࡀᚲせ࡜࡞ࡿࠋ኱つᶍィ⟬ࢆྍ⬟࡟ࡍࡿᡭἲ࡜ࡋ࡚ࠊࣇࣛࢢ࣓ࣥࢺศ๭ᆺ㟁Ꮚ≧ែィ⟬ἲࡀᩘከࡃ㛤Ⓨࡉࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊࡇࢀࡽࡢィ⟬ᡭἲ࡛ࡣ㟁Ꮚ≧ែィ⟬ࡢ┦㛵ࣞ࣋ࣝ࡟ᛂࡌࡓㄗᕪ࡟ຍ࠼࡚ࠊࣇࣛࢢ࣓ࣥࢺศ
๭࡟క࠺࢚ࢿࣝࢠ࣮ㄗᕪࡀ᪂ࡓ࡟⏕ࡌࡿࠋᡃࠎࡣศ๭⤫἞㸦'&㸧6&) ィ⟬࡟࠾࠸࡚ࠊ࢚ࢿࣝࢠ࣮ㄗᕪ࡟ᇶ࡙
࠸࡚ࣇࣛࢢ࣓ࣥࢺศ๭ࢆ⮬ືⓗ࡟Ỵᐃࡍࡿᡭἲࢆࡍ࡛࡟
ᥦ᱌ࡋࡓࠋᮏ◊✲࡛ࡣࠊཎᏊ㌶㐨㸦$2㸧࡟ᇶ࡙ࡃ /DSODFH

⾲  Ỉ  ศᏊࡢィ⟬࡟࠾ࡅࡿ '&03 ┦㛵࢚ࢿࣝࢠ࣮㸦 (FRUU㸧࡜㒊ศ⣔ࡢᖹᆒ୺㍈༙ᚄኚ᥮ 03 ἲࢆཧ⪃࡟ࠊ㟁Ꮚ┦㛵ࢆྵࡴ '&03 ィ⟬࡟

FRUU
FRUU
㸧ࡢ࢚ࢿࣝࢠ࣮ㄗᕪチᐜ㜈್㸦 HWKUHVK㸧㸦 OORFDO

ᑐࡋ࡚࢚ࢿࣝࢠ࣮ㄗᕪ࡟ᇶ࡙࠸࡚⮬ືⓗ࡟ࣇࣛࢢ࣓ࣥࢺ

࡟ᑐࡍࡿ౫Ꮡᛶ

ศ๭ࢆ⾜࠺ᡭἲࢆ㛤ⓎࡋࡓࠋFRUU
HWKUHVK P (K


(FRUU
(K

FRUU
OORFDOcỈศᏊ  ಶࡢ⟽ᆺࣔࢹࣝ⣔࡟ᑐࡋ࡚ᮏᡭἲࢆ㐺⏝

±

ࡋࠊ㟁Ꮚ┦㛵࢚ࢿࣝࢠ࣮ㄗᕪ࡟ᑐࡍࡿ㜈್౫Ꮡᛶࢆㄪ࡭

±



FRUU
ࡓ㸦⾲ 㸧
ࠋ㜈್ HWKUHVKࢆཝࡋࡃࡍࡿࡇ࡜࡛ࠊ࢚ࢿࣝࢠ࣮ㄗ

±

ᕪࡣ⣔⤫ⓗ࡟ῶᑡࡋ࡚࠸ࡿࠋࡲࡓࠊ㜈್ࡀᑠࡉࡃ࡞ࡿ࡟

±





±



FRUU
ࡘࢀ࡚ࠊྛ㒊ศ⣔࡟࠾ࡅࡿ㛗㍈༙ᚄࡢᖹᆒ್ OORFDOࡶቑຍࡋ࡚࠸ࡿࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊྛ㒊ศ⣔ࡀ࢚ࢿࣝࢠ࣮࡟ᑐࡋ࡚㐺ษ࡞ࣂࢵࣇ࢓㡿ᇦࢆ㑅ᢥࡋ࡚࠸ࡿࡇ࡜ࡀ
☜ㄆ࡛ࡁࡓࠋࡲࡓࠊィ⟬᫬㛫࡟ࡘ࠸࡚ࡶᚑ᮶ࡢ '& ἲ࡜ྠᵝ࡟⥺ᙧࢫࢣ࣮ࣜࣥࢢࢆ㐩ᡂࡋࡓࠋගච␿⒪ἲ⸆๣ ,5 ࡢග໬Ꮫ཯ᛂ㐣⛬ࡢゎ᫂⡿ᅜᅜ❧ࡀࢇ◊✲ᡤࡢᑠᯘஂ㝯୺௵◊✲ဨࡽ࡟ࡼࡾぢฟࡉࢀࡓ᪂ࡋ࠸ࡀࢇ἞⒪ἲ࡛࠶ࡿගච␿⒪ἲࡣࠊࡀࢇ⣽⬊௨እ࡟ᑐࡋ࡚࡯࡜ࢇ࡝ẘᛶࢆ♧ࡉ࡞࠸ࡓࡵࠊ๪స⏝ࡢᴟࡵ࡚ᑠࡉ࠸἞⒪ἲ࡛࠶ࡿࠋࡉࡽ࡟ࠊࡀࢇච␿
ࢆྜ⌮ⓗ࡟άᛶ໬ࡉࡏࡿຠᯝࡀ࠶ࡿࡇ࡜ࡶⓎぢࡉࢀ࡚࠾ࡾࠊ㌿⛣ࡋࡓࡀࢇ࡬ࡶ᭷ຠ࡛࠶ࡿ࡞࡝ࠊ௒ᚋࡢࡀࢇ
἞⒪ࢆ኱ࡁࡃኚ࠼ࡿྍ⬟ᛶࡀ࠶ࡿ἞⒪ἲ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋගච␿⒪ἲ࡛ࡣࠊ,5 ࡜࠸࠺Ỉ⁐ᛶࡢࢣ࢖⣲ࣇࢱࣟࢩ࢔ࢽࣥ໬ྜ≀ࢆ⤖ྜࡉࡏࡓᢠయ㸦ᢠయ,5 」ྜయ㸧ࢆࡀࢇ⣽⬊࡟⤖ྜࡉࡏࡿࠋᢠయ,5 」
ྜయࢆᢞ୚ࡋࡓᚋࠊ㏆㉥እගࢆ↷ᑕࡍࡿ࡜ࠊ,5 ࡢỈ⁐ᛶࡢ㍈㓄఩Ꮚࡀษ᩿ࡉࢀ࡚⸆๣ࡀจ㞟ࡍࡿࡇ࡜࡛ࠊ
⸆๣ࡀ⤖ྜࡋࡓࡀࢇ⣽⬊ࡢࡳࢆẅࡍࡇ࡜ࡀ࡛ࡁࡿࠋ
ࡋ࠿ࡋࠊ㏆㉥እ⥺ࡀ࡝ࡢࡼ࠺࡟⸆๣࡟స⏝ࡋ࡚Ỉ⁐ᛶ㍈㓄఩Ꮚࡢษ᩿ࡀ㉳ࡇࡿࡢ࠿ࠊࡲࡓࠊࡇࡢ཯
ᛂࡢࢫ࢖ࢵࢳࡣ㏆㉥እ⥺࡛࡞ࡃ࡚ࡣ࠸ࡅ࡞࠸ࡢ࠿
ࡣᮍゎ࡛᫂࠶ࡗࡓࠋ
ᮏ◊✲࡛ࡣࠊ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸࡚ ,5 ࣔࢹ࡛ࣝࡑࡢග໬Ꮫ཯ᛂ㐣⛬ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡎࠊ
,5 ࡢỈ⁐ᛶ㍈㓄఩Ꮚࡀษ᩿ࡉࢀࡿ཯ᛂࡣ㸪໬Ꮫⓗ࡟ࡣ ,5 ࡢ࿘㎶࡟࠶ࡿỈศᏊ࡜ࡢຍỈศゎ࡟ࡼࡾ㉳ࡇࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢ஦ᐇࡣࠊ2 Ỉࢆ⏝࠸ࡓᐇ㦂ࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊᐇ㦂ⓗ࡟ࡶド᫂ࡉࢀࡓࠋࡲࡓࠊ,5 ࡟㏆㉥እ⥺ࡀ↷ᑕࡉࢀ࡚⏕ࡌࡓᅗ ㏆㉥እ⥺㸦1,5㸧↷ᑕࡣ,5ࡢỈ⁐ᛶ㍈㓄఩Ꮚບ㉳≧ែ࠿ࡽ┤᥋Ỉ⁐ᛶ㍈㓄఩Ꮚࡢษ᩿ࡀ㉳ࡇࡿษ᩿ࢆ┤᥋ᘬࡁ㉳ࡇࡍࡶࡢ࡛ࡣ࡞ࡃࠊ,5ࣛࢪ࢝ࣝ

ࡢ࡛ࡣ࡞ࡃࠊ㑏ඖ๣࡟ࡼࡿࣛࢪ࢝ࣝ࢔ࢽ࢜ࣥ⏕ᡂ࢔ࢽ࢜ࣥࡢ⏕ᡂ࡟ࡢࡳ౑ࢃࢀࡿࠋ

- 128 -

ࢆ⤒࡚ỈศᏊ࡜཯ᛂࡋࠊ㍈㓄఩Ꮚࡀษ᩿ࡉࢀࡿࡇ࡜ࡀィ⟬໬Ꮫⓗ࡟♧၀ࡉࢀࡓ㸦ᅗ 㸧ࠋࡇࡢࡇ࡜࠿ࡽࠊS+
࡟ࡼࡾ㍈㓄఩Ꮚษ᩿཯ᛂࡢ㏿ᗘࡀኚ໬ࡍࡿࡇ࡜ࢆணぢࡋࠊᐇ㝿࡟ᐇ㦂ࢆ⾜ࡗ࡚ࡇࢀࢆド᫂ࡋࡓࠋ௨ୖࡢ⤖ᯝ࠿ࡽࠊ,5 ࡢࣛࢪ࢝ࣝ࢔ࢽ࢜ࣥ≧ែࢆసࡾฟࡍࡇ࡜ࡀ࡛ࡁࢀࡤࠊ㏆㉥እ⥺ࢆ⏝࠸࡞ࡃ࡚ࡶᢠయ,5 」ྜయࢆ⏝࠸ࡓࡀࢇ἞⒪ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
 ྂ඾ⓗከḟඖᑻᗘᵓᡂἲ࡟ࡼࡿᅛ᭷཯ᛂ⤒㊰ࡢྍど໬࡜ 0' ࢺࣛࢪ࢙ࢡࢺࣜࡢ࣐ࢵࣆࣥࢢ ᅛ᭷཯ᛂᗙᶆ㸦,5&㸧ࡣ⣲཯ᛂ㐣⛬ࢆ⾲ࡍ㟼ⓗ཯ᛂ⤒㊰࡛࠶
ࡾࠊ,5& ࡟ἢࡗࡓ࢚ࢿࣝࢠ࣮ኚ໬ࡸᵓ㐀ኚ໬࠿ࡽ໬Ꮫ཯ᛂᶵᵓ
࡟ᑐࡍࡿ┤ឤⓗᥥീࡀᚓࡽࢀࡿࠋ,5& ࢆᵓᡂࡍࡿศᏊᵓ㐀⩌ࡣ
1± ḟඖࡢከḟඖࢹ࣮ࢱ࡛࠶ࡿࡓࡵࠊ㐺ษ࡞పḟඖ✵㛫࡬ࡢྍど໬ࡣᅔ㞴࡛࠶ࡗࡓࠋᡃࠎࡣࡇࢀࡲ࡛࡟ࠊከḟඖࢹ࣮ࢱ㛫ࡢ㊥㞳㛵ಀࢆ࡛ࡁࡿࡔࡅಖࡘࡼ࠺࡞ḟඖ⦰⣙ἲ࡛࠶ࡿྂ඾ⓗከḟඖᑻᗘᵓᡂ㸦&0'6㸧ἲࢆ ,5& ࡟ἢࡗࡓศᏊᵓ㐀⩌࡟㐺⏝ࡍࡿࡇ࡜࡛ࠊ཯ᛂᶵᵓ࡟㛵ࡍࡿ஦๓▱㆑࡞ࡋ࡟཯ᛂࢆグ㏙ࡍࡿ୺ᗙᶆࢆᚓࡿࡇ࡜࡟ᡂຌࡋ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊRXWRIVDPSOH ࡟ᣑᙇࡉࢀࡓ &0'6 ἲࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊ,5& ࢿࢵࢺ࣮࣡ࢡ
࡟ࡼࡗ࡚ᐃ⩏ࡉࢀࡓ୺ᗙᶆ✵㛫ୖ࡟ RQWKHIO\ ศᏊືຊᏛ
㸦0'㸧ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡿࢺࣛࢪ࢙ࢡࢺࣜࢆᑕᙳࡍࡿ᪉ἲ
ࢆᥦ᱌ࡋࠊືⓗ཯ᛂ⤒㊰ࡢྍど໬ࢆ⾜ࡗࡓࠋ 61 ཯ᛂ㸦2+í&+) Ѝ >&+2+͐)@í㸧ࢆゎᯒᑐ㇟࡜ࡋ࡚
㑅ࢇࡔࠋࡇࡢ⣔ࡣ 76 ࠿ࡽ㉮ࡽࡏࡓྂ඾㌶㐨ࡢ⣙  ๭ࡀ ,5& ࠿ࡽ㐓⬺ࡍࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋᅗ  ࡟ࠊ௦⾲ⓗ࡞ྂ඾㌶㐨
ࢆ ,5& ࡢ୺ᗙᶆ✵㛫ୖ࡟ᑕᙳࡋࡓ⤖ᯝࢆ♧ࡍࠋィ⟬ࡋࡓ  ᮏ
ࡢྂ඾㌶㐨ࡢ࠺ࡕ  ᮏࡣ ,5& ࡟ἢࡗ࡚⏕ᡂ≀㡿ᇦ࡟฿㐩ࡋࠊ ᮏࡣ ,5& ࠿ࡽ㐓⬺ࡋࡓࠋ⏕ᡂ≀㡿ᇦ࡟฿㐩ࡍࡿྂ඾㌶㐨ࡣ
,5& ࡀ኱ࡁࡃ᭤ࡀࡿ㡿ᇦࡢᡭ๓࡛ ,5& ࠿ࡽ㞳ࢀࡿࡀࠊ෌ࡧ ,5&࡟㏆࡙ࡁࠊ⏕ᡂ≀㡿ᇦ࡟฿㐩ࡍࡿ㸦ᅗ  D 㸧
ࠋ୍᪉ࠊ&) ゎ㞳⤒㊰࡟㐍ࡴྂ඾㌶㐨ࡣࠊྠࡌ㡿ᇦ࡛኱ࡁ࡞㐲ᚰຊࢆឤࡌࠊ,5& ࠿ࡽ㐓⬺ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ㸦ᅗ  E 㸧ࠋࡉࡽ࡟ࠊᅗ  F࡟♧ࡋࡓྂ඾㌶㐨࡛ࡣࠊ୍ᗘྠࡌ㡿ᇦ࡛ ,5& ࠿ࡽ㐓⬺ࡋ࡚ )í
ࡀゎ㞳ࡋጞࡵࡿࡀࠊ㟼㟁ᘬຊ࡟ᘬࡁᐤࡏࡽࢀ࡚ ,5& ࠿ࡽ᏶඲࡟
㐓⬺ࡍࡿࡇ࡜ࡀ࡛ࡁࡎ࡟᣺ືࡍࡿᵝᏊࡀ☜ㄆࡉࢀࡓࠋᮏᡭἲ࡟
ࡼࡾࠊ,5& ࡟ࡼࡗ୍࡚ព࡟ᐃ⩏ࡉࢀࡿ୺ᗙᶆ✵㛫࡟ྂ඾㌶㐨ࢆᑕᙳࡍࡿࡇ࡜ࡀྍ⬟࡟࡞ࡾࠊ,5& ࡢ᭤⋡࡟ࡼࡿ㐲ᚰຊຠᯝ࡜࠸
ࡗࡓືⓗ཯ᛂ㐣⛬ࡢ┤ឤⓗᥥീࢆᚓࡿࡇ࡜࡟ᡂຌࡋࡓࠋ


- 129 -ᅗ ,5& ࡟ࡼࡗ࡚ᐃ⩏ࡉࢀࡓ୺ᗙᶆ
✵㛫࡟ᑕᙳࡉࢀࡓྂ඾㌶㐨ࠋ D  ,5&࡟ἢࡗ࡚⏕ᡂ≀㡿ᇦ࡟฿㐩ࠊ E ,5&ࡀ኱ࡁࡃ࣮࢝ࣈࡍࡿ㡿ᇦ࡛ ,5& ࠿ࡽ㐓⬺ࠊ F  &+2+ ࡟ᘬࡁᐤࡏࡽࢀ࡚
,5& ࠿ࡽ㐓⬺࡛ࡁࡎࠋⰍࡣ࣏ࢸࣥࢩ
࢚ࣕࣝࢿࣝࢠ࣮ࢆ⾲ࡍࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ  Ṋḟᚭஓࠕ཯ᛂ⤒㊰࡟ᇶ࡙ࡃືຊᏛຠᯝࡢ⪃ᐹ㸸᭤⋡࣭ศᒱ࣭㑄⛣ࠖࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ ࠖ ࢜ࣥࣛ࢖ࣥ  77DNHWVXJX³2QWKHIO\PROHFXODUG\QDPLFVDSSURDFKWRH[FLWHGVWDWHEUDQFKLQJUHDFWLRQ´7KHWK4XDQWXP6FLHQFH 46 V\PSRVLXP7KH0DLQ6\PSRVLXPRI,&&06(&RPSXWDWLRQDO &KHPLVWU\ DQG &RPSXWDWLRQDO 3K\VLFV ,&1$$0  9LGHR &RQIHUHQFH   5KRGHV
6KHUDWRQ*5((&( RQOLQH    ᒾబ㇦ࠕ཯ᛂ⤒㊰⮬ື᥈⣴ἲࢆ⏝࠸ࡓࢡࣛࢫࢱ࣮ゐ፹ࡢ⌮ㄽ◊✲ࠖ,4&( 㔞Ꮚ໬Ꮫ᥈⣴ㅮ₇఍ ࠕ㔞Ꮚ໬Ꮫ࡛᥈ࡿ໬Ꮫࡢ᭱ඛ➃ࠖ  ࢜ࣥࣛ࢖ࣥ   ㉥㛫▱Ꮚࠕ₇⟬Ꮚኚ᥮࡟ᇶ࡙ࡃຠ⋡ⓗ࡛ỗ⏝ⓗ࡞᫬㛫Ⓨᒎἲࡢ㛤Ⓨ㸸 㡯㛫₞໬ᘧἲࠖ➨  ᅇ㟁Ꮚ≧ែ⌮ㄽࢩ࣏ࣥࢪ࣒࢘ ࢜ࣥࣛ࢖ࣥ  77DNHWVXJX77VXWVXPLDQG<2QR³9LVXDOL]DWLRQRIUHDFWLRQSDWKJOREDOUHDFWLRQURXWHPDSDQG
RQWKHIO\ WUDMHFWRULHV´ 1HZ +RUL]RQV LQ 6FLHQWLILF 6RIWZDUH IURP /HJDF\ &RGHV WR 0RGXODU (QYLURQPHQWV 1+,66 -HMX,VODQG.RUHD RQOLQH    ᒾబ㇦ࠕ཮ᴟᏊ㏆ఝࢆ㉸࠼ࡓ㏆᥋ሙග࡜ศᏊࡢከ㔜ᴟ┦஫స⏝࡜ບ㉳≧ែไᚚ࡟ྥࡅ࡚ࠖศᏊ◊◊✲఍ࠕࢼࣀ✵㛫࡛ගࡀ⧊ࡾ࡞ࡍศᏊ᧯స࣭໬Ꮫ཯ᛂไᚚࡢ᪂ᒎ㛤ࠖ ࢜ࣥࣛ࢖ࣥ   ᑠᯘṇேࠕ㔞Ꮚ໬Ꮫィ⟬࡜ࢹ࣮ࢱ⛉Ꮫࡢే⏝࡟ࡼࡿゐ፹࣭⾲㠃྾╔⣔ࡢゎᯒ࡜ணࠖィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࣭ࢼࣀࢸࢡࣀࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗྜྠ࣮࣡ࢡࢩࣙࢵࣉ ࢜ࣥࣛ࢖ࣥ   ᑠᯘṇேࠕ㔞Ꮚ໬Ꮫィ⟬î࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿゐ፹࣭⾲㠃྾╔⣔ࡢゎᯒࠖᒱ㜧኱Ꮫேᕤ▱⬟ࢭࣥࢱ࣮ㅮ₇఍ ࢜ࣥࣛ࢖ࣥ  $/\DOLQDQG77DNHWVXJX³7KHRUHWLFDO0RGHOOLQJRID6LQJOH3KDVH
%RURSKHQH/D\HURQ0HWDO6XSSRUW´3&R06 ࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍
  RQOLQH   7 7DNHWVXJX ³9LVXDOL]DWLRQ RI UHDFWLRQ SDWK DQG G\QDPLFDO WUDMHFWRU\ LQ UHGXFHGGLPHQVLRQ´UG,&5H'',QWHUQDWLRQDO6\PSRVLXPRQOLQH   ᒾబ㇦ࠕ➨୍ཎ⌮ィ⟬࡟ࡼࡿ㏆᥋ሙ᣺ືศගࠖ᪥ᮏ≀⌮Ꮫ఍➨  ᅇᖺḟ኱఍  ᖺ   ࢜ࣥࣛ࢖ࣥ   ሐᣅᮁ㸪ᑠ㔝ࡺࡾᏊ㸪Ⲩ
஭㎿㸪Ṋḟᚭஓࠕḟඖ⦰⣙཯ᛂ✵㛫࡟࠾ࡅࡿ RQWKHIO\ ྂ඾㌶㐨ゎᯒࠖจ⦰⣔ࡢ⌮ㄽ໬Ꮫ  ࢜ࣥࣛ࢖ࣥ 㸦௨ୖᣍᚅㅮ₇ࡢ୍㒊ࠊ௚ከᩘ㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ  ‫ۻ‬70DFKLGD7,ZDVD77DNHWVXJX.6DGDDQG..RNDGR&KHP(XU-26     ‫ۻ‬-/L
0*DR67RQJ&/XR+=KX77DNHWVXJX.8RVDNLDQG0:X(OHFWURFKLP$FWD340     ‫ۻ‬<2RWDQL$6DWRK<+DUDEXFKLDQG77DNHWVXJX-&RPSXW&KHP41     ‫ۻ‬07DNHQDND7
7DNHWVXJXDQG7,ZDVD-&KHP3K\V152     ‫ۻ‬%:DQJ0*DR.8RVDNLDQG77DNHWVXJX
3K\V&KHP&KHP3K\V22     ‫ۻ‬0.RED\DVKL0+DUDGD+7DNDNXUD.$QGR<*RWR
77VXQHGD02JDZDDQG77DNHWVXJX&KHP3OXV&KHP85     ‫ۻ‬+1DEDWD07DNDJL.6DLWD
DQG 6 0DHGD 56& $GY 10      ‫ۻ‬7 7VXWVXPL < 2QR = $UDL DQG 7 7DNHWVXJX - &KHP
7KHRU\&RPSXW16     ‫<ۻ‬.RQGR<*RWR0.RED\DVKL7$NDPD71RURDQG77DNHWVXJX
3K\V &KHP&KHP 3K\V22     ‫ۻ‬ᑠᯘṇே ࣐ࢸࣜ࢔ࣝࢫࢸ࣮ࢪ 20    ‫ۻ‬6(ELVDZD77VXWVXPLDQG77DNHWVXJX-&RPSXW&KHP42     ‫ۻ‬07DNHQDND77DNHWVXJXDQG7,ZDVD-&KHP3K\V 154     ‫<ۻ‬1LWWD26FKDON+,JDUDVKL6:DGD77VXWVXPL.
6DLWD77DNHWVXJXDQG76HNLNDZD-3K\V&KHP/HWW12     ‫ۻ‬7)XMLPRUL0.RED\DVKLDQG
77DNHWVXJX-&RPSXW&KHP 40±     ‫ۻ‬ᑠᯘṇே㸪⸨᳃ಇ࿴㸪Ṋḟᚭஓ-&RPSXW&KHP-DS
LQSUHVV- 130 -

㉸⌫㠃᥈⣴ἲࢆ⏝࠸ࡓศᏊᵓ㐀ࠊ⤖ᬗᵓ㐀ࡢ᥈⣴
Exploration of molecular structure and crystal structure using the SHS
method‫ۑ‬ᒣ㛛 ⱥ㞝ࠊྥ஭ ᚨ㸦࿴ḷᒣ኱Ꮫ㸧1◊✲┠ⓗ➹⪅ࡽࡣࠊ2004 ᖺ࡟኱㔝࣭๓⏣࡟ࡼࡾ㛤Ⓨࡉࢀࡓ㉸⌫㠃᥈⣴ἲࡸࠊ2010 ᖺ࡟኱㔝࣭㛗⏣࣭๓⏣࡟ࡼࡾⓎ⾲ࡉࢀࡓ୍⯡໬㉸⌫㠃᥈⣴ἲࢆ⏝࠸࡚ࠊศᏊࡢ┦ᑐ㓄⨨ࡸ⤖ᬗᵓ㐀ࢆ᥈⣴ࡍࡿ◊✲ࢆࡇࢀࡲ࡛⾜ࡗ࡚ࡁ࡚࠸ࡿࠋ
௒ᖺᗘࡣࠊ㉸⌫㠃᥈⣴ἲࡢ౑⏝᫬࡟ࠊⓏࡾ᥈⣴ཎᏊࢆ㣕ࡧ㣕ࡧ࡟ᣦᐃࡍࡿ᪉ἲ(㞳ᩓཎᏊᣦᐃἲ/PDrCA(Picking
up Discrete reaction Atoms)ἲ)ࡀ࠺ࡲࡃ㉮ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࢢࣜࢩ࡛ࣥࡢሙྜࢆᣑᙇࡋࠊࡼࡾ኱ࡁ࠸ศᏊ
(࢔ࣛࢽࣥ࠿ࡽ࡞ࡿ࣌ࣉࢳࢻࡸࢭࣜࣥࠊࢩࢽࣙࣜࣥ➼)࡟㐺⏝ࡋࠊⓏࡾ᥈⣴ཎᏊࡢ㑅ࡧ᪉࡜ࠊEQ Ⅼࡢぢࡘ࠿ࡾ᪉ࡢ㛵ಀ࣭ഴྥࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ❧య㓄ᗙ␗ᛶయ(ࢥࣥࣇ࢛࣐࣮)ࡢ᥈⣴ᑐ㇟ศᏊ࡜ࡋ࡚࢔ࣛࢽࣥศᏊࠊ࢔ࣛࢽࣥࢪ࣌ࣉࢳࢻࠊࢭࣜࣥࠊཬࡧࢩ

ࢽࣙࣜࣥࢆ㑅ࡧࠊࡲࡓィ⟬࡟ࡣ GRRM14 ࣉࣟࢢ࣒ࣛ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿȣ-ADDF ἲࠊཬࡧ࢚ࢿࣝࢠ࣮ィ⟬࡟ࡣ Gaussian09 ࢆ౑⏝ࡋࡓࠋ(ࢩࢽࣙࣜࣥ௨እࡣ B3LYP/6-31G ࢆࠊࢩࢽࣙࣜࣥ࡟ࡘ࠸࡚ࡣ AM3 ࢆ౑⏝ࡋࡓ)

3◊✲ᡂᯝ௒ᖺᗘࡣࠊᙜ◊✲ࢢ࣮ࣝࣉࡢ஦᝟࡟ࡼࡾࠊィ⟬⤖ᯝ࡜ࡋ࡚ࡣࠊPDrCA ἲ࡜ẚ㍑ᑐ㇟࡜ࡍࡿࡓࡵࡢ GRRM ࡛ࡢ඲㠃᥈⣴⤖ᯝࡸࠊPDrCA ἲ୍࡛㒊ࡢ᥈⣴⤖ᯝࢆᚓࡿ࡟␃ࡲࡗࡓࠋᚓࡽࢀࡓ EQ ᵓ㐀ࡢ୍㒊ࢆᅗ 1㹼ᅗ 3 ࡟
♧ࡍࠋ

  
  
ᅗ 1. ࢔ࣛࢽࣥ    ᅗ 2. ࢔ࣛࢽࣥࢪ࣌ࣉࢳࢻ    ᅗ 3. ࢩࢽࣙࣜࣥ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࣭㉸⌫㠃᥈⣴ἲࢆ⏝࠸ࡓ㞳ᩓཎᏊᣦᐃἲ࡟ࡼࡿ࢔ࣛࢽࣥ࡜ࡑࡢ஧㔞యࡢ❧య㓄ᗙ᥈⣴ྥ஭ ᚨ, ᒣ㛛 ⱥ㞝཯ᛂ⤒㊰᥈⣴ࢩ࣏ࣥࢪ࣒࢘ 6536 3 ᖺ  ᭶.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࣭&RQIRUPDWLRQ 6HDUFK RI *O\FLQH E\ $SSO\LQJ WKH 6FDOHG +\SHUVSKHUH 6HDUFK 0HWKRG WR 'LVFUHWH $WRPV LQ WKH0ROHFXOH <XXNL 0LGRUR <RVKLWRPR .RGD\D 7DNXWR 2NL $NLUD 0XNDL +LGHR <DPDNDGR .RLFKL 2KQR &KHPLVWU\/HWWHUV9RO1R  - 131 -

ศᏊືຊᏛཬࡧ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓࢭ࣮ࣝࣟࢫ㛵㐃ศᏊ࠾ࡼࡧ㧗ศᏊࡢᵓ㐀࡜ᶵ⬟ࡢ◊✲ ̺ ࣌ࣉࢳࢻ㸰㔞యࡢ⮬ᕫ㞟ྜయᙧᡂ
Study of the structure and functions of cellulose and its related molecules and macromolecules
using molecular dynamics and quantum chemical calculations: The formation of self-assembled structure of dipeptides.
‫⩏୍ ⏣ୖۑ‬㸦ᶓ὾ᅜ❧኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲㝔㸧

1◊✲┠ⓗࠊෆᐜ
⮬ᕫ㞟ྜయࢆᙧᡂࡍࡿࣂ࢖࣐࢜ࢸࣜ࢔ࣝࡢࢹࢨ࢖ࣥ࡜ࢥࣥࢺ࣮ࣟࣝࡣࡑࡢᛂ⏝ࡢほⅬ࠿ࡽࡶ㏆ᖺὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋᶓ὾ᅜ❧኱ᏛᕤᏛ◊✲㝔ᕝᮧฟ◊✲ᐊ࡛ࡣࠊࣆࣞࣥࡢ⤖ྜࡋࡓ /࢔ࣛࢽࣥ࡜ /ࣇ࢙ࢽࣝ࢔ࣛࢽࣥࡢࢪ࣌ࣉࢳࢻ L-Py-L-Phe ࡢᙧᡂࡍࡿࣇ࢓࢖ࣂ࣮ᵓ㐀ࡸ / యࢆ ' య࡟ኚ᭦ࡋࡓ D-Py-L-Phe ࢪ࣌ࣉࢳࢻ࡟ࡘ࠸࡚ࠊᵓ㐀␗ᛶయࡀ⮬ᕫ㞟ྜయࡢᵓ㐀ᙧᡂ࡟ཬࡰࡍᙳ㡪➼ࢆ 105 ἲࢆ୺࡞ᡭẁ࡜ࡋ࡚◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋᡃࠎࡣࠊᵓ㐀ᙧᡂࡀศᏊ࡛ࣞ࣋ࣝ࡝ࡢࡼ࠺࡟㐍ࢇ࡛࠸ࡿࡢ࠿ࢆ᳨ウࡍࡿࡓࡵࠊศᏊືຊᏛ
ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓඹྠ◊✲ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲ࣭ィ⟬᪉ἲࢪ࣌ࣉࢳࢻ L-Py-L-Phe ࡜ D-Py-L-Phe ࡢᵓ㐀ࢆᅗ㸯࡟♧ࡍࠋࡇࢀࡽࢪ࣌ࣉࢳࢻࡢ⁐ᾮ୰࡟࠾ࡅࡿᵓ㐀ᙧᡂ㐣⛬ࢆほᐹࡍࡿࡓࡵ࡟ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋᐇ㦂ࡢ⁐ᾮ⤌ᡂ᮲௳࡟ᚑ࠸ỈศᏊ  ಶ࡜ +),3 ⁐፹ศᏊ  ಶ࠿ࡽ࡞ࡿΰྜ⁐ᾮ୰࡟ྛࠎ㸰㸲ಶࡢࢪ࣌ࣉࢳࢻࢆࣛࣥࢲ
࣒࡟ศᩓࡋࡓ⣔ࢆึᮇᵓ㐀࡜ࡋࡓࠋᅽຊ 1 bar, ᐊ࡛ࡢNPT ࢔ࣥࢧࣥࣈ࣭ࣝ࿘ᮇቃ⏺᮲௳ୗ࡛ࠊྛ⣔ࡑࢀࡒࢀ 1500

Fig. 1 Structures of dipeptides

ns ⛬ᗘࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥィ⟬ࢆ⾜ࡗࡓࠋィ⟬ࢯࣇࢺ࡟ࡣ MD ィ⟬࡟ GROMACS-5.1.4 ࢆࠊຊሙࣃ࣓ࣛ
࣮ࢱ࣮࡟ࡣ charmm36 ຊሙࢆ⏝࠸ࡓࠋᵓ㐀ࡢྍど໬࡟ࡣ VMD ࢆ⏝࠸ࡓࠋ3◊✲ᡂᯝ㸰✀㢮ࡢࢪ࣌ࣉࢳࢻ⁐ᾮ࡟ࡘ࠸࡚ศᏊືຊᏛ
ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ㞟ྜయࡢᵓ㐀ᙧᡂ࡟ࡘ࠸᳨࡚ウࡋࡓࠋᅗ㸰ཬࡧᅗ㸱࡟ࠊࢪ࣌ࣉࢳࢻ L-Py-L-Phe ࡜
D-Py-L-Phe࡟ࡘ࠸࡚ほࡉࢀࡓ≉ᚩⓗ࡞ࣇ࢓࢖ࣂ࣮

ᵓ㐀ࢆ♧ࡍࠋࡇࢀࡽࡣࡽࡏࢇᙧࡢࢼࣀࢳ࣮ࣗࣈᵓ㐀ᙧ

Fig. 2. Snapshot of the Structures of
L-Py-L-Phe extracted during the simulationᡂࡢึᮇẁ㝵ࢆ♧ࡋ࡚࠸ࡿ࡜ᛮࢃࢀࡿࠋᮏሗ࿌᭩࡛ࡣ
ゎᯒࡢ⤖ᯝࡢ⤂௓࡟࡜࡝ࡵヲ⣽ࡣ㏙࡭࡞࠸ࡀࠊࡑࢀࡽ࡟ࡘ࠸࡚ࡣཧ⪃ᩥ⊩  ࢆཧ↷㡬ࡁࡓ࠸ࠋ㞟ྜయࢆ- 132 -

ᙧᡂࡍࡿ┦஫స⏝࡟ࡘ࠸࡚ゎᯒࡋࡓ⤖ᯝࠊ࣌ࣉࢳ ࢻ 㙐 㒊 ศ ࡢ ᵓ 㐀 ᙧ ᡂ ࡛ ࡣ 1+͐&22 ࡜1+͐&22Ỉ⣲⤖ྜࡀࠊL-Py-L-Phe ࢪ࣌ࣉࢳࢻ
ࡢሙྜࡀ D-Py-L-Phe ࡟ẚ࡭ከࡃᙧᡂࡉࢀ࡚࠸ࡿ
ࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓࠊ1+͐&2 Ỉ⣲⤖ྜ࡟ࡘ࠸࡚ࡣ D-Py-L-Phe ࡢ࡯࠺ࡀࢃࡎ࠿࡟ከ࠸ࡀࠊ
඲య࡜ࡋ࡚ࡣ L-Py-L-Phe ࡀ D-Py-L-Phe ࡟ẚ࡭ࢪ࣌ࣉࢳࢻศᏊ㛫࡛ࡢỈ⣲⤖ྜࢆከࡃᙧᡂࡋ࡚
࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ㏫࡟ࠊD-Py-L-Phe ࡛ࡣ࣌ࣉࢳ
ࢻ㙐ࡢ1+ࠊ&22ࠊ1+ ࡀ࿘ࡾࡢỈ࡜ࡼࡾከࡃ┦஫

Fig. 3. Snapshot of the Structures of
D-Py-L-Phe extracted during the simulationస⏝ࡋ࡚࠸ࡿᵝᏊࡀศ࠿ࡗࡓࠋ
ḟ࡟ࠊഃ㙐࡟ࡘ࠸࡚ほᐹࡍࡿ࡜ࠊL-Py-L-Phe ࡜ D-Py-L-Phe ࡛ࡣഃ㙐ࡢ㓄ྥࡀ␗࡞ࡗ࡚࠸ࡿࠋL-Py-L-Phe࡛ࡣࣆࣞࣥ࡜ࣇ࢙ࢽࣝᇶࡀᆶ┤᪉ྥ࡟㓄ྥࡋ࡚࠸ࡿࡢ࡟ᑐࡋ D-Py-L-Phe ࡛ࡣᖹ⾜࡟㓄⨨ࡋ࡚࠸ࡿᵝᏊ
ࡀぢࡽࢀࡿࠋゎᯒࡢ⤖ᯝࠊD-Py-L-Phe ࡟࠾࠸࡚ࡣ⎔ྠኈࡢȧȧࢫࢱࢵ࢟ࣥࢢ࡟ࡼࡾഃ㙐ྠኈࡢ⮬ᕫ㞟ྜࡀ L-Py-L-Phe ࡟ẚ࡭ࡼࡾከࡃᙧᡂࡉࢀ࡚࠸ࡿᵝᏊࡀぢࡽࢀࡓࠋD-Py-L-Phe ࡟࠾ࡅࡿ⎔ྠኈࡢ㔜࡞ࡾࡣഃ㙐ࡢ㐠ືࢆᢚไࡋ⮬ᕫ㞟ྜయࡢᙧᡂ࡟ᐤ୚ࡋ࡚࠸ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋ⮬ᕫ㞟ྜయࡢᙧᡂࡣᮍ
ࡔึᮇ㐣⛬࡛࠶ࡾࠊ௒ᚋࡉࡽ࡟࣌ࣉࢳࢻࡢᩘࢆቑࡸࡋࡓ⣔࡛ࡉࡽ࡟㛗᫬㛫ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ௒ᚋࡉ
ࡽ࡟⾜ࡗ࡚࠸ࡃணᐃ࡛࠶ࡿࠋ

ཧ⪃ᩥ⊩
[1]

Batsaikhan Mijiddorj, et. al., BCSJ, 93, 969-977 (2020).Ⓨ⾲ࠊฟ∧ᐇ⦼ࡲࡓࡣணᐃ
(1) ‫"ۻ‬Structural characterization of cellulose nanofibers isolated from spent coffee grounds and theircomposite films with poly (vinyl alcohol) : A new non-wood source ”, Noriko Kanai, Takumi Honda,
Naoki Yoshihara, Toshiyuki Oyama, Akira Naito, Kazuyoshi Ueda, Izuru Kawamura, Cellulose, 27,
5017-5028 (2020). https://doi.org/10.1007/s10570-020-03113-w(2) "Effect of insertion of bathocuproine buffer layer at grating-structured cathode–organic-layerinterface in bulk-heterojunction solar cells ”, Masaru Sakomura, Yuya Yokokura, Yusuke Takagi andKazuyoshi Ueda, AIP Advances, 10, 015144 (2020). https://doi.org/10.1063/1.5129351(3) ‫“ۻ‬Separation of of D-amino acid-containing peptide phenylseptin using 3,3’- pheny- 1,1’binaphthyl-18-crown-6-ether columns”, Izuru Kawamura, Batsaikhan Mijiddorj, Yohei Kayano, Yuta
Matsuo, Yumi Ozawa, Kazuyoshi Ueda, and Hisako Sato, BBA-Proteins and Proteomics, 1868, 140429,(2020). https://doi.org/10.1016/j.bbapap.2020.140429(4) “Aggregability of β(1→4)-linked glucosaminoglucan originating from a sulfur-oxidizing bacterium
Thiothrix nivea”, Minoru Takeda, Keiko Kondo, Ryo Tominaga, Honomi Mori, Mana Kato, Ryoji Usami,
Tomoi Murakami, Kazuyoshi Ueda, Ichiro Suzuki, Masato Katahira, Bioscience, Biotechnology, andBiochemistry, 84, 2085-2095 (2020). https://doi.org/10.1080/09168451.2020.1785838(5) ‫"ۻ‬Stereochemical effects on the self-assembly of pyrenylalanine-phenylalanine dipeptide”
Batsaikhan Mijiddorj, Hiroki Shirakata, Tetsuya Nakagawa, Kazuyoshi Ueda,Yasushi Yokoyama, Izuru
Kawamura BCSJ, 93, 969-977 (2020) . doi:10.1246/bcsj.20190376- 133 -











Theoretical studies on complex chemical system based on quantum
chemistry and statistical mechanics
8µQtÖW0ÆLNm.Î zx©Ýwg0Ã:´Ý>
4}ÅW¹²ÛozÑ?z}IÝ<¢Ç}¯7QjÞ3ÏWZßaC=XW R{ÛYÞWZß

1

¡§
5HZ^Ä¸ØH(d(­Ì¥ÒYFZrÐ)(l®¿FZ¾)(iº (hHZÄ*DY£Z¨V"ÒYHZ %®¿FZ

iÙ(h~n*Ô-Ü;(hE&2¼G

DY×S&ÀÈ()&*¶Mu&|¡§ÁÚHZÄ.³½«*p |cf1¡§C\*6/¢1.1 UHZÌ¥^(vÂÔ_ÒYHZ(®¿FZUu»nÔ*·#)&*Ü;¿ª*ÉBTyHZJk$Í¤Ó`@­*O!¸M¬9ÕËDY°(HZ±P (be¬*^Ä[Ä¾*"(*¡§*·%'A9(+)KB¬]fÕsÂUu9ÂÔ(,) ¦Êq±$DYnÁ %)&Ò
YHZ¿ª*³ M vÔ( ) Ú´ÝØY%,)5{Â$ DFT *9«Dv¥oÂ³ MÔ %)*£CHZÌ¥ k£() 1½l×MÌ¥*^Ä-:v¥o$wDv¥oUDY×SlÇ*ÀÈ(nÔ*·

1.2 CDYGlÕ(Â¡§\V+6$G+6GlesÛ*W

T°elÆ(|ÁÚ

X(



#ceDYl*º|( Óº7,7,8,8-Tetracyanoquinodimethane (TCNQ)\V+6eDfl*¾0 TCNQ W\VÔel Ý()ÔÔ(F[

( +"56e0W\VÔ)%'l A8809e0%'#¨ÔE'¤%D DYSFZ(MD).37:49 QM/MM *£ TCNQ Q
É#6:eDfl¾*· &5+88(

6 a (BChl a)QÉ{ÊÝÎ·^Ì¥¾#·BChl a GM}×GÌ¥#6:25+ÓºtP*¾­
(¬2QÉ{( Qx{ &¬.QÉ {( Qª¥fÊÝÎ( §&)(y{ ·^+9e0 100 (/¤37:49*£ÊÝÎ·^Ì¥*¾

- 134 -

'Ú MD .

1.3 G×+9! (QÉ#6:¤SDYÂ¾
GM}¬

%Jk0x(N*G×+9!])(9'Ç%(G#6:\V?Ï(G×+9!CÑO)(¾­QÉ#6:W*ÐMOv(ÝR¢#6:¤S*Ï}(Å²%D&Íc~¡½Ý­fÂ¾n*£G×+9!QÉ#6:¤S,!.¾
*· |cf¯¾²ÀG×+9! LH2 C¾­QÉ#6:¾*·

1.4 GM}Jk0x (NØ¿DÖÌ¥DYÂ¾
GM}Jk0xG×+9!%'?Ï)G#6:*£NØ¿DÖ

É (Íc¡§%'Ò­ÚT(¯¾²ÀJk0xÌ¶¾Jk0xNØ¿DÖÌ¥*JkÔdVÎf<v*%'ÐH(º9'Çw²Ê$&%(#º&)(NØ¿DÖÐH&)(

A9I&

~NØ¿DÖÌ¥DYÂ¾*p¶¾Jk0xO )( 6 
88(
Õs

6¾­ØY {¾*·iº(

(#&)¡§h~%'#Ý­f,926

,926ÕsU(ÒYHZ¿ª#&yW'

iº|cf)& 2 _Ú¾"ÒYHZ¿ªnÂ,926ÕsÝ­fH*·¯¾²ÀJk0xO)(¾­QÉ#6:#¾


1.5 9'Ç-UÇÕ¦=B£S+6¦Õ¾
¼9'ÇUÇ$,9¦=B£*¾(;IJiÈbDGÚmqFn(S+6aHDYÂÉ*¾([Ý¡§`×'DY.

37:49%(¾iº)() ~JY¡§»KÃ©ÃK(ZkW)6:*h)¼9'ÇS+6¾*·|cfcfpµ +$

9 A X\9C+$9S+6¾*·2A2¡§v¡§}

2.1 UHZÌ¥^(vÂÔ_rÄÁÚÕË4cfu&)}.ÑÉ'º®)(Þ+ßKB¬]fÕs³ 0cUYDY9*(Â*g}RISM *O!cDYl9®¿FZÂ¦=B£Þ,ßÕËÖÕs³DYÕ¦=B£*Á(CDYÒ­%­*,2DYÕ¦=B£)&Þ¦ÜßÕsÞÉm

ÙØ¦=B£¨ËÖ¦=B£ßÁ)()½ºvDYSFZ.37:49L¸¬*c16 £)(.vjH¥z'KB]fÕsÂ0@¹>i#¾ ~£16*¬.U¨V
hoH(}$P &Y16ecÓI;'

> ]fÍU½¤#6:Õs^(d7v¥ojÞ,ß.³HZJk¸s­JkÌ¥

T°9*^Ä¿ª}$O )(YeJkBTC'Ì¥µÉ(º &)( c~#6:Cgq±*ÒYHZ¿ª³- 135 -

&

Ë

M (

9:TÐ@Y*y( Ru a9%(D¾Jk*^Ä#6:9  :*º4Í¤Ó`a9*}(Ð@YÑD*]ÌF\½¤f*O!
"Ü#6:Ê*?Nl9 csf-()&Nl9SÌAf1R)'#6:.:Â:':, 9])(Ê*.vJk|Ç*aHÝf1*Ê

(Ï})N(:':,9ÕÍ¤X ( '¬I9d7Ê*y(*[Jk¬*^ÄA9¢Þ ß.³ÒYHZ¿ªu&)DYØY {Ú¥9[_¬2ÒYHKªYU¾(n*Ô)%'DY[_¿ªPUYPM(JhÊH½ &¾( &T(hEÜN'.³ÒYHZ¿ªu&)(]f·!Þ ( P ·!Ó'«D·!«ß &\A¿ª&T(^Ä(ØYs>9\A( #&)(BT9-:¬()9$

96/+.  #ÐMP*


(



2.2 CDYGlÕ(Â¡§
TCNQ QÉ#6:eDfl¾DËµ916%D(D "MD .37:49 QM/MM *£PG[ÝP*hÒ(}$
(,eDY*ÒYHZW'Óº(

&

[ÝP6N("¿ªEÂ*O"Å²¾*pµ.Ñe·h(Surface hopping *£BChl a 02@¹(-# /PM(Ð@YO BChl a  Qx (sÛ

{ &·^Ì¥*¾Ð@Y (VM·^BÕ WbJ6[ÝPV.U*¢·^BÕJ6Ð@YDY[_ ¾­ HOMO−1 [_q¦=B£
HOMO−1& LUMO

3

1 Q

x

{#6: / 'Q

x

{ Q

y

{#6:8 5("D 

2.3 G×+9! (QÉ#6:¤SDYÂ¾
LH2  B850  B800 ])(GZlN( 2 M

¾­×M9*?R¢#6:¤ÔÒYHZ¿ª MD .37:49*R¢³

S*Ï}(~M ( &T MMSIC *£B850  B800 ¾­Ý­f,926ÕsB}}$&)QÉ#6:[ÝP &)(#WN"Ø¿¤S

&4<#p µ ¾(h(2.4 GM}Jk0x (NØ¿DÖÌ¥DYÂ¾)¾¶¾Jk0xO )(88(=/*U MMSIC %',926Õs*B}
W

Df(

­

"]fÕsO¾²ÀJk0xOµÒYHZ¿ª*·)#[Ý&)()('0:sÛ*Â& ''0:*Z(@)hÒ.UX&)"p{sÛ*º|6¾­Eb"6U)fM

QÉ#6:W sÛ ( """6U*H['¾­QÉ#6:uX&)

I¾¾*^"(h(YH¯)(¾­QÉ#6:¾*·+26++])(2Ò96b

 4 ¾­QÉ#6:[ÝP%.U+26++2Ò9 QM/MM- 136 -

¿ªP*º|(V.U X&) %M0#QÉ#6:&`X&)-\V+6¾On

'4<#p µ¾*·h(2.5 9'Ç-UÇÕ¦=B£S+6¦Õ¾
[Ý¡§+$9 A X\9C0S+6+"9ÑD

)
a

2A

&^5:ÑDN( D

( ) ~¡§+$9+"9ÑDS+6[ÝPV.U*¢#5:ÑDSs¨
9ÐnWDf("yW'iº(

D ÒYHZ¿ªPÌ &ÐMDYFV*£ MD .37:499*59QM/MM S+6*¿ªP[ÝP%.UP
9Ðn

N(

u&)X\90+$9¨S+6`1º+(& pµÅ²¾

*^"(

3

Á[Q

h

Masahiro Higashi, “Toward a Molecular Understanding of Photosynthetic Proteins,” The International Chemical
Congress of Pacific Basin Societies 2021, Honolulu, Hawaii, USA, December 2021, Áh.
Masahiro Higashi, “Toward a Molecular Understanding of Photoinduced Charge Separation Process in Organic Solar
Cells with Computational Approaches,” 239th ECS meeting, Digital Meeting, June 2021, Áh.
 ÖWiL¸¬

(GJk,!.Â¾
i¬ 24 *G£ZWn¡§i9,9Ôi2020 c 11 D.

4

L[Q

h

Kaho Nakatani, Masahiro Higashi, Ryoichi Fukuda, Hirofumi Sato, “An analysis of valence electronic structure froma viewpoint of resonance theory: tautomerization of formamide and diazadiboretidine,” J. Comput. Chem. in press.
Masahiro Higashi, Naoto Shibata, Suguru Takeno, Tetsuya Satoh, Masahiro Miura, and Hirofumi Sato, “A theoretical
study of product selectivity in rhodium-catalyzed oxidative coupling reaction caused by the solvation effect,”
Heterocycles in press.
Tomoaki Yagi and Hirofumi Sato, “Self-consistent construction of bridge functional based on the weighted density
approximation,” J. Chem. Phys. 2020, 154, 124113 (8 pages).
Yuichiro Yoshida, Satoru Iuchi, and Hirofumi Sato, “A quantum chemical model for a series of self-assembled
nanocages: the origin of stability behind the coordination-driven formation of transition metal complexes up to[M L ] ,” Phys. Chem. Chem. Phys. 2021, 23, 866-877.
12

24

24+

Tomoaki Yagi and Hirofumi Sato, “Density functional theory for molecular liquids based on interaction site modeland self-consistent integral equations for site–site pair correlation functions,” J. Chem. Phys. 2020, 153, 164102 (9pages).
Yuichiro Yoshida, Hayato Yokoi, and Hirofumi Sato, “Energy landscape study of water splitting and H evolution at a2

ruthenium(II) pincer complex,” J. Comput. Chem. 2020, 41, 2240-2250.

- 137 -

❧య㑅ᢥⓗ཯ᛂ࡟࠾ࡅࡿ⁐፹ຠᯝ࡜཯ᛂᶵᵓ࡟㛵ࡍࡿ⌮ㄽ◊✲
Theoretical studies of solvent effect and mechanism on stereoselective
reaction‫ۑ‬㔠㔝 ኱ຓࠊబࠎᮌ ⩏❶ࠊྜྷỌ ᭷భࠊ▼ᘓ ⯙⨾㸦㧗▱኱㝔⥲ྜ㸧1◊✲┠ⓗĮ ఩࡟⨨᥮ᇶࢆ᭷ࡍࡿࣉࣟࣆ࢜ࣇ࢙ࣀࣥ 1 ࡢࣄࢻࣜࢻ㑏ඖ࡟ࡼࡗ࡚⏕ᡂࡍࡿ࢔ࣝࢥ࣮ࣝ 2 ࠾ࡼࡧ 3 ࡢࢪ࢔ࢫࢸࣞ࢜㑅ᢥᛶ࡟ࡘ࠸࡚ᡃࠎࡣࡇࢀࡲ࡛࡟㸪Į ఩࡟ᵝࠎ࡞࣊ࢸࣟ⨨᥮ᇶ㸦 X = OMe, OPh, SMe, SPh, SeMe,
SePh㸧ࢆ᭷ࡍࡿࣉࣟࣆ࢜ࣇ࢙ࣀࣥࢆྜᡂࡋ㸪ࡇࢀࡽࢆ⏝࠸࡚ᵝࠎ࡞⁐፹୰࡛ࣄࢻࣜࢻ㑏ඖࢆ⾜࠺ࡇ࡜࡛㸪Į఩ࡢ⨨᥮ᇶ࠾ࡼࡧ⁐፹✀ࡢ㐪࠸࡟ࡼࡗ࡚㑅ᢥᛶࡀ኱ࡁࡃኚ໬ࡍࡿࡇ࡜ࡸ㸪㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿࢩ࣑࣮ࣗࣞࢩ
ࣙࣥ࡞࡝࡟ࡼࡾ㸪཯ᛂ⁐ᾮ୰࡛ࡣᖖ࡟」ᩘࡢ⁐፹ศᏊࡀࣄࢻࣜࢻヨ⸆࡟㓄఩ࡋ࡚࠾ࡾ㸪ࣄࢻࣜࢻヨ⸆࡜ᇶ㉁ࡀ཯ᛂࡍࡿ㝿࡟ࡣ㸪ࣄࢻࣜࢻヨ⸆࡟㓄఩ࡋࡓ⁐፹ࡢ❧యຠᯝࡀ཯ᛂ㏿ᗘࡸ㑅ᢥᛶ࡟኱ࡁࡃᙳ㡪ࡋ࡚࠸ࡿྍ⬟ᛶ࡞࡝ࢆぢฟࡋ࡚࠸ࡿ㸦Scheme 1㸧ࠋScheme 1.+\GULGHUHDFWLRQRIĮVXEVWLWXWHGSURSLRSKHQRQHᮏ◊✲࡛ࡣࡇࡢ཯ᛂ࡟ࡘ࠸࡚ࡇࢀࡲ࡛࡟ᚓࡽࢀࡓ▱ぢ࡟ᇶ࡙ࡁ㸪ศᏊࢧ࢖ࢬࡢ␗࡞ࡿ࢚࣮ࢸࣝ⁐፹୰࡛ࡑࢀࡒࢀࣄࢻࣜࢻ㑏ඖࢆ⾜࠺ࡇ࡜࡛㸪⁐፹ࡢ❧యຠᯝࡀ㑅ᢥᛶ࡟ཬࡰࡍᙳ㡪ࢆᐇ㦂ⓗ࡟᳨ドࡍࡿ࡜࡜ࡶ࡟㸪ศᏊ㌶㐨ィ⟬࡟ࡼࡗ࡚ࡇࡢ཯ᛂ࡟࠾ࡅࡿ㑄⛣≧ែᵓ㐀ࢆゎᯒࡍࡿࡇ࡜࡛㸪⁐፹ศᏊࡢ❧యຠᯝࡀ㑄⛣≧ែࡢᵓ㐀࠾ࡼࡧᏳᐃᛶ࡟࡝ࡢࡼ࠺࡞ኚ໬ࢆ୚࠼ࡿ࠿࡟ࡘ࠸࡚ࡶ᳨ドࡍࡿࡇ࡜࡛㸪⁐፹ຠᯝࡀࢪ࢔ࢫࢸࣞ࢜㑅ᢥᛶ࡟ཬࡰࡍᙳ㡪ࡢ㉳※ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲĮ ఩࡟ᵝࠎ࡞࣊ࢸࣟ⨨᥮ᇶࢆ᭷ࡍࡿࣉࣟࣆ࢜ࣇ࢙ࣀࣥ 1a-1f ࡢ LiAlH4 㑏ඖࢆ㸪ᮏ཯ᛂ୍࡛⯡ⓗ࡟⏝࠸ࡽࢀࡿ⁐፹࡛࠶ࡿ THF㸪Et2O ࡢ௚㸪❧యⓗ࡟࠿ࡉ㧗࠸࢚࣮ࢸ࡛ࣝ࠶ࡿ methyl tert-butyl ether (MTBE)ࡸ cyclopentyl
methyl ether (CPME)⁐፹୰࡛⾜࠺ࡇ࡜࡛㸪⁐፹ࡢ❧యຠᯝࡀ㑅ᢥᛶ࡟ཬࡰࡍᙳ㡪ࢆᐇ㦂ⓗ࡟᳨ドࡋࡓࠋ୍᪉
࡛㸪ศᏊ㌶㐨ィ⟬㸦Gaussian16 ࣉࣟࢢ࣒ࣛ㸧ࢆ⏝࠸࡚㸪ᮏ཯ᛂ࡟࠾ࡅࡿᇶᗏ≧ែࡸ㑄⛣≧ែࡢᵓ㐀᭱㐺໬࠾ࡼࡧ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜ࡗࡓࠋ࠸ࡎࢀࡢᑐ㇟໬ྜ≀࡟࠾࠸࡚ࡶከᩘࡢ㓄ᗙ␗ᛶయࡀᏑᅾࡍࡿࡓࡵ㸪- 138 -

M06/6-31+G(d,p)ࣞ࣋ࣝࡢィ⟬࡟࠾࠸࡚ࡍ࡭࡚ࡢ㓄ᗙ␗ᛶయ࡟ࡘ࠸࡚⥙⨶ⓗ࡟ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓᵓ㐀࡟ࡘ࠸࡚㸪 CPCM ἲ࡟ࡼࡿ⁐፹ຠᯝィ⟬ࢆ⾜࠺ࡇ࡜࡛ྛᵓ㐀␗ᛶయࡢᏑᅾẚࢆ᳨ウࡋ཯ᛂᶵᵓ
ゎᯒ࡟⏝࠸ࡓࠋ

3◊✲ᡂᯝ
MTBE ࡲࡓࡣ CPME ࢆ⁐፹࡜ࡋ࡚⏝࠸ࡓሙྜࡢᐇ㦂⤖ᯝࡣ㸪Et2O ⁐፹୰࡛ࡢ㑅ᢥᛶ࡜኱ࡁࡃኚ໬ࡣࡏࡎ㸪⁐፹ศᏊࡢࢧ࢖ࢬ࡟ࡼࡿኚ໬ࡣほࡉࢀ࡞࠿ࡗࡓࠋࡲࡓࡇࢀࡲ࡛ࡢ◊✲⤖ᯝ࡟ࡼࡾ㸪ࡇࡢ⣔࡛ࡣࣄࢻࣜࢻヨ⸆⏤᮶ࡢ㔠ᒓ࡟⁐፹ศᏊࡀ 2 ศᏊ㓄఩ࡋࡓ≧ែ࡛཯ᛂࡀ㐍⾜ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡓࡓࡵ㸪௒ᅇࡢィ⟬࡟࠾࠸
࡚ࡶྠᵝ࡟㸪⁐፹ศᏊࢆ 2 ศᏊ㓄఩ࡉࡏࡓ≧ែ࡛ྛ཯ᛂࡢ㑄⛣≧ែࢆồࡵࡓࠋࡑࡢ⤖ᯝ㸪⁐፹ศᏊࡀ࣮࢟ࣞ
ࢺᙧᡂࢆ㜼ᐖࡋࡓᵓ㐀ࡀ᭱ࡶᏳᐃ࡞㓄ᗙ࡛࠶ࡗࡓ୍᪉࡛㸪⁐፹✀ࢆࢪ࣓ࢳ࢚࣮ࣝࢸࣝ㸦THF ࡢࣔࢹࣝศᏊ࡜
ࡋ࡚௦⏝㸧࠿ࡽ MTBE ࡸ CPME ࡟⨨ࡁ᥮࠼࡚ࡶ㸪t-butyl ᇶࡸ cyclopentyl ᇶ࡞࡝ࡢ኱ࡁ࡞⨨᥮ᇶࢆ࠺ࡲࡃ㓄⨨ࡍࡿࡇ࡜࡛㸪㑄⛣≧ែᵓ㐀࡟ࡣ኱ࡁ࡞ኚ໬ࡀ㉳ࡇࡽ࡞࠸ࡓࡵ㸪㑅ᢥᛶࡀኚ໬ࡋ࡞࠸ྍ⬟ᛶࡀ♧၀ࡉࢀࡓ㸦Figure
1㸧ࠋ



   





G7607%(  G760H2 Figure 1. 0RVW VWDEOH WUDQVLWLRQ VWDWH VWUXFWXUHV RI /L$O+ UHGFWLRQ RI VHOHQRPHWK\OSURSLRSKHQRQH ZLWKGLPHWK\OHWKHUFRRUGLQDWLRQ 3d-TS-2Me2O DQGZLWKPHWK\OWHUWEXW\OHWKHU 3d-TS-2MTBE RSWLPL]HGDW
0* GS OHYHO

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫▼ۻ‬ᘓ㸪す㒓㸪⏣㒊஭㸪๓⏣㸪⦾ཎ㸪ᒣ㷂㸪㔠㔝㸪᪥ᮏ໬Ꮫ఍➨ 101 ᅇ᫓Ꮨᖺ఍㸪2021 ᖺ 3 ᭶ 19 ᪥㸪࢜ࣥࣛ࢖ࣥ㸪[2] ‫▼ۻ‬ᘓ㸪す㒓㸪⏣㒊஭㸪๓⏣㸪㔠㔝㸪➨ 47 ᅇ᭷ᶵ඾ᆺඖ⣲໬Ꮫウㄽ఍㸪2020 ᖺ 12 ᭶  ᪥㸪࢜ࣥࣛ࢖ࣥ㸪[3] ‫▼ۻ‬ᘓ㸪す㒓㸪⏣㒊஭㸪๓⏣㸪㔠㔝㸪2020 ᖺ᪥ᮏ໬Ꮫ఍୰ᅜᅄᅜᨭ㒊኱఍㸪2020 ᖺ 11 ᭶ ᪥㸪࢜ࣥࣛ࢖ࣥ㸪[4] ‫ۻ‬బࠎᮌ㸪㧗ᶫ㸪᭷⃝㸪㇂㸪㔠㔝㸪2020 ᖺ᪥ᮏ໬Ꮫ఍୰ᅜᅄᅜᨭ㒊኱఍㸪2020 ᖺ 11
᭶  ᪥㸪࢜ࣥࣛ࢖ࣥ㸪[5] ‫ྜྷۻ‬Ọ㸪㔠㔝㸪2020 ᖺ᪥ᮏ໬Ꮫ఍୰ᅜᅄᅜᨭ㒊኱఍㸪2020 ᖺ 11 ᭶  ᪥㸪࢜ࣥࣛ࢖ࣥ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ۻ‬Ichikawa, Y.; Kaneno, D.; Saeki, N.; Minami, T.; Matsuda, T.; Yoshida, K.; Kondo, T.; Ochi, R., Carbohydr.

Res., in press.[2] Fukami, K.; Takagi, F.; Sonoda, K.; Okamoto, H.; Kaneno, D.; Horikawa, T.; Takita, M., Animals,
2021, 11, 567.

- 139 -







Molecular dynamics study on biological activity of heronamides
in lipid bilayer
"

#

!



$

1 
be/f% W^uW\/{+Þ^u(12L­ªaM°eM¿Õopb/O«bv85>J®´£,ß W\ )^uªaMVeM] ¯³\(¯³ÒÞ¸jÒ,¼.- +Þ ´|±Ó[,ß) W^uS¯³\q,O«bv7EH?6N8IL²*- +Þ-*^u¿ ÞbvÞv^Ð$*cv(_º^Ð'yÓËÏ½ÂØ,ß) W^uS Þ¯³/ , W·"g¨ÞÉÌÞÕ¶/T¼.-,ß  W^u wµÄ·/ÁÃ(g¨)·\Ve,ßµÄ·d+Æ#-^u Þz³WÜµÄC84JÝ ÞU¯³·"»e,¯³\^uÅÈ x,ß)·/Tbv
7EH?6N8IL^uG3?9F¿& Þbe(DA;=M:L@4Ä­ W^
u·VewÑ¤ÀZ ×,ß Ç}Þbe(DA;=/f% W^u·Ve^uG3?9F¿ Þbe(DA;=  Þ-/d+k%µÄ·'f&a¤Ê(¦RX¡¿ Ï½,©¬ rmh
-Þr ¥/Ô&,[Meth. Enzymol. 294(1999)208]ßY!Þ§¹/,BK>E=Ù
ÚilµÄ· :1<°e,OÞQÚilµÄ· ~ °e, mh-,[J. Am.
Chem. Soc. 2014, 136, 5209.]ß)BK>E=µÄ·"°eÍ ÞBK>E=µÄ·\,°eÊ(¦RX¡Í),'²*-,ß.ÞµÄ· Ve^u´£&n+Þbe(DA;= Î·toP ´/sb,·¢/,ß)^uVe·¢¿ Ve^uµÄ·a¤Ê(¦RX¡ÀZ ÂØ, Þ`^u/f0eµÄ· xÛ¾Ö&Þ-* *  Þ^u8EH"N8IL),¿w p#-,ß r¶©¬ Þ)be(DA;=·"¢¤Ve¿/¥¤Þ+PÔ©¬ÂØ/¼ß
1. beÜBK>E=ÙÝ/f0µÄ·ÊM¦RX¡¿w
2. beÜBK>E=ÙÝ·Ve¤JN®eÈ£
3. µÄMbe^u pbU,^uVepb}³-)+xLbeMDA;=µÄ·"·VeÌÜg¨MÉÌMÕ¶Ý,a¤Ê(¤JNpb´¯ * ,*.¨ -! 1-3 ÂØ©¬)_*-sÑ®N:/{v¢/¡ÔM¿wÞ4. k«beÈ£&^u±®hÅÜJÝ/$,ß¤ Þ®J/'k«be/jzÞe MÀZxÛ'¼'w,ß

- 140 -

2 
r¶©¬ ®vÜ^ua5v8EH"N8ILM¤JN®M{v¢Ý/¡Þ:N<bewµÄ·"°eMÉÌMÕ¶´/Ï]',e/È£,ß*Þ®N:/'{v¢J/È£,Þk«be±®Me MÀZ/`¿,&®N/_,ß+P3W¤xl®/°.

1. beÜBK>E=ÙÝ/f0µÄ·ÊM¦RX¡¿w
i¹M©s­1¼©¬),ÞµÄ·/ ,µÄ^uÆÇ(ÆQÚi])
be·"g¨MÉÌ´ s pb, *-,ßrÂØ ¤µÄÆÆÇ(QÚi]/pµÄ·/!L5Þ-*µÄ·be(DA;=/`!L5(
MD 8EH"N8IL/xlÞA,·(beÊÞF¾µÄ(^u¦RX¡´¯/* ,ß

2. beÜBK>E=ÙÝ·Ve¤JN®eÈ£Uº,be·VeU,¤JNpb/Ï¿MÏ]ÀZ,®eMAK5 FÈ£/¼ß#<}³®/xlÞÈ£e]Þ®JNA<´¯}³/¼ßr¶©¬

©¬85£,|Pa&È£¤JN®ÜLogMFDÝ/¡ÞCe/ MD ®A 51LAK5 F*-, Plumed x§®AK5 F/¡,ßrÂØ CAK5 F/µÄ·®g^MWÈÞbe·VeMÉÌMÕ¶U,¤JNpbÀZ/¼ß

3. µÄMbe^u pbU,^uVepb}³©¬ÂØÒ!L5µÄ·Þbe /p^u/`°e¤J
Nn/®Þ^u Í),¤JNpb}³,ßbeµÄ·"
·VeÜg¨MÉÌMÕ¶ÝÌ4&Þbeftu,/Â MD 8EH"N8IL/¼ß-)+xÛ ¾HÖÞ·VeÌ,be^uÂE(µÄ·°eÊ´¯ *,ßbeµÄ·Ò¦RX¡\²ÜiMËÊM¦RX¡Ý/yTM¿wM¼,)+Þbe¢S$,¦RX¡´¯/3W¤* ,ß4. k«be±®Me MÀZ#° 1-3 ©¬ÂØ)_*-®N:ÔM¿w)Þk«beÈ£&^u±®hÅÜJÝ/$,ß3W¤ ÞÔ&®xÛN:/¡Þ^uVe/',{v¢J/,ß*ÞxÉ!L5be·"Ve´/8EH"N8IL({v¢J)+ÀZMÎbÞ¤ Þjzbee MÀZxÛ'¼ß

3 
i¹­xÛ),BK>E= C

DMPC )ÚilµÄ· :1<°e,OPOPC( DOPC )QÚilµÄ· ~ °e, mh-#OBK>E= A- 141 -BK>E

= C  µÄ·"°e Ì|~'-,)BK>E=µÄ·"°e¢Í BK>E= C)

A µÄ·\,°eÊ(¦RX¡Í),'²*-, ·\^uÊ¾Ö)+* -O@­ C¯³·¹/,BK>E=Ùe ©¬/5¤À&, r©¬ -*xÛ)+e MÀZ-,BK>E=ÙµÄ·,^ua5vÜMDÝ

8EH"N8IL/xlBK>E=Ù·\°e/3W¤* ,BK>E= C, ( A 9WµÄ·, MD ®`@­ e BK>E=ÙµÄ·Abe·\, MD ®/xl,,°e- (^uÂEÍ/´¯¿wÊ(¦RX¡Í¸·,*BK>E=·\]pbU,·Ê(¦RX¡pb'­<,
8-deoxyheronamide C/DMPC heronamide C/DMPC

heronamide A/DMPC

I 1. MD 8EH"N8IL), DMPC (ÏX·%
IÒ MD 8EH"N8IL), DMPC (ÏX·%

heronamide B/DMPC,BK>E=^uÂEu,BK>E=^uÂEu/

-«ÙBK>E= '7"KNJ­C )^u%ÃN­/·iXEE )ÂE,°x -
heronamide C/DMPC

IÓ. BK>E= C  DMPC ·\,>A8I<([)·KEU,;u^\Ü%Ý
ÂE

^\Ü?Ý

I 2 BK>E= C ·\=C

,>A8I<;u^\ÂE^\¿w°x/BK>E

ÃN/·iXÎME ÂEÃN ·~N*ÇÎM^\, - 142 -

-bÆ (ÏX·%bÁ+r QL,°xBK>E=^u»·:E
U,¬]^\°x/IÓ?I¿w°xBK>E= C
QL,^\ 'r -C°x) 20 ]];J<c8-deoxyheronamide C/DMPC 'ª*-

heronamide A/DMPC

IÔ. BK>E= A  DMPC ·\,>A8I<([)·KEU,;u^\Ü%Ý
ÂE

^\Ü?Ý

IÔBK>E= C ·\=A

,>A8I<;u^\ÂE^\¿w°x/BK>E

^u%ÃN ^u%-'QL, *BK>E= C  ·:EUs0ÂE, -)ÂE BK>E= A ·:EU,;u^\(¬]^\°x '`¤^\-¿w°xBK>E= A) 60 ]];J<cQL,^\ 'r -
heronamide B/DMPC

I 4. BK>E= B  DMPC ·\,>A8I<([)·KEU,;u^\Ü%Ý
ÂE

^\Ü?Ý

C·\,^uÂE BK>E= B 'Á-I 4 BK>E= B ·\,

>A8I<;u^\ÂE^\¿w°x/BK>E= B ne^u!L5ÁÎM s
0ÂE, bÆ ·KEÂE,°x-*ÂE ^u\

- 143 -,

ÃN QL,nÍ),'²*--* ·~MiÎM¦RX¡,)+·\·:EU,;u^\(ÂE^\ pb,'²*-,

4 
1.  ^ua5v8EH"N8IL/¡BK>E=Ù·\Ê]/Q, bv7EH?6N
8ILKL 6 G2È8LF 2019, 2019 } 12 o 9 mÜoÝÕ10 m (), d¡Psvm

BL@, Ð¦s@
2.  Dynamical structure and thermal stability of polyene macrolactam heronamide in lipid bilayer: a molecular
dynamics study

International Conference on Molecular Simulation (ICMS 2019), 2019 } 11 o 3 m~6 m Í

JM Z, Hiroaki Saito, Naoki, Kanoh
3.  Development of a pharmacokinetics prediction system using multiscale integrated modeling:16. Prediction ofsites of metabolism of drug by CYP2C9 by molecular simulation()Ñ24 m(q)CBI vV 2019 }sV, 2019 } 10 o 22 mv)M¥O, Hiroaki Saito, Takao Otsuka, Noriaki Okimoto, Makoto Taiji

4.  LogMFD ),µÄ^u·ÉÌ¤JNn, ^uv¯·V 2019, 2019 } 9 o 17 mÜÝÕ20 mÜÄÝ,D>Vsv, Ð¦s|Pa&5


 Structural Feature of Lipid Scrambling Model Transmembrane Peptides: Same-Side Positioning of Hydrophilic

Residues and Their Deeper Position. The journal of physical chemistry letters, 1662  1667, Hiroyuki Nakao, Yuta
Sugimoto, Keisuke Ikeda, Hiroaki Saito, Minoru Nakano
2 bv£ ®bv£7 '*!L=-=RWÒ=L58EH"N 8IL),^u±® 6,#, ^u8EH"N8ILvVµ " LLJ", 21, 196-203, #x, ÏY½, Ð¦s- 144 -

ᵓ㐀ከ⢾ᮦᩱ࠾ࡼࡧ㛵㐃ࢱࣥࣃࢡ㉁ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲Molecular dynamics study of structural polysaccharides
and carbohydrate-related proteins‫‮ۑ‬஭ ᩄᩥ㸦ᐑᓮ኱ᏛᕤᏛ㒊㸧ࠊᏱ㒔 ༟ஓ㸦ᐑᓮ኱Ꮫࢸࢽࣗ࢔ࢺࣛࢵࢡ᥎㐍ᶵᵓ㸧
1◊✲┠ⓗࠊෆᐜ
ᵓ㐀ከ⢾࡛࠶ࡿࢭ࣮ࣝࣟࢫ࡜࢟ࢳࣥࡣᮌ㉁⣽⬊ቨࡸ⏥Ẇ㢮እ㦵᱁࡞࡝ࡢ୺ᡂศ࡛ࠊఱᮏࡶࡢศᏊ㙐ࡀ㞟ྜࡋࡓ㧗⤖ᬗᛶ⧄⥔࡜ࡋ࡚⏕⏘ࡉࢀࡿࠋࢭ࣮ࣝࣟࢫࡣゎ⧄ࠊ⁐ゎ࣭෌⏕ฎ⌮ࠊㄏᑟయ໬ࠊຍỈศゎ࡞࡝ࢆ⤒࡚ࠊ⧄⥔࣭ࣂ࢖࢜ࢣ࣑࢝ࣝ⣲ᮦࡸࣂ࢖࢜⇞ᩱ࡜࠸ࡗࡓ⏘ᴗ฼⏝ࡀ᥎㐍ࡉࢀ࡚࠸ࡿࠋ᭱㏆࡛ࡣࠊࢭ࣮ࣝࣟࢫ࣭࢟ࢳ
ࣥ⤖ᬗ⧄⥔ࢆᚤ⣽໬ࡉࡏࡓࢼࣀࣇ࢓࢖ࣂ࣮ࡀ⎔ቃㄪ࿴ᆺࡢᶵ⬟ᛶᮦᩱ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠾ࡾࠊᵝࠎ࡞⏘Ꮫᐁศ㔝࡛ࡢ฼⏝ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊᵓ㐀ከ⢾ᮦᩱࡣ㧗⤖ᬗᛶ⧄⥔ࡢࡓࡵ࡟Ỉࡸ୍⯡ⓗ࡞᭷ᶵ⁐፹࡟㞴⁐࡛ຍᕤᛶ࡟ஈࡋ࠸ࠋࡉࡽ࡟ࠊ⏘ᴗ㠃࡟࠾࠸࡚ࡶ㔜せ࡜࡞ࡿゎ⧄ࠊྍ⁐໬ࠊ┦㌿⛣ࠊ࢟ࣛࣝㄆ㆑ࠊ⏕ྜᡂᶵᵓࠊ㓝⣲ศゎ࡞࡝ࡢ⏺㠃࣭㧗ḟᵓ㐀ᙧᡂ࣓࢝ࢽࢬ࣒࡟㛵ࡍࡿศᏊㄽⓗ⌮ゎࡣ୙᫂Ⅼࡀከ࠸ࠋࡇ࠺ࡋࡓၥ㢟ࡀᵓ㐀ከ⢾ᮦᩱࡢ◊✲࣭㛤Ⓨࡢ࣎ࢺࣝࢿࢵࢡ࡜࡞ࡗ࡚࠾ࡾࠊィ⟬ᶵࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿᮦᩱタィᣦ㔪ࡢ☜❧ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋ୍᪉ࠊࢩ࣑࣮ࣗࣞࢩࣙࣥࡀ⌮ㄽ࣭ᐇ㦂࡟ḟࡄ➨ 3 ࡢ᪉ἲ࡜ゝࢃࢀ࡚ஂࡋ࠸ࡀࠊ≀ᛶண࡞࡝࡟ᇶ࡙ࡃᮦᩱ㛤Ⓨࡣ⢭ᗘࡸィ⟬ࢥࢫࢺࡢ㠃࡛ᩘከࡃࡢㄢ㢟࡟ྲྀ⤌ࡴᚲせࡀ࠶ࡿࠋᮏ◊✲ࣉࣟࢪ࢙ࢡࢺ
࡛ࡣࠊᵓ㐀ከ⢾ᮦᩱࡢᚤ⣽໬ᣲືࠊࢤࢫࢺศᏊࡢໟ᥋࣭⬺㞳ࢆక࠺⤖ᬗ㌿⛣ࣉࣟࢭࢫࠊ⢾㉁㛵㐃ࢱࣥࣃࢡ㉁࡜ࡢ┦஫స⏝ࠊ࢟ࣛࣝㄆ㆑ᶵᵓࡢゎᯒ࡟ྲྀ⤌ࢇ࡛ࡁࡓࠋ
ᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊᵓ㐀ከ⢾ᮦᩱ࠾ࡼࡧ㛵㐃ࢱࣥࣃࢡ㉁ࡢㅖၥ㢟ࢆศᏊືຊᏛ㸦MD㸧ィ⟬࡜㔞Ꮚ໬Ꮫ
㸦QM㸧ィ⟬࡟ࡼࡗ࡚ゎᯒࡋ࡚ࡁࡓࠋ2020̽2021 ᖺ࡟࠾ࡅࡿ◊✲ᡂᯝ࡜ࡋ࡚ࠊཎⴭㄽᩥ 7 ሗ࡜⥲ㄝ࣭ゎㄝ 3 ሗࢆฟ∧ࡋࠊᏛ఍Ⓨ⾲ࢆ 3 ௳⾜ࡗࡓࠋ≉➹ࡍ࡭ࡁⅬ࡜ࡋ࡚ࠊ◊✲ᡂᯝㄽᩥࡀⱥᅜ⋤❧໬Ꮫ఍ PCCP ㄅ࡜ RSC Adv.
ㄅࡢὀ┠ㄽᩥࠊⱥᅜ⋤❧໬Ꮫ఍ PCCP ㄅ࡜⡿ᅜ໬Ꮫ఍ JCTC ㄅࡢᥖ㍕ྕ࢝ࣂ࣮࢔࣮ࢺ࡟㑅ฟࡉࢀࡓࠋᮏሗ࿌
᭩࡛ࡣࠊձࢭ࣮ࣝࣟࢫ⏕ྜᡂ࡟㛵ࢃࡿࢱࣥࣃࢡ㉁ࡢᵓ㐀࡜ᶵ⬟ࠊղࢭ࣮ࣝࣟࢫ⤖ᬗ⏺㠃࡛㐍⾜ࡍࡿ཯ᛂᶵᵓࠊ
ճ࢟ࢳࣥࡀ⬺࢔ࢭࢳࣝ໬ࡋࡓ໬Ꮫᵓ㐀࡛࠶ࡿ࢟ࢺࢧࣥ–ሷ໬ள㖄」ྜయࡢ⤖ᬗᵓ㐀ゎᯒ࡟ࡘ࠸࡚㏙࡭ࡿࠋ

2

◊✲᪉ἲ

2. 1 㓑㓟⳦⏤᮶ࢭ࣮ࣝࣟࢫྜᡂ㓝⣲ࢧࣈࣘࢽࢵࢺ D㸫⢾㙐」ྜయࣔࢹࣝࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ
㓑㓟⳦⏤᮶ࢭ࣮ࣝࣟࢫྜᡂ㓝⣲ࢧࣈࣘࢽࢵࢺ '㸦&H6'㸧ࡢ⤖ᬗᵓ㐀ࢹ࣮ࢱ㸦3'% $- ࡜ $(㸧ࢆฟⓎᵓ㐀࡟ࡋ࡚ࠊ&H6' ࡢ⢾㙐」ྜయࣔࢹࣝࡢ࣐ࢽࣗ࢔ࣝࣔࢹࣜࣥࢢ࡛సᡂࡋࡓࠋᚓࡽࢀࡓ」ྜయࣔࢹࣝ
㸦CeSD-G12㸧ࢆ⁐፹࿴ MD ィ⟬ࡢᑐ㇟࡜ࡋࡓࠋィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣ $PEHU ࢆ౑⏝ࡋࠊ⢾࡜ࢱࣥࣃࢡ㉁ࣃ
࣓࣮ࣛࢱ࡟ࡣࠊࡑࢀࡒࢀ *O\FDP ࡜ II6% ࢆ㐺⏝ࡋࡓࠋᐃ

.ࠊᐃᅽ EDU ࡢ 0' ィ⟬ࢆ ȝV ᐇ᪋ࡋࡓࠋࡉࡽ࡟ࠊCeSD-G12 ࡢࡼࡾ࡟ᇶ࡙࠸ࡓࢻࢵ࢟ࣥࢢᵓ㐀ࢆ᳨ウࡍࡿࡓࡵ࡟ࠊQM/MM-MD ィ⟬ࢆྠᵝࡢ᮲௳࡛50 ns ᐇ᪋ࡋࡓࠋ40 ィ⟬࡟ࡣࠊ6&&')7% ἲ࡛ 6ODWHU.RVWHU ࣃ࣓࣮ࣛࢱࡣ PLR ࢆ㐺⏝ࡋࡓࠋ* ࡢ୰ኸ ṧᇶࢆ 40 㡿ᇦ࡜ࡋࠊ&H6'* ࡢṧࡾࡢ㒊ศ࡜ỈศᏊࠊ࢖࢜ࣥ࡟ࡘ࠸࡚ࡣ 00 㡿ᇦ࡜ࡋࡓࠋ
2. 2 ࢭ࣮ࣝࣟࢫ⤖ᬗ⾲㠃࡛㐍⾜ࡍࡿ୙ᩧ཯ᛂࢩ࣑࣮ࣗࣞࢩࣙࣥኳ↛ , ᆺࢭ࣮ࣝࣟࢫ⤖ᬗᵓ㐀ࢹ࣮ࢱ࡟ᇶ࡙࠸࡚ࠊ 㔞య  ศᏊࡢ &1) ࣔࢹࣝࢆᵓ⠏ࡋࡓࠋᇶ㉁㸦ࢽࢺࣟ࣋ࣥࢬ࢔ࣝࢹࣄࢻ㸧࡜࢚ࢼ࣑ࣥ୰㛫యࢆ  ಶྵࢇࡔ 11ࢪ࣓ࢳ࣒ࣝ࣍ࣝ࢔࣑ࢻ⁐ᾮ୰࡟ &1) ࣔࢹࣝࢆ㓄- 145 -

⨨ࡋࠊᐃ. ࣭ᐃᅽ EDU ࡢ 0' ィ⟬ࢆ  V ᐇ᪋ࡋࡓࠋḟ࡟ࠊ&1) ⾲㠃ୖࡢᇶ㉁ࡀ࢚ࢼ࣑ࣥ୰㛫య࡜⤖ྜࡍࡿ୙ᩧ࢔ࣝࢻ࣮ࣝ཯ᛂࢆゎᯒࡍࡿࡓࡵ࡟ࠊ4000᧯⯦ศᏊືຊᏛ㸦60'㸧ィ⟬ࢆ SV ᐇ᪋ࡋࡓ㸦ヨ⾜ᩘ  ᅇ㸧ࠋࡇࡢ㝿ࠊᇶ㉁࡜࢚ࢼ࣑ࣥ୰㛫యࡣ 40 㡿ᇦࠊࡑࢀ௨እࡢ㒊ศࢆ 00 㡿ᇦ࡜ࡋࡓࠋ40 ィ⟬࡟ࡣ 6&&')7% ἲ࡛ 6ODWHU.RVWHU ࣃ࣓࣮ࣛࢱࡣ PLR ࢆ㐺⏝ࡋࡓࠋィ⟬ࣉࣟࢢ࣒ࣛࡣ $PEHU ࢆ౑⏝ࡋࡓࠋ
2. 3 ࢟ࢺࢧࣥ㸫ሷ໬ள㖄」ྜయࡢ⤖ᬗᵓ㐀ゎᯒ; ⥺ᅇᢡᙉᗘࢹ࣮ࢱࢆ⏝࠸࡚⤖ᬗᵓ㐀ࢆゎᯒࡋࡓࠋゎᯒࣉࣟࢢ࣒ࣛ࡜ࡋ࡚ /inked-atom least-squares㸦LALS㸧ࢆ⏝࠸ࠊࡢ࡭ 2,000 ⛬ᗘࡢ⤖ᬗᵓ㐀ࣔࢹࣝ⥙⨶ⓗ࡟Ⓨ⏕ࡉࡏࠊ; ⥺ᅇᢡᙉᗘࢹ࣮ࢱ࡜୍⮴ࡋࠊཎᏊ㛫❧య཯
Ⓨࡢᑡ࡞࠸᭱⤊ᵓ㐀ࢆ㑅ᢥࡋࡓࠋỴᐃࡋࡓ᭱⤊ᵓ㐀ࡢᗙᶆࢆᇶ࡟࢟ࢺࢧࣥ 6 㔞య 25 ศᏊ࠾ࡼࡧ 9 ศᏊࡢ⤖ᬗࣔࢹࣝࢆసᡂࡋࠊࡇࢀࡽࢆᑐ㇟࡟ Gaussian 09 ࢆ⏝࠸ࡓ⤖ᬗᵓ㐀ࡢ⢭ᐦ໬ࢆ⾜ࡗࡓࠋ6 㔞య 25 ศᏊࡢ⤖ᬗࣔࢹ
ࣝࡢ 2 ఩࢔࣑ࣀᇶ࡜ 6 ఩Ỉ㓟ᇶ㓄ྥࡢྍ⬟࡞ࡍ࡭࡚ࡢ⤌ࡳྜࢃࡏ࠿ࡽ 6,561 ಶࡢࣔࢹࣝࢆ⏕ᡂࡋࠊUniversal
force field㸦UFF㸧ศᏊຊሙἲ࡟ࡼࡿ❧యᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋࡇࡢ㝿ࠊ3 ఩Ỉ㓟ᇶࡣࠊO3H—O5 ศᏊෆỈ⣲⤖ྜࡀᙧᡂࡉࢀࡿ㓄ྥ࡟タᐃࡋࡓࠋࡇࢀࡼࡾồࡵࡓ᭱Ᏻᐃ❧యᵓ㐀࠿ࡽ 6 㔞య 9 ศᏊ⤖ᬗࣔࢹࣝࢆసᡂ
ࡋࠊ༙⤒㦂ศᏊ㌶㐨ィ⟬㸦PM6㸧ἲ࡟ࡼࡿ❧యᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠸ࠊሷ໬ள㖄㓄⨨ࢆ⢭ᐦ໬ࡋࡓࠋ

3.

◊✲ᡂᯝ

3. 1 㓑㓟⳦⏤᮶ࢭ࣮ࣝࣟࢫྜᡂ㓝⣲ࢧࣈࣘࢽࢵࢺ D㸫ࢭ࣮ࣝࣟࢫ」ྜయᵓ㐀ࡢࢲ࢖ࢼ࣑ࢡࢫᣲື
2010 ᖺ௨㝆ࠊࢭ࣮ࣝࣟࢫ⏕ྜᡂ࡟㛵ࢃࡿࢱࣥࣃࢡ㉁ࡢ⤖ᬗᵓ㐀ゎᯒ

7RS
SYLHZZ         6LGH
HYLHZࢹ࣮ࢱࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ㓑㓟⳦ࡀ⏕⏘ࡍࡿࣂࢡࢸࣜ࢔ࢭ࣮ࣝࣟࢫࡢ
ྜᡂᶵᵓ࡜ࡋ࡚ࠊࢭ࣮ࣝࣟࢫྜᡂ㓝⣲ࢧࣈࣘࢽࢵࢺ⩌㸦CeSA-CeSD㸧
࡛ᵓᡂࡉࢀࡿྜᡂ㓝⣲」ྜయ㸦TC㸧ࡀᥦ᱌ࡉࢀ࡚࠸ࡿࠋࡇࡢෆࠊCH6' ࡢ 1 ᮎ➃Ḟᦆᰴ࡛ࡣࠊࢭ࣮ࣝࣟࢫ⏕⏘⬟ࡀ኱ࡁࡃపୗࡍࡿࡇ࡜ࡀ▱ࡽࢀࡿࠋ&H6' ❧యᵓ㐀㸦ᅗ 㸧ࡣࠊ ࢝ᡤࡢ⢾㙐⤒㊰ࢆ᭷ࡍࡿ෇ᰕ≧ࡢ࣍ࣔ  㔞య࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ࡚࠾ࡾࠊᅗ 㻝䠊㻯㼑㻿㻰 ඵ㔞య䛾❧యᵓ㐀䛸ᴫ␎ᅗ⢾㙐⤒㊰ࡣ⳦యෆ࡛ྜᡂࡉࢀࡓࢭ࣮ࣝࣟࢫ㙐ࡢࣛࣥࢲ࣒࡞఍ྜࢆ㜵ࡂࠊຠ⋡ⓗ࡞ྜᡂ࡜㍺㏦㸦᤼ฟ㸧࡟ᐤ୚ࡋ࡚࠸ࡿྍ⬟ᛶࡀ♧၀ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊCeSD⢾㙐⤒㊰ෆ࡟࡝ࡢࡼ࠺࡟ࢭ࣮ࣝࣟࢫศᏊ㙐ࡀ㓄⨨ࡋ࡚࠸ࡿ࠿࡟ࡘ࠸࡚ࡣ୙᫂░࡛࠶ࡗࡓࠋ
ศᏊࣔࢹࣜࣥࢢᡭẁࢆ㥑౑ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊ4 ࢝ᡤ
࠶ࡿ CeSD ஧㔞య⏺㠃ࡢ⢾㙐⤒㊰࡟ἢࡗ࡚ࢭ࣮ࣝࣟࢫศ
Ꮚ㙐ࢆ⤖ྜࡉࡏࡓࠋࡑࡢ⤖ᯝࠊ⢾㙐⤒㊰ࡣ┤⥺࡛ࡣ࡞ࡃࠊ ᅗ䠎䠊㻯㼑㻿㻰 䛾⢾㙐⤒㊰䛻⤖ྜ䛧䛯䝉䝹䝻䞊䝇㙐ࢭ࣮ࣝࣟࢫศᏊ㙐ࡣ 2 ࢝ᡤ࡛ᢡࢀ᭤ࡀࡿ S Ꮠᙧ≧ࢆ♧ࡋࡓ㸦ᅗ 2 ᕥ㸧ࠋḟ࡟ࠊ㒊ศⓗ࡟㟁Ꮚᵓ㐀ࢆ⪃៖࡛ࡁࡿ㧗⢭ᗘ࡞࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ࠊCeSD ࠾ࡼࡧࢭ࣮ࣝࣟࢫศᏊ㙐ࡢ❧యᵓ㐀ࡺࡽࡂࢆほᐹࡋࡓ࡜ࡇࢁࠊCeSD ࡢືࡁ࡟ྜࢃࡏ࡚ࠊࢭ࣮ࣝࣟࢫศᏊ㙐ࡢᒅ᭤㒊࡟࠶ࡿࢢࣝࢥ࣮ࢫṧᇶࡢ❧యᵓ㐀ࡀኚᙧ࡜ᅇ᚟ࢆ࿘ᮇⓗ࡟⧞ࡾ㏉ࡍࡇ࡜ࢆ☜ㄆࡋࡓ㸦ᅗ 2 ྑ㸧ࠋࡍ࡞ࢃࡕࠊ⢾㙐⤒㊰࡟⤖ྜࡋࡓࢭ࣮ࣝࣟࢫศᏊ㙐ࡣࠊCeSD⾲㠃࠿ࡽࡢᙉ࠸ไ㝈ࡢࡶ࡜࡛⛣ືࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ௨ୖࡢࡇ࡜࠿ࡽࠊCeSD ඲యࡢ࿘ᮇⓗ࡞❧యᵓ㐀ࡺࡽࡂ࡟ేࡏ࡚ 4 ᮏࡢࢭ࣮ࣝࣟࢫศᏊ㙐ࡀ⢾㙐⤒㊰ࢆྠᮇࡋ࡚⛣ືࡍࡿࡢ࡛ࡣ࡞࠸࠿࡜᥎ ࡋࡓࠋࢭࣝࣟ
࣮ࢫศᏊ㙐ࡀ 4 ᮏ༢఩࡛⛣ືࡍࡿࡇ࡜࡛ࠊศᏊ㙐ࡀつ๎ṇࡋࡃ㓄ิࡉࢀࡸࡍࡃ࡞ࡾࠊCeSD ࢱࣥࣃࢡ㉁ࡀࢭࣝ
࣮ࣟࢫࡢ㧗⤖ᬗᛶ໬࡟ᐤ୚ࡍࡿ⧄⥔ᙧᡂᶵᵓࢆᥦ᱌ࡋࡓࠋ

- 146 -

3. 2 ࢭ࣮ࣝࣟࢫ⤖ᬗ⏺㠃ࡀㄏ㉳ࡍࡿ୙ᩧ཯ᛂᶵᵓ
㧗ᗘ࡟❧య໬Ꮫ㑅ᢥⓗ࡞᭷ᶵྜᡂ཯ᛂࡢ㛤ᣅࡣࠊே㢮ࡢ≀㉁ᩥ᫂ࡢ
Ⓨᒎࡢ㘽ࢆᥱࡗ࡚࠸ࡿࠋࡇࢀࡲ࡛࡟ࠊ࢔࣑ࣀ㓟ࡢࣉࣟࣜࣥࢆゐ፹࡜ࡍࡿ࢔ࣝࢻ࣮ࣝ཯ᛂ࡟࠾࠸࡚ࠊࢭ࣮ࣝࣟࢫࢼࣀࣇ࢓࢖ࣂ࣮㸦&1)㸧ࡀࠊ∦᪉ࡢ㙾ീ␗ᛶయࢆ㧗཰⋡࡛సࡾศࡅࡽࢀࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ㸦ᅗ 㸧ࠋᐇ㦂⣔ࢢ࣮ࣝࣉ࡜༠ാࡋ࡚ࠊᙜヱ཯ᛂᶵᵓࡢゎ᫂࡟ྲྀ⤌ࢇࡔࠋ
ᇶ㉁࡜࢚ࢼ࣑ࣥ୰㛫యࡢ 11ࢪ࣓ࢳ࣒ࣝ࣍ࣝ࢔࣑ࢻ⁐ᾮ୰࡟࠾ࡅ

ᅗ䠏䠊㻯㻺㻲 ⏺㠃䛜ㄏ㉳䛩䜛୙ᩧ᭷ᶵ཯ᛂࡿ &1) ࣔࢹࣝࡢ 0' ィ⟬࡛ࡣࠊᇶ㉁㸦ࢽࢺࣟ࣋ࣥࢬ࢔ࣝ
ࢹࣄࢻ㸧ࡣࠊ&1) ␯Ỉᛶ⾲㠃࡟ྍ㏫ⓗ࡟྾╔ࡋࡓࠋ&1)⾲㠃࡟࠾ࡅࡿ྾╔㔞ศᕸࢆ࣐ࢵࣆࣥࢢࡋࡓ࡜ࡇࢁࠊࢭࣟࣅ
࣮࢜ࢫṧᇶࡈ࡜࡟࣋ࣥࢮࣥ⎔࡟⏤᮶ࡍࡿ㧗ᐦᗘ㡿ᇦࡀᚓࡽࢀࠊ୍ᐃࡢ㓄ྥᣲືࢆక࠺ᇶ㉁ࡢ⏺㠃⃰⦰ࢆほᐹࡋࡓࠋḟ࡟ࠊ400060' ィ⟬࡟ࡼࡗ࡚ࠊ࢚ࢼ࣑ࣥ୰㛫యࡢ࢝ࣝ࣎࢟ࢩࣝᇶ࠿ࡽᇶ㉁ࡢ࢝ࣝ࣎ࢽࣝ㓟⣲࡬ࡢࣉࣟࢺࣥ

ᅗ䠐䠊㻯㻺㻲 ⾲㠃䛷㐍⾜䛩䜛୙ᩧ䜰䝹䝗䞊䝹཯ᛂ⛣ືࡀ㉳ࡇࡿࡇ࡜࡛ &D㸫&į ⤖ྜࡀᙧᡂࡍࡿ཯ᛂᗙᶆࢆࢩ࣑ࣗࣞ
࣮ࢺࡋࡓࠋ&1) ␯Ỉ㠃࡟྾╔ࡋࡓᇶ㉁࡜࢚ࢼ࣑ࣥ୰㛫యࡀ≉␗࡞㑄⛣≧ែᵓ㐀ࢆᙧᡂࡍࡿࡇ࡜ࢆほᐹࡋࡓ㸦ᅗ 㸧ࠋࡉࡽ࡟ࠊ᝿
ᐃࡉࢀ࡚࠸࡞࠿ࡗࡓࣉࣟࣜࣥศゎࢆక࠺ࡼ࠺࡞๪཯ᛂࢆⓎぢࡋࡓࡇ࡜࡛ࠊ཯ᛂᶵᵓࡢ඲యീࢆ⪃ᐹࡍࡿࡇ࡜࡟ࡶ㈉⊩ࡋࡓࠋ
3. 3 ࢟ࢺࢧࣥ㸫ሷ໬ள㖄」ྜయࡢ⤖ᬗᵓ㐀ゎᯒࡇࢀࡲ࡛ᮍỴᐃࡢࡲࡲ࡛࠶ࡗࡓ࢟ࢺࢧࣥ㸫ሷ໬ள㖄」ྜయࡢ⤖ᬗᵓ㐀ࢆゎᯒࡋࡓࠋᅇᢡⅬࡼࡾồࡵࡓ༢఩᱁Ꮚࣃ࣓࣮ࣛࢱ
㸦a=1.1677 nmࠊb=1.7991ࠊc=1.030711 nm㸦⧄⥔㍈㸧㸧ࠊ࠾ࡼࡧ⤖ᬗ
ヨᩱࡢᐦᗘࢹ࣮ࢱࢆᇶ࡟ࠊ
༢఩᱁Ꮚ୰࡟ 2 ᅇࡽࡏࢇศᏊ㙐ࢆ 4 ᮏࠊሷ໬ள㖄ࢆ 4 ศᏊྵࡴࡇ࡜ࡀศ࠿ࡗࡓࠋ࢟ࢺࢧࣥ༢⊂ࡢ⤖ᬗᵓ㐀ࢆ᰿ᣐ࡟ࠊa ㍈ࡲࡓࡣ b ㍈࡟ 2 ᅇࡽࡏࢇᑐ⛠ࢆタᐃࡋࡓ㏫ᖹ⾜ศᏊ㙐ࣃࢵ࢟ࣥࢢᵓ㐀ࢆ௬ᐃࡋࡓࠋ㉥㐨⥺ᅇᢡࢹ࣮ࢱࢆ⏝࠸ࡓ ab ᢞᙳ㠃ᵓ㐀ࡢ᥈⣴⤖ᯝ࠿ࡽࠊa ㍈࡟ 2 ᅇࡽࡏࢇᑐ⛠ࢆᣢࡘ P21/a ✵㛫⩌ᅗ䠑䠊䜻䝖䝃䞁㻙ሷ໬ள㖄」ྜయ䛾⤖ᬗᵓ㐀ୖ䠅㼍㼎 ᢞᙳ㠃ᵓ㐀䚸ୗ䠅㼍㼏 ᢞᙳ㠃ᵓ㐀䜘䜚䚸㻞 ✀䛾ศᏊ㙐䝅䞊䝖ᵓ㐀ࢆ㑅ᢥࡋࡓࠋ
ᅗ 5 ࡟ X ⥺⤖ᬗᵓ㐀ゎᯒࡼࡾồࡵࡓ᭱⤊ᵓ㐀ࢆ♧ࡍࠋab ᢞᙳ㠃ࡼࡾ᫂ࡽ࠿࡞ࡼ࠺࡟ࠊศᏊ㙐ࡣࢪࢢࢨࢢ࡟ᢡࢀ᭤ࡀࡗࡓศᏊ㙐ࢩ࣮ࢺᵓ㐀ࢆᙧᡂࡋࠊ஫࠸࡟ O6—O6ࠊO6—N2ࠊN2—N2 ࡢศᏊ㛫Ỉ⣲⤖ྜ࡛㐃⤖ࡉࢀ࡚࠸ࡿࠋࡲࡓࠊሷ໬ள㖄ࡣศᏊ㙐ࢩ࣮ࢺࡢᢡࢀ᭤ࡀࡾ௜㏆࡟㓄⨨ࡋࡓࠋࡇࡢࢪࢢࢨࢢ≧ࡢศᏊ㙐ࢩ࣮ࢺᵓ㐀ࡸࢤࢫࢺศᏊࡢ㓄⨨ᵝᘧࡣ࢟ࢺࢧࣥ㸫ࣚ࢘⣲ሷ⤖ᬗᵓ㐀࡟⨨࠸࡚ࡶሗ࿌ࡉࢀ࡚࠾ࡾࠊ࢟ࢺࢧࣥࡢ✀ࠎࡢ㔠ᒓ㘒యࡸ㓟ሷࡢ⤖ᬗᵓ㐀࡟ඹ㏻ࡍࡿ≉ᚩ࡛࠶ࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ
ሷ໬ள㖄ࡢள㖄ཎᏊࡣࠊᙜึࠊ᝿ᐃࡉࢀ࡚࠸ࡓ࢟ࢺࢧࣥ 2 ఩࢔࣑ࣀᇶ࡜㘒యࢆᙧᡂࡍࡿ᫂☜࡞≉ᚩࡣぢࡽࢀࡎࠊ㒊ศⓗ࡟ 6 ఩Ỉ㓟ᇶ࡜ࡢ㘒యᵓ㐀ࡀ᥎ᐃࡉࢀࡓࠋᅗ 6 ࡣ PM6 ᭱㐺໬ᵓ㐀ࡢ ab ᩿㠃ᅗࢆ♧ࡍࠋሷ໬ள㖄ࡢศᏊ㙐㍈ࡀ⧄⥔㍈࡜࡯ࡰ୍⮴ࡍࡿࡼ࠺࡟ሷ໬ள㖄㓄⨨ࡀኚ໬ࡋࡓࠋ

- 147 -

ᅗ䠒䠊䜻䝖䝃䞁䠉ሷ໬ள㖄⤖ᬗ䝰䝕䝹䠄㻢 㔞య㽢㻥 ศᏊ䠅䛾 㻼㻹㻢 ᭱㐺໬ᵓ㐀

4. Ⓨ⾲ᐇ⦼‫ ۻ‬Ӌ౐୐໷ ஦ଞষଣ ࢃ‫ݫ‬࿪࠺ ໵ઔ५Ҳʰ߮ો߻੔ υΨΫεΠϝϫʖη͹߶࣏ߑଆմੵͳࣙ‫ހ‬ૌ৭Կ‫ڏ‬ಊʱ ೧થңָճ೧࣏୉ճ ౨‫ރߒ౐ښ‬ઔۢʤ޳ಆ൅නɼ ೧  ݆ʥ‫ ۻ‬୉੤޻࿪ ٤ҬҲ‫ ى‬Ӌ౐୐໷ʰΦʖτϩ࢐ો‫ࢢݬ‬Νଈ࠱Ͷ༙ͤΖϒϫϨζωΤϞ‫ܗ‬΢Ψϱӹର͹ࣰ‫ݩ‬ʀཀྵ࿨దΠϕϫʖοͶΓΖߑଆ෼੓૮‫ڂݜؖ‬ʱ΢Ψϱӹର‫ڂݜ‬ճक࠷΢Ψϱӹରϭʖέεϥρϕ
 Ψϱϧ΢ϱ֋࠷ʤϛηνʖ൅නɼ ೧  ݆ʥ‫ ۻ‬Ӌ౐୐໷ʰ‫ࢋܯ‬Կָͳ $, Ν༧߻ͪ͢ଡ౸ࡒྋ͹෾ࢢεϝϣϪʖεϥϱ‫ڂݜ‬ʱιϩϫʖηָճ‫ؖ‬੤ࢩ෨ ୊  յऑघιϝψʖ Ψϱϧ΢ϱ֋࠷ʤডଶߪԍɼ ೧  ݆ʥ

5. ฟ∧ᐇ⦼‫ ۻ‬78WR00LQDPL]DNLDQG7<XL 0ROHFXODUG\QDPLFVVLPXODWLRQRIFHOOXORVH,±HWK\OHQHGLDPLQHFRPSOH[FU\VWDOPRGHOV-3K\V&KHP% 124  ±   ᰝㄞ᭷ࠊIF: 2.857
 ‫ ۻ‬7 8WR 6 1DNDPXUD . <DPDPRWR DQG - .DGRNDZD  (YDOXDWLRQ RI DUWLILFLDO FU\VWDOOLQH VWUXFWXUH IURPDP\ORVH DQDORJ SRO\VDFFKDULGH ZLWKRXW K\GUR[\ JURXSV DW & SRVLWLRQ &DUERK\GU 3RO\P 240  ±   ᰝㄞ᭷ࠊIF : 7.182
 ‫ ۻ‬7 <XL DQG 7 8WR 'RFNLQJ DQG PROHFXODU G\QDPLFV VWXG\ RI WKH FDUERK\GUDWH ELQGLQJ PRGXOH IURP7ULFKRGHUPDUHHVHL &HO$RQWKHVXUIDFHVRIWKHFHOOXORVH,,,, FU\VWDO-5HQHZ0DWHU 8   ±  ᰝㄞ᭷䛷౫㢗ㄽᩥ䚸IF: 1.419
 ‫ ۻ‬. <RVKLL  7 8WR  1 7DFKLNDZD DQG < .DWD\DPD 7KH SRVLWLRQ RI WKH HWKHU R[\JHQ DWRP LQ
S\UUROLGLQLXPEDVHG URRP WHPSHUDWXUH LRQLF OLTXLGV IRU WKH SK\VLFRFKHPLFDO SURSHUWLHV 3K\V &KHP &KHP
3K\V20  ±   ᰝㄞ᭷䛷ⱥᅜ⋤❧໬Ꮫ఍ 3&&3 ㄅ䛾ώρέΩώʖ࡟㑅ฟ䚸IF: 3.430
 ‫ ۻ‬1 - 5DQDLYRDULPDQDQD ;+DEDNL 78WR..DQRPDWD 7 <XL DQG7.LWDRND  1DQRFHOOXORVH HQULFKHVHQDQWLRPHUVLQDV\PPHWULFDOGROUHDFWLRQV56&$GY 10  ±   ᰝㄞ᭷࡛ⱥᅜ⋤❧໬Ꮫ఍56&$GYDQFHV ㄅࡢ +27$UWLFOH&ROOHFWLRQ ࡟㑅ฟࠊIF: 3.070  ‫ ۻ‬78WR<,NHGD16XQDJDZD.7DMLPD0<DR DQG 7<XL  0ROHFXODUG\QDPLFVVLPXODWLRQRIFHOOXORVHV\QWKDVHVXEXQLW'RFWDPHUZLWKFHOOXORVHFKDLQVIURPDFHWLFDFLGEDFWHULD,QVLJKWLQWRG\QDPLFEHKDYLRUVDQG
WKHUPRG\QDPLFVRQVXEVWUDWHUHFRJQLWLRQ-&KHP7KHRU\&RPSXW 17  ±   ᰝㄞ᭷࡛⡿ᅜ໬Ꮫ
఍ -&7& ㄅࡢᥖ㍕ྕࣇࣟࣥࢺ࢝ࣂ࣮࡟㑅ฟࠊIF: 5.011
 ‫ ۻ‬7 <XL  7 8WR DQG . 2JDZD 0ROHFXODU DQG FU\VWDO VWUXFWXUH RI D FKLWRVDQí]LQF FKORULGH FRPSOH[1DQRPDWHULDOV11   DUWLFOHQXPEHU  㸦ᰝㄞ᭷ࠊIF: 4.324
 ‫ ۻ‬Ᏹ㒔༟ஓ㸪‫‮‬஭ᩄᩥ ࠕࢭ࣮ࣝࣟࢫࡢᐇ㦂࡜ゎᯒἲࢩ࣮ࣜࢬ㸸ศᏊຊᏛィ⟬࡟࠾ࡅࡿ⿵᏶ຊሙ
ࣃ࣓࣮ࣛࢱࡢసᡂࠖ&HOOXORVH&RPPXQ 27  ±   ౫㢗ㄽᩥ ‫ ۻ‬Ᏹ㒔༟ஓ ࠕศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㞴⁐ᛶࣂ࢖࣐࢜ࢫࡢ⁐፹᥈⣴ࠖ%LRVFLHQFH ,QGXVWU\79  ±   ౫㢗ㄽᩥࠊ⏘Ꮫᐁ࡛ᵓᡂࡉࢀࡿࣂ࢖࢜࢖ࣥࢲࢫࢺ࣮ࣜ༠఍ㄅࡢゎㄝグ஦ ‫‮ ۻ‬஭ᩄᩥ ࠊᏱ㒔༟ஓࠕศᏊࣞ࣋ࣝ࠿ࡽゎࡁ᫂࠿ࡍࢭ࣮ࣝࣟࢫ⧄⥔ࡢ୙ᛮ㆟̿ศᏊࡢ❧యᵓ㐀࡜ືࡁ࠿ࡽ⏕ྜᡂࡢࡋࡃࡳࢆ᥈ࡿࠖ᭶ห໬Ꮫ 76   ±  ౫㢗⥲ㄝⱥᅜ⋤❧໬Ꮫ఍ 㻼㻯㻯㻼 ㄅ➨ 㻞㻞 ᕳ 㻟㻡 ྕ䝞䝑䜽䜹䝞䞊- 148 -

⡿ᅜ໬Ꮫ఍ 㻶㻯㼀㻯 ㄅ ➨ 㻝㻣 ᕳ 㻝 ྕ䝣䝻䞁䝖䜹䝞䞊඲ཎᏊศᏊືຊᏛィ⟬ࡢ㧗ศᏊ◊✲࡬ࡢᒎ㛤
$SSOLFDWLRQRIDOODWRPPROHFXODUG\QDPLFVVLPXODWLRQWRSRO\PHU
FKHPLVWU\‫ۑ‬ᒸᓮ 㐍ࠊỌ஭ ဴ㑻ࠊ‫ ‮‬அஓ㸦ᮾி኱Ꮫ኱Ꮫ㝔᪂㡿ᇦ๰ᡂ⛉Ꮫ◊✲⛉㸧




◊✲┠ⓗ
ᮏ◊✲ㄢ㢟࡛ࡣࠊ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㧗ศᏊ⛉Ꮫ◊✲࡬࡜ᒎ㛤ࡍࡿࠋࡇࡢ┠ⓗࡢࡓࡵ࡟ࠊᚲせ࡟ᛂࡌ࡚ศᏊືຊᏛἲࡢᡭἲ㛤Ⓨࢆ᪂つ࡟࠾ࡇ࡞࠸ࠊ㧗ศᏊ࡟㛵ࢃࡿㅖ⌧㇟ࡢゎᯒ࡟ᛂ⏝ࡍࡿࠋࡇࢀࡽ
ࡢ୰࡛ࠊ≉࡟ࠊ୙ᆒ୍⣔ࢆᵓᡂࡍࡿ㧗ศᏊᮦᩱ࡟࠾ࡅࡿ≀㉁㍺㏦࡞ࡽࡧ࡟㠀ᬗᶞ⬡ࡢຊᏛ≉ᛶ࡟ὀ┠ࡋࠊศᏊᶵᵓࢆศᏊࣞ࣋ࣝ࠿ࡽ᫂ࡽ࠿࡟ࡍࡿࠋ
 ୙ᆒ୍⣔࡟࠾ࡅࡿ≀㉁㍺㏦ࡢศᏊᶵᵓࡢゎ᫂㧗ศᏊࡀᙧᡂࡍࡿ୙ᆒ୍⣔࡟࠾ࡅࡿᑠศᏊࡢ㍺㏦ᶵᵓࢆゎ᫂ࡍࡿᡭἲࢆ㛤Ⓨࡋࠊᐇᅾ⣔࡟࠾ࡅࡿၥ㢟࡬࡜ᛂ⏝ࡍࡿࠋ㧗ศᏊ㟁ゎ㉁⭷ࡣࠊ㧗ศᏊ࡜ᾮయ࡜ࡀ࣑ࢡࣟ࡟┦ศ㞳ࡋࡓ୙ᆒ୍⣔ࢆᙧᡂࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡞
୙ᆒ୍⣔࡛ࡢᑠศᏊࡢᣑᩓⓗ࡞㐠ືࢆࠊ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘ࡜⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧ࡟ࡼࡾグ㏙ࡍࡿࠋ୍⯡ⓗ࡟ࡣࠊࡇࢀࡽࡢ஧ࡘࡢ≀⌮㔞ࢆ୙ᆒ୍✵㛫୰ࡢྛⅬ࡛ồࡵࡿࡇ࡜࡛ࠊᑠศᏊࡢ㍺㏦ࡢ㥑ືຊ࡜㥑ືຊ࡟ᑐࡍࡿ᢬ᢠࡢ஧ࡘࡢᅉᏊ࡟ศ㞳ࡋࡓᙧ࡛≀㉁㍺㏦ࢆ㆟ㄽࡍࡿࡇ࡜ࡀ࡛ࡁࡿࡀࠊᮏ◊✲࡛ࡣࡇࢀࡽࢆࡼࡾᐃ㔞ⓗ࡟グ㏙ࡍࡿࡓࡵ࡟ࠊ☜⋡㐣⛬࡜ࡋ࡚ᑠศᏊ࡟ᑐࡍࡿ⢒ど໬ࢲ࢖ࢼ࣑ࢡࢫࢆసᡂࡍࡿࠋࡇࡢ⢒ど໬ࢲ࢖ࢼ࣑
ࢡࢫࢆືⓗࣔࣥࢸ࢝ࣝࣟἲ࡞࡝࡟ࡼࡾゎࡃࡇ࡜࡛ࠊ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ᫬㛫ࢆ㉸࠼ࡓ㛗᫬㛫ࡢࢲ࢖ࢼ࣑ࢡࢫࢆゎᯒ࡛ࡁࡿࠋࡇࡢࡼ࠺࡞ゎᯒᡭἲࢆ☜❧ࡍࡿࡓࡵ࡟ࡣࠊ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘ࡜⮬⏤࢚ࢿࣝࢠ࣮ࢆศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽồࡵࡿᚲせࡀ࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ๓⪅࡟㛵ࡋ࡚ࠊᚑ᮶ᡭἲ
࡛ࡣ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘࢆ㐣ᑠホ౯ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡑࡇ࡛ࠊ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘࡢ᪂ࡋ࠸ホ౯᪉ἲࢆᥦ᱌ࡋ☜❧ࡍࡿࠋᛂ⏝౛࡜ࡋ࡚ࡣࠊ⇞ᩱ㟁ụ࡟฼⏝ࡉࢀࡿ QDILRQ ⭷ࠊ࢞ࢫศ㞳⭷ࡸ⏕య⭷ࡢ≀㉁㏱㐣ࢆ᳨ウࡍࡿࠋ 㧗ศᏊᶞ⬡ࡢຊᏛ≉ᛶ㧗ศᏊᶞ⬡ࡢຊᏛ≉ᛶࢆศᏊࣞ࣋ࣝ࠿ࡽゎ᫂ࡍࡿࠋ㏆ᖺྍ⬟࡟࡞ࡗ࡚࠸ࡿ኱つᶍศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ
ࣙࣥ࡟ࡼࡾࠊ✀ࠎࡢᶞ⬡ࡢ⾪ᧁ◚ቯࢩ࣑࣮ࣗࣞࢩࣙࣥࡀ⌧ᐇⓗ࡞᫬㛫ࢫࢣ࣮࡛ࣝ⾜࠼ࡿࡼ࠺࡟࡞ࡾࡘࡘ࠶ࡿࠋ
ࡑࡢࡓࡵ࡟ࠊ⢒ど໬ᶍᆺࡔࡅ࡛ࡣ฿㐩࡛ࡁ࡞࠸໬Ꮫⓗ≉ᛶ࡜ຊᏛ≉ᛶ࡜ࡢ㛵㐃ࡔࡅ࡛࡞ࡃࠊᐇ㦂ࡔࡅ࡛ࡣᚓ
ࡿࡇ࡜ࡢ㞴ࡋ࠸ศᏊᵓ㐀࡜ຊᏛ≉ᛶ࡜ࡢ㛵ಀ࡟ᑐࡍࡿ⌮ゎࡀᛴ⃭࡟῝ࡲࡿ࡜ணࡉࢀࡿࠋࡇࢀࡲ࡛࡟ 300$ ࡸ

3& ࡞࡝ࡢ㠀ᬗᶞ⬡ࡢ◚ቯࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࡁࡓ⤒㦂ࢆ⏕࠿ࡋ࡚ࠊࣂ࢖࣏࣐࣮࡛࢜ࣜᵓᡂࡉࢀࡿᶞ⬡࡞࡝ࡢຊᏛ≉ᛶࢆࠊ໬Ꮫⓗ≉ᛶࡸศᏊᵓ㐀࡜㛵㐃௜ࡅ࡚ゎ᫂ࡍࡿࠋ
- 149 -

◊✲᪉ἲࠊィ⟬᪉ἲ ୙ᆒ୍⣔࡟࠾ࡅࡿ≀㉁㍺㏦ࡢศᏊᶵᵓࡢゎ᫂
QDILRQ ⭷࡟࠾ࡅࡿ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧ࡜ᣑᩓಀᩘࡢィ⟬ࢆ⾜࠺ࠋࡍ࡛࡟సᡂࡋ࡚࠸ࡿᵝࠎ࡞ྵỈ⋡࡛ࡢ

QDILRQ ⭷ࡢࣔࢹࣝ࡟ᑐࡋࠊRYHUODSGLVWULEXWLRQ ἲࠊ⢏Ꮚᤄධἲ࡟ᇶ࡙࠸࡚఩⨨࡟౫Ꮡࡋࡓ⁐㉁ศᏊࡢ⮬⏤࢚ࢿࣝࢠ࣮ࢆホ౯ࡋࡓࠋࡲࡓࠊᴫࡡ QP ⛬ᗘࡢゎീᗘ࡛✵㛫࣓ࢵࢩࣗ࡟ࡃࡂࡾࠊྛ࣓ࢵࢩࣗ࡟࠾࠸࡚ࣇࣛ
ࢵࢺ࣎ࢺ࣒࣏ࢸࣥࢩࣕࣝ࡟ࡼࡿᣊ᮰ࢆᤄධࡍࡿ⁐㉁ศᏊ࡟༳ຍࡋࡓ࡚ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊᖹᆒຊ࡞ࡽࡧ࡟ᣑᩓಀᩘࢆホ౯ࡍࡿࠋᚓࡽࢀࡓᖹᆒຊ࠿ࡽྛ࣓ࢵࢩࣗෆ࡛ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࢆࠊࡲࡓࠊ⁐㉁ศᏊࡢ㐠ື࠿ࡽᣑᩓಀᩘࢆồࡵࡓࠋ 㧗ศᏊᶞ⬡ࡢຊᏛ≉ᛶࡇࢀࡲ࡛సᡂࡋࡓ 300$ࠊ3& ཬࡧ 36 ࡢ⣔࡛ࠊศᏊ㔞ศᕸࠊ࠿ࡽ
ࡳ࠶࠸ᐦᗘ࡜័ᛶ༙ᚄࡢㄪᩚࡢ᭷↓ཬࡧࡑࢀࡒࢀࡢ෭༷㏿ᗘࡣ࢞ࣛࢫ㌿⛣ᗘ࡜ᘬᙇᙎᛶ⋡࡟ᙳ㡪ࢆ᳨ウࡋ࡞ࡀࡽ㐺ษ࡞ࣂ࢖࢜㧗ศᏊࡢࣔࢹࣝ⣔ࢆసᡂࡋࠊ࢞ࣛࢫ㌿⛣ᗘཬࡧᘬᙇᙎᛶ⋡ࢆィ⟬ࡋࡓࠋᮏ◊✲࡛ࡣ࣏ࣜ࢖࣑ࢲࢰ࣮ࣝ㢮㧗ศᏊࡢ 3%,ࠊ3%,S3$ࠊ
3%,3%2P3$ ࡜ 3%,3%2S3$ ࡢᅄ✀㢮ࡢ㧗ศᏊ࡟࠾࠸࡚ศᏊ㔞ศᕸཬࡧ័ᛶ༙ᚄࢆᐇ㦂ࢹ࣮ࢱ࡟ྜࢃࡏ࡚ࡑࢀࡒࢀࡢ㧗ศᏊࡢⓒ୓ཎᏊࢆᣢࡘ඲ཎᏊࣔࢹࣝ⣔ࢆసᡂࡋࠊ㧗ࡢ . ࠿ࡽᐊࡲ࡛  ࢼࣀ⛊ẖ࡟ . ࢆୗࡆ࡞ࡀࡽᖹ⾮໬ィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ෭
༷ィ⟬ࡢ⤖ᯝࢆ⏝࠸࡚ࡑࢀࡒࢀࡢ㧗ศᏊࡢ࢞ࣛࢫ㌿⛣ᗘࢆࡗࡓࠋ⌧ᅾࠊ෭༷ィ⟬ࢆ . ࡲ࡛ᐇ⾜ࡋࡓ࡜ࡇࢁ࡛࠶ࡿࠋ⥆࠸࡚ࠊ᪤ᐃࡢᗘ୍࡛㍈ᘏఙࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࠋࡑࡇ࡛ࠊ

Ỉ⣲⤖ྜ࡞࡝ࡢ࣮࣮࢟࣡ࢻ࡟ᇶ࡙࠸࡚㝆అᛂຊࡸᙎᛶ⋡ࡸ◚᩿ఙᗘ࡞࡝ࡢᶵᲔⓗ≉ᛶཬࡧ࢞ࣛࢫ㌿⛣࡞࡝ࡢ⇕ຊᏛⓗᛶ㉁࡜ᵓ

ᅗ㸯㸸Ỉ⣲ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࡢ᩿㠃ᅗ࡜ᑐᛂࡍࡿศᏊᵓ㐀ࠋ⮬⏤࢚ࢿࣝࢠ࣮
ࡢ㧗ప࡜ศᏊᵓ㐀ࢆ┤᥋ẚ㍑࡛ࡁࡿࠋ㐀ࡢ㛵ಀࢆゎ᫂ࡍࡿࠋศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡣ 0RG\ODV࡜ *URPDFV ࡜࠸࠺ࢯࣇࢺ࢙࢘࢔ࢆ฼⏝ࡋ࡚⾜ࡗࡓࠋ୍᪉ࠊ࣏࣮ࣜ࢝࣎ࢿ࣮ࢺ㸦3&㸧࡜ 300$ ࡢ᪤Ꮡࡢ෭༷ࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝࢆ⏝࠸࡚ࠊ࢞ࣛࢫ㌿⛣࡟࠾ࡅࡿ◊✲ࢆᒎ㛤ࡋࡓࠋศᏊෆ໬Ꮫ⤖ྜࡢᅇ㌿㸦஧㠃ゅ㸧ᵓ㐀ࡢ㑄⛣⋡࡜⮬ᕫ┦㛵㛵ᩘࠊ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࠊ
័ᛶ༙ᚄࠊࣔࣀ࣐࣮ࡢ࣎ࣟࣀ࢖య✚ࠊྛ⮬⏤ᗘࡢ┦㛵ಀᩘ࡞࡝ࡢᛶ㉁ࢆ⮬సࣉࣟࢢ࣒࡛ࣛゎᯒࡋࡓࠋ◊✲ᡂᯝ ୙ᆒ୍⣔࡟࠾ࡅࡿ≀㉁㍺㏦ࡢศᏊᶵᵓࡢゎ᫂఩ ⨨࡟ ౫Ꮡ ࡋࡓ⮬ ⏤࢚ ࢿࣝ ࢠ࣮ ࢆ✵ 㛫ゎീ ᗘ  ύ࡛ ィ⟬ ࡋホ ౯ࡋࡓ ࠋィ ⟬ᡭ ἲ࡟ ࡣࠊ 2YHUODSSLQJ'LVWULEXWLRQ ἲ࡜⢏Ꮚᤄධἲࢆ฼⏝ࡋࡓࠋᅗ㸯࡟ࠊྵỈ⋡ࡀ  ࡢࢼࣇ࢕࢜ࣥྵỈ≀࡟࠾ࡅࡿỈ⣲ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࡢ᩿㠃ᅗ࡜ࠊࡑࡢ᩿㠃࡟ᑐᛂࡍࡿศᏊᵓ㐀ࢆ㔜ࡡࡓࡶࡢࢆ♧ࡍࠋࡇࡢࡼ࠺࡟ࡍࡿࡇ࡜࡛ࠊ⮬⏤࢚ࢿࣝࢠ࣮࡜ศᏊᵓ㐀࡜ࡢ㛵ಀࢆ᫂ࡽ࠿࡟ࡋࠊ㍺㏦ࡢ࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡟ࡋࡼ࠺࡜ࡋ࡚࠸ࡿࠋỈ⣲ࡸ㓟⣲ࡢ㏱㐣
⤒㊰࡟㛵ࡋ࡚ࡣ㛫᥋ⓗ࡞ᐇ㦂⤖ᯝ࠿ࡽỈ┦ࢆ㏻ࡿ࡜࠸࠺ㄝࡶ㧗ศᏊ┦ࢆ㏻ࡿ࡜࠸࠺ㄝࡶᏑᅾࡋ࡚࠸ࡿࠋᡃࠎ

- 150 -

ࡢ⤖ᯝࡣࠊ‽ഛẁ㝵࡛ࡣ࠶ࡿࡶࡢࡢࠊ┤᥋ⓗ࡟ᚋ⪅ࡢㄝࢆᨭᣢࡋ࡚࠸ࡿࠋ 㧗ศᏊᶞ⬡ࡢຊᏛ≉ᛶ࣏ࣜ࢖࣑ࢲࢰ࣮ࣝ㢮㧗ศᏊࡢᶵᲔⓗ≉ᛶཬࡧ⇕ຊᏛ≉ᛶࢆ◊✲ࡍࡿࡓࡵ࡟ࠊ኱つᶍศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋศᏊ㔞ศᕸࡸ័ᛶ༙ᚄࢆᐇ㦂ࢹ࣮ࢱ࡟ྜࢃࡏ࡚ᅄ✀㢮ࡢ 3%, 㢮㧗ศᏊࡢⓒ୓ཎᏊ⣔ࢆసᡂࡋࡓࠋ⥆࠸࡚ࠊ. ࡢ㧗࠿ࡽ  ࢼࣀ⛊ẖ࡟ . ࡢ㏿ᗘ࡛ࡑࢀࡒࢀࡢி࡟ᑐࡋ࡚࢔ࢽ࣮ࣜࣥࢢࢆ⾜ࡗࡓࠋ⌧ᅾࠊ. ࡲ࡛෭༷ࡋࠊࡑࢀࡒࢀࡢ⣔ࡢ࢞ࣛࢫ㌿⛣ᗘࢆᐃࡋࡓࠋࡑࡢ⤖ᯝࠊ஧ඖ⣔࡜୕ඖ⣔ࡢඹ㔜ྜయࡣඖࠎࡢ 3%, ࡼࡾప࠸࢞ࣛࢫ㌿⛣ᗘࢆᣢࡘࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡇࡢࡇ࡜ࡣࠊᐇ㦂ᅗ㸰㸬ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ
⟬ฟࡋࡓ࣏ࣜ࢖࣑ࢲࢰ࣮ࣝ㢮㧗ศᏊࡢ࢞ࣛࢫ㌿⛣

ᗘࠋ⤖ᯝ࡜ࡶ୍⮴ࡍࡿ㸦ᅗ㸰㸧ࠋࡇࡢ᣺ࡿ⯙࠸࡟ᑐࡋ࡚ࠊ⌧ᅾỈ⣲⤖ྜ࡟╔┠ࡋࡓゎᯒࢆ⾜ࡗ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ
୍᪉࡛ࠊ࢞ࣛࢫ㌿⛣⌧㇟ࡢศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ
࡟ࠊ3& ࡜ 300$ ࡢ෭༷ࡢࢺࣛࢪ࢙ࢡࢺ࣮ࣜࢆ⏝࠸࡚ࠊᵝࠎ࡞ゎᯒࢆ⾜ࡗࡓ⤖ᯝࠊ㧗ศᏊࡢ୪㐍ࠊᅇ㌿ࠊࢥ࣓࣮ࣥ࣍ࢩ
ࣙࣥ➼ࡢࡑࢀࡒࢀࡢ⮬⏤ᗘࡣࡑࢀࡒࢀูࡢ

ᗘ࡛࢞ࣛࢫ㌿⛣ࢆ㉳ࡇࡍࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸦ᅗ㸱㸧ࠋࡇࡢࡇ࡜ࢆ཯ᫎ
ࡋ࡚ࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥほࡣᗈ࠸ࡍࡿ࢞ࣛࢫ㌿⛣ᗘᖜࡢ㌿⛣ࢆ♧ࡍࠋ୍᪉ࠊ506) ࡸ஧㠃ゅࡢ≧ែ㑄⛣⋡ࡢィ⟬࠿ࡽࡣࠊ㧗ศᏊࡢᮎ➃ࡣ㧗࠸㐠ືᛶࢆ♧ࡋ࡞ࡀࡽ࢞ࣛࢫ㌿⛣࡟ᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࡶ᫂ࡽ࠿࡜࡞ࡗࡓࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᅗ㸱㸬࣏࣮ࣜ࢝࣎ࢿ࣮ࢺࡢᅇ㌿⮬⏤ᗘཬࡧ‫ ‮‬அஓࠊᒸᓮ㐍ࠋࠕ㧗ศᏊࡢ࢞ࣛࢫ㌿⛣࡟࠾ࡅࡿ஧㠃ゅ࡟࠾ࡅࡿูࠎࡢ࢞ࣛࢫ㌿⛣ࠋศᏊᶵᵓࡢ◊✲ࠖ➨㸵㸮ᅇ㧗ศᏊウㄽ఍  ᖺⓎ⾲ணᐃỌ஭ဴ㑻㸪⸨ᮏ࿴ኈ㸪ᒸᓮ㐍㸪㺀఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘࡢ᪂つホ౯ᡭἲࡢ㛤Ⓨ㸸኱つᶍ୙ᆒ୍⣔࡟࠾ࡅࡿ≀㉁㍺㏦ゎ᫂࡟ࡴࡅ࡚㺁㸪➨  ᅇ⌮ㄽ໬Ꮫウㄽ఍㸪࢜ࣥࣛ࢖ࣥ㸪 ᖺ  ᭶  ᪥̽ ᪥Ọ஭ဴ㑻㸪⸨ᮏ࿴ኈ㸪ᒸᓮ㐍㸪ࠕ㧗ศᏊ㟁ゎ㉁⭷࠾ࡼࡧ⇞ᩱ㟁ụ㟁ᴟ⏺㠃࡟࠾ࡅࡿ≀㉁㍺㏦ᶵᵓゎ᫂࡟ྥࡅࡓศᏊືຊᏛィ⟬᪂つᡭἲ㛤Ⓨࠖࠊィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔࣒㸦3&R06㸧ࢩ࣏ࣥࢪ࣒࢘㸪࢜ࣥࣛ࢖ࣥ㸪 ᖺ  ᭶  ᪥̽ ᪥㸬Ọ஭ဴ㑻㸪ᘻᕳ࿘ᖹ㸪ᾆ㔝ㄹ㸪⸨ᮏ࿴ኈ㸪⠛⏣΅㸪ᒸᓮ㐍㸪ࠕ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘࡢ᪂つホ౯᪉ἲ࡟ᇶ࡙ࡃ୙ᆒ୍⣔࡟࠾ࡅࡿ≀㉁㍺㏦ࠖ
㸪᪥ᮏ≀⌮Ꮫ఍  ᖺ⛅Ꮨ኱఍㸪࢜ࣥࣛ࢖ࣥ㸪 ᖺ ᭶  ᪥̽ ᭶  ᪥㸬- 151 -

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
͙ =KL\H7DQJ.D]XVKL)XMLPRWR6XVXPX2ND]DNL$FRPSDULVRQRIWKHEULWWOH300$ZLWKWKHGXFWLOH3&
RQ WKH HODVWLFLW\ DQG \LHOGLQJ IURP D PROHFXODU G\QDPLFV SHUVSHFWLYH 3RO\PHU 226    
KWWSVGRLRUJMSRO\PHU͙ 7 1DJDL 6KXKHL 7VXUXPDNL 5\R 8UDQR .D]XVKL )XMLPRWR :DWDUX 6KLQRGD DQG 6XVXPX 2ND]DNL
³3RVLWLRQGHSHQGHQWGLIIXVLRQFRQVWDQWRIPROHFXOHVLQWKHKHWHURJHQHRXVV\VWHPVDVHYDOXDWHGE\WKHORFDO
PHDQ VTXDUHG GLVSODFHPHQW´ -RXUQDO RI &KHPLFDO 7KHRU\ DQG &RPSXWDWLRQ 16 ±  
KWWSVGRLRUJDFVMFWFF

= 7DQJ . )XMLPRWR DQG 6 2ND]DNL $OODWRP PROHFXODU G\QDPLFV VWXG\ RI LPSDFW IUDFWXUH RI JODVV\SRO\PHUV ,, 0LFURVFRSLF RULJLQV RI VWUHVVHV LQ HODVWLFLW\ \LHOGLQJ DQG VWUDLQ KDUGHQLQJ 3RO\PHU 207  KWWSVGRLRUJMSRO\PHU



͙ .D]XVKL )XMLPRWR 0RWRKLUR )XNDL 5\R 8UDQR :DWDUX 6KLQRGD 7HWVX\D ,VKLNDZD .DWVXPL 2PDJDUL<DVXKLWR 7DQDND $WVXVKL 1DNDJDZD 6XVXPX 2ND]DNL )UHH HQHUJ\ SURILOH RI SHUPHDWLRQ RI (QWHFDYLUWKURXJK+HSDWLWLV%YLUXVFDSVLGVWXGLHGE\PROHFXODUG\QDPLFVFDOFXODWLRQ3XUH$SSO&KHP92    KWWSVGRLRUJSDF

͙ 58UDQR:6KLQRGD1<RVKLLDQG62ND]DNL([DFWORQJUDQJH&RXORPELFHQHUJ\FDOFXODWLRQIRUQHWFKDUJHGV\VWHPVQHXWUDOL]HGE\XQLIRUPO\GLVWULEXWHGEDFNJURXQGFKDUJHXVLQJIDVWPXOWLSROHPHWKRGDQG
LWV DSSOLFDWLRQ WR HIILFLHQW IUHH HQHUJ\ FDOFXODWLRQ - &KHP 3K\V 152    
KWWSVGRLRUJ



0.LWDEDWD77DGGHVHDQG62ND]DNL:HWWDELOLW\RID3RO\ YLQ\OLGHQHIOXRULGH 6XUIDFHE\D3XUH*RRG
6ROYHQW DQG D *RRG 6ROYHQW1RQVROYHQW 0L[WXUH $OO$WRP 0ROHFXODU '\QDPLFV 6WXG\ /DQJPXLU 36  KWWSVGRLRUJDFVODQJPXLUE

͙ 1 <RVKLL < $QGRK DQG 6 2ND]DNL )DVW PXOWLSROH PHWKRG IRU WKUHH̺GLPHQVLRQDO V\VWHPV ZLWKSHULRGLF ERXQGDU\ FRQGLWLRQ LQ WZR GLUHFWLRQV - &RPSXW &KHP 41 
KWWSVGRLRUJMFF

- 152 -

 













Analysis of adsorption mechanism of heavy metal ionsin aqueous solutions on activated carbon
¹ŝ 

1 ŪųťţÎņ ƏǨĆîÕÜǩ

â

6'*V *ě7:9Ł+,ĩ4ǈƛ)Ʃǡ&%9

8{&4ǈǊëŃĶÂǡ,ĥĉ)ƞńł37:Ý&Ź$Ǧªř)ǈǊëǔ±Ň'%ňĊŐ*69½Ũ¢ǘŇĈŜ:%½ŨhEYPg,ĭ"yħ&

L@V(Jm_>@VƕǞ+ǛÙǚ)*½Ũ9ƞħ,ǂč:%

)



+

% 3EňĊŐ+Jm_>@VƕǞ*½

9 ÿJoua+ƓŪų*

+ŧǑĊ< +6$% ¥*68ƨħ!>@ǭƴ7Ũ9'<Ï¾%8

9

@Ds(3E),ƴ7¢Ùpbo*9Ʀž)½ŨhEYPg+

&įŪų&,¢Ù«¨Ü(0')MfkpuMls*68 ŐŽžÚ+}

Ǌë@Ds½ŨĖ«*$%¢Ùpbo+ķơ<Ɠ#!

7* ƕǞw&+½Ũư+ImOQučǎ*Ǒ9ŢêƩǡ'%Ƒŀŧ7+¢Ù½Ũ+ƞĴ<Ɠ)#!

FO¢ǘtƯƒ5ƟØ´Ĉ)(*%

MOTg{*ÛÉ9ŁƑŀ½Ũ§tƟØ*½Ũ

9'ƛÅ&ĽƉ<ǒá2!,ƿ9'ũ7:%9+ŁƑŀ½ŨŚƬ<śƞ9!3+ÍŬţŪų,ǝó*ǈƛ&ŐŽİģ.+ŁƑŀ½Ũ*$

%

ǧǋ¬ú

žÚĂ¢ò

Ýß!ĊƉ<ą9!3*
9 Ď

ÇƕǞ.

+ŪųJoua&,:2&*½Ũŋú+āǟ*$%àǤţ)ķơ<Ɠ)#![2] +ƀĵ Ł¢Ù,ÞƉÍ<Ʊő'!ŁImOQu<Āč9'&½ŨƿƓ +ImOQučǎ*,ŋúǝó*ǈƛ)ÅÙ&9'ƀƫ!

OQučǎǁů<æƬ'!Ūų,ŚÉ2&*Ï¾,)
&,MD MfkpuMls<Ŝ)7ŁƑŀ½ŨƿƓ*+ŋúÛĊ+Ï¾4)

Im

&įŪų

%ŐŽwÞƉÍ.+ŁƑŀ½ŨĖ«6-ŋúÛĊ*$%ķơ

! ½Ũŋú 263 - 328 K +ŋúÌ*9Jm_>@VÍùǞ6-Jm_>@VĹƽw*ƣƇ!ÞƉ
Í.+Ł¢ÙĖ«<ƻƳ9'&2 ŪųĤŇ

½ŨŋúŁImOQučǎ*³1āǟ*$

%Ƥ!

ƠŷĤŇ

0' MfkpuMls, *520$&6 \SKuN<Ŝ! ǛƞưŁōŉź+Ơŷ, . + 197?sLs`o&àƓ!
s'% &O2!, 12<

ōØ+Ł* 63&( iUo<ǅŜ½Ũư+Ǌë@Ds* 3E

7*½Ũ§'%ǝƐǛŐŽ°Ù7č9Jm_>@V  QPî QP +Jm_BsMuV< ] ƶĤ»* $% Ë&  ìŲìûļ<Çß <Ŝ!
QP +ǐǕ<EAsQu@DžÚ'Ɯŵ%!

Jm_>@V+  ìť'  ìť*

QPîQPî] Jm_>@V¯  žÚô QP +Mfkpu

MlscSIO+ [\] ƶ{Ö*Jm_>@V<ǇƇŴǖ* PRO/ +Ǌë@DsŁōŉ<Ō!!ŗ

Č<£ĬĹƽ'! ǝƀ¸ŧ~Ŝ, /HQQDUG-RQHV /- dTsMjo' &RXORPE dTsMjo+À'¨Ð\mhuQ'% 3E*, /L 7>@+°Ù*$%, *52026 $ +<::Ŝ!

àŴǐ+ŧ~ŜESVD_­Ă, QP '! CZoHuĩè¬ă* SV +öƔ¬<Ɠ#!ă ƞĴ
Ŝ'%¸Ơ QV + 0' MfkpuMls<Ɠ#!

- 153 -

Ƒŀŧ+½Ũ+ 0' Ơŷ, . + 197 ?sLs`o&àƓ! ŧ~Ŝ+Ơŷ*,Ơŷ¨Ð,
23/6$$ <Ŝ!
! ®v+Ĳ[ \ ] Ĥ»*¿ĬÑşĲ<ǅŜàŴǐ+ŧ~ŜESVD_­Ă<  QP '!8 ¸Ơ  QV 4,:w+½ŨĖ«<Ɲå! Ł¢Ù+¨Ð*,óŋƸ+

ǣÀƑŀ<ĿƷţ6Ś9'+Ï¾

9 63& iUo<ęŜ!

½Ũ§')9Jm_>@V, 

QP   QP +Jm_BsMuV< ] ƶĤ»* $% Ë&  ìŲì9'&Ĺč!
, -RHJH 7+EocGMÍ

]WqGMÍiUo+  ŰǢ<ęŜÞƉÍ\mhuQ

wǆJm_>@Vì{Ö*  ǇƇ

+Jm_>@VĹƽ< QP  QP  ]QP +MfkpuMlscSIOùǆ*ǇƇ!

ƑŀÈ*9äú*ŧÿ9Ġ+Ł¢Ù<MfkpuMlscSIO*msRg&ǇƇ!
ǣÀƑŀÈĸ3%)9  . *Ǔ8ǣÀƑŀÈ+  '!

!

:

!"

«Ă¢òǑĠ 5') *69ƞĴ<Ɠ

9Ĩ¤*9 5') ƞĴƀĵ,ImOQuL@P+Ƥ<Ɠ#!

ǣÀ¦ă  OTSa¢+UuQ<öÊ:+½Ũŋú*9ImOQuL@P,ŧæÈ  <Ƣǌ!Ĩő<đ¡!&öÊ<µ8Ƥ!

3

Ūųčĵ
2 ǛƞưŁōŉź&+čĵ*$%½Ũư* 3E

* &O' 12<::Ŝ

EAsQu@Ds!!Ă  QP *%ƺ/9 žÚ

%MfkpuMls<Ɠ)LJ * 3E' &O12@Ds+žÚŏú+ſ#!

ĨÓ¬<ŭ ?YDs &O&9Ð¸ 3E' &O,

*žÚŏú*0'=(Ó¬Œ[oIǆ'ž

Ú+@Dsŏú,Ó¬)#! vĤ ?YDs
12&9Ð¸, 3E6- 12+ŏúĄQV ſǁĨ*,!

ú+Ż  ')8













 ! žÚ+@Dsŏú,£Ĭŏ

)LJ žÚ@DsŏúÓ¬ žÚĂ QPžÚÔ[oIŏú684Ǧ)#)LJ * QV 7 QV *9žÚ@Ds+] Ĥ»ǨJm_BsöǞ*æ9ŇƃĤ»ǩ+öÊÛ12,žÚƕǞƸ+ÛÉūřǦ žÚƕǞ*½Ũ%9';9 :,č:9'*68 

Éūř¢ò<ŭ &O,žÚ&vĺ*ÛÉ9



 
 



9 &O'ĿƷ

%Jm_>@VƕǞ'+ü¨ţ)¢Ùǐŧ~Ŝ



 









12  °Ù&Ĺ®°Ù@Ds&

!





*wĦ


 
 
 











)LJ žÚ+@DsöÊÛÉūř¢òǨQVǩ<ĕ$'*69'ƈ7:9 7*, 3E+ÛÉūř¢ò,EAsQu@Ds+āǟ<þ¶9'¢#! EAsQu@Ds &O+'žÚ&vĺ* 12+'Jm_>@VƕǞƸǆ* 3E¢ò! EAsQu@Ds 12+' 3E+ÛÉūř^uI, 12684Jm_>@VƕǞ7Ǆ
Ƈ*ÛÉ9'73E,Jm_>@VƕǞ*½Ũ! 127þǜǛü¨<¶ǛƐƘ9ŗČ& 12<9'*68Jm_>@VƕǞ*½Ũ9'ŭÁ:!
3E&O ōŉ' 3E 12  ōŉ<Ŝ<:

:żŁ*ōƞ%

Ơŷ*æĈ9àǤ'% ŰǢ+ñƮňĊŐ*æ9öƔ½ŨƥǤ<Ɠ#!

 PJ/ +ōŉ<ƪġ!

- 154 -



3E&O ' 3E 12 ·ōŉ  P/ < 33 ƙǄŅŸ*ñƮňĊŐ

J'*: . +ċŋĻ*ƣƇ!qumuËĘŤÃ*68  K ĝĒ9'&öƔ½ŨƥǤ<ƓöƔōŉ'£Ĭōŉ+ōŉŏú< ,&3$(6Ƨçƀ¸amPeŢ¢¢ĴƖƇ*%ńß½Ũǉ<#!

ŷ¡! +ƀĵ 3E&O <Ŝ!'684 3E 12  <Ŝ!'+ 3EǣÀ½ŨǉňĊŐŰ*%Õ)#!

w7ƿ9'ŭÁ:!
ľ*

Jm_>@VƕǞ*½Ũ! 12  3E+Jm_>@VƕǞ.+½Ũ<½Ũŋú  . *Ƒŀŧ+½Ũ&+čĵ*Ǒ%ƺ/9

Ũ'ImOQuĀč< 0' MfkpuMls*68ƪ/!
ǇƇ:!Ł¢Ù,%

EocGMÍ¿Æ.+ŁƑŀ½

MfkpuMlscSIO*msRg*£ĬƠŷǏ×Ż  QV ă* ¢Ùǀ«*68MfkpuMlscSIO<ƋŞ*Ů«$+Ł¢ÙÞƉÍ.+ĚƟÞƉÍ'ŁŽƀ¸<Āč%½Ũ!
7ÞƉÍ.ĚƸ!Ł¢ÙvúŁ¢Ù+½ŨƱ9'ƾƁ%ÞƉÍ*½Ũ!Ł5ÞƉÍ+4+*ĚƟ½Ũ!

ŀŧ½Ũă

+Ł¢Ù*,¢Ùǀ«*68Ĝ7)74ŁŽƀ¸<Ƃĕ)7ÞƉÍ¿Æ6-Jm_BsƕǞ*ŎÞƉÍ'+ǐ*Ł¢Ù<  $wė=&+Ł¢Ù+½Ũ+Ð¸*,Š!

ŁŽƀ¸+ZSVruI<Āč%½Ũ9!3'%¢Ùǀ«*ƊŨ+ǠúǦ)#!

ŀŧ.+ƊŨ,0'=()#!

Ł¢Ù'ÞƉÍ+ǐ*ƚĠ+ÞƉÍ*ŦĚ½Ũ9Ł¢Ù684½Ũ,ý28!"ƊŨ!Ł¢Ù,Jm_>@VƕǞw<ƕǞĔğ+6)hEYPg&Ł¢Ù½Ũ'ƊŨ<Ɔ8ƹ)7Ą

ŧæÈ  +'Āč!ImOQuL@PĩÕ')#!

*ImOQučǎƀĵ+ImOQu,Jm_>@V [\ öǞw&ÞƉÍ'Ǎŗ+ŁŽƀ¸ZSVruI+ĮŶ*Ƈ9Ł¢Ù'+ǈćǐ+Ʋǘ*%ĩÕ  QP ůúǨImOQu*¼2:9Ł¢Ù+Ġ,  ǩ2&  ľţ*čǎ!
!ÄƵǀ«<%9';#!

ƕǞ7+ /- *

ŧ~Ŝ+ãz*68

ÞƉÍ<ƶ'ImOQu+ ] ƶĤ».+L@P,Ł¢Ù.+Jm_>@V2!

Ł¢Ù  ¢Ùůú+Ǧ*Š2#!

ÞƉÍ<]WqGMÍ'!' ImOQučǎǁů*9Ł¢Ù+½ŨĖ«,01ºĺ&
EocGMÍ+Ð¸'š)8Ł¢ÙĠ7)9ImOQu+ƊŨǠƅ*Ɲ7:!

#!ƊŨ!ImOQu,Jm_>@VƕǞw.öǞĔğ%ÞƉÍ.+½ƊŨ<Ɔ8ƹEocGMÍ+''ºĺ*ŧæÈ &ImOQuL@PĩÕ')#!

EocGMÍ']WqGMÍ&ImOQučǎǁů*9Ł¢Ù+½ƊŨĖ«+ǃ

,

EocGMÍ*  ď+ǛƐ¢òŁ¢Ù+ēı¨*ð<z

9+*æ]WqGMÍ,  ď&½Ũ!Ł¢Ù+ÝßĊǨƊŨ+Ǚǩ*ãz%·ÞƉÍ*½Ũ9Ǘ*Ğ¡9½Ũœ+Õè74ħ7&WqGMÍ*æ9½Ũ684Õ)½ŨœĞ¡:9ŁImOQuL@P'½Ũŋú*$

%

9

:,

9'
Ł¢Ù

EocGMÍ.+Ł¢Ù+½Ũ+Ĥ]5') 68·ŋú*9ImOQuL@P6-ĹčŁ¢ÙĠ<ł3!ƀĵ ImOQuL@P,EocGMÍ  ]WqGMÍ'4*½Ũŋú . 7 . .Ò©
 . w*9ImOQuL@P,EocGMÍ&ƎõŊ9*!#%Ò©9'¢#!
é

]WqGMÍ&,ÕŊé!

ƍţ)ŕś½ŨŚƬ,Ũ')9+*æŪųŭ!
'vƌ9½Ũ*

CsQo^uÓ¬ǉƭ&!9'7Ţœįƀĵ,ǥ/'*Ƽ+Ė«<ŭŐŽİģ.+ŁƑŀ½Ũ*
+àǤ7,Ď½Ũŋú

v

0(½+ŪųJoua*68+àǤţ%½Ũŋú<x9'ǣÀ½ŨǉŊé9Ł¢Ù+ǀ«Ċŋú*Û

Qu+L@Pè)9'&%

ImOQuL@P'½Ũ¢ÙĠ+ÒŊ+»,01vƌ!

'

ƀĵ>@

ŋ+Ĥ¢Ù+ǀ«ĊŁImO

ImOQu+¸vƱ8*)8½ŨǉŊé9'ŭÁ:įŪųƀĵ,:<Ɨ94+&9 . w*9EocGMÍ']WqGMÍ*Āč:9ImOQuL@P+ŊéĖ«+ǃ- 155 -,

ÞƉÍŁ¢Ùǐ+ŧ~Ŝ+ǃý*ƱÅ9 ]WqGMÍ+ĤEocGMÍ'Ŀ/%Ł¢Ù'+ŧ~Ŝ!3 ½ŨŋúǦ)8¢Ù+ǀ«ĊÒ'ImOQuL@Pè)9 !" . +']WqGMÍ*½Ũ!¢ÙĠ  . +'684é)#!

:,¢Ù+ǀ«Ċ*ƱÅǦŋ+¢Ù0(ǀ«ĊǦ

OQuL@P'ºImOQu<Āč!'<ŭÁ9')#%ImOQučǎ0' 74ū37:!
ŨŋúwĦ*&!

*4;7ºůú+ImOQuL@P&
!3é)

w68

¢ÙĠ&  . +'+Im

ÞƉÍ.+Ł¢Ù+ĚƸVnFuŁ¢Ù½ƊŨ<Ɔ8ƹ)7īǓL@P+ImOQuĀč9'

½Ũŋú  . 7  . *ŁƑŀ½ŨǉÒ©9'%Āč9ImOQuL@P,Õ)8

àǤ7ą7:!Ŗšţ)ƀĵ< 0' &4½

Ś9'

4 ²ƈĢŘ
[1] $.XURNL0+LURWR<8UXVKLKDUD7+RULNDZD.6RWRZDDQG-5$OFDQWDUD$YLOD$GVRUSWLRQPHFKDQLVPRIPHWDOLRQVRQDFWLYDWHGFDUERQ$GVRUSWLRQ9RO1R
>@7+RULNDZD76KLOLDQJ'''R.6RWRZD-5$OFDQWDUD$YLODDQG'1LFKROVRQ&DUERQ
[3] P. Li, %35REHUWV'.&KDNUDYRUW\DQG.00HU]-UJ. Chem. Theory Comput. 9, 2733, 2013. 5 ŢƕàƄ2!,|ßǨǪǩíį àĳ, Îņ Ə, ¹ŝ  : }Ǌë@Ds+ŐŽžÚ½ŨR@XfIO, ¬ÜïÜøîÕ 2020, 11, 2020 ÷ 12 Ī.
ǨǫǩK. Yoshida: 14N NMR Study on Initial Steps of Hydrothermal Decomposition of Ethylamine and Butylamine inSupercritical Water, IAPWS Annual Meeting 2021, online, Aug. 2021.

6 ¡ŔàƄ2!,|ßǨǪǩQ. K. Loi, T. Horikawa, S. Tan, L. Prasetyo, D.D. Do, and D. Nicholson: Characterization of Cabot BP280 withargon and nitrogen adsorption at temperatures above and below the triple point - Energetic vs Structural Heterogeneities-, Microporous and Mesoporous Materials, 293, 109762, 2020.
ǨǫǩK. Yoshida, H. Yoshioka, N. Ushigusa, M. Nakahara: 14N NMR Evidence for Initial Production of NH3
Accompanied by Alcohol from the Hydrolysis of Ethylamine and Butylamine in Supercritical Water, &KHP/HWW
 
ǨǬǩT. Horikawa, R. Yuasa, K. Yoshida, and D.D Do: Đű{.

- 156 -

ከཎᏊศᏊ࠿ࡽ࡞ࡿ⁐㉁ࡢ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࢆṇ☜࡟ồࡵࡿ OZ ⌮ㄽࡢ㛤ⓎDevelopment of OZ theory for accurate calculation of solvation freeenergy of polyatomic solute‫ۑ‬ᐑ⏣ ❳ᙪ㸦ឡ፾኱㝔⌮ᕤ㸧1◊✲┠ⓗ
RISM ⌮ㄽ࡛ࡣࠊ௚ࡢཎᏊෆ㒊࡟᏶඲࡟ᇙࡶࢀࡓཎᏊ࡟㛵ࡍࡿືᚄศᕸ㛵ᩘࡢグ㏙ࡀ㠀ᖖ࡟ᝏ࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࡢၥ㢟ࢆᨵၿࡍࡿ┠ⓗ࡛ࠊࡇࢀࡲ࡛ᮏ◊✲ᐊ࡛ࡣ AAOZ ἲࡢ㛤Ⓨ࡞࡝ࢆ⾜ࡗ࡚ࡁࡓࠋࡲࡓࠊ
SEB ⿵ṇἲ㸦LJ ࣏ࢸࣥࢩ࡛ࣕࣝ┦஫స⏝ࡍࡿ⣔࡟ᑐࡍࡿࣈࣜࢵࢪ⿵ṇἲࡢࡦ࡜ࡘ㸧ࡢᥦ᱌ࡶ⾜࡞࠸ࠊ༢ཎᏊ⁐㉁࡟ᑐࡍࡿ SEB ࣃ࣓࣮ࣛࢱࡀከཎᏊ⁐㉁࡬ࡶࡑࡢࡲࡲ㐺⏝࡛ࡁࡿࡇ࡜ࢆࡇࢀࡲ࡛࡟ぢฟࡋ࡚ࡁ࡚࠸ࡓࠋࡇ
ࢀࡽࡢ◊✲ࡣ࠸ࡎࢀࡶࠊ⁐㉁ࡀ஧ཎᏊศᏊࡢሙྜ࡟࡜࡝ࡲࡗ࡚࠸ࡓࠋᮏ◊✲࡛ࡣ 3 ಶ௨ୖࡢཎᏊ࠿ࡽ࡞ࡿ⁐㉁ࢆᑐ㇟࡜ࡋ࡚ࠊAAOZ ἲࡢ⢭ᗘ☜ㄆ࡜ SEB ࣃ࣓࣮ࣛࢱࡢ⛣᳜ᛶ☜ㄆࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ⁐፹࡜ࡋ࡚༢ཎᏊ LJ ศᏊࢆ⪃࠼ࠊ⁐㉁࡜ࡋ࡚ࡣỈࠊᅄሷ໬Ⅳ⣲ࠊࢡ࣒ࣟࣟ࣍ࣝࢆ⪃࠼ࡓࠋࡇࢀࡽࡢ⣔࡟ᑐࡋ࡚ AAOZ ⌮ㄽࠊ3D-OZ ⌮ㄽࠊRISM ⌮ㄽࢆ㐺⏝ࡋࡓࠋࡲࡓẚ㍑ࡢࡓࡵࠊศᏊືຊᏛ㸦MD㸧ἲࡲࡓࡣࣔࣥ
ࢸ࢝ࣝࣟ㸦MC㸧ἲࡶᐇ⾜ࡋࡓࠋィ⟬࡟ࡣࡍ࡭࡚⮬సࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ3◊✲ᡂᯝ༢ཎᏊ⁐㉁࡟ᑐࡋ࡚ồࡵࡽࢀ࡚࠸ࡓ SEB ࣃ࣓࣮ࣛࢱ್ࢆࡑࡢࡲࡲ 3D-OZ ⌮ㄽ࡬㐺⏝ࡋࡓ࡜ࡇࢁࠊືᚄศ

ᕸ㛵ᩘࡢ❧ࡕୖࡀࡾ㡿ᇦࡣ MD ἲࡲࡓࡣ MC ἲࡢࡑࢀ࡜㠀ᖖ࡟ࡼࡃ୍⮴ࡋࡓࠋࡑࡢ⤖ᯝࠊHNC ㏆ఝࡸ KH ㏆
ఝ࡜ẚ࡭࡚⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࡢ⢭ᗘࡀ๻ⓗ࡟ᨵၿࡋࡓࠋAAOZ ⌮ㄽࡢືᚄศᕸ㛵ᩘࡣࠊỈ㸦≉࡟Ỉ⣲ཎᏊ࡟ὀ┠ࡋࡓ㸧࡟ᑐࡋ࡚ࡣ࠿࡞ࡾṇ☜࡛࠶ࡗࡓࡀࠊᅄሷ໬Ⅳ⣲ࡸࢡ࣒ࣟࣟ࣍ࣝ࡟ࡘ࠸࡚ࡣᮇᚅࡋࡓ⢭ᗘ࡟⮳ࡽ࡞࠿ࡗࡓࠋAAOZ ⌮ㄽࡣࠊ௚ࡢཎᏊෆ㒊࡟᏶඲࡟ᇙࡶࢀ࡚࠸ࡿཎᏊ࡟ࡘ࠸࡚ࡣ⢭ᗘᨵၿࡀぢ㎸ࡵࡿࡶࡢࡢࠊ
ࡑࢀ௨እࡢཎᏊ࡟ࡘ࠸࡚ࡣࡸࡸ⢭ᗘ࡟ၥ㢟ࡢ࠶ࡿࡇ࡜ࡀศ࠿ࡗ࡚ࡁࡓࠋ࡞࠾ࠊỈࡢỈ⣲ཎᏊ㸦㓟⣲ཎᏊ࡟᏶඲࡟ᇙࡶࢀ࡚࠸ࡿ㸧࡟ᑐࡋ࡚ࠊRISM ⌮ㄽࡣ⁐፹࡜ࡢ┤᥋᥋ゐࢆ♧၀ࡍࡿ㠀≀⌮ⓗ࡞⤖ᯝࢆ୚࠼ࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
௒ᖺᗘ࡟Ꮫ఍Ⓨ⾲ணᐃ㸦᫖ᖺᗘࡣࢥࣟࢼ⚝࡟ࡼࡾⓎ⾲ࢆணᐃࡋ࡚࠸ࡓᏛ఍ࡀᘏᮇࡉࢀࡓ㸧ࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫[ ۻ‬1] T. Miyata, S. Nishida, and Y. Ogasawara, AIP adv., 11 (2021) 025026.
‫[ ۻ‬2] T. Miyata, N. Yabuki, and J. Leung, Chem. Lett., 49 (2020) 1372.
‫[ ۻ‬3] T. Miyata, Chem. Phys. Lett., 755 (2020) 137777.

- 157 -

ගྜᡂ㓟⣲Ⓨ⏕୰ᚰ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࠊ㟁Ꮚ࣭ࢫࣆࣥ≧ែ࠾ࡼࡧ཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical studies of electronic and spin states and reactivity of theCaMn4O5 cluster in the oxygen evolving complex of photosystem II‫ۑ‬ᒣཱྀ ඙㸦኱㜰኱Ꮫࢼࣀࢧ࢖࢚ࣥࢫᩍ⫱◊✲ࢭࣥࢱ࣮㸧ࠊỿ ೺ோࠊ☾㒊 ᐶ㸦ᒸᒣ኱Ꮫ␗ศ㔝ᇶ♏◊✲ᡤ㸧ࠊ୰㇂࿴ᙪ㸦኱㜰኱Ꮫ⏘ᴗ⛉Ꮫ◊✲ᡤ㸧ࠊ⚄㇂ಙኵ㸦኱㜰ᕷ❧኱Ꮫ」ྜ
ඛ➃◊✲ᶵᵓ㸧ࠊᗉྖග⏨ࠊᐑᕝ᫭୍㸦⟃Ἴ኱Ꮫィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮㸧ࠊᕝୖ㈗㈨㸦኱㜰኱Ꮫ⌮Ꮫ◊✲⛉㸧1◊✲┠ⓗኳ↛ගྜᡂࡢỈศゎ཯ᛂࡣග໬Ꮫ⣔ II(PSII)ࡢ㓟⣲Ⓨ⏕୰ᚰ(OEC)࡟࠾࠸࡚ࡣ⾜ࢃࢀࠊኴ㝧ග࢚ࢿࣝࢠ࣮ࢆ฼⏝ࡋ࡚ỈศᏊ࠿ࡽ㟁Ꮚ࡜ࣉࣟࢺࣥࡀྲྀࡾฟࡉࢀࡿ࡜࡜ࡶ࡟ࠊ㓟⣲ศᏊࡀᨺฟࡉࢀࡿ:2H2O + 4hν → O2 + 4H+ + 4e–(1)ᮏ཯ᛂࡣࠊPSII ࡟Ꮡᅾࡍࡿ࣐ࣥ࢞ࣥࢡࣛࢫࢱ࣮(CaMn4O5)
࡛ゐ፹ࡉࢀࠊKok ࢧ࢖ࢡࣝ࡜࿧ࡤࢀࡿ 5 ẁ㝵ࡢࢫࢸࢵࣉ
(S0-S4)ࢆ⤒࡚㐍⾜ࡍࡿ(ᅗ 1)ࠋ
ᮏ◊✲ࡣ 2011 ᖺ࡟ᱵྡࡽ࡟ࡼࡾⓎぢࡉࢀࡓ S1 ≧ែࡢ OECࡢ㧗ศゎ⬟ X ⥺ᅇᢡ(XRD)ࡢᵓ㐀[1]࡟❧⬮ࡍࡿࡶࡢ࡛࠶ࡾࠊ

ᅗ1

Kok ࢧ࢖ࢡࣝ

2015 ᖺ௨㝆࡛ࡣ S1 ≧ែ௨እࡢ‽Ᏻᐃ≧ែ࡟ᑐࡋ࡚ࡶࣇ࢙࣒
ࢺ⛊⮬⏤㟁Ꮚ࣮ࣞࢨ࣮(XEFL)࡟ࡼࡾࠊࡑࡢᵓ㐀ኚ໬ࢆほࡉࢀࡿࡼ࠺࡟࡞ࡾ OEC ࡢ཯ᛂᶵᵓࡢゎ᫂ࡀᐇ㦂࠿ࡽ࡛ࡶ㐍ࡵࡽࢀ࡚࠸ࡿࠋ୰࡛ࡶ S2 ≧ែ࠿ࡽ S3 ≧ែ࡛᪂ࡋࡃᤄධࡉࢀࡿỈศᏊ⏤᮶ࡢ㓟⣲ཎᏊ O(6)࡜ CaMn4O5
ࢡࣛࢫࢱ࣮ࡢ O(5)ཎᏊ࡜ࡢ O(5)-O(6)㛫㊥㞳ࡣ㓟⣲Ⓨ⏕ࡢ⤖ྜᙧᡂ࡜῝ࡃ㛵㐃ࡀ࠶ࡾ≉࡟㔜せ࡜࡞ࡿࠋ2017 ᖺࡢ
Ⳣࡽࡢ S3 ≧ែ࡛ࡢ O(5)-O(6)㛫㊥㞳ࡣ 1.5 Å ࡛࠶ࡾࠊ⤖ྜྍ⬟ᛶࢆ♧၀ࡍࡿࡶࡢ࡛࠶ࡗࡓ[2]ࠋ୍᪉ࠊ2018 ᖺ࡟
Kern ࡽ࡟ࡼࡾⓎぢࡉࢀࡓ XEFL ࡢᵓ㐀࡛ࡣ O(5)-O(6)㛫㊥㞳ࡣ 2.1 Å ࡛࠶ࡾ S3 ≧ែ࡛ࡢ O(5)-O(6)ࡢ⤖ྜྍ⬟ᛶࡀ୙ྍ⬟࡞ࡶࡢ࡛࠶ࡗࡓ[3]ࠋ2019 ᖺ࡟Ⳣࡽࡀሗ࿌ࡋࡓ S3 ≧ែ࡛ࡢ O(5)-O(6)㛫㊥㞳ࡣ 1.9 Å ࡛࠶ࡾࠊoxyl-oxo ࢱ࢖ࣉࡢࡶࡢ࡛࠶ࡿ࡜࠸࠺⤖ᯝ࡛࠶ࡗࡓ[12]ࠋࡲࡓࠊIbrahim ࡽ࡟ࡼࡿ᪂ࡓ࡞ XEFL ࡟ࡼࡾࠊS2 ≧ែ࠿ࡽ S3 ≧ែࡢ㑄⛣࡟㛵ࡋ࡚ࠊỈࡢᤄධ㐣⛬࡜࡜ࡶ࡟ S3 ≧ែࡢᵓ㐀࡛ࡢ O(5)-O(6)ࡢ㊥㞳ࡀ 2.2 Å ࡜ሗ࿌ࡉࢀࡓ[4]ࠋX ⥺ᵓ㐀ゎᯒࡢศゎ⬟࡟௜㝶ࡍࡿ୙☜ᐃᛶࡢࡓࡵࠊᚤጁ࡞ᵓ㐀ࡢ┦㐪ࡀ⏕ࡌࡿࠋࡇࢀࡽࡢᐇ㦂⤖ᯝࢆゎᯒࡍࡿࡓࡵ
࡟ᚑ᮶࠿ࡽࠊBroken Symmetry(BS)-ᐦᗘỗ㛵ᩘ⌮ㄽ(DFT)ࡢᡭἲࢆ⏝࠸ࡓ QM ࡸ QM/MM ィ⟬࡟ࡼࡾ OEC ࡢ
CaMn4O5 ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࠊ㟁Ꮚ࣭ࢫࣆࣥ≧ែࠊ཯ᛂ㐣⛬ࡢゎᯒ࡟࠾࠸࡚ BS-DFT ࡢᡭἲࡢ᭷⏝ᛶࢆ♧ࡋ࡚ࡁࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ཯ᛂࡢ┦ᑐ࢚ࢿࣝࢠ࣮ࡢᐃ㔞ⓗ࡞ホ౯࡟ࡣ༑ศ࡛ࡣ࡞ࡃࠊ౛࠼ࡤࠊS3 ≧ែࡢࣁ࢖ࣈࣜ
ࢵࢻ DFT ࡟ࡼࡿゎᯒ࡟ࡼࡾ⌮ㄽⓗ࡟⪃࠼ࡽࢀࡿ୰㛫య㛫ࡢ┦ᑐ࢚ࢿࣝࢠ࣮ࡣ BS-ࣁ࢖ࣈࣜࢵࢻ DFT(HDFT)ࡢィ⟬࡟࠾࠸࡚ Hartree-Fock ᡂศࡢኚ໬࡟ᑐࡋ࡚㠀ᖖ࡟ࢭࣥࢩࢸ࢕ࣈ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓ[5]ࠋᚑࡗ࡚ࠊྛ

- 158 -

୰㛫య(S0-S4)࡟࠾ࡅࡿᵓ㐀␗ᛶయࡢᐃ㔞ⓗ࡞ホ౯࡟ࡣ⤖ྜࢡࣛࢫࢱ࣮ (CC) ἲࡢࡼ࠺࡞ DFT ࢆ㉸࠼ࡓᡭἲࡢᚲせᛶࡀࢃ࠿ࡿࠋ
ᮏሗ࿌᭩࡛ࡣࠊ௨๓ࡼࡾ⾜ࡗ࡚ࡁࡓ኱つᶍ࡞㔞Ꮚ໬Ꮫィ⟬(QM, QM/MM)࡟ࡼࡿ OEC ࡢ཯ᛂ㐣⛬ࡢ⌮ㄽⓗゎ᫂ࢆ┠ⓗ࡜ࡍࡿ࡜࡜ࡶ࡟ࠊDFT ࢆ㉸࠼ࡓᡭἲ࡜ࡋ࡚ᒁᅾ໬ᑐ⮬↛㌶㐨((D)LPNO)࡟ᇶ࡙࠸ࡓ CC ἲ࡛࠶ࡿDLPNO-CC ἲ[6]ࢆ⏝࠸ࡓᵓ㐀␗ᛶయ㛫ࡢ┦ᑐ࢚ࢿࣝࢠ࣮ཝᐦ࡞ẚ㍑ࢆ⾜࠸ࠊᚑ᮶⾜ࡗ࡚࠸ࡓ DFT ࡟ࡼࡿ⤖ᯝ࡜ࡢẚ㍑᳨ウࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬࡟⏝࠸ࡓᵓ㐀ࡣᱵྡࡽࡢ㧗ゎീᗘࡢ S1 ≧ែࡢ XRD ᵓ㐀(PDB ID 3WU2)ࢆ⏝࠸ᅗ 2 ࡟♧ࡋࡓࡼ࠺࡟ࠊ

࣐ࣥ࢞ࣥࡢ㓟໬ᩘ࡜ O(5)ࠊW2ࠊW1ࠊO(4)ࡢࣉࣟࢺࣥ໬≧ែ࡜ࢆኚ໬ࡉࡏࡓᵓ㐀ࢆసᡂࡋࠊྛᵓ㐀࡟ᑐࡋ࡚ࡢ
ᵓ㐀᭱㐺໬ࡣ NWChem ࢆ⏝࠸ࠊQM ィ⟬ࢆᐇ⾜ࡋࡓࠋᵓ㐀᭱㐺໬ࡢᡭἲ࡟ࡣ UB3LYP ࡟ Grimme ࡢ D3 ࢱ࢖ࣉࡢศᩓ⿵ṇࢆຍ࠼ࡓࡶࡢࢆ⏝࠸ࠊᇶᗏ㛵ᩘ࡟ࡣ all-electron ࡢᇶᗏ࡛࠶ࡿ Def2-TZVP ࢆ⏝࠸ࡓ(⣙ 2000 ᇶᗏ)ࠋࡲࡓ⎔ቃຠᯝࢆ COSMO (ㄏ㟁⋡ ε = 8.0) ࡟ࡼࡾྲྀࡾධࢀࡓࠋ᭱㐺໬࡟ࡣྛᵓ㐀࡟ࡘ࠸࡚ࠊ⣙ 100 ࢧ࢖ࢡࣝ⛬ᗘࡢ཯᚟ࡀᚲせ࡜࡞ࡾࠊ406Rh-2 ࢆ୪ิ౑⏝ࡍࡿࡇ࡜࡟ࡼࡾ㧗㏿࡞ィ⟬ࡀྍ⬟࡜࡞ࡗࡓࠋ
┦ᑐ࢚ࢿࣝࢠ࣮ࡢẚ㍑ࡢࡓࡵ HDFT ࡜ DLPNO-CC ࡢᡭἲࢆ⏝࠸ࠊ᭱㧗ࢫࣆࣥ≧ែ (S=15/2) ࡟ᑐࡋ࡚ᇶᗏ
㛵ᩘ࡟ࡣ Def2-TZVP ࢆ⏝࠸࡚ィ⟬ࢆ⾜࠸ (⣙ 2000 ᇶᗏ)ࠊ⎔ቃຠᯝ࡟ࡣ COSMO ࡲࡓࡣ CPCM ࢆ⏝࠸ࡓࠋ
HDFT
࡟ࡣ B3LYP ࡜ࡑࡢࡢ Hartree-Fock ᡂศࢆኚ໬ࡉࡏࡓỗ㛵ᩘࢆ⏝࠸ࠊẚ㍑ࡢࡓࡵ B3LYP-D3 ࡜ࢲࣈࣝ HDFT ࡛࠶ࡿ B2PLYP ࢆ⏝࠸ࡓࠋDLPNO-CC ࡢィ⟬࡟ࡣ DLPNO-CCSD ἲ࡜ DLPNO-CCSD(T0)ἲࢆࡑࢀࡒࢀ PNO ࡢ㜈್ࡢ᮲௳ࢆኚ໬(Normal ࡜ Tight)ࡉࡏホ౯ࡋࡓࠋࡲࡓࠊDef2-SVP ࡢᇶᗏ㛵ᩘࢆ⏝࠸࡚ࠊTZVP ࡢᇶᗏ࡜ඹ࡟
CBS ࡢእᤄࢆ⾜ࡗࡓ⤖ᯝ࡜ࡢẚ㍑ࡶ⾜ࡗࡓࠋࡲࡓࠊྛ≧ែ࡟ࡘ࠸࡚୰㛫ࢫࣆࣥ≧ែࢆ DFT (B3LYP) ࡛ồࡵࠊࣁ࢖ࢮࣥ࣋ࣝࢡࢫࣆࣥࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸࡚ࠊ☢Ẽⓗᛶ㉁ࡢゎᯒࡶ⾜ࡗࡓࠋDFT ࡢィ⟬࡟ࡣ NWChem ࢆ⏝࠸ࠊDLPNO-CC ἲ࡟ࡣ ORCA4 ࡢࣉࣟࢢ࣒ࣛࢆ OpenMPI3 ࡛୪ิฎ⌮ࡉࡏࡿࡼ࠺࡟ࡋ࡚౑⏝ࡋࡓࠋDLPNO-CC ィ⟬࡟ࡣከᩘࡢ࣓ࣔࣜ࡜ࢫࢡࣛࢵࢳࣇ࢓࢖ࣝࡢ㧗㏿࡞ㄞࡳ᭩ࡁࡀᚲせ࡜࡞ࡿࡓࡵࠊ኱ᐜ㔞ࡢ࣓ࣔࣜࢆ✚ࢇࡔ 110Rh-1 ࡢ౑⏝࡟ࡼࡾ㧗㏿࡞ィ⟬ࡀྍ⬟࡛࠶ࡗࡓࠋ

ᅗ2

PSII ࡢ OEC ࡟࠾ࡅࡿ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢィ⟬ࣔࢹࣝࠋ(II, III, IV, IV)࡜(III, III, III, IV)ࡢࣂࣞࣥࢫ≧ែ࡟ࡘ࠸࡚ 4 ࡘࡢྍ⬟ᛶࡢ࠶ࡿ≧ែࢆᶍᘧⓗ࡟♧ࡋ࡚࠸ࡿࠋ

- 159 -

3◊✲ᡂᯝOEC ࡢ࣐ࣥ࢞ࣥࡢ㓟໬≧ែࡣ High-valent ࡞㓟໬≧ែࢆ௬ᐃࡋࠊ࣐ࣥ࢞ࣥࡢ≧ែࡀ(II, III, IV, IV)࡜࡞ࡿ≧ែ࡜(III, III, III, IV)࡜࡞ࡿ≧ែ࡟ࡘ࠸࡚ࡑࢀࡒࢀ⌮ㄽⓗ࡟ྍ⬟࡞୰㛫యࡢ࢚ࢿࣝࢠ࣮ẚ㍑ࢆ⾜ࡗࡓࠋᮏሗ࿌᭩࡛
ࡣࠊKok ࢧ࢖ࢡࣝࡢ S0 ≧ែ[10]ࡢ⤖ᯝ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ
ᅗ 3 ࡟ᚓࡽࢀࡓᵓ㐀࡟ࡘ࠸࡚ᅗ♧ࡋࡓࠋᅗ 3 ࡢ(C)ࡣ(Mn1, Mn2, Mn3, Mn4)= (III, IV, IV, II)ࠊ(D)ࡣ(Mn1, Mn2,
Mn3, Mn4)= (II, IV, IV, III)ࠊ(E)ࡣ(Mn1, Mn2, Mn3, Mn4)= (III, IV, III, III)ࠊ(F)ࡣ(Mn1, Mn2, Mn3, Mn4)= (III, III, IV, III)ࡢࣂࣞࣥࢫࡑࢀࡒࢀࡶࡘࡶࡢ࡛࠶ࡿࠋࡇࡇ࡛ࠊO(5)=XࠊW2=YࠊW1=ZࠊO(4)=W ࡢࣉࣟࢺࣥ໬≧ែࢆ O2– = aࠊ
OH– = bࠊH2O = c ࡜グࡋ࡚ࠊྛ≧ែࢆ S0XYZW ࡜ࡋ࡚࠸ࡿ(ᅗ 2 ཧ↷)ࠋ᭱㐺໬ࡋࡓᵓ㐀࡟ࡘ࠸࡚ホ౯ࡍࡿ࡜ࠊ(II,III, IV, IV)ࡢࣂࣞࣥࢫࢆᣢࡘ C ≧ែ࡜ D ≧ែ࡛ࡣ Ca ᵓ㐀࡜ Da ᵓ㐀ࡣ R-open (㛤࠸ࡓ࢟ࣗࣂࣥᵓ㐀) ࡟┦ᙜࡍࡿࡶࡢ࡜⌮ゎࡉࢀࡿࠋ୍᪉ࠊCb ᵓ㐀࡜ Db ᵓ㐀ࡣ࣐ࣥ࢞ࣥ㛫ࡢ㊥㞳ࡀᑠࡉࡃ࡞ࡗ࡚࠾ࡾࠊXFEL ࡢ⤖ᯝ࡜␗࡞

ᅗ3

PSII ࡢ OEC ࡟࠾ࡅࡿ Kok ࢧ࢖ࢡࣝࡢ S0 ≧ែ࡛ࡢ UB3LYP-D3 / Def2-TZVP ࡟ࡼࡿྍ⬟࡞୰㛫యࡢ᭱㐺໬ᵓ㐀ࠋ(Mn1,Mn2,Mn3,Mn4)࡟ࡘ࠸࡚ C ࡣ(3442)ࠊD ࡣ(2443)ࠊE ࡣ(3433)ࠊF ࡣ(3343)
ࡢࣂࣞࣥࢫࢆࡑࢀࡒࢀᣢࡘࠋ

- 160 -

ࡿࡶࡢ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡿࠋ(III, III, III, IV)ࡢࣂࣞࣥࢫࢆᣢࡘ E ᵓ㐀࡜ F ᵓ㐀ࡣ࠸ࡎࢀࡶ R-open ࡢᵓ㐀ࢆ୚࠼࡚࠸ࡿࠋEb ࡢᵓ㐀ࡣ XFEL ࡢ⤖ᯝ࡟୍⮴ࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋ୍᪉ࠊFb ᵓ㐀ࡣ XFEL ࡜␗࡞ࡿࡶࡢ࡜࡞ࡗ
࡚࠸ࡿࠋEa ≧ែ࡜ Fa ≧ែ࡛ࡣ Jahn-Teller ຠᯝ࡟ࡼࡾ Mn4-O5 㛫ࡢ⤖ྜࡀఙࡧ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋ୍᪉ࠊEb≧ែ࡜ Fb ≧ែ࡛ࡣ Mn4-O4 㛫ࡢ㊥㞳ࡀఙࡧ࡚࠸ࡿ࡜⌮ゎ࡛ࡁࡿࠋᚑࡗ࡚ Jahn-Teller ṍࡢ㍈ࡣ O5 ཎᏊࡲࡓࡣ
O4 ཎᏊࡢࣉࣟࢺࣥ໬≧ែ࡟౫Ꮡࡍࡿࡇ࡜ࡀศ࠿ࡿࠋ୍᪉ࠊEc ≧ែ࡜ Fc ≧ែࡣ O4 ཎᏊ࡜ O5 ཎᏊࡢࣉࣟࢺࣥ໬
࡟ࡼࡾ Mn3-Mn4 㛫ࡢ㊥㞳ࡀఙࡧ࡚࠾ࡾ XFEL ࡢᵓ㐀࡜ࡣ୍⮴ࡋ࡞࠸ࠋᅗ 4ࠊ5 ࡣࡑࢀࡒࢀ S0bbcb(3433) (Ec)≧ែࡢ࢚ࢿࣝࢠ࣮ࢆᇶ‽࡜ࡋ࡚ẚ㍑ࡋࡓࡶࡢ࡛࠶ࡿࠋᅗ 4 ࡣ HDFT ࠾ࡼࡧࢲࣈࣝࣁ࢖ࣈࣜࢵࢻ DFT ࡛࠶ࡿ B2PLYP ࡢᡭἲࢆ⏝࠸࡚ẚ㍑ࡋࠊᅗ 5 ࡣ DLPNO-CCSD ἲ࡜ T ࡢᦤືࢆධࢀࡓ DLPNO-CCSD(T0)ἲ࠾ࡼࡧ T ࡢᦤືࢆ཯᚟ⓗᡭἲ࡟ࡼࡾධࢀࡓ DLPNO-CCSD(T)ἲ࡟ࡼࡾẚ㍑ࡋࡓࡶࡢ࡛࠶ࡿࠋHDFT ࡢ⤖ᯝ࡛ࡣ(III, III, III, IV)ࡢࣂࣞࣥࢫࢆᣢࡘ S0bbcb(3433) (Ec)≧ែࡀ᭱ࡶᏳᐃᛶ࡞୰㛫య࡛࠶ࡿࡇ࡜ࡀ♧ࡉࡓࠋࡲࡓࠊྠࡌࣂࣞࣥࢫ≧ែࡢ S0bbcb(3343) (Fb)≧ែ࡜ࡢ࢚ࢿࣝࢠ࣮ᕪࡶᑠࡉ࠸ࡇ࡜ࡀุ᫂ࡋࡓࠋ
୍᪉ࠊ(II, III, IV, IV)ࡢࣂࣞࣥࢫࢆᣢࡘ D ࡢ≧ែࡣࡑࡢ࢚ࢿࣝࢠ࣮ࡢ୙Ᏻᐃࡉ࠿ࡽ S0 ≧ែࡢ୰㛫య࡜ࡋ࡚⌧ࢀࡿࡇ࡜ࡣ㞴ࡋ࠸࡜ᛮࢃࢀࡿࠋࡲࡓࠊྠࡌࣂࣞࣥࢫ≧ែࡢ C ≧ែࡶ Ec ≧ែ࡜ẚ㍑ࡋ࡚୙Ᏻᐃ࡛࠶ࡿࡇ࡜ࡀศ࠿
ࡿࠋᚑࡗ࡚ࠊHDFT ࡟ࡼࡿ⤖ᯝ࡛ࡣᚑ᮶ࡢ⤖ᯝ࡜ྠᵝ࡟ S0 ≧ែࡢ୰㛫య࡜ࡋ࡚(III, III, III, IV)ࡢࣂࣞࣥࢫࢆᣢ
ࡘᵓ㐀ࢆ࡜ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࢲࣈࣝࣁ࢖ࣈࣜࢵࢻ DFT ࡢ⤖ᯝ࡛ࡣ(II, III, IV, IV)ࡢࣂࣞࣥࢫࢆ
ᣢࡘ Cb ≧ែ࡜ Ec ≧ែ࡜ࡀ࡯ࡰ⦰㏥ࡍࡿ࢚ࢿࣝࢠ࣮ᕪ࡜࡞ࡾࠊ㟁Ꮚ┦㛵ࡢຠᯝ࡟ࡼࡿ␗࡞ࡿࣂࣞࣥࢫࢆᣢࡘ
≧ែ㛫ࡢ┦ᑐᏳᐃᛶ࡬ࡢᙳ㡪ࡣ⯆࿡῝࠸࡜ࡇࢁ࡛࠶ࡿࠋ

ᅗ3

PSII ࡢ OEC ࡢ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢ S0 ≧ែࡢ 10 ᵓ㐀࡟ᑐࡍࡿ HDFT ࡜ DHDFT ࡢィ⟬࡟ࡼࡿ┦ᑐ࢚ࢿࣝࢠ࣮ࠋDLPNO-CC ࡢ⤖ᯝ࡛ࡣࠊHDFT ࡢᡭἲ࡛ᚓࡽࢀࡓ⤖ᯝ࡜ྠᵝ࡟(III, III, III, IV)ࡢࣂࣞࣥࢫࢆᣢࡘ Ec ≧ែࡢᏳᐃᛶࡀ♧ࡉࢀࡓࡀࠊ(II, III, IV, IV)ࡢࣂࣞࣥࢫࢆᣢࡘ Cb ≧ែࡣ DFT ࡢ⤖ᯝ࡜␗࡞ࡾࠊ10 ࡢ␗ᛶయࡢ୰࡛᭱
᭱ࡶᏳᐃ࡞ᵓ㐀࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢഴྥࡣ B2PLYP ࡟ࡼࡿ⤖ᯝ࡟ࡶ⌧ࢀࡿࡶࡢ࡛࠶ࡗࡓࠋ≉࡟࢚ࢿࣝࢠ
࣮ᕪࡢᑠࡉ࠸ Ec ᵓ㐀࡜ Cb ᵓ㐀࡜ࡢ┦ᑐᏳᐃᛶ࡟ࡘ࠸࡚ࠊࢺࣜࣉࣝ ζ ࡜ࢲࣈࣝ ζ ࡢᇶᗏ㛵ᩘࢆ⏝࠸࡚ CBS እ- 161 -

ᅗ3

PSII ࡢ OEC ࡢ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢ S0 ≧ែࡢ 10 ᵓ㐀࡟ᑐࡍࡿ DLPNO-CCSD ࡜DLPNO-CCSD(T)ࡢィ⟬࡟ࡼࡿ┦ᑐ࢚ࢿࣝࢠ࣮ࠋ
ᤄࢆ⾜࠸ぢ✚ࡶࡗࡓࠋEc ≧ែࢆᇶ‽࡜ࡋࡓ┦ᑐ࢚ࢿࣝࢠ࣮ࡣ DLPNO-CCSD(T0)ἲ࡟ࡘ࠸࡚ࡑࢀࡒࢀ -2.05(-0.97) kcal/mol ࡜࡞ࡾࢺࣜࣉࣝ ζ ࡢᇶᗏ㛵ᩘ࡟ࡼࡿ⤖ᯝ࡜ྠᵝࡢഴྥࢆ♧ࡋࠊCb ≧ែࡀ᭱Ᏻᐃ≧ែ࡛࠶ࡿࡇ
࡜ࢆ♧ࡋࡓࠋ(ࡇࡇ࡛࢚ࢿࣝࢠ್࣮ࡣ NormalPNO ࡢ㜈್ࢆ⏝࠸ࡓ⤖ᯝࢆ♧ࡋ࡚࠾ࡾࠊᣓᘼෆࡣ TightPNO ࡢ㜈್ࢆ⏝࠸ࡓ⤖ᯝ࡛࠶ࡿࠋ)⾲ 1ࠊ2 ࡣ UB3LYP ἲ࡟ࡼࡾồࡵࡓ J ್ࢆࡶ࡜࡟ཝᐦᑐゅ໬࡟ࡼࡾồࡵࡓᑕᙳᅉᏊ࡜ᇶᗏ≧ែ࡜➨୍ບ㉳≧ែ࡜ࡢ࢚ࢿࣝࢠ࣮ᕪࢆࡲ࡜ࡵ࡚࠶ࡿࠋS0 ≧ែࡢ EPR ࢫ࣌ࢡࢺࣝࡣ஧㔜㡯 (S = 1/2) ≧ែࡢᏑᅾࢆ♧ࡋ࡚࠸ࡿࠋ
ึᮇࡢ EPR ࡢᐇ㦂࡛ࡣ S = 1/2 ≧ែ࡜ࡋ࡚(II, III, IV, IV)ࡢࣂࣞࣥࢫ(௒ᅇࡢ⤖ᯝࡢ C ≧ែ)࡟࢔ࢧ࢖ࣥࡉࢀࡿ⤖ᯝࡀᚓࡽࢀ࡚࠸ࡿࠋ୍᪉ࠊ᭱㏆ࡢ EPR ࡢ⤖ᯝࡣ S = 1/2 ≧ែ࡜ࡋ࡚(III, III, III, IV)ࡢ≧ែࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠸
ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ⾲ 2 ࠿ࡽࢃ࠿ࡿࡼ࠺࡟(III, III, III, IV)ࡢࣂࣞࣥࢫ≧ែ(E ≧ែ࠾ࡼࡧ F ≧ែ)࡛ࡣ S = 1/2 ≧ែࡼࡾࡶ㧗࠸ࢫࣆࣥ≧ែࡢࡶࡢࡀᏳᐃ≧ែ࡜ࡋ࡚ᚓࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊCaMn4O5 ࢡࣛࢫࢱ࣮ࡢపࢫ
⾲ 1.

(II, III, IV, IV)≧ែࡢཝᐦᑐゅ໬࡟ࡼࡿᇶᗏ≧ែࠊ➨୍ບ㉳≧ែ࡜ᑕᙳᅉᏊ

Systems

State

Energy

ρ1

ρ2

ρ3

ρ4

Ca: S0bcca(3442)

1/2

0.00

–0.681

0.346–0.996

2.331

3/2

16.4

0.660

–0.327–0.499

1.165

1/2

0.00

–1.1791.567–0.048

0.660

3/2

14.5

–0.390

0.686

0.382

0.322

5/2

0.0

–0.672

0.435

0.491

0.747

7/2

57.3

–0.128

0.260

0.331

0.538

5/2

0.00

–0.494

0.341

0.359

0.793

7/2

15.1

–0.027

0.232

0.226

0.569

Cb: S0accb(3442)

Da: S0bcca(2443)

Db: S0accb(2443)- 162 -

ࣆࣥ࡜୰㛫ࢫࣆࣥ≧ែࡢᏳᐃᛶࢆヲ⣽࡟㆟ㄽࡍࡿࡓࡵ࡟ࡣࠊከཧ↷(MR)ࡢᡭἲ࡛࠶ࡿ MRCC ἲࡸ᏶඲άᛶ✵㛫(CAS)ἲ࡟ᇶ࡙࠸ࡓ᪉ἲ࡞࡝ࡀᚲせ࡜࡞ࡿࠋࡇࢀࡽࡢᡭἲࢆ⏝࠸ࡓヲ⣽࡞ゎᯒࢆ௒ᚋࡢㄢ㢟࡜ࡋࡓ࠸ࠋ
ࡲࡓࠊ᭦࡞ࡿᐃ㔞ⓗ࡞ホ౯࡟ࡣ CaMn4O5 ࢆྲྀࡾᅖࡴỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡸࢱࣥࣃࢡ㉁ࢆྵࡵࡓ S0 ≧ែࡢ኱つᶍィ⟬ࡀᚲせ࡛࠶ࡿࠋ⾲ 2.

(III, III, III, IV)ࡢ≧ែࡢཝᐦᑐゅ໬࡟ࡼࡿᇶᗏ≧ែࠊ➨୍ບ㉳≧ែ࡜ᑕᙳᅉᏊ

Systems

State

Energy

ρ1

ρ2

ρ3

ρ4

Ea: S0bcca(3433)

9/2

0.00

0.401

–0.256

0.413

0.442

7/2

26.5

0.291

–0.297

0.513

0.493

7/2

0.00

–0.359

0.312

0.477

0.571

5/2

25.3

–0.335

0.227

0.431

0.627

7/2

0.00

0.293

–0.268

0.510

0.464

9/2

1.89

0.394

-0.244

0.406

0.444

7/2

0.00

–0.426

0.556

0.381

0.489

9/2

15.3

–0.084

0.433

0.286

0.365

15/2

0.00

0.267

0.267

0.200

0.267

13/2

55.7

0.198

0.290

0.209

0.303

7/2

0.00

–0.430

0.554

0.376

0.500

9/2

19.7

–0.088

0.429

0.277

0.382

Eb: S0accb(3433)

Ec: S0bbcb(3433)

Fa: S0bcca(3343)

Fb: S0accb(3343)

Fc: S0bbcb(3343)

ཧ⪃ᩥ⊩[1] Y. Umena et al., Nature, 473, 55-60 (2011). DOI: 10.1038/nature09913.
[2] M. Suga et al., Nature, 543, 131-135 (2017). DOI: 10.1038/nature21400.
[3] J. Kern et al., Nature, 563, 421-425 (2018). DOI: 10.1038/s41586-018-0681-2.
[4] M. Ibrahim et al., Proc. Natl. Acad. Sci. U.S.A., 117, 12624-12635 (2020). DOI: 10. 10.1073/pnas.2000529117.
[5] H. Isobe et al., Inorg. Chem., 55, 502-511 (2016). DOI: 10.1021/acs.inorgchem.5b02471.
[6] M. Saitow et al., J. Chem. Phys., 146, 164105 (2017). DOI: 10.1063/1.4981521.

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃᒣཱྀ ඙, ᕝୖ㈗㈨, ᐑᕝ᫭୍, Ỉศゎ཯ᛂᶵᵓࡢ⌮ㄽゎᯒ㸸M=O ⤖ྜࡢᵓ㐀࡜཯ᛂᛶ෌ゼ, ➨ 3 ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘, 2021.1.22-1.23, Online (Oral) [᪂Ꮫ⾡㡿ᇦ◊✲ࠕගྜᡂศᏊᶵᵓࡢᏛ⌮ゎ᫂࡜᫬✵㛫ไᚚ࡟ࡼࡿ㠉᪂ⓗග ̿ ≀㉁ኚ᥮⣔ࡢ๰〇ࠖ].
T. Kawakami, K. Miyagawa, Y. Suzuki, H. Isobe, M. Shoji, S. Yamanaka, M. Okumura, T. Nakajima, and K.
Yamaguchi, Beyond-DFT Calculations by DMRG CAS methods for Effective Exchange Integrals in Binuclear
Manganese Complex, ACMM 2020.3.8-3.11, ⚟ᒸЍᘏᮇ Online (2021.3.7-3.10) (Poster).
ᕝୖ㈗㈨, 㕥ᮌ㞝ኴ, ᅵᕝ┿⌮ᜨ, ᐑᕝ᫭୍, ᒣ୰⚽௓, ዟᮧග㝯, ୰ᔱ㝯ே, ᒣཱྀ඙, Mn-O2-Mn ᵓ㐀࡛ࡢ

- 163 -

☢Ẽⓗ┦஫స⏝࡟㛵ࡍࡿ QMC-CASCI ἲ࡟ࡼࡿゎᯒ, ➨ 101 ᫓Ꮨᖺ఍, 2021.3.19-3.22, Online (Oral).
M. Shoji, Recent Progress in the Reaction Mechanism of Water-Splitting in Photosystem II, 70th JSCC,
2020.9.28-9.30, Online (Oral).

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

★[7] Relative stability among intermediate structures in S2 state of CaMn4O5 cluster in PSII by using hybrid and
DLPNO-CC methods and evaluation of magnetic interactions between Mn ion, K. Miyagawa, T. Kawakami, Y.
Suzuki, H. Isobe, M. Shoji, S. Yamanaka, M. Okumura, T. Nakajima and K. Yamaguchi, J. Photochem. Photobiol.
A 405, 112923 (14 pages) (2021). DOI: 10.1016/j.jphotochem.2020.112923.
★[8] Exploring reaction pathways for the structural rearrangements of the Mn cluster induced by water binding in the
S3 state of the oxygen evolving complex of photosystem II, H. Isobe, M. Shoji, T. Suzuki, J.-R. Shen and K.
Yamaguchi,

J.

Photochem.

Photobiol.

A

405,

112905(14

pages)(2021).

DOI:

10.1016/j.jphotochem.2020.112905.
★[9] A three states model for hydrogen abstraction reactions with the cytochrome P450 compound I is revisited.
Isolobal and iso spin analogy among Fe(IV)=O, O=O and O, K. Miyagawa, H. Isobe, M. Shoji, T. Kawakami, S.
Yamanaka and K. Yamaguchi, J. Photochem. Photobiol. A 405, 112902 (14 pages) (2021). DOI:
10.1016/j.jphotochem.2020.112902.
★[10] Electronic and spin structures of CaMn4Ox clusters in the S0 state of the oxygen evolving complex ofphotosystem II. Domain-based local pair natural orbital (DLPNO) coupled-cluster (CC) calculations using
optimized geometries and natural orbitals (UNO) by hybrid density functional theory (HDFT) calculations, K.
Miyagawa, S. Yamanaka, H. Isobe, M. Shoji, T. Kawakami, M. Taniguchi, M. Okumura and K. Yamaguchi, Phys.
Chem. Chem. Phys. 22, 27191-27205 (2020). DOI: 10.1039/D0CP04762G.
★[11] Development of broken-symmetry (BS) methods in chemical reactions. A theoretical view of water oxidation inphotosystem II and related systems, K. Yamaguchi, H. Isobe, M. Shoji, K. Miyagawa, S. Yamanaka, T.
Kawakami and T. Nakajima, J. Photochem. Photobiol. A 402, 112791 (22 pages) (2020). DOI:
10.1016/j.jphotochem.2020.112791.
★[12] Theory of chemical bonds in Metalloenzymes XXIV. Electronic and spin structures of FeMoco and Fe-S clusters
by classical and quantum computing, K. Miyagawa, M. Shoji, H. Isobe, S. Yamanaka, T. Kawakami, M.
Okumura and K. Yamaguchi, Mol. Phys. 118, 21-22, e1760388(28 pages) (2020). DOI: 10.1080/
00268976.2020.1760388.
★[13] Theory of chemical bonds in Metalloenzymes XXIII. Fundamental principles for the photo-induced wateroxidation in oxygen evolving complex of photosystem II, K. Yamaguchi, S. Yamanaka, H. Isobe, M. Shoji, K.
Miyagawa

andT.

Kawakami,

Mol.

Phys.

118,

21-22,

e1725168(30pages)(2020).

DOI:

10.1080/00268976.2020.1725168.
★[14] UNO(ULO) active space for multireference calculations on classical and quantum computers. Revisit to theiron-sulfur complexes, K. Miyagawa, M. Shoji, H. Isobe, S. Yamanaka, T. Kawakami, M. Okumura and K.
Yamguchi, Chem. Phys. Letters. 746, 137252 (8 pages). DOI: 10.1016/j.cplett.2020.137252.
[15] Clarification of the relationship between the magnetic and conductive properties of infinite chains intrioxotrianqulene radical crystals by spin-projected DFT/plane-wave calculations, T. Tada, T. Kawakami, S.

- 164 -

Tanaka, M. Okumura, K. Yamaguchi, Adv. Theory and simulations, (2020). DOI: 10.1002/ adts.202000050.
[16] Comparison of effective exchange integrals of H-H and H-He-H chains vs single molecules: A theoretical study, K.
Tada, T. Kawakami, Y. Kitagawa, M. Okumura, K. Yamaguchi, S. Tanaka, Chem. Lett. 49, 137-140 (2020). DOI:
10.1246/cl.190806.

- 165 -

ࣃ࢖ඹᙺ⣔⎔≧໬ྜ≀ࡢྜᡂ◊✲࡜ග≀ᛶࡢゎ㔘
6\QWKHVLVDQG7KHLU3KRWRSK\VLFDO3URSHUWLHVRIʌ&RQMXJDWHG&\FOLF&RPSRXQGV‫ۑ‬㛗㇂ᕝ


┿ኈࠊୖ⏣

ᑗྐࠊ㔝ᓥ

⿱㥽㸦໭㔛኱㝔⌮㸧◊✲┠ⓗȧඹᙺ⣔ࣘࢽࢵࢺࡀ⎔≧࡟⧅ࡀࡗࡓ໬ྜ≀ࡣ኱ࡁ࡞✵Ꮝࢆᣢࡘࡇ࡜࠿ࡽࠊࡑࡢ࣍ࢫࢺࢤࢫࢺ໬Ꮫ࡟⯆࿡ࡀᣢࡓࢀࡿࠋࡲࡓࠊᵓ㐀ࡀ๛┤࡞ࡓࡵ⺯ගࡸ࢟ࣛࣝගᏛ≉ᛶ࡞࡝ࡢග≀ᛶࡶᮇᚅ࡛ࡁࡿࠋᮏ◊✲࡛ࡣࠊྜᡂ࡛

ᚓࡽࢀࡓ✀ࠎࡢ໬ྜ≀ 1±3 ࡟ࡘ࠸࡚ࠊᐇ㦂ࢹ࣮ࢱࢆඖ࡟྾཰ࢫ࣌ࢡࢺࣝཬࡧⓎගࢫ࣌ࢡࢺࣝࡢゎ㔘ࢆ⌮ㄽィ⟬࡟ࡼࡾ⾜࠸ࠊࡇࢀࡽࡢ㟁Ꮚᵓ㐀ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ໬ྜ≀ 1 ࡢ྾཰ࢫ࣌ࢡࢺࣝ࠾ࡼࡧ㓟໬㑏ඖ㟁఩ࡢホ౯ࡢࡓࡵ࡟ࠊᵓ㐀᭱㐺໬ィ⟬࡜ 7'')7 ィ⟬ࢆ⾜࡞ࡗࡓ %/<3* GS ࠋࡲࡓࠊ࣎࢘ࣝ≧ࡢᵓ㐀ࢆᣢࡘ໬ྜ≀ 2 ࡢ཯㌿㞀ቨࡢぢ✚ࡶࡾࢆ %/<3* ࣞ࣋ࣝࠊ7'')7 ィ⟬ࢆ &$0%/<3* ࡛ࣞ࣋ࣝ⾜࡞ࡗࡓࠋ໬ྜ≀ 3 ࡟㛵ࡋ࡚ࡣᇶᗏ≧ែ࠾ࡼࡧບ㉳≧ែࡢィ⟬ࢆ
ࡑ

ࢀ

ࡒ

ࢀ

ࠊ

%/<3* GS

࠾

ࡼ

ࡧ

&$0%/<3* GS ࡛⾜࡞ࡗࡓࠋ◊✲ᡂᯝ໬ྜ≀ 1 ࡣከẁ㝵ࡢ㓟໬㑏ඖ≉ᛶࢆ♧ࡍࠋィ⟬ࡢ⤖ᯝࠊ+202 ࡀᯫᶫࢭࣞࣥ㒊఩ࡼࡾᗈࡀࡗ࡚࠸ࡓࠋࡑࡢ

ࡓࡵࠊ6H6HOHQRSKHQH6H 㒊ศ࠿ࡽ㓟໬ࡀ㐍⾜ࡋ࡚࠸ࡿ࡜⤖ㄽ࡙ࡅࡿࡇ࡜ࡀ࡛ࡁࡓࠋ໬ྜ≀ 2 ࡣ࣎࢘ࣝ≧ࡢᵓ㐀ࢆᣢࡘࠋ㑄⛣≧ែࡢᵓ㐀ィ⟬࠿ࡽぢ✚ࡶࡗࡓ཯㌿㞀ቨࡣ  N-PRO ࡛ࠊᐊ࡛ࡣࣛࢭ࣑໬ࡀᐜ᫆࡟㐍⾜ࡍࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡇࢀࡽࡢィ⟬ࡣ཯㌿㞀ቨ࢚ࢿࣝࢠ࣮ࢆቑຍࡉࡏࡿศᏊࢆタィࡍࢀࡤྛ࢚ࢼࣥࢳ࣐࣮࢜ࡀ
ศ㞳ྍ⬟࡛࠶ࡿࡇ࡜ࢆ♧၀ࡋࡓࠋ໬ྜ≀ 3 ࡣᙉ࠸⺯ගⓎග࡜෇೫ගⓎගࢆ♧ࡍࠋᇶᗏཬࡧບ㉳≧ែࡢィ⟬࠿ࡽࠊࡡࡌࢀࡓ࢜ࣜࢦࣇ࢙ࢽࣞࣥࣘࢽࢵࢺࡀࡇࢀࡽࡢせᅉ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ  ௳୰  ௳ࢆグ㍕ ‫   ۻ‬6PDOO ILJXUHHLJKW PROHFXOHV RI GRXEOHWZLVWHG WHWKHUHG F\FOLF ELQDSKWK\OV GLVSOD\ HQKDQFHG FLUFXODUO\SRODUL]HGOXPLQHVFHQFH´0+DVHJDZD7KHWK,QWHUQDWLRQDO6\PSRVLXPRI4XDQWXP%HDP6FLHQFHฟ∧ᐇ⦼  ௳୰  ௳ࢆグ㍕ ‫  ۻ‬7ULVNHOLRQ6KDSHGʌ/XPLQRSKRUHV%HDULQJ&RXPDULQ6\QWKHVHV6WUXFWXUHVDQG/XPLQHVFHQFH3URSHUWLHV0
8HGD0.RNXEXQ<0D]DNL &KHP3KRWR&KHP2020‫  ۻ‬6HOHQDFDOL[>@VHOHQRSKHQH 6\QWKHVLV 6WUXFWXUH DQG *HO )RUPDWLRQ RI &\FOLF 6HOHQRHWKHU RI 6HOHQRSKHQH 0
+DVHJDZD6+DJD71LVKLQDJD<0D]DNL 2UJ/HWW2020 ±‫&  ۻ‬LUFXODUO\ 3RODUL]HG /XPLQHVFHQFH RI $ 6WHUHRJHQLF &XUYHG 3DUDSKHQ\OHQH $QFKRULQJ $ &KLUDO %LQDSKWK\O LQ
6ROXWLRQDQG6ROLG6WDWH.6DWR0+DVHJDZDHWDO &KHP(XU-2021

- 166 -

㠀ᖹ㠃ᆺࣃ࢖ඹᙺศᏊࡢᵓ㐀࡜≀ᛶStructure and Properties of non-planar S-conjugated molecules‫ۑ‬ὠ␃㷂 㝧኱, ᾆ 㔛⳹Ꮚ, ⣽ᕝ ᭸ె㸦኱㜰ᗓ❧኱Ꮫ኱Ꮫ㝔⌮Ꮫ⣔◊✲⛉㸧1◊✲┠ⓗࠊෆᐜ
ྵࣜࣥ⎔≧໬ྜ≀ࡣࠊ㑄⛣㔠ᒓゐ፹཯ᛂࡢ㓄఩Ꮚࡸᶵ⬟ᛶᮦᩱ࡞࡝ࡢほⅬ࠿ࡽᗈࡃ◊✲ࡉࢀ࡚࠸ࡿࡓࡵࠊ

ຠ⋡ⓗ࡞ྜᡂᡭἲࡢ㛤Ⓨࡣ㔜せ࡛࠶ࡿࠋࡈࡃ᭱㏆ࠊ㔠(I)ゐ፹ࢆ⏝࠸ࡓ o-࢚ࢳࢽࣝ࢔࣮ࣜࣝ࣍ࢫ࣍ࢽ࣒࢘ሷ 1࡟ᑐࡍࡿศᏊෆࣄࢻࣟ࢔࣮ࣜࣝ໬཯ᛂ࡟ࡼࡾࠊ7-endo ⎔໬⏕ᡂ≀࡛࠶ࡿ࣍ࢫࣇ࢙ࣆࣥ 2 ࡜ 6-exo ⎔໬⏕ᡂ≀࡛࠶ࡿࢪࣄࢻࣟ࣍ࢫࣇ࢕ࢽࣥ 3 ࡀᚓࡽࢀࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ(Scheme 1)ࠋᮏ཯ᛂࡣ௨ୗࡢ 2 Ⅼࡢ≉ᚩࢆ᭷ࡋ࡚࠸ࡿࠋ1) ࢔ࣝ࢟ࣥୖࡢ⨨᥮ᇶ(R3)ࡀ㑅ᢥᛶ࡟኱ࡁ࡞ᙳ㡪ࢆ୚࠼ࠊ≉࡟ 2-࣓ࢺ࢟ࢩࣇ࢙ࢽࣝᇶࡢሙྜ࡟ࡣ࣍
ࢫࣇ࢙ࣆࣥ 2 ࡀࠊᮎ➃࢔ࣝ࢟ࣥࡢሙྜ࡟ࡣࢪࣄࢻࣟ࣍ࢫࣇ࢕ࢽࣥ 3 ࡀ㑅ᢥⓗ࡟ᚓࡽࢀࡿࠋ2) ᮏ཯ᛂ࡟ࡣ࣍ࢫ
࣍ࢽ࣒࢘ሷࢆ⏝࠸ࡿᚲせࡀ࠶ࡾࠊࣜࣥཎᏊୖ࡟ྠࡌ⨨᥮ᇶࢆᣢࡘ࣍ࢫࣇ࢕ࣥ࢜࢟ࢩࢻࡸ࣍ࢫࣇ࢕ࣥࢫࣝࣇ࢕
ࢻ࡛ࡣ཯ᛂࡀ඲ࡃ㐍⾜ࡋ࡞࠸ࠋᮏ◊✲࡛ࡣࠊࡇࡢ 2 ࡘࡢ཯ᛂᛶࡢ㐪࠸࡟㛵ࡍࡿ▱ぢࢆᚓࡿࡓࡵ࡟ࠊィ⟬໬Ꮫࡢᡭἲࢆ⏝࠸ࡓ᳨ウࢆᐇ᪋ࡋࡓࠋ

6FKHPH 

2◊✲᪉ἲࠊィ⟬᪉ἲ*DXVVLDQ  ࠾ ࡼ ࡧ *550 ࢆ ฼ ⏝ ࡋ ࡓ ࠋ

06'' $X  * G  3 2 & +  ࣞ࣋ࣝࢆᇶ
ᗏ㛵ᩘ࡜ࡋ࡚ࠊᏳᐃᵓ㐀࠾ࡼࡧ㑄⛣≧ែࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓ 3&0 &+&O ࠋᚓࡽࢀࡓᵓ㐀࡟ࡘ࠸࡚ࡣࠊྠࣞ࣋ࣝ࡟࡚᣺ືᩘィ⟬ࢆ⾜࠺ࡇ࡜࡟ࡼ
ࡾᏳᐃᵓ㐀ࡶࡋࡃࡣ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡲࡓࠊ㑄⛣≧ែ࡟ࡘ࠸࡚ࡣ ,5& ィ⟬ࢆᐇ᪋ࡋࠊ஧ࡘࡢᏳᐃᵓ㐀ࢆࡘ࡞ࡄ㑄⛣≧ែ࡛࠶ࡿࡇ࡜
ࡶ࠶ࢃࡏ࡚☜ㄆࡋࡓࠋ

3◊✲ᡂᯝ᭱ึ࡟ࠊࡉࡲࡊࡲ࡞⨨᥮ᇶ(R3 = H, SiMe3, Ph,

2-MeOC6H4 ࡞࡝)ࢆ᭷ࡍࡿ⏕ᡂ≀ 2 ࠾ࡼࡧ 3 ࡢ┦ᑐ࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡋࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊᮏ཯ᛂ
ࡢ⏕ᡂ≀ࡢ㑅ᢥᛶࢆ༑ศ࡟ㄝ᫂ࡍࡿࡇ࡜ࡣ࡛ࡁ

)LJXUH  ศᏊෆࣄࢻࣟ࢔࣮ࣜࣝ໬཯ᛂࡢ࢚ࢿࣝࢠ࣮
ᅗ. 'G ್(kcal molí1)ࢆグ㍕. ࠼ࡡ㹰ࡂ࣮ࡎ

- 167 -

࡞࠿ࡗࡓࠋࡋࡓࡀࡗ࡚ࠊ⇕ຊᏛⓗ⏕ᡂ≀࡛ࡣ࡞
ࡃࠊ㏿ᗘㄽⓗ⏕ᡂ≀࡛࠶ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ
ḟ࡟ࠊ㔠(I)ゐ፹ࡢ⎔໬␗ᛶ໬཯ᛂࡢ཯ᛂᶵᵓ
ࢆࡶ࡜࡟ࠊᚊ㏿ẁ㝵࡜⪃࠼ࡽࢀࡿྵࣜࣥභဨ⎔࠾ ࡼ ࡧ ୐ ဨ ⎔ ⏕ ᡂ ࡢ 㑄 ⛣ ≧ ែ (TS6exo ࠾ ࡼ ࡧ
TS7endo)ࢆィ⟬ࡋࡓ(Figure 1)ࠋィ⟬ࢥࢫࢺࡢ㛵ಀୖࠊ㔠ཎᏊୖࡢ࢝ࣝ࣋ࣥ㓄఩Ꮚ࡟ࡘ࠸࡚ࡣࠊ2,6ࢪ࢖ࢯࣉࣟࣆࣝࣇ࢙ࢽࣝᇶࡢ࠿ࢃࡾ࡟࣓ࢳࣝᇶ
࡜ࡋࡓࠋ㔠(I)㒊఩ࡀᇶ㉁ 1 ࡢ࢔ࣝ࢟ࣥ࡟㓄఩ࡋࡓ୰㛫య IN1 ࠿ࡽࠊ7-endo ࠾ࡼࡧ 6-exo ௜ຍ⏕ᡂ≀ࢆ୚࠼ࡿ୰㛫య(IN2 ࠾ࡼࡧ IN3)࡬ࡢ㑄⛣≧)LJXUH  ࣇ࢙ࢽࣝ⨨᥮ㄏᑟయ(R3 = Ph)ࡢ(a) 6-exo ࠾ࡼࡧ(b) 7-endo ⎔໬཯ᛂ࡟࠾ࡅࡿ㑄⛣≧ែࡢ᭱㐺ᵓ㐀.

ែࢆồࡵࡓ࡜ࡇࢁࠊᮎ➃࢔ࣝ࢟ࣥ(R3 = H)࡛ࡣࠊ
6-exo ௜ຍ⏕ᡂ≀ࢆ୚࠼ࡿ࡯࠺᭷฼࡛࠶ࡗࡓࡢ
࡟ᑐࡋࠊࣇ࢙ࢽࣝᇶ(R3 = Ph)ࡢሙྜ࡛ࡣࠊ7-endo௜ຍ⏕ᡂ≀ࢆ୚࠼ࡿ࡯࠺ࡀ᭷฼࡛࠶ࡗࡓࠋࡇࡢ
⤖ᯝࡣࠊᐇ㦂⤖ᯝࢆ෌⌧ࡋ࡚࠸ࡓࠋTS6exo-Ph ࡜
TS7endo-Ph ࡢ㑄⛣≧ែࡢ᭱㐺ᵓ㐀ࢆẚ㍑ࡋࡓ࡜ࡇࢁࠊTS7endo-Ph ࡢሙྜ࡛ࡣࣇ࢙ࢽࣝᇶࡣ㐲ࡊ࠿ࡗ࡚࠸ࡓࡢ࡟ᑐࡋ(Figure 2b)ࠊTS6exo-Ph ࡢሙྜ࡛ࡣ
ࣇ࢙ࢽࣝᇶ࡜ࢪ࣓ࢺ࢟ࢩࣇ࢙ࢽࣝᇶࡣᖹ⾜࡟఩⨨ࡋ࡚࠸ࡓ(Figure 2a)ࠋࡇࡢ 2 ࡘࡢⰾ㤶⎔ࡢ㊥㞳ac ࡣࠊⅣ⣲㛫ࡢࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫ༙ᚄࡢ࿴  c ࡼࡾ▷࠸ࡇ࡜࠿ࡽࠊ❧య཯Ⓨ࡟ࡼࡾάᛶ໬㞀ቨࡀୖ᪼ࡋࡓࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ
ḟ࡟ࠊࣜࣥཎᏊୖࡢඖ⣲ࡢᙳ㡪࡟ᑐࡍࡿィ⟬ࢆ⾜ࡗࡓࠋ࢝ࣝࢥࢤࣥཎᏊ(㓟⣲ࡶࡋࡃࡣ◲㯤)ࡀ࢔ࣝ࢟ࣥ࡟ồ᰾௜ຍࡍࡿ㑄⛣≧ែ(TSE)ࢆồࡵ
ࡓ࡜ࡇࢁ(Figure 3)ࠊ㓟⣲࣭◲㯤ࡢ࠸ࡎࢀࡢሙྜ

)LJXUH  ࣍ࢫࣇ࢕ࣥ࢝ࣝࢥࢤࢽࢻ࡟࠾ࡅࡿศᏊෆࣄࢻ
ࣟ࢔࣮ࣜࣝ໬཯ᛂ࡜࢝ࣝࢥࢤࣥ௜ຍ࡟ᑐࡍࡿ࢚ࢿࣝࢠ࣮
ᅗ. 'G ್(kcal molí1)ࢆグ㍕. ࡟࠾࠸࡚ࡶࠊTS6exo ࡜ TS7endo ࡼࡾࡶ᭷฼࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡑࡢࡓࡵࠊ࣍ࢫࣇ࢕ࣥ࢝ࣝࢥࢤࢽࢻࢆᇶ㉁࠼ࡡ㹰ࡂ࣮ࡎ
࡜ࡋࡓሙྜ࡟ࡣࠊ6-exo ࠾ࡼࡧ 7-endo ௜ຍ⏕ᡂ≀ࡀ඲ࡃᚓࡽࢀ࡞࠿ࡗࡓࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ

4

ฟ∧ᐇ⦼

‫ۻ‬

$ 7VXUXVDNL + 6KLPDWDQL . .DPLNDZD ³*ROG , &DWDO\]HG ,QWUDPROHFXODU +\GURDU\ODWLRQ RI

R(WK\Q\ODU\OSKRVSKRQLXP6DOW/HDGLQJWRWKH)RUPDWLRQRI6HYHQDQG6L[PHPEHUHG3KRVSKDF\FOHV´$VLDQ-2UJ&KHP2021
‫ ۻ‬7 .DZDVKLPD < 0DWVXPRWR 7 6DWR < 0 $ <DPDGD & .RQR $ 7VXUXVDNL . .DPLNDZD ³6\QWKHVLV6WUXFWXUHDQG&RPSOH[DWLRQRIDQ66KDSHG'RXEOH$]DKHOLFHQHZLWK,QQHU(GJH1LWURJHQ$WRPV´&KHP(XU-2020
 - 168 -

ࢼࣀ࣮࣭࢝࣎ࣥ࢔࣑ࣀ㓟࣭ࢡࣛࢫࢱ࣮ࡢ཯ᛂືຊᏛࡢ㔞Ꮚ໬Ꮫⓗ◊✲
4XDQWXP&KHPLFDO6WXG\RQ5HDFWLRQ'\QDPLFVRI1DQRFDUERQV$QLPR$FLGVDQG&OXVWHUV‫ۑ‬ᒣ໭ ెᏹࠊ㧗ᶫ ᾴࠊὸぢ 㝣ࠊ∦ᒸ ❳㤿ࠊᒣཱྀ ៞࿃ࠊᰓ ᾈὈ㸦㟁㏻኱㝔᝟ሗ⌮ᕤ㸧1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࡢ┠ⓗࡣḟࡢ஦㡯࡟㛵ࡍࡿ㔞Ꮚ໬Ꮫⓗ◊✲࡛࠶ࡿࠋձከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲㸦PAH㸧ࡢ He*(23S)࡜ࡢ 3

ḟඖ┦஫స⏝࣏ࢸࣥࢩࣕࣝ࠾ࡼࡧ࣐ࣛࣥᩓ஘᩿㠃✚ࠊղศᏊෆᅇ㌿ࢆ᭷ࡍࡿ࢔࣑ࣀ㓟ࡸ࣋ࣥࢮࣥㄏᑟయࡢศᏊෆᅇ㌿࣏ࢸࣥࢩࣕࣝࠊճࣛࣥࢱࣀ࢖ࢻࡸ㑄⛣㔠ᒓ࡟ศᏊࡀ྾╔ࡋࡓࢡࣛࢫࢱ࣮ࡢゐ፹཯ᛂάᛶࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲձ࡟ࡘ࠸࡚ࠊ࢔ࣥࢺࣛࢭࣥ࡞࡝ࡢ PAH ࡟㛵ࡋ࡚➼౯እẆ࡛࠶ࡿ Li ࢆ⏝࠸࡚ࠊ┦஫స⏝࢚ࢿࣝࢠ࣮ࢆ MP2࡛ࣞ࣋ࣝ Counterpoise ἲࢆ౑ࡗ࡚ィ⟬ࡋࠊ࢖࢜ࣥ໬࢚ࢿࣝࢠ࣮ࢆ OVGF ἲ࡛ィ⟬ࡋࡓࠋPAH ࢆྵࡴ㠀ᖹ㠃ࢼࣀⅣ⣲ࡢ࣐ࣛࣥᙉᗘࢆィ⟬ࡋࡓࠋղ࡟ࡘ࠸࡚ࡣࠊࢳ࢜ࢫࣞ࢜ࢽࣥࡢศᏊෆ┦஫స⏝࡟ࡘ࠸࡚ࠊỈ⣲⤖ྜ࢚ࢿࣝࢠ࣮ࢆ NBO ィ⟬࡟ࡼࡾồࡵࡓࠋ࢝ࣝࢥࢤࣀ࢔ࢽࢯ࣮ࣝࡢศᏊෆᅇ㌿㞀ቨ࡟ࡘ࠸࡚ࠊMolpro ࡛㟁Ꮚ┦㛵ࢆ⪃៖ࡋ CASSCF, CASPT2 ィ⟬࡞ࡽࡧ࡟ NBO ࡢィ⟬ࢆ⾜ࡗࡓࠋճ࡟ࡘ࠸࡚ࡣࠊLa+࡟࢔ࢭࢺࣥࡀ 2㹼4 ศᏊ㓄఩ࡋࡓࢡࣛࢫࢱ࣮࢖࢜ࣥࡢ཯ᛂ⤒㊰᥈⣴ࢆ GRRM ࣉࣟࢢ࣒࡛ࣛ⾜ࡗࡓࠋ3◊✲ᡂᯝձ࡟ࡘ࠸࡚ࠊ࢔ࣥࢺࣛࢭࣥࡢ He*(23S)⾪✺࡟ࡼࡿ࣌ࢽࣥࢢ࢖࢜ࣥ໬཯ᛂ࡟ࡘ࠸࡚ࠊࢺࣛࢪ࢙ࢡࢺࣜィ⟬࡛᫂ࡽ࠿࡟ࡋࡓ[1,2]ࠋ」ᩘࡢ㠀ᖹ㠃ࢼࣀⅣ⣲࡟࠾࠸࡚ࠊపἼᩘ㡿ᇦ࡟ᙉ࠸࣐ࣛࣥᙉᗘࡀィ⟬ࡉࢀࡿࡇ࡜ࢆ᫂ࡽ
࠿࡟ࡋࡓ[3,4]ࠋղ࡛ࡣࠊ࢔࣑ࣀ㓟ࡢᐁ⬟ᇶ౫Ꮡᛶࢆ
ศᏊෆỈ⣲⤖ྜࡢほⅬ࠿ࡽ᫂ࡽ࠿࡟ࡋࡓࠋ࢝ࣝࢥ
ࢤࣀ࢔ࢽࢯ࣮ࣝࡢศᏊෆᅇ㌿࡟క࠺ n-S࠾ࡼࡧV-SᏳᐃ໬ᶵᵓ࡜㌶㐨࢚ࢿࣝࢠ࣮ࡢኚ໬ࢆ᫂ࡽ࠿࡟ࡋ
ࡓ[5]ࠋճ࡟࠾࠸࡚ࠊLa+࡟㓄఩ࡋࡓ࢔ࢭࢺࣥ㸦AC㸧
㸰ศᏊࡀ࣓ࢩࢳࣝ࢜࢟ࢩࢻ㸦MOX㸧ࢆ⏕ᡂࡍࡿ཯ᛂ⤒㊰ࢆぢฟࡍࡇ࡜ࡀ࡛ࡁࡓ㸦ᅗ㸯㸧[6]ࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

ᅗ㸯㸬La+(AC)3 ࡢ཯ᛂ⤒㊰‫[ۻ‬1] ∦ᒸ㸪ᒣ໭㸪ศᏊ⛉Ꮫ఍࢜ࣥࣛ࢖ࣥウㄽ఍㸦2020㸧
㸪1D14㸬‫[ۻ‬2] ∦ᒸ㸪ᒣ໭㸪᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍㸦2021㸧
㸪A05-2am-01㸬‫[ۻ‬3] ᒣཱྀ㸪ᒣ໭㸪኱㔝㸪➨ 10 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2020㸪P6-012㸬‫[ۻ‬4] ὸぢ㸪ᒣ໭㸪᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍㸦2021㸧㸪A26-3pm-02㸬‫[ۻ‬5] ᰓ㸪ᒣ໭㸪᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍㸦2021㸧
㸪
P04-1am-11㸬‫[ۻ‬6] 㧗ᶫ㸪ୗᕝཎ㸪ᒣ໭㸪➨ 10 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2020㸪P9-001㸬

5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] Y. Shigekawa, Y. Kasamatsu, Y. Yamakita, Y. Yasuda, E. Watanabe, N. Kondo, H. Haba, A. Shinohara, Nucl. Inst.
Methods Phys. Res. A, 976, 164207 (2020). 10.1016/j.nima.2020.164207 ‫[ۻ‬2] Y. Ishiguro, Y. Yamakita, and N.
Hayashi, Chem. Phys. Lett., 754, 137653 (2020). 10.1016/j.cplett.2020.137653- 169 -

࣑࢜ࢩࣥ 9, ࡢ཯ᛂࢧ࢖ࢡࣝ඲యࡢືⓗࣛࣥࢻࢫࢣ࣮ࣉ࡟ࡼࡿ
ࢫࢸࢵࣉ㐠ືᶵᵓࡢゎ᫂(OXFLGDWLRQRIWKHPHFKDQLVPRIP\RVLQ9,VWHSSLQJE\G\QDPLF
ODQGVFDSHVRIZKROHUHDFWLRQF\FOH‫ۑ‬ᑎ⏣ ᬛᶞࠊ➲஭ ⌮⏕㸦ྡྂᒇ኱Ꮫ㸧




◊✲┠ⓗ
ࢱࣥࣃࢡ㉁ࢲ࢖ࢼ࣑ࢡࢫࡢࣛࣥࢻࢫࢣ࣮ࣉ⌮ㄽࡣࠊࢱࣥࣃࢡ㉁ࡢ࢔࣑ࣀ㓟㓄ิ࡟ࡼࡗ࡚ኳ↛ᵓ㐀ࡀỴࡲࡿ࡜ࠊࡑࡢ࿘ࡾ࡛ࡢ⇕ᦂࡽࡂࡢࡋ࠿ࡓࡶᐃࡲࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ࡚ࡁࡓࠋࡇࡢ⪃࠼᪉ࡣࠊᙜึࡣࢱࣥࣃࢡ㉁ࣇ
࢛࣮ࣝࢹ࢕ࣥࢢ◊✲ࡢᩥ⬦࡛ᥦ᱌ࡉࢀࠊ᳨ドࡉࢀ࡚ࡁࡓࡀࠊ⌧ᅾ࡛ࡣࢱࣥࣃࢡ㉁ࡢᶵ⬟ࢲ࢖ࢼ࣑ࢡࢫ࡟࠾࠸
࡚ࡶ᭷ຠ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࡼ࠺࡟࡞ࡗ࡚࠸ࡿࠋࡇ࠺ࡋࡓὶࢀࡢ୰࡛ࢃࢀࢃࢀࡣࠊ᭱Ᏻᐃᵓ㐀ࡢ㏲ḟⓗ࡞ኚ໬࡟ࡼࡗ࡚ࣔࢹࣝ໬ࡉࢀࡿࡇ࡜ࡀከ࠸ศᏊ࣮ࣔࢱ࣮ࢱࣥࣃࢡ㉁ࡢᶵ⬟Ⓨ⌧࣓࢝ࢽࢬ࣒࡟࠾࠸࡚ࡶࠊࣛࣥࢻࢫ
ࢣ࣮ࣉ⌮ㄽࡢ⪃࠼᪉ࡀ᭷ຠ࡛࠶ࡿ࡜⪃࠼࡚ࠊ࢔ࢡࢳ࣭࣑ࣥ࢜ࢩࣥ⣔ࢆᑐ㇟࡜ࡋࡓ୍㐃ࡢ◊✲ࢆ⾜ࡗ࡚ࡁࡓࠋ
㐣ཤࡢ◊✲࡛ࢃࢀࢃࢀࡣࠊ➽཰⦰ࢆ⏕ࡳฟࡍศᏊ࣮ࣔࢱ࣮ࢱࣥࣃࢡ㉁࡛࠶ࡿ࣑࢜ࢩࣥ ,, ࡢ㢌㒊ࡢ࢔ࢡࢳࣥ
ࣇ࢕࣓ࣛࣥࢺࡢ࿘ᅖࡢࣈࣛ࢘ࣥ㐠ື࡟ࡘ࠸࡚ࠊᐇ㦂ⓗ࡟Ỵᐃࡉࢀࡓᵓ㐀ࢆ⏝࠸࡚⢒ど໬ࣔࢹࣝࢆᵓ⠏ࡋࠊࣛࣥࢪࣗࣂࣥືຊᏛィ⟬࡜ :+$0 ἲࢆ⤌ࡳྜࢃࡏ࡚⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࢆィ⟬ࡍࡿᡭἲࢆ㛤Ⓨࡋࡓࠋࡇࡢᡭἲ࡟ࡶ࡜࡙ࡃィ⟬࡟ࡼࡾࠊ࣑࢜ࢩࣥ ,, ࡢ㢌㒊࡟࠾ࡅࡿ໬Ꮫኚ໬࡜࢝ࢵࣉࣝࡋࡓᵓ㐀ኚ໬࡟ࡼࡗ࡚ࠊ
ࣈࣛ࢘ࣥ㐠ືࡢ⮬⏤࢚ࢿࣝࢠ࣮᭱ᑠࡢ఩⨨ࡀ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺ࡟ἢࡗ࡚⛣ືࡋࠊࡇࡢຠᯝࡀ➽཰⦰࡟኱ࡁࡃᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ㸦1LHHWDO3K\V&KHP&KHP3K\V   ࠊ1LHHWDO3/R6&RPS%LRO  ࠊᑎ⏣ᬛᶞ ⏕≀≀⌮  㸧ࠋᮏ◊✲࡛ࡣࠊ⣽⬊ෆ≀㉁㍺㏦࡟࠿࠿ࢃࡿ࣑࢜ࢩࣥࣇ࢓࣑࣮ࣜࢱࣥࣃࢡ㉁࡛࠶ࡿ࣑࢜ࢩࣥ 9, ࢆᑐ㇟࡜ࡋ࡚ࠊ
࣑࢜ࢩࣥ ,, ࡛☜❧ࡋࡓᡭἲࢆ⏝࠸࡚ࠊࣛࣥࢻࢫࢣ࣮ࣉ⌮ㄽࢆᒎ㛤ࡍࡿࠋ࣑࢜ࢩࣥ 9, ࡣ  ࡘࡢ㢌㒊ࡀᑿ㒊ࢆ
㏻ࡌ࡚ࡘ࡞ࡀࡗࡓᵓ㐀ࢆᣢࡕࠊ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺ࡟ἢࡗ࡚Ṍࡃࡼ࠺࡞㐠ືࢆ♧ࡍࠋࡇࡢ㐠ືࡢ᪉ྥࡀ௚
ࡢከࡃࡢ࣑࢜ࢩࣥࣇ࢓࣑࣮ࣜࢱࣥࣃࢡ㉁࡜ࡣ㏫ྥࡁ࡛࠶ࡿࡇ࡜࡟ຍ࠼࡚ࠊ࣑࢜ࢩࣥࡢࣞࣂ࣮࢔࣮࣒࡟┦ᙜࡍࡿ㡿ᇦࡀ▷࠸࡟ࡶ࠿࠿ࢃࡽࡎ  ࢼࣀ࣓࣮ࢺࣝ๓ᚋ࡟࠾ࡼࡪ㛗࠸ࢫࢸࢵࣉࡢ㐠ືࢆ♧ࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊ
ࡇࢀࡣࣞࣂ࣮࢔࣮࣒ᶍᆺ࡜ࡼࡤࢀࡿ᭱Ᏻᐃᵓ㐀ࡢ㏲ḟⓗ࡞ኚ໬࡟ࡶ࡜࡙ࡃ࣓࢝ࢽࢬ࣒࡛ࡣㄝ࡛᫂ࡁ࡞࠸ࠋࡇ
ࡢࡇ࡜࠿ࡽࠊ᭱Ᏻᐃᵓ㐀௨እࡢᵓ㐀ᦂࡽࡂࡸࣈࣛ࢘ࣥ㐠ືࡢࣛࣥࢻࢫࢣ࣮ࣉࡢᙧ≧ࡀࠊ࣑࢜ࢩࣥ 9, ࡢᶵ⬟Ⓨ⌧࡟࡜ࡗ࡚㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ
࣑࢜ࢩࣥ 9, ࡢ  ࡘࡢ㢌㒊ࡀ࡝ࡢࡼ࠺࡟ࡋ࡚ࡘ࡞ࡀࡗ࡚࠸ࡿ࠿࡟ࡘ࠸࡚ࡣࠊᐇ㦂ⓗ࡞◊✲࠿ࡽ  ࡘࡢࣔࢹࣝ
ࡀᥦၐࡉࢀ࡚࠸ࡿࠋ6SXGLFK ࣔࢹࣝ࡟࠾࠸࡚ࡣࠊVLQJOHDOSKDKHOL[GRPDLQ ࡛ࡣࢥ࢖ࣝࢻࢥ࢖ࣝ㡿ᇦࢆᙧᡂࡏࡎࠊ
ࡼࡾ & ᮎ➃ഃࡢ FDUJRELQGLQJ GRPDLQ ࡛  ࡘࡢ㢌㒊ࡀ఍ྜࡍࡿ୍᪉ࠊ ࡘࡢ㢌㒊ࡑࢀࡒࢀࡢ WKUHHKHOL[ EXQGOHࡀࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸦6SLQN HW DO 1DW 6WUXFW 0RO %LRO  㸧ࠋࡇࢀ࡟ᑐࡋ࡚ࠊ
6ZHHQH\+RXGXVVH ࣔࢹࣝ࡟࠾࠸࡚ࡣࠊVLQJOH DOSKDKHOL[ GRPDLQ ࡢ୍㒊ࡀࢥ࢖ࣝࢻࢥ࢖ࣝ㡿ᇦࢆᙧᡂࡍࡿࡇ࡜࡟ࡼࡾ  ࡘࡢ㢌㒊ࡀ఍ྜࡍࡿ୍᪉ࠊ ࡘࡢ㢌㒊ࡑࢀࡒࢀࡢ WKUHHKHOL[EXQGOH ࡀ࢔ࣥࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸦0XNKHUMHDHWDO0RO&HOO  㸧ࠋࡇࢀࡽ  ࡘࡢࣔࢹࣝࡣ࡜ࡶ࡟ࠊ ࢼࣀ࣓࣮ࢺࣝࢫࢸࢵࣉࢆྍ

- 170 -

⬟࡟ࡍࡿࡓࡵ࡟ࠊ࡝࠺ࡍࢀࡤ  ࡘࡢ㢌㒊ࡀ  ࢼࣀ࣓࣮ࢺࣝ㛫㝸࡛࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺ࡟⤖ྜ࡛ࡁࡿ࠿࡟ࡘ
࠸࡚ࡢ⪃ᐹ࡟ᇶ࡙࠸࡚࠸ࡿࡀࠊࢫࢸࢵࣉ≧㐠ື࡜࠸࠺ࢲ࢖ࢼ࣑ࢡࢫࡢ≉ᚩࡀࡇࢀࡽࡢࣔࢹࣝࡢ㑅ᢥ࡟ࡼࡾ࡝
ࡢࡼ࠺࡟ኚ໬ࡍࡿࡢ࠿࡟ࡘ࠸࡚ࡣࠊࡇࢀࡲ࡛඲ࡃ㆟ㄽࡉࢀ࡚࠸࡞࠸ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊࢃࢀࢃࢀࡀ࣑࢜ࢩ
ࣥ ,, ࡟ᑐࡋ࡚㛤Ⓨ࣭㐺⏝ࡋ࡚ࡁࡓィ⟬ᡭἲࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊࡇࢀࡽ  ࡘࡢࣔࢹࣝ࡟㛵ಀࡍࡿᵝࠎ࡞᮲௳࡟ࡘ࠸࡚ࠊࣈࣛ࢘ࣥ㐠ືࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡢᙧ≧ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊ ࢼࣀ࣓࣮ࢺࣝࢫ
ࢸࢵࣉࢆྍ⬟࡟ࡍࡿ᮲௳ࢆ᥈ࡿ࡜࡜ࡶ࡟ࠊ࣑࢜ࢩࣥ 9, ࡢࣈࣛ࢘ࣥ㐠ື࡟࠾ࡅࡿᵓ㐀࢔ࣥࢧࣥࣈࣝࡢ≉ᚩࢆ᫂ࡽ࠿࡟ࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ࢔࣑ࣀ㓟  ṧᇶࢆ  ⢏Ꮚ࡜ࡋ࡚⾲⌧ࡍࡿ⢒ど໬ࣔࢹࣝࢆ⏝࠸࡚ࠊ࣑࢜ࢩࣥ 9, ࡢ๓㊊࡜ᚋࢁ㊊࡟┦ᙜࡍࡿ ࡘࡢ㢌㒊࡜࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺࢆィ⟬ᶵୖ࡟⾲⌧ࡍࡿ࡜࡜ࡶ࡟ࠊࡇࢀࡽࡑࢀࡒࢀࡢෆ㒊ࡢ┦஫స⏝࡜ࡋ࡚ᙎᛶࢿࢵࢺ࣮࣡ࢡࣔࢹࣝࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊࡑࢀࡒࢀࡢᵓ㐀ࡀ᭱Ᏻᐃᵓ㐀ࢆ୰ᚰ࡜ࡋ࡚⇕ᦂࡽࡂࡍࡿᵝᏊࢆ⾲⌧ࡋࡓࠋࡲࡓࠊ ࡘࡢ࣑࢜ࢩࣥ㢌㒊ࡢ & ᮎ➃ഃ࡟ࡣ VLQJOH DOSKDKHOL[ GRPDLQ ࡜ࡼࡤࢀࡿࠊȘ࣊ࣜࢵࢡࢫ
༢య࡛Ᏻᐃ࡟Ꮡᅾࡋ࡚࠸ࡿ㡿ᇦࡀ࠶ࡾࠊࡑࢀࡽࢆ௓ࡋ࡚  ࡘࡢ㢌㒊ࡀ఍ྜࡋ࡚࠸ࡿࡀࠊࡇࢀࡽࡢ㡿ᇦࡢᵓ㐀
ࢆ 9 Ꮠᆺ࡟⤖ྜࡋࡓ  ࡘࡢᙎᛶᱱ࡜ࡋ࡚࠶ࡽࢃࡋࠊࡇࢀࡽࡢᙎᛶኚᙧࡢ࢚ࢿࣝࢠ࣮ࢆ  ࡘࡢ㢌㒊ࡢ & ᮎ➃௜㏆ࡢᗙᶆࢆ⏝࠸࡚⾲ࡋࡓࠋࡉࡽ࡟ࠊᚋࢁ㊊࡟┦ᙜࡍࡿ࣑࢜ࢩࣥ㢌㒊ࡀ࣑࢜ࢩࣥ ,, ࡜ྠᵝࡢྥࡁ࡛࢔ࢡࢳࣥࣇ
࢕࣓ࣛࣥࢺ࡜⤖ྜࡋ࡚࠸ࡿ࡜௬ᐃࡍࡿ୍᪉ࠊ๓㊊࡟┦ᙜࡍࡿ࣑࢜ࢩࣥ㢌㒊ࡣ㟼㟁┦஫స⏝࡜ࣇ࢓ࣥࢹ࣮ࣝ࣡
ࣝࢫ┦஫స⏝࡛࢔ࢡࢳࣥ࡜┦஫స⏝ࡍࡿ࡜௬ᐃࡋࡓࠋ
௨ୖ࡟㏙࡭ࡓ┦஫స⏝࡟ຍ࠼࡚ࠊ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺࡢ⾲㠃ࡢᗈ⠊ᅖࢆ࢝ࣂ࣮ࡍࡿࡼ࠺࡟ࠊ࢔ࢡࢳࣥ୰
ᚰ㍈ࡢ࿘ࡾࡢᅇ㌿᪉ྥ࡟  ㏻ࡾࠊ୰ᚰ㍈ࡢ᪉ྥ࡟  ㏻ࡾࠊ୰ᚰ㍈࠿ࡽࡢ㊥㞳ࡢ᪉ྥ࡟  ㏻ࡾ࡛ྜィ 
㸻 ㏻ࡾࡢ࢔ࣥࣈ࣏ࣞࣛࢸࣥࢩࣕࣝࢆ࠿ࡅ࡚ࠊࣛࣥࢪࣗࣂࣥືຊᏛィ⟬࡟ࡼࡿࢧࣥࣉࣜࣥࢢࢆ⾜ࡗࡓࠋࡇࡢィ⟬࠿ࡽᚓࡽࢀࡓ࢔ࣥࢧࣥࣈࣝࢆ :+$0 ἲ࡛⤌ࡳྜࢃࡏࡿࡇ࡜࡟ࡼࡾࠊ࣑࢜ࢩࣥ 9, ࡢ๓㊊࡟┦ᙜࡍࡿ㢌㒊ࡢࣈࣛ࢘ࣥ㐠ືࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࢆィ⟬ࡋࡓࠋ



◊✲ᡂᯝ
ᮏ◊✲࡛ࡣࠊࢃࢀࢃࢀࡀ࣑࢜ࢩࣥ ,, ࡟ᑐࡋ࡚㛤Ⓨ࣭㐺⏝ࡋ࡚ࡁࡓィ⟬ᡭἲࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊࡇࢀࡽ ࡘࡢࣔࢹࣝ࡟㛵ಀࡍࡿᵝࠎ࡞᮲௳࡟ࡘ࠸࡚ࠊࣈࣛ࢘ࣥ㐠ືࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡢᙧ≧ࢆẚ㍑ࡍ
ࡿࡇ࡜࡟ࡼࡾࠊ ࢼࣀ࣓࣮ࢺࣝࢫࢸࢵࣉࢆྍ⬟࡟ࡍࡿ᮲௳ࢆ᥈ࡗࡓࠋࡑࡢ⤖ᯝ࡜ࡋ࡚ࠊ  +RXGXVVH6ZHHQH\
ࣔࢹࣝࡼࡾࡶ 6SXGLFK ࣔࢹࣝࡢ᪉ࡀ኱ࡁ࡞ࢫࢸࢵࣉࢧ࢖ࢬ࡬ྥ࠿࠺ࣂ࢖࢔ࢫࢆㄝ᫂ࡋࡸࡍ࠸ࡇ࡜ࠊ   ๓㊊ࡢ࣑࢜ࢩࣥ㢌㒊ࡢᵓ㐀ࡀ SUHVWURNH ᵓ㐀࠿ࡽ SRVWVWURNH ᵓ㐀࡟ኚ໬ࡍࡿࡇ࡜࡟ࡼࡾࠊ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ
࣮ࣉࡢࣂ࢖࢔ࢫࡀᙉࡲࡿࡇ࡜ࠊ WKUHHKHOL[EXQGOH ࡀ࢔ࣥࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿ࡜ࣂ࢖࢔ࢫࡀᙅࡲࡿࡇ࡜ࠊ ࡘࡢ࣑࢜ࢩࣥ㢌㒊ࢆࡘ࡞ࡄ࣑࢜ࢩࣥᑿ㒊ࡢᣢ⥆㛗ࡢ್ࡀ኱ࡁ࠸࡯࡝⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉ࡟ᙉ࠸ࣂ
࢖࢔ࢫࡀࡶࡓࡽࡉࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋᖹᡂ  ᖺᗘࡢ⤊ࢃࡾࡢ᫬Ⅼ࡛ࠊ௨ୖࡢࡼ࠺࡞⤖ᯝࡀᚓࡽࢀ࡚࠸ࡓ୍᪉ࠊࡇࡇࡲ࡛࡟ᚓࡽࢀ࡚࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡣ஧ᅇᑐ⛠ᛶࢆᣢࡘ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺ࡟ἢࡗࡓ஧ᮏࡢ⁁ࡀ࡯ࡰ➼ࡋ࠸⮬⏤࢚ࢿࣝࢠ࣮ࢆᣢࡗ࡚࠾ࡾࠊࡇࡢⅬࡣࠊ࣑࢜ࢩࣥ 9, ࡀ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺࡢ⿬ഃ࡟ᅇࡾ㎸ࡲࡎ࡟ᩘ࣐࢖ࢡ࣓࣮ࣟࢺ
ࣝ࡟ࢃࡓࡗ࡚┤⥺ⓗ࡟Ṍ⾜ࡍࡿ࡜࠸࠺ᐇ㦂஦ᐇ࡜ᩚྜࡋ࡚࠸࡞࠸ࡓࡵࠊࡇࢀࡲ࡛ࡢࣔࢹࣝ࡟㊊ࡾ࡞࠸㒊ศࡀ࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋ ࡘࡢ࣑࢜ࢩࣥ㢌㒊ࢆࡘ࡞ࡄ࣑࢜ࢩࣥᑿ㒊ࡢ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺ࡜ࡢ⾪✺ࢆ⾲⌧ࡋࡓ࣏ࢸࣥࢩࣕࣝࢆ᪂ࡓ࡟⪃᱌࣭ᐇ⿦ࡋࡓࡀࠊࡇࡢ࣏ࢸࣥࢩࣕࣝࡀാ࠸࡚࠸࡚ࡶ࣑࢜ࢩࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡵ

- 171 -

࡚ࡋࡲ࠺ࡓࡵࠊࡇࢀࡔࡅ࡛ࡣ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡢᙧ≧ࡣ࡯࡜ࢇ࡝ኚࢃࡽ࡞࠿ࡗࡓࠋ

ᅗ  D 6SXGLFK ࣔࢹࣝࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࠋE  ࢚ࢿࣝࢠ࣮⏤᮶ࡢᡂศࠋF  ࢚ࣥࢺࣟࣆ࣮⏤᮶ࡢᡂศࠋG  ࣑࢜ࢩࣥ࡜࢔ࢡࢳࣥࡢ࠶࠸ࡔ࡟ാࡃ㟼㟁┦஫స⏝ࠋH  ࡘࡢ࣑࢜ࢩࣥ㢌㒊ࢆࡘ࡞ࡄ  ࡘࡢᙎᛶᱱࡢᙎᛶኚᙧࡢ࢚ࢿࣝࢠ࣮ࠋ
ࡑࡇ࡛௧࿴ඖᖺᗘ࡟ࡣࠊࡇࡢ࣑࢜ࢩࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡴ⌧㇟ࢆᢚไࡍ࡭ࡃࠊ࣑࢜ࢩࣥᑿ㒊࡟ᑐࡍࡿ࣏
ࢸࣥࢩࣕࣝࡢ෌᳨ウࢆ⾜ࡗࡓࠋࡲࡎ࣑࢜ࢩࣥᑿ㒊ࡢࡡࡌࡾᙎᛶࡢ࣏ࢸࣥࢩࣕࣝࢆ㏣ຍࡋࡓࡶࡢࡢࠊ࣑࢜ࢩࣥ
㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡴ⌧㇟࡟ࡣኚ໬ࡀ࡞࠿ࡗࡓࠋࡲࡓࠊ஧ࡘࡢ࣑࢜ࢩࣥᑿ㒊ࡢ࡞ࡍ஧㠃ゅ࡟ᑐࡍࡿ࣏ࢸࣥࢩ
ࣕࣝࢆ㏣ຍࡋࡓࡀࠊࡇࢀ࡛ࡶ࣑࢜ࢩࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡴ⌧㇟࡟ࡣኚ໬ࡀ࡞࠿ࡗࡓࠋḟ࡟ࠊ ࡘࡢ࣑࢜ࢩ
ࣥ㢌㒊ࢆࡘ࡞ࡄ࣑࢜ࢩࣥᑿ㒊ࡢ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺ࡜ࡢ⾪✺ࢆ⾲⌧ࡋࡓ࣏ࢸࣥࢩࣕࣝࡢࣃ࣓࣮ࣛࢱࢆኚ᭦
ࡋ࡚ᐇຠⓗ࡞࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺࡢ༙ᚄࢆ኱ࡁࡃࡋࡓ࡜ࡇࢁࠊ࣑࢜ࢩࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡴ⌧㇟ࡀῶᑡࡋࡓࠋࡉࡽ࡟࣑࢜ࢩࣥᑿ㒊࡜Ș࣊ࣜࢵࢡࢫࡢ᥋ྜ㒊࡟࠾ࡅࡿゅᗘ࡟ᑐࡍࡿ࣏ࢸࣥࢩࣕࣝࢆࡼࡾᙉࡃࡋ࡚ࠊࡇࡢゅᗘࡢᦂࡽࡂࢆᢚ࠼ࡿ࡜ࠊ࣑࢜ࢩࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡴ⌧㇟ࡀ᫂ࡽ࠿࡟ῶᑡࡋࡓࠋࡇࡢࡇ࡜ࡣࠊ࣑࢜ࢩ

- 172 -

ࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡴࡉ࠸࡟ࡣࠊ᥋ྜ㒊ࡀ኱ࡁ࡞ゅᗘ࡛᭤ࡀࡿࡇ࡜࡟ࡼࡗ࡚Ᏻᐃ࡞┦஫స⏝ࡀᐇ⌧ࡉࢀ࡚ࡋࡲࡗ࡚࠸ࡓࡇ࡜ࢆព࿡ࡋ࡚࠸ࡿࠋࡇࡢ᮲௳ࡢࡶ࡜࡛ᚓࡽࢀࡓ 6SXGLFK ࣔࢹࣝࡢࣛࣥࢻࢫࢣ࣮ࣉ࡛ࡣࠊ
7KUHHKHOL[ EXQGOH ࡀ࢔ࣥࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿሙྜࢆ㝖࠸࡚ࠊ࣑࢜ࢩࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡴ⌧㇟ࡀῶᑡࡋ࡚
࠸ࡿ୍᪉ࠊୖグࡢ  ࠿ࡽ  ࡢ୺せ࡞⤖ㄽ࡟ࡣኚ᭦ࡀ࡞࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ௧࿴  ᖺᗘ࡟ࡣࠊ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡢᙧ≧ࢆỴᐃࡍࡿせᅉࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚ࠊ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࢆ࢚ࢿࣝࢠ࣮⏤᮶ࡢᡂศ࡜࢚ࣥࢺࣟࣆ࣮⏤᮶ࡢᡂศ࡟ศゎࡋࡓࡾࠊࡉࡽ࡟࢚
ࢿࣝࢠ࣮ࢆࡉࡲࡊࡲ࡞ᡂศ࡟ศゎࡋࡓࡾࡍࡿィ⟬ࢆ⾜ࡗࡓࠋᅗ D ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࢆᵓᡂࡍ
ࡿ࢚ࢿࣝࢠ࣮⏤᮶ࡢᡂศࢆᅗ Eࠊ࢚ࣥࢺࣟࣆ࣮⏤᮶ࡢᡂศࢆᅗ F ࡟ࡑࢀࡒࢀ♧ࡍࠋ࢚ࢿࣝࢠ࣮⏤᮶ࡢᡂศ࡜࢚ࣥࢺࣟࣆ࣮⏤᮶ࡢᡂศࡣ஫࠸࡟ࢺ࣮ࣞࢻ࢜ࣇࡢ㛵ಀ࡟࠶ࡾࠊࡑࢀࡽࡢᚤጁ࡞ࣂࣛࣥࢫ࠿ࡽࠊ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡢᙧ≧ࡀỴࡲࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ࢚ࢿࣝࢠ࣮ࢆᵓᡂࡍࡿせ⣲ࡢ࠺ࡕࠊ࣑࢜
ࢩࣥ࡜࢔ࢡࢳࣥࡢ࠶࠸ࡔ࡟ാࡃ㟼㟁┦஫స⏝ࡢᡂศࢆᅗ Gࠊ ࡘࡢ࣑࢜ࢩࣥ㢌㒊ࢆࡘ࡞ࡂྜࢃࡏࡿ 9 Ꮠᆺ࡟⤖ྜࡋࡓ  ࡘࡢᙎᛶᱱࡢᙎᛶኚᙧࡢ࢚ࢿࣝࢠ࣮ࢆᅗ H ࡟ࡑࢀࡒࢀ♧ࡍࠋ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺࡢࡽࡏࢇᑐ⛠ᛶ࡟ࡋࡓࡀࡗ࡚୪ࡪᏳᐃ࡞⤖ྜ㒊఩ࡀ㟼㟁┦஫స⏝࡟ࡼࡗ࡚ᙧᡂࡉࢀ࡚࠸ࡿ୍᪉ࠊᚋࢁ㊊ࡢ఩⨨࠿ࡽࡢ㊥㞳ࡢ㛵ᩘ࡜ࡋ࡚Ỵࡲࡿࣂ࢖࢔ࢫࡀᙎᛶᱱࡢᙎᛶኚᙧࡢ࢚ࢿࣝࢠ࣮࡟ࡼࡗ࡚⏕ࡲࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ  ‫ۻ‬.DLPD0DWVXGD0DVDNL6DVDL7RPRNL37HUDGD7KUHHVWDWHPRGHORIPXVFOHFRQWUDFWLRQZLWKVZLWFKHGIUHH

HQHUJ\ODQGVFDSHVDQGSRZHUVWURNH ➨  ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ ࢜ࣥࣛ࢖ࣥ㛤ദ  ᖺ  ᭶ 
  7DLVHL 1DJDWD 0DVDNL 6DVDL 7RPRNL 3 7HUDGD &RQIRUPDWLRQDO WUDQVLWLRQ RI 1WU& HOXFLGDWHG E\ WKHLPSURYHPHQW RI GLKHGUDO DQJOH SRWHQWLDO LQ FKDPHOHRQ PRGHO ➨  ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ ࢜ࣥࣛ࢖ࣥ㛤ദ ᖺ  ᭶   ‫ۻ‬7RPRNL 3 7HUDGD 4LQJ0LDR 1LH 0DVDNL 6DVDL $ ODQGVFDSHEDVHG YLHZ RQ WKH VWHSSLQJ PRYHPHQW RI
P\RVLQ9, ➨  ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ ࢜ࣥࣛ࢖ࣥ㛤ദ  ᖺ  ᭶  ฟ∧ᐇ⦼ࡲࡓࡣணᐃ  ‫ۻ‬4LQJ0LDR1LH0DVDNL6DVDL7RPRNL37HUDGD&RQIRUPDWLRQDOIOH[LELOLW\RIORRSVRIP\RVLQHQKDQFHVWKH

JOREDOELDVLQWKHDFWLQP\RVLQLQWHUDFWLRQODQGVFDSH3K\VLFDO&KHPLVWU\&KHPLFDO3K\VLFV㸦 ᖺ ᭶㸧  ‫ۻ‬4LQJ0LDR 1LH $NLR 7RJDVKL 7DNHVKL 1 6DVDNL 0LWVXQRUL 7DNDQR 0DVDNL 6DVDL 7RPRNL 3 7HUDGD&RXSOLQJ RI /HYHU $UP 6ZLQJ DQG %LDVHG %URZQLDQ 0RWLRQ LQ $FWRP\RVLQ 3/R6 &RPSXWDWLRQDO %LRORJ\   H㸦 ᖺ  ᭶㸧 %KDVZDWL%KDWWDFKDU\\D-LQ:DQJ0DVDNL6DVDL6WRFKDVWLFHSLJHQHWLFG\QDPLFVRIJHQHVZLWFKLQJ3K\VLFDO
5HYLHZ(    ᖺ  ᭶  0DVDNL6DVDL0HFKDQLVPRIDXWRQRPRXVV\QFKURQL]DWLRQRIWKHFLUFDGLDQ.DL$%&UK\WKP6FLHQWLILF5HSRUWV  ᖺ  ᭶ - 173 -

ࢱࣥࣃࢡ㉁࡜ศᏊ㞟ྜయࡢศᏊᶵ⬟ࡢ⌮ㄽィ⟬
7KHRUHWLFDOFDOFXODWLRQVRIPROHFXODUIXQFWLRQVRISURWHLQVDQG
PROHFXODUDVVHPEOLHV‫ۑ‬ᯘ 㔜ᙪࠊ಴㔜 భ㍤ࠊᡂ ࢭ࢖ࠊᒣᮏ ⿱⏕ࠊᑠᒣ ⣊ࠊ໭ᮧ ┤኱ࠊᯇᒣ ⥤ኟࠊすᑿ ᐀୍㑻ࠊ㮵಴ ၨྐࠊ㧗ᶫ ᏹᘺࠊ➉ෆ ⨾ᶞࠊୖ⏣ ዲᶵࠊ᱓⏣ ⚈ᕼࠊᚋ⸨ ᓅ㸦ி㒔኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧◊✲┠ⓗ7077) ⣔ࡢ㔞Ꮚ┦㌿⛣ศᏊᶵ⬟ࡢ࣓࢝ࢽࢬ࣒ࢆࠊ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾ᫂ࡽ࠿࡟ࡍࡿࠋࡲࡓࠊࢱࣥࣃࢡ㉁࡞

࡝ࡢ㐜࠸ࢲ࢖ࢼ࣑ࢡࢫࢆ᭷ࡍࡿศᏊᶵ⬟࡟㛵ࡋ࡚ࠊࣁ࢖ࣈࣜࢵࢻ 4000 ἲࠊཬࡧศᏊືຊᏛ㸦0'㸧ἲࢆ⏝࠸ࡓ◊✲ࢆ⾜࠺ࠋ1.1㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ TMTTF ⣔ࡢ㔞Ꮚ┦㌿⛣ࡢ⌮ㄽⓗゎᯒศᏊ㛫ࡢ㟁Ⲵ⛛ᗎࡢᵓ㐀ࡣศᏊᛶᑟయࡢ୰ᚰⓗ࡞ၥ㢟ࡢ୍ࡘ࡛࠶ࡿࠋ≉࡟ 7077) ⣔࡟࠾ࡅࡿ㟁Ⲵ⛛ᗎ┦ࡣ㟁Ⲵᒁᅾ┦࠿ࡽ

ᗘࢆୗࡆ࡚࠸ࡃ࡜ࠊほྍ⬟࡞ศᏊᵓ㐀ࡢኚ໬ࢆకࢃࡎ࡟⌧ࢀࡿࡼ࠺࡟ぢ࠼ࡿࡇ࡜࠿ࡽࠊ

ࡇࡢ㟁Ⲵᒁᅾ㟁Ⲵ⛛ᗎ┦㔞Ꮚ┦㌿⛣ࡣ VWUXFWXUHOHVV WUDQVLWLRQ ࡜࿧ࡤࢀࠊᮍゎ᫂࡞ၥ㢟࡜࡞ࡗ࡚࠸ࡓࠋ㏆ᖺࠊ㧗⢭ᗘ ; ⥺ᵓ㐀ゎᯒ࡟ࡼࡾ㟁Ⲵ⛛ᗎ┦࡛ࠊ7077) ศᏊ୰ࡢ & & ⤖ྜࡀ c ⛬ᗘࡢኚ໬ࡍࡿࡼ࠺࡞ศᏊෆ
ᵓ㐀ኚ໬ࢆ㉳ࡇࡍࡇ࡜࡛཯㌿ᑐ⛠ᛶࢆ◚ࡗ࡚࠸ࡿࡇ࡜ࡀሗ࿌ࡉࢀࡓࠋ୍᪉ࠊࣔࢹࣝィ⟬࡟ᇶ࡙ࡃ⌮ㄽⓗ࡞ゎᯒ࠿ࡽࡣࠊᣑᙇ +XEEDUG ᶍᆺࡢ⌮ㄽィ⟬࡟ࡼࡿ࡜᭱㏆᥋ࢡ࣮ࣟࣥ┦஫స⏝ࡢ኱ࡁࡉࡀ㟁Ⲵ⛛ᗎ┦ࡢⓎ⌧࡟㔜せ࡜ࡉࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊࡇࢀࡽࡢィ⟬ࡣᖹᆒሙ㏆ఝ࡟ࡼࡿྲྀᢅ࠸࡟ᇶ࡙࠸࡚࠾ࡾࠊࡲࡓᐇ㝿ࡢᵓ㐀ኚ໬࡟క࠺ࣃ࣓࣮ࣛࢱࡢኚ໬ࢆᐃ㔞ⓗ࡞ほⅬ࠿ࡽ⪃៖࡟ධࢀࡓ⌮ㄽィ⟬ࡣ࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊ࿘ᮇቃ⏺᮲௳ࢆㄢࡋ
ࡓ㔞Ꮚ໬Ꮫィ⟬࡜ࠊࡑࡇ࡛ᚓࡽࢀࡓ┦஫స⏝ࡢ኱ࡁࡉࢆࣃ࣓࣮ࣛࢱ࡜ࡋ࡚⏝࠸ࡓᣑᙇ +XEEDUG ᶍᆺࢆ⏝࠸ࡿ⌮ㄽィ⟬ࢆ⾜࠸ࠊ⌧ᐇⓗ࡞ࣃ࣓࣮ࣛࢱ㡿ᇦࡢ୰࡛ࡢ㔞Ꮚ┦㌿⛣ࡢᶵᵓ࡟ࡘ࠸᳨࡚ウࡋࡓࠋࡲࡓࠊࡇࡢ 7077) ⣔ࡣࠊᑐ࢔ࢽ࢜ࣥ࡟ࡼࡾ㟁Ꮚ≧ែࡀ኱ࡁࡃᙳ㡪ࢆཷࡅࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ≉࡟ࠊᑐ࢔ࢽ࢜ࣥࡀ 6E)$V)3) ࡜㍍ࡃ࡞ࡿ࡟ࡘࢀࠊຍᅽ࡟ࡼࡾ㉸ఏᑟ┦ࡀ⌧ࢀࡿ⮫⏺ᅽຊࡀపࡃ࡞ࡿ࡜ࡢሗ࿌
ࡀ࠶ࡾ໬Ꮫⓗᅽຊ࡜࿧ࡤࢀࡿࠋࡉࡽ࡟ࡇࡢ໬Ꮫⓗᅽຊࡀ኱ࡁ࠸࡯࡝㟁Ⲵ⛛ᗎࡀ୙Ᏻᐃ࡟࡞ࡿࡇ࡜ࡶほ࡚࠸ࡿࠋᐇ㝿ࡇࡢ⮫⏺ᅽຊࡢࡉࢀᐃࡀ 6E)$V)3) ࡢᑐ࢔ࢽ࢜ࣥࢆᣢࡘ 7077) ⣔࡛⾜ࢃࢀࡓ⤖ᯝࠊ⮫⏺ᅽ

ຊࡣ 6E)!!$V)!3) ࡜࡞ࡾ ࡑࢀࡒࢀ *3D*3D*3D ࠊ㉸ఏᑟࡢᏑᅾࡍࡿᅽຊ⠊ᅖࡶ 6E)!!$V)
Ҹ3) ࡜࡞ࡗࡓ ࡑࢀࡒࢀ *3D*3D*3D ࡲ࡛Ꮡᅾ ࠋࡇࡢᑐ࢔ࢽ࢜ࣥࡀ 6E) ࡢሙྜࡢ㟁Ꮚ≧ែࡢ␗ᖖᛶࢆࠊ
ᣑᙇ +XEEDUG ᶍᆺࢆ୰ᚰ࡜ࡋࡓ⌮ㄽィ⟬࡟ࡼࡾ᫂ࡽ࠿࡟ࡋࡓࠋ
1.2

ගྜᡂ⣔ II㸦PSII㸧ࡢ࣐ࣥ࢞ࣥࢡࣛࢫࢱ㓟໬㐣⛬ࡢ⌮ㄽⓗゎᯒ36,, ࡣࠊ᳜≀ࡸࣂࢡࢸࣜ࢔ࡢගྜᡂ࡟࠾ࡅࡿ㓟⣲ศᏊⓎ⏕ࢆᢸ࠸ࠊග྾཰࡛ᚓࡓ࢚ࢿࣝࢠ࣮ࢆ⏝࠸࡚ࠊ஧ࡘ
ࡢỈศᏊ࠿ࡽ㓟⣲ศᏊࢆ㓟໬ⓗ࡟ྜᡂࡍࡿࠋᮏ◊✲࡛ࡣࠊ40005:)(6&) ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ
㐀᭱㐺໬ࢆ⾜࠸ࠊ㓟⣲ศᏊⓎ⏕཯ᛂࡢ๓ẁ㝵࡛࠶ࡿ 6 ≧ែࡢศᏊᵓ㐀ཬࡧ㟁Ꮚ≧ែࡢゎ᫂ࢆ⾜࠺ࠋࡇࢀࡲ
࡛ࡢ◊✲࡛ࠊᬯ≧ែ࡛࠶ࡿ 6 ≧ែࠊཬࡧ୍㟁Ꮚග㓟໬≧ែ࡛࠶ࡿ 6 ≧ែࡢᵓ㐀࡜ࣉࣟࢺࣥ໬≧ែࢆ⌮ㄽⓗ࡟᫂ࡽ࠿࡟ࡋࡓࠋḟࡢග㓟໬≧ែ࡛࠶ࡿ 6 ≧ែ࡟ᑐࡋ࡚ࡣࠊ; ⥺⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡾࠊⓎ⏕ࡍࡿ㓟⣲ศᏊࡢ୍㒊࡟࡞ࡿ࡜⪃࠼ࡽࢀࡿỈศᏊࡀ࣐ࣥ࢞ࣥࢡࣛࢫࢱ࡟㓄఩ࡋᤄධࡉࢀࡓᵓ㐀ࡀ♧၀ࡉࢀ࡚࠸ࡿࡀࠊ㓟⣲
ศᏊⓎ⏕ࡢ཯ᛂᶵᵓࡢ⌮ゎ࡟㔜せ࡜࡞ࡿ㓄఩ࡢ⤖ྜᵝᘧࡸࣉࣟࢺࣥ໬≧ែ࡟㛵ࡋ࡚ࡣ౫↛୙᫂ࡢࡲࡲ࡛࠶ࡿࠋ
ᮏ◊✲࡛ࡣࠊᚓࡽࢀࡓ 6 ≧ែࡢࣔࢹࣝ࡟ᇶ࡙ࡁᵓ⠏ࡋࡓ 6 ≧ែࡢᵝࠎ࡞ࣉࣟࢺࣥ໬࣭㓟໬≧ែࣔࢹࣝ࡟ᑐ

- 174 -

ࡋ࡚⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠸ࠊ⌮ㄽⓗゎᯒࢆ⾜࠺ࠋ1.3ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡣࠊග㑇ఏᏛࡢ㔜せ࡞ࢱࣥࣃࢡ㉁ࢶ࣮࡛ࣝ࠶ࡿࠋග㥑ື࢔ࢽ࣏࢜ࣥࣥ
ࣉ࡛࠶ࡿࣁࣟࣟࢻࣉࢩࣥ㸦K5㸧ࡣࠊග↷ᑕ࡟ࡼࡗ࡚⚄⤒⣽⬊ࡢάᛶ໬ࢆᢚไࡍࡿࡓࡵ࡟⏝࠸ࡽࢀ࡚࠸ࡿࠋ᭦
࡟ࠊ᭱㏆ ; ⥺⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡾࡑࡢᵓ㐀ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ *W$&5 ࡣࠊගឤཷᛶࡢ࢔ࢽ࢜ࣥࢳࣕࢿ࡛ࣝ
࠶ࡾ +5 ࡼࡾ㧗ຠ⋡࡞⚄⤒⣽⬊ࡢᢚไࡀྍ⬟࡜࡞ࡗ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡑࡢ࢖࢜ࣥఏᑟᗘࡣࠊෆᅾᛶࡢ࢖࢜ࣥ
ࢳࣕࢿࣝ࡜ẚ㍑ࡋ࡚኱ࡁࡃຎࡗ࡚࠾ࡾࠊ㧗࠸࢖࢜ࣥఏᑟᗘࢆ᭷ࡍࡿኚ␗యࡢ㛤Ⓨࡀồࡵࡽࢀ࡚࠸ࡿࠋࡲࡓࠊ
K5 ࡜ *W$&5 ࡣ㠀ᖖ࡟Ⰻࡃఝࡓᵓ㐀ࢆ᭷ࡍࡿࡀࠊࡑࡢᶵ⬟ࡣ࣏ࣥࣉ㸦⬟ື㍺㏦㸧࡜ࢳࣕࢿࣝ㸦ཷື㍺㏦㸧
࡜␗࡞ࡗ࡚࠾ࡾࠊࡑࡢ㐪࠸ࢆ୚࠼ࡿศᏊᶵᵓࡣᮍゎࡢࡲࡲ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ40005:)(6&) ἲ࡜ 0'ἲࢆ⏝࠸࡚ K5 ࡜ *W$&5 ࡢගάᛶ໬ᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ
1.4

HIV ࣉࣟࢸ࢔࣮ࢮࡢ㓝⣲཯ᛂᶵᵓࡢゎᯒ

+,9 ࣉࣟࢸ࢔࣮ࢮࡣ +,9 ࢘࢖ࣝࢫឤᰁࢆ㜼ᐖࡍࡿ⸆๣㛤Ⓨࡢࢱ࣮ࢤࢵࢺ࡟࡞ࡗ࡚࠾ࡾࠊࡑࡢ㓝⣲཯ᛂࡢ㑄⛣≧ែࢆᶍೌࡋࡓ㑄⛣≧ែ࢔ࢼࣟࢢᆺࡢ⸆๣ࡀ㛤Ⓨࡉࢀ࡚࠸ࡿࡀࠊ୍᪉࡛㧗࠸⸆๣⪏ᛶ⬟ࢆ᭷ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࢀࡲ࡛ࡢィ⟬࡟ࡼࡾࠊኚ␗ᑟධ࡟ࡼࡾ⸆๣ศᏊࡢ⤖ྜ࢚ࢿࣝࢠ࣮ࡀ኱ᖜ࡟పୗࡍࡿࡇ࡜ࡀ᫂
ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ40005:)(6&) ἲࢆ⏝࠸࡚ࠊኳ↛ᇶ㉁ศᏊࡢ㓝⣲཯ᛂࡢศᏊᶵ
ᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡟ࡼࡾࠊ⸆๣⪏ᛶࡢศᏊᶵᵓ࡟㛵ࡍࡿ▱ぢࢆᚓࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ

2.1

㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ TMTTF ⣔ࡢ㔞Ꮚ┦㌿⛣ࡢ⌮ㄽⓗゎᯒ୍ḟඖᣑᙇ +XEEDUG ᶍᆺࡢྛࣃ࣓࣮ࣛࢱࢆỴᐃࡍࡿࡓࡵࠊᐇ㦂࡛ほࡉࢀࡓ✀ࠎࡢᵓ㐀ኚ໬ࢆ⪃៖ࡋࡓᵓ㐀ࣔࢹࣝ࡟ᇶ࡙ࡁᐦᗘỗ㛵ᩘ⌮ㄽィ⟬ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ୍㟁Ꮚᅛ᭷㛵ᩘ࠿ࡽ᭱ᒁᅾ :DQQLHU ㌶㐨 7077) ศᏊࡢ +202 ࢆィ⟬ࡋࠊࡑࡢ㌶㐨࢚ࢿࣝࢠ࣮ཬࡧ⛣ື✚ศࢆィ⟬ࡋࡓࠋỗ㛵ᩘࡣ 3HUGHZ%XUNH(UQ]HUKRI 3%(ỗ㛵ᩘࠊᨃ࣏ࢸࣥࢩࣕࣝࡣࣀ࣒ࣝಖᏑᆺᨃ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸ࡓࠋࡉࡽ࡟஧㟁Ꮚࢡ࣮ࣟࣥ┦஫స⏝ࢆぢ✚ࡶࡿࡓࡵ࡟ࠊ࿘ᮇቃ⏺᮲௳ࢆㄢࡋࡓ㔞Ꮚ໬Ꮫィ⟬+DUWUHH)RFN ἲࢆୖグᵓ㐀࡟࠾࠸࡚ィ⟬ࡋࡓࠋࡇࢀࡽࡢィ⟬࠿ࡽᚓࡽࢀࡓ┦஫స⏝ࣃ࣓࣮ࣛࢱࢆ⏝࠸ࡓᣑᙇ +XEEDUG ᶍᆺ࡟ࡘ࠸࡚ཝᐦᑐゅ໬ᡭἲ࡟ࡼࡾᇶᗏ≧ែࢆồࡵࠊ」⣲ศᴟ⋡ࡸ㟁Ⲵ୙ᆒ໬ࢆぢ✚ࡶࡿࡓࡵ࡟୍⢏Ꮚᐦᗘ⾜ิࢆィ⟬ࡋࡓࠋࡑࡋ࡚ࡇࢀࡽࡢ≀ᛶ್࠿ࡽ㟁Ⲵࢠࣕࢵࣉࢆぢ✚ࡶࡗࡓࠋ
ྠᵝࡢィ⟬ᡭἲ࡟࡚ຍᅽ࡟ࡼࡿᵓ㐀ኚ໬ࢆཷࡅࡓ㝿ࡢ୍ḟඖᣑᙇ +XEEDUG ᶍᆺࡢࣃ࣓࣮ࣛࢱࢆぢ✚ࡶࡗࡓࠋຍᅽࡢຠᯝࢆᶍᆺ࡟ྲྀࡾ㎸ࡴࡓࡵ࡟⛣ື✚ศࢆ኱Ẽᅽ࡛ࡢ್ࢆ୰ᚰ࡜ࡋ࡚ࡉࡲࡊࡲ࡞್࡟ኚ໬ࡉࡏࠊ≀ᛶ್ࡢኚ໬ࢆぢ✚ࡶࡗࡓࠋࡉࡽ࡟ࠊ7077) ⣔࡛ほࡉࢀ࡚࠸ࡿศᏊࡢ㟁Ꮚⓗ࡞஧㔞య໬࡞ࡽࡧ࡟ศᏊෆᵓ㐀ኚ໬࡟ࡘ࠸࡚⤖ᬗᵓ㐀࠿ࡽࡢᵓ㐀ኚ໬ࢆࣔࢹࣝ໬ࡋࠊ⛣ື✚ศ࡜㟁Ꮚⓗ࡞஧㔞య໬࡞ࡽࡧ࡟ࠊ⛣ື✚ศ࡜ศᏊෆ
ᵓ㐀ኚ໬࡟ᑐࡍࡿ」⣲ศᴟ⋡࡜㟁Ẽ᢬ᢠࡢᣦᶆ࡜࡞ࡿ 'UXGH 㔜ࡳ್ࡢኚ໬ࢆཝᐦᑐゅ໬࡟ࡼࡾᚓࡽࢀࡓᇶᗏ
≧ែゎࢆ⏝࠸࡚ィ⟬ࡋࠊࡇࢀࡽ㸰ࡘࡢᵓ㐀ኚ໬࡟ᑐࡍࡿ஧ḟඖ┦ᅗࢆồࡵゎᯒࢆ⾜࡞ࡗࡓࠋ
2.2

ගྜᡂ⣔ II㸦PSII㸧ࡢ࣐ࣥ࢞ࣥࢡࣛࢫࢱ㓟໬㐣⛬ࡢ⌮ㄽⓗゎᯒ࣐ࣥ࢞ࣥࢡࣛࢫࢱ཯ᛂ୰ᚰ㒊఩ࢆ 40 㡿ᇦ࡜ࡋ࡚ 4000 5:)(6&) ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋ40 㡿ᇦࡢィ⟬ࡣ %/<3 ἲ㸦⣙  ᇶᗏ㛵ᩘᩘ㸧ࢆ⏝࠸࡚⾜ࡗࡓࠋ00 㡿ᇦࡣ⣙ ཎᏊ࡛ࠊ$PEHU ศᏊຊሙࢆ⏝࠸࡚グ㏙ࡋࡓࠋ4000 ィ⟬ࡣࠊ⊂⮬ࡢ 4000 ࢖ࣥࢱ࣮ࣇ࢙࣮ࢫ
ࢆ⤌ࡳ㎸ࢇࡔ *$0(66ࠊ00 㡿ᇦࡢ 0' ィ⟬ࡣ $PEHU ࣉࣟࢢ࣑ࣛࣥࢢࣃࢵࢣ࣮ࢪࢆ⏝࠸ࡓࠋ
2.3

ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ

- 175 -

ⓎⰍᅋศᏊ㒊ศ㸦 ཎᏊ㸧ࢆ 40 㡿ᇦ࡜ࡋࠊ4000 5:)(6&) ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ࠊ
ཬࡧ 0' ィ⟬ࢆ⾜ࡗࡓࠋࡇࡢ㝿ࠊ40 㡿ᇦࡢィ⟬ࡣ 0;* 㸦⣙  ᇶᗏ㛵ᩘ㸧ࢆ⏝࠸ࠊ00 㡿
ᇦࡣ *W$&5 ࡀ⣙  ୓ཎᏊࠊK5 ࡀ⣙  ୓ཎᏊ࡛ࠊ$PEHU ཬࡧ &+$500 ศᏊຊሙࢆ⏝࠸࡚グ㏙ࡋࡓࠋ
0' ィ⟬ࡣࡑࢀࡒࢀ $PEHU ཬࡧ 1$0' ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࢆ⏝࠸ࡓࠋ
2.4

HIV ࣉࣟࢸ࢔࣮ࢮࡢ㓝⣲཯ᛂᶵᵓࡢゎᯒኳ↛ᇶ㉁ศᏊࢆྵࡴ཯ᛂάᛶ㒊఩ࡢ  ཎᏊࢆ 40 㡿ᇦ࡜ࡋ࡚㸦ᇶᗏ㛵ᩘᩘ 㸧 40005:)(6&) ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋ00 㡿ᇦࡣ⣙  ཎᏊ࡛ $PEHU ศᏊຊሙࢆ⏝࠸࡚グ㏙ࡋࡓࠋ


3.1

◊✲ᡂᯝ
㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ TMTTF ⣔ࡢ㔞Ꮚ┦㌿⛣ࡢ⌮ㄽⓗゎᯒ࿘ᮇቃ⏺᮲௳ࡢ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚Ỵࡵࡓࢡ࣮ࣟࣥ┦஫స⏝ࢆ⏝࠸ࡿ࡜ࠊᐇ㦂࡛ᚓࡽࢀࡓᚤᑠ࡞ᵓ㐀ኚ໬࡛㟁Ⲵ⛛ᗎ㔞Ꮚ┦㌿⛣ࢆ෌⌧࡛ࡁࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ࿘ᮇቃ⏺᮲௳ࡢ㔞Ꮚ໬Ꮫィ⟬ࡣ㟁Ꮚ㟁Ꮚ┦஫స⏝ࡀ᱁Ꮚ࡟ࡼࡾࢫࢡ࣮ࣜࢽࣥࢢࡉࢀࡿຠᯝࢆྲྀࡾධࢀࡿࡇ࡜ࡀྍ⬟࡛࠶ࡾࠊ➨஧㏆᥋ࢡ࣮ࣟࣥ┦஫స⏝ࡀᘬຊⓗ࡟࡞ࡿࠋࡇࡢᘬຊ┦஫స⏝ࡢᏑᅾୗ࡛」⣲ศᴟ⋡ࡢィ⟬࠿ࡽࠊᚤᑠ࡞ศᏊෆᵓ㐀ኚ໬࡟ࡼࡿᛴ⃭࡞⤯⦕໬ࠊ୪ࡧ࡟  ⢏Ꮚᐦᗘ⾜ิࡢィ⟬࠿ࡽᛴ⃭࡞㟁Ⲵࡢ୙ᆒ໬ࡀほࡉࢀࡓࠋ㉸ఏᑟࡢⓎ⌧࡟㟁Ꮚⓗ஧㔞య໬୪ࡧ࡟ࠊ

ศᏊෆᵓ㐀ኚ໬ࡀ㔜せ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ㟁Ꮚⓗ஧㔞య໬ࡣ㟁Ⲵࢠࣕࢵࣉࢆ㛤ࡃຠᯝࡀ࠶ࡿࡀࠊ㟁Ẽ᢬ᢠ࡟ࡣ࡯࡜ࢇ࡝ᙳ㡪ࢆ୚࠼࡞࠸ࠋ㟁Ꮚⓗ஧㔞య໬ࡀ༑ศ࡟ᑠࡉ࠸࡜ࠊ㟁Ⲵࢠࣕࢵࣉࡣ㛢ࡌࠊ㉸ఏᑟ┦࠿ࡽ㔠ᒓ┦࡟㌿⛣ࡍࡿࠋศᏊෆᵓ㐀ኚ໬ࡣࠊ㟁Ⲵࢠࣕࢵࣉࠊ㟁Ẽ᢬ᢠࡢ୧᪉࡟ᙳ㡪ࢆ୚࠼ࡿࠋศᏊෆᵓ㐀ኚ໬࡟ࡼࡾࠊ㟁Ⲵࢠࣕࢵࣉࡀ኱ࡁ࠸⛣ື✚ศ࡛ࡶ㛤ࡁࠊ㟁Ẽ᢬ᢠࡀࢮࣟ࡟࡞ࡿ⛣ື✚ศࡢ⠊ᅖࡀ㧗ᅽഃ࡟ᗈࡀࡿࠋ
6E) ሷ࡛ࡣ㟁Ⲵ⛛ᗎࡀ≉࡟ᙉ࠸ࡓࡵࠊศᏊෆᵓ㐀ኚ໬ࡀᖖᅽ࡛኱ࡁ࠸࡜ண᝿ࡉࢀࠊ㉸ఏᑟ㌿⛣ࡀ㉳ࡇࡿ⮫⏺
ᅽຊࡀ㧗ᅽഃ࡟ࡎࢀࠊ㉸ఏᑟ┦ࡢᏑᅾࡍࡿᅽຊ⠊ᅖࡀᗈ࠸ࡇ࡜ࡀ⌮ゎࡉࢀࡿࠋ
3.2

ගྜᡂ⣔ II㸦PSII㸧ࡢ࣐ࣥ࢞ࣥࢡࣛࢫࢱ㓟໬㐣⛬ࡢ⌮ㄽⓗゎᯒ

6 ≧ែ⏕ᡂ࡟ࡼࡾࠊ࣐ࣥ࢞ࣥࢡࣛࢫࢱ 2 ࡜ 0Q ཎᏊࡢ㛫࡟ᇶ㉁ỈศᏊࡀᤄධࡋࠊ࣐ࣥ࢞ࣥࢡࣛࢫࢱࡢࣉ
ࣟࢺࣥࡀ୍ಶᨺฟࡉࢀࡿࡇ࡜ࡀᐇ㦂ⓗ࡟▱ࡽࢀ࡚࠸ࡿࠋ6 ≧ែ࡜ࡋ࡚ྍ⬟ᛶࡢ㧗࠸≧ែ࡜ࡋ࡚ࠊᤄධࡉࢀࡓ
ỈศᏊ࠿ࡽ୍ಶࣉࣟࢺࣥࡀ⬺㞳ࡋ 2 ཎᏊࡣࣉࣟࢺࣥ໬ࢆಖࡗ࡚࠸ࡿ≧ែࠊཬࡧ 2 ࠿ࡽࣉࣟࢺࣥࡀ⬺㞳ࡋᤄධࡉࢀࡓỈศᏊࡢࣉࣟࢺࣥࡣ࣐ࣥ࢞ࣥࢡࣛࢫࢱ࡟ಖᣢࡉࢀ࡚࠸ࡿ≧ែࡀ⪃࠼ࡽࢀࡿࠋ᭦࡟ࠊᚋ⪅࡟࠾࠸࡚ࡣࠊᤄධỈศᏊࡀ  ಶࡢࣉࣟࢺࣥࢆಖᣢࡋ࡚࠸ࡿ≧ែࠊཬࡧ 2 ཎᏊཬࡧᤄධỈศᏊࡀࡑࢀࡒࢀ  ಶࡎࡘࣉࣟࢺࣥ໬ࡋ࡚࠸ࡿ≧ែࡀ⪃࠼ࡽࢀࡿࠋࡲࡓࠊ㓟໬≧ែ࡜ࡋ࡚ࠊ0Q ཎᏊࡀ㓟໬ࡉࢀࡓ≧ែ࡜ᤄධỈศᏊࡀ㓟໬ࡉࢀࡓ≧ែࡢ஧ࡘࡢ≧ែࡶྍ⬟࡛࠶ࡿࠋࡑࡇ࡛ࠊࡑࢀࡽࡢྍ⬟࡞≧ែ࡟ᑐࡋ࡚ 4000 5:)(6&) ἲ࡟ࡼࡿ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋ࠸ࡃࡘ࠿ࡢ≧ែ࡟㛵ࡋ࡚ࡣᵓ㐀᭱㐺໬ࡀ᏶஢ࡋࠊ0Q ཎᏊࡀ㓟໬ࡉࢀࡓ≧ែ࡟㛵ࡋ࡚᭷ᮃ࡞ࣉࣟࢺࣥ໬≧ែࢆྠᐃࡋࡓࠋᤄධỈศᏊࡀ㓟໬ࡉࢀࡓ≧ែ࡟㛵ࡋ࡚ࡣࠊᏳ
ᐃᛶࡀࣁ࢖ࣈࣜࢵࢻỗ㛵ᩘࡢࣁ࣮ࢺ࣮ࣜࣇ࢛ࢵࢡ஺᥮㡯ࡢ๭ྜ࡟኱ࡁࡃ౫Ꮡࡍࡿࡓࡵࠊࣁ࣮ࢺ࣮ࣜࣇ࢛ࢵࢡ
஺᥮㡯ࡢẚ⋡ࢆኚ໬ࡉࡏࡓᵓ㐀᭱㐺໬ィ⟬ࢆ㛤ጞࡋࡓࠋ
3.3

ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ

*W$&5 ࢱࣥࣃࢡ㉁ࡢᬯ≧ែཬࡧࣞࢳࢼ࣮ࣝⓎⰍᅋศᏊࡢග␗ᛶ໬཯ᛂ┤ᚋࡢ . ୰㛫≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮᭱㐺໬ᵓ㐀ࢆ 4000 5:)(6&) ィ⟬࡟ࡼࡾỴᐃࡋࠊࡑࡢᵓ㐀࡟ᑐࡋ࡚  ࣐࢖ࢡࣟ⛊ࡢ 0' ィ⟬ࢆ⾜࠸ᵓ㐀Ᏻᐃᛶࡸ࢖࢜ࣥศᕸࡢゎᯒࢆ⾜ࡗࡓࠋࡑࡢ㝿ࠊࣞࢳࢼ࣮ࣝⓎⰍᅋศᏊࡢࣉࣟࢺࣥ໬ࢩࢵࣇሷᇶࡢᑐ࢖
࢜ࣥ࡜⪃࠼ࡽࢀࡿ஧ࡘࡢ࢝ࣝ࣎ࣥ㓟ഃ㙐㸦*OX ཬࡧ $VS㸧ࡢࣉࣟࢺࣥ໬≧ែࡀᐇ㦂ⓗ࡟☜ᐃࡋ࡚࠸࡞࠸

- 176 -

ࡓࡵࠊ␗࡞ࡿࣉࣟࢺࣥ໬≧ែ࡟ᑐࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ*OX ࡀ⬺ࣉࣟࢺࣥ໬ࡋ࡚࠸ࡿ≧ែ࡟㛵ࡋ࡚ࡣࠊᬯ≧ែ࡟࠾࠸࡚⣽⬊ෆഃࢳࣕࢿࣝࡢ㛢ሰᵓ㐀ࡀᔂቯࡋ୙Ᏻᐃ࡞ᵓ㐀࡜࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ୍᪉ࠊ*OX
ࡀࣉࣟࢺࣥ໬ࡋ࡚࠸ࡿ≧ែ࡟࠾࠸࡚ࡣࠊࢱࣥࣃࢡ㉁ᵓ㐀ࡀᏳᐃ࡟᥎⛣ࡋࡓࠋ᭦࡟ࠊ㉥እศගᐇ㦂࡟ࡼࡾ♧၀ࡉࢀ࡚࠸ࡿ $VS ࡢ࢝ࣝ࣎ࣥ㓟ഃ㙐ࡀࣉࣟࢺࣥ໬ࡋ࡚࠸ࡿ≧ែ࡟ᑐࡋ࡚ࡣࠊࣂࣝࢡ୰ࡢሷ⣲࢖࢜ࣥࡀ⣽⬊እഃࢳࣕࢿࣝ࡟౵ධࡋ⤖ྜࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋሷ⣲࢖࢜ࣥࡣࢳࣕࢿࣝෆ࡛኱ࡁࡃືࡁᅇࡾࠊࢳࣕࢿࣝᶵ⬟࡟ᚲせ࡞ᖹᆠ࡞⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝ࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡲࡓࡇࡢሷ⣲࢖࢜ࣥࡢ⣽⬊እഃࢳࣕࢿࣝ࡬ࡢ⤖ྜࡣ . ୰㛫≧ែ࡟࠾࠸࡚ࡶಖᣢࡉࢀࡓࠋ
ḟ࡟ K5 ࡟㛵ࡋ࡚ࡣࠊ㉥እศගᐇ㦂࡟ࡼࡾ♧၀ࡉࢀ࡚࠸ࡿග୰㛫≧ែ࡟࠾ࡅࡿ⣽⬊እഃࢳࣕࢿࣝධࡾཱྀࡢ
࢝ࣝ࣎ࣥ㓟ഃ㙐࠿ࡽࡢࣉࣟࢺࣥ㞳⬺ࢆྵࡴගࢧ࢖ࢡࣝ࡟ᑐࡍࡿᬯ≧ែཬࡧග୰㛫≧ែࡢࣔࢹࣜࣥࢢࢆࠊ
40005:)(6&) ἲࢆ⏝࠸࡚⾜ࡗࡓࠋࡇࡢගࢧ࢖ࢡ࡛ࣝࡣᬯ≧ែཬࡧึᮇග୰㛫≧ែ࡟࠾࠸࡚ࡣ࢝ࣝ࣎ࣥ
㓟ഃ㙐ࡀࣉࣟࢺࣥ໬ࡋ࡚࠸ࡿࠋᬯ≧ែ࡟࠾࠸࡚ࡣࠊ; ⥺⤖ᬗᵓ㐀࡛♧၀ࡉࢀ࡚࠸ࡿࡼ࠺࡟ሷ⣲࢖࢜ࣥࡣࣞࢳ
ࢼ࣮ࣝⓎⰍᅋศᏊ㏆ഐ࡟⤖ྜࡉࢀ࡚࠸ࡓࡀࠊึᮇග୰㛫≧ែ࡛ࡣࢳࣕࢿࣝෆ࡛ࡢ⣽⬊እഃ࡬ࡢ⛣ືࡀぢࡽࢀࡓࠋ᭦࡟ࠊ⣽⬊እഃࢳࣕࢿࣝෆࡢ࢔ࣝࢠࢽࣥഃ㙐ࡢᵓ㐀ࢆኚ໬ࡉࡏࠊ⣽⬊እഃࢳࣕࢿࣝධࡾཱྀࡢ࢝ࣝ࣎ࣥ㓟ࡀ⬺ࣉࣟࢺࣥ໬ࡋࡓ୰㛫≧ែࡢࣔࢹࣝࢆᵓ⠏ࡋ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋ
2.4

HIV ࣉࣟࢸ࢔࣮ࢮࡢ㓝⣲཯ᛂᶵᵓࡢゎᯒࡇࢀࡲ࡛ࡢ◊✲࡛ᚓࡽࢀ࡚࠸ࡿຍỈศゎ཯ᛂࡢ๓༙㒊ศ࡛࠶ࡿỈศᏊࡀ௜ຍࡋࡓ≧ែࢆฟⓎᵓ㐀࡜ࡋࠊ㏆ഐࡢỈศᏊࡢࣉࣟࢺࣥ⛣ື࡟ࡼࡾゎ㞳࢔࣑ࣥᇶࡀࣉࣟࢺࣥ໬ࡋࡓ≧ែ࡬ࡢ⤒㊰ࢆ᥈⣴ࡋࡓࠋࡑࡢ⤖ᯝࠊ㏆ഐỈศᏊࡢᅇ㌿࡟ࡼࡾࣉࣟࢺࣥ⛣ື⤒㊰ࡀ☜❧ࡋࠊ࢔࣑ࣥᇶࡀࣉࣟࢺࣥࢆཷᐜࡋࡓ୰㛫≧ែࡢ᭱㐺໬ᵓ㐀ࢆᚓࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫  ➨ ۻ‬ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ ࢜ࣥࣛ࢖ࣥ  ᖺ  ᭶  ᪥ ´$WRPLVWLFDOO\ GHFLSKHULQJ IXQFWLRQDODFWLYDWLRQSURFHVVHVRISURWHLQVZLWKPROHFXODUVLPXODWLRQV6KLJHKLNR+D\DVKL㸦ᣍᚅㅮ₇㸧‫  ➨ ۻ‬ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ ࢜ࣥࣛ࢖ࣥ  ᖺ  ᭶  ᪥㹼  ᪥ ³)UHH HQHUJ\ FDOFXODWLRQV RI
+,9SURWHDVHELQGLQJLQGLQDYLUDQGLWVGUXJUHVLVWDQWPXWDQW´0DVDKLUR7DJXFKL5\R2\DPD0DVDKLNR.DQHVR
DQG6KLJHKLNR+D\DVKL㸦࣏ࢫࢱ࣮Ⓨ⾲㸧‫  ➨ ۻ‬ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ ࢜ࣥࣛ࢖ࣥ  ᖺ  ᭶  ᪥㹼  ᪥ ³7KHRUHWLFDO VWXG\ RQ PROHFXODUPHFKDQLFVRIQDWXUDODQLRQFKDQQHOUKRGRSVLQ*W$&5´7DGDIXPL6KLNDNXUD&KHQJ&KHQJDQG6KLJHKLNR+D\DVKL㸦࣏ࢫࢱ࣮Ⓨ⾲㸧‫  ➨ ۻ‬ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ ࢜ࣥࣛ࢖ࣥ  ᖺ  ᭶  ᪥㹼  ᪥ ³7KHRUHWLFDO VWXG\ RQ PROHFXODUPHFKDQLVP RI D OLJKWGULYHQ LRQ WUDQVSRUW RI +DORUKRGRSVLQ´ 5\R 2\DPD 7DLVXNH +DVHJDZD DQG 6KLJHKLNR+D\DVKL㸦࣏ࢫࢱ࣮Ⓨ⾲㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬$ELQLWLRHYDOXDWLRQRIWKHUHGR[SRWHQWLDORIF\WRFKURPHF&&KHQJDQG6+D\DVKL-&KHP7KHRU\&RPSXW17  $FRPSXWDWLRQDOPHWKRGWRVLPXODWHJOREDOFRQIRUPDWLRQDOFKDQJHVRISURWHLQVLQGXFHGE\FRVROYHQW67DQLPRWR.
7DPXUD6+D\DVKL1<RVKLGDDQG+1DNDQR-&RPSXW&KHP42  
7LPHUHVROYHGVHULDOIHPWRVHFRQGFU\VWDOORJUDSK\UHYHDOVHDUO\VWUXFWXUDOFKDQJHVLQFKDQQHOUKRGRSVLQ.2GD ͐
6+D\DVKL ͐0.XER71LVKL]DZDDQG21XUHNL㸦 ே୰  ␒┠㸧H/LIH10H  - 177 -

⺮ⓑ㉁࡟ࡼࡿ '1$ ຍỈศゎ࡟࠾ࡅࡿ⁐፹ࡢᙺ๭
7KHUROHRIVROYHQWLQ'1$K\GURO\VLVZLWKDSURWHLQ‫ۑ‬ධబ ṇᖾ㸦஑ᕞᕤᴗ኱Ꮫ኱Ꮫ㝔᝟ሗᕤᏛ㝔㸧1◊✲┠ⓗࠊෆᐜ
II ᆺࡢไ㝈㓝⣲ࡢ୍ࡘ࡛࠶ࡿ EcoRV ࡣ࣍ࣔࢲ࢖࣐࣮࡛࠶ࡾࠊ

ࢧࣈࣘࢽࢵࢺ࠶ࡓࡾ㸯ಶ࠶ࡿάᛶ㒊఩࡛ࡢ DNA ࡢຍỈศゎ࡟㸰ಶࡢ Mg 2+ ࢖࢜ࣥࢆᚲせ࡜ࡍࡿࠋ DNA ࡢຍỈศゎ࡛ࡣࠊỈศᏊࡣ࿘ࡾࡢ⎔ቃ࡜ࡋ࡚ࡢ⁐፹࡜ࡋ࡚ാࡃࡔࡅ࡛࡞ࡃࠊ┤᥋ồ᰾ᨷᧁࢆ⾜࠺ỈศᏊࠊࡲࡓᇶ㉁࡜ࡋ࡚ࡢỈศᏊࠊ࡜ࡋ࡚ാࡃࠋᡃࠎࡢ◊✲ᐊ࡛ࡣࡇࢀࡲ࡛ࠊ EcoRV̽DNA 」ྜయࡢ཯ᛂ㒊఩ࡢỈศᏊ࠾ࡼࡧ
Mg 2+ ࢖࢜ࣥࡢᙺ๭ࢆィ⟬⛉Ꮫᡭἲ࡛⪃ᐹࡋ࡚ࡁࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲࡇࢀࡲ࡛ࡢ◊✲࡛ࡣ୺࡟㸰ࡘࡢࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋ 1. ཯ᛂ㒊ᅗ  6WUXFWXUH 0 DQ HTXLOLEULXP DFWLYHVLWHVWUXFWXUH REWDLQHG IURP 0' WUDMHFWRULHV LQ RXUSUHYLRXV VWXG\ 7ZR UHDFWLRQ FRRUGLQDWHV 5&V 
3±2: GLVWDQFH 5&  DQG ERQGOHQJWK RI WKHVFLVVLOHERQG 5&  DUH DGRSWHG WR DQDO\]H WKHUHVXOWVRI4000PHWDG\QDPLFV఩ࡢỈศᏊ࠾ࡼࡧ Mg 2+ ࢖࢜ࣥࡢ఩⨨࡜ᩘࢆ 3D-RISM⌮ㄽࢆ⏝࠸࡚Ỵᐃࡋࠊࡑࡢᵓ㐀ࢆᇶ࡟ศᏊືຊᏛ
(Molecular Dynamics, MD) ィ⟬ࢆ⾜࠺ࡇ࡜࡛ຍỈศゎ཯ᛂࡢ๓㥑యࡢ❧యᵓ㐀ࢆᚓࡓࠋ 2. ࡇࡢ๓㥑యࡢ❧యᵓ㐀࠿ࡽ㔞Ꮚ໬Ꮫィ⟬ (QM/MM MD) ࢆ⾜࠸ࠊ DNA ษ᩿ࡢຍỈศゎ࡟࠾ࡅࡿ཯ᛂ࣮ࣝࢺࢆ᥈⣴ࡋࡓ⤖ᯝࠊdissociative reaction path ࡜ associative reaction path ࡢ 2ࡘࡢ࣮ࣝࢺࢆᚓࡓࠋ௒ᅇࡣࠊ཯ᛂ୰࡟࡝ࡢࡼ࠺࡟ࣉࣟࢺ
ࣥࡀ⛣ືࡋ࡚࠸ࡿ࠿ࢆࠊศᏊࢢࣛࣇ࢕ࢡࢫࢯࣇࢺ࢙࢘࢔
࡛࠶ࡿ UCSF Chimera ࢆ౑⏝ࡋື⏬ࢆసᡂࡍࡿࡇ࡜࡛ࠊ
཯ᛂ㒊఩࡛ࡢゐ፹ṧᇶࠊỈศᏊࠊࡑࡋ࡚ Mg 2+ ࢖࢜ࣥࡢᙺ๭ࢆㄪ࡭ࡓࠋ

3

ᅗ 2: PMF surface obtained from QM/MM
metadynamics. The minimum energy pathway was
dissociative (solid line). The associative pathway isalso plotted (dashed dotted line). Two reaction
coordinates, P–nucleophilic water O distance (RC1)and bond-length of the scissile-bond (RC2), are◊✲ᡂᯝ㔞Ꮚ໬Ꮫィ⟬࡛ࡣ㸰ࡘࡢ཯ᛂᗙᶆࢆ⏝࠸࡚࠸ࡿ(ᅗ 1)ࠋࡑࡢ୍ࡘ (RC1) ࡣࠊồ᰾๣࡛࠶ࡿỈศᏊࡢ㓟⣲ཎᏊ
࡜ࠊ scissile ࣜࣥ㓟ᇶࡢ⇥ཎᏊࡢ㊥㞳ࠊࡶ࠺୍ࡘ(RC2) ࡣࠊ scissile bond ࡢ㛗ࡉ࡛࠶ࡿࠋ㸰ࡘࡢ཯ᛂᗙᶆ࡟
ࡼࡿ⮬⏤࢚ࢿࣝࢠ࣮ࡢ㸰ḟඖ࣐ࢵࣉ(ᅗ 2)ࡢ୰ࡢࠊᴟᑠ್ࢆ⧅࠸࡛ᚓࡽࢀࡓ 2 ࡘࡢ࣮ࣝࢺ࡟ἢࡗࡓ」ᩘࡢ఩
⨨(」ᩘࡢ (RC1,RC2) ࡢ⤌ࡳྜࢃࡏ)࡛ࠊ⁐፹ศᏊࢆྵࡴάᛶ㒊఩ࡢᵓ㐀ࡢኚ໬ࢆື⏬࡟ࡋࡓࠋฟⓎᵓ㐀
(scissile bond ࡀษࢀࡿ๓ࡢ๓㥑యࡢᵓ㐀 , structure M) ࡛ࡢྛཎᏊࡢࣛ࣋ࣝࢆಖᣢࡋ࡚࠸ࡿࡓࡵࠊࣉࣟࢺࣥ⛣ືࡀ㉳ࡇࡗ࡚࠸࡚ࡶࠊࡑࡢࣉࣟࢺࣥࡢ⤖ྜࡋ࡚࠸ࡓඖࡢṧᇶࡸỈศᏊࢆ≉ᐃ࡛ࡁࡓࠋ Structure M  ࡢࢧࣈࣘ ࢽࢵࢺ A ࡢ ⤖ᯝ ࡟㝈ᐃ ࡋ ࡚௒ ᅇࡣほᐹ ࡋࡓࠋ௨ ୗࡣ associative reaction path ࡟ࡘ ࠸࡚グ ㏙ࡍࡿࠋ
(RC1=1.8Å, RC2=1.6Å) ࡢ scissile bond ࡀษ᩿ࡉࢀ࡚࠸࡞࠸≧ែ࡛ồ᰾๣ࢆ㏆࡙ࡅࡓ❧యᵓ㐀࡛ࡣࠊLys92 ࡢ- 178 -

ഃ㙐ࡢ NH +3 ࡢࣉࣟࢺࣥࡀ Asp90 ࡢഃ㙐࡟⛣ືࡋࠊ Lys92 ࡜ Asp90 ࡀ㟁Ẽⓗ࡟୰ᛶ࡟࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ ࠋ ྠ ᵝ ࡟ ௚ ࡢ ⤌ ࡳ ྜ ࢃ ࡏ ࡛ ࡢ ཯ ᛂ 㐣 ⛬ ࡢ ࣉ ࣟ ࢺ ࣥ ⛣ ື ࡢ ᵝ Ꮚ ࡣ ࠊ (RC1=1.9Å, RC2=1.7),(RC1=1.9Å, RC2=1.8Å) ࡛ࡣࠊ Lys92 ࡢ NH +3 ࡢࣉࣟࢺࣥࡀ Asp90 ࡟ྥ࠿ࡗ୍࡚▐㞳ࢀࡓᚋࠊࡍࡄ࡟ Lys92࡟ᡠࡗࡓࠋࡉࡽ࡟ࠊ scissile bond ษ᩿ᚋ࡟┦ᙜࡍࡿ (RC1=1.8Å, RC2=2.3) ࡛ࡣࠊษ᩿࡟ࡼࡗ࡚᪂ࡓ࡟⏕ࡌࡓ
3̓ᮎ➃ࡢ㓟⣲࡟ᇶ㉁ ࡢ Ỉศ Ꮚ ࠿ࡽ ࣉࣟࢺࣥࡀ⛣ືࡋࡓࠋ
ࡲࡓࠊ Lys92 ࠿ࡽ
Asp90

⤒ ⏤ ࡛

scissile ࣜࣥ㓟ᇶࡢ㓟 ⣲ ࡟ࣉ ࣟ ࢺࣥ ࡀ⛣ ື ࡋࡓ ࠋ ࡲࡓ ࠊ
Asp90 ࡀ ồ ᰾ ᨷ ᧁࢆ ⾜ ࠺Ỉ ศ Ꮚ࠿ ࡽࣉ ࣟ ࢺࣥ ࢆ ዣࡗ ࡚࠸ࡓࠋ㔞Ꮚ໬Ꮫィ⟬ࡢ MD ࡢࢺࣛࢪ࢙ࢡ ࢺ ࣮ࣜ ࢆ ྍど ໬ࡋ ື ⏬࡟ ࡋ ࡚ほ ᐹࡋ ࡓ ⤖ ᯝ ࠊ
associative

reaction

path ࡟ἢࡗࡓ཯ᛂ
࡛ࡣࠊḟࡢኚ໬ࡀ㡰࡟㉳ࡇࡗ࡚࠸ࡿྍ⬟ᛶࡀ♧ࡉࢀࡓࠋ1.

ຍỈศゎ๓࡛ࡣ Lys92 ࡜ Asp90 ࡣ୧᪉࡜ࡶ㟁㞳≧ែࠋ

2.

Lys92 ࡜ Asp90 ࡢ୧᪉ࡀ㟁Ẽⓗ࡟୰ᛶ≧ែ࡟࡞ࡿࠋ

3.

ồ᰾๣ࡢỈศᏊࡀ scissile ࣜࣥ㓟ᇶࡢ P ࡟㏆࡙࠸࡚ scissile bond ࡀษࢀࡿࠋ

3.1. ᇶ㉁ࡢỈศᏊࡢࣉࣟࢺࣥࡀ DNA ࡢ 6 ṧᇶ┠ࡢࢳ࣑ࣥࡢ O3̓࡟⛣ືࡍࡿࠋ
3.2. ồ᰾๣ࡢỈศᏊࡀ scissile ࣜࣥ㓟ᇶࡢ⇥ཎᏊ࡟⤖ྜࡍࡿࠋ
3.3. ồ᰾๣ࡢỈศᏊࡢࣉࣟࢺࣥࡣ Asp90 ࡢ ț ఩⨨ࡢᕥഃࡢ㓟⣲ཎᏊ࡟⛣ືࡍࡿࠋ
3.4. Asp90 ࡢ ț ఩⨨ࡢྑഃࡢ㓟⣲ཎᏊࡢࣉࣟࢺࣥࡀ scissile ࣜࣥ㓟ᇶࡢ O1 ࡟⛣ືࡍࡿࠋ୍᪉ࠊ associative reaction path ࡟ἢࡗ࡚࠸࡞࠸཯ᛂᗙᶆ࡛ࡣࠊࣉࣟࢺࣥ⛣ືࡣ 2 ࠿ᡤ (RC1=1.8Å, RC2=1.6Å)࡜ (RC1=1.8Å, RC2=2.1Å) ௨እࡣぢࡽࢀ࡞࠿ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

Ⓨ⾲ணᐃ: ‫ ➨ۻ‬59 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, 2021 ᖺ 11 ᭶ 25 ᪥–27 ᪥, ࢜ࣥࣛ࢖ࣥ.
Ⓨ⾲ணᐃ: ‫ ➨ۻ‬43 ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘, 2021 ᖺ 10 ᭶ 28 ᪥ –30 ᪥, ࢜ࣥࣛ࢖ࣥ.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

ᢞ✏‽ഛ୰- 179 -

Ỉࠊịࠊࢡࣛࢫ࣮ࣞࢺࣁ࢖ࢻ࣮ࣞࢺࡢᵓ㐀┦㌿⛣ࡢ⌮ㄽ◊✲
7KHRUHWLFDOVWXGLHVRQWKHSKDVHWUDQVLWLRQRIOLTXLGZDWHULFHDQG
FODWKUDWHK\GUDWHVżᯇᮏ ṇ࿴ࠊᖹ⏣ 㞞඾ࠊ▮ࢣᓮ ⌶☻ࠊ⏣୰ ⚽ᶞ㸦ᒸᒣ኱Ꮫ㸧◊✲┠ⓗࠊෆᐜịࡣ  ✀௨ୖࡢᏳᐃࠊ‽Ᏻᐃࡢከᙧࡀ▱ࡽࢀ࡚࠸ࡿࠋ≉࡟ᴟ➃᮲௳ୗࡢịࡢᵓ㐀࡜ᛶ㉁ࡣࠊᇶ♏◊✲ࡢぢᆅ࠿ࡽࡢ㔜せᛶ࡟ຍ࠼࡚ࠊᝨᫍ⛉Ꮫ࠿ࡽࡶ⯆࿡ࡀᣢࡓࢀࠊ⌮ㄽ㠃࠿ࡽࡢ◊✲ࡀᚅᮃࡉࢀ࡚ࡁࡓࠋࡲࡓࠊࢡࣛ
ࢫ࣮ࣞࢺࣁ࢖ࢻ࣮ࣞࢺࡸ ILOOHG LFH ࡜࠸ࡗࡓỈࢆ୺ᡂศ࡜ࡍࡿከᡂศᅛయࡶᵝࠎ࡞┦ࢆᣢࡘࠋࡑࢀ࡝ࡇࢁ࠿ࠊ
Ỉࡢሙྜࠊ㏻ᖖࡢ≀㉁࡜␗࡞ࡾࠊᾮయ≧ែࡍࡽ」ᩘࡢ┦ࢆᣢࡘ࡜࠸࠺ㄝࡀᥦ᱌ࡉࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊịࠊໟᦤỈ࿴≀ࠊᾮయ࡞࡝ࠊỈ࡟㛵ࡍࡿᵝࠎ࡞┦ࡢᵓ㐀ࠊᏳᐃᛶࠊࡑࡋ࡚ࢲ࢖ࢼ࣑ࢡࢫࡢໟᣓⓗ࡞⌮ゎࢆ┠ᣦࡍࠋ◊✲᪉ἲࠊィ⟬᪉ἲ ᮏㄢ㢟࡛ࡣࠊ」ᩘࡢ␗࡞ࡿ⣔ࢆᑐ㇟࡜ࡋ࡚࠸ࡿࡀࠊ࠸ࡎࢀࡢሙྜࡶศᏊືຊᏛ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ

୺࡞ᡭἲ࡜ࡋ࡚࠸ࡿࠋ0' ィ⟬ࡢ࡯࡜ࢇ࡝ࡣ *520$&6 ࣃࢵࢣ࣮ࢪࢆ౑⏝ࡋ࡚࠸ࡿࠋ୍㒊ࡢ 0' ィ⟬࡜ゎᯒ࡟ࡘ࠸࡚ࡣ⮬సࡢࢥ࣮ࢻࢆ౑⏝ࡋ࡚࠸ࡿࠋ



◊✲ᡂᯝ
ᴟ㝈≧ែ࡛ࡢࢡࣛࢫ࣮ࣞࢺỈ࿴≀ࡢⓎ⏕Ỉࡢಙ㢗࡛ࡁࡿྂ඾ⓗ࡞ศᏊ㛫┦஫స⏝ࣔࢹࣝࢆ⏝࠸ࡓ‽ㄪ࿴㏆ఝ࡟ࡼࡾࠊ⤖ᬗᛶ࡜࢔ࣔࣝࣇ࢓ࢫࡢ୧᪉ࡢ  ࡢịࡢᙧែ࡟࠾ࡅࡿ᣺ື᣺ᖜ࡜ࣇ࢛ࣀࣥᒁᅾ໬ࡢ⛬ᗘࢆㄪ࡭ࡓࠋపᅽịࡢ᣺ᖜࡣᅽ⦰࡜࡜ࡶ࡟ቑຍࡍࡿ
ࡀࠊ୰ᅽị࡜㧗ᅽị࡛ࡣ㏫ࡢഴྥࡀぢࡽࢀࡓࠋ㓟⣲ཎᏊࡢ᣺ᖜࡣࠊࢮࣟⅬ᣺ືࡢᐤ୚ࢆ㝖ࡅࡤࠊపᅽị୰ࡢỈ⣲ࡢ᣺ᖜ࡜ኚࢃࡽ࡞࠸ࠋࡇࢀࡣࠊ୪㐍᣺ື࡜ᅇ㌿᣺ືࡢΰྜ࡟࠾ࡅࡿࢥࣄ࣮ࣞࣥࢺ࡛࠶ࡿࡀ㏫఩┦ࡢ㐠ື࡟ࡼࡗ࡚ㄝ᫂ࡉࢀࡿࠋ୪㐍ࡀᨭ㓄ⓗ࡞㐠ື࡜ᅇ㌿ࡀᨭ㓄ⓗ࡞㐠ືࡢศ㞳࡟ࡼࡾࠊ࠶ࡽࡺࡿịࡢᙧែࡢ᣺ື᣺
ᖜࡀ኱ᖜ࡟ῶᑡࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋị ,,, ࡢ᣺ᖜࡣࠊ௚ࡢ࡝ࡢ⤖ᬗịᙧែࡼࡾࡶࡣࡿ࠿࡟኱ࡁ࠸ࠋ᣺ື࣮ࣔ
ࢻࡢ≉ᛶࢆㄪ࡭ࡿࡓࡵ࡟ࠊ㏫ཧຍẚ࡜࿧ࡤࢀࡿಶࠎࡢࣇ࢛ࣀ࣮ࣥࣔࢻࡢཎᏊኚ఩ࡢ࣮࣓ࣔࣥࢺẚࢆィ⟬ࡋࠊ⤖ᬗ㉁ị࡜࢔ࣔࣝࣇ࢓ࢫị࡟࠾ࡅࡿࣇ࢛ࣀࣥࡢᒁᅾ໬ࡢ⛬ᗘࢆィ⟬ࡋࡓࠋỈ⣲⛛ᗎ໬ịᙧែࡢࣇ࢛ࣀ࣮ࣥࣔ
ࢻࡣࠊఏ᧛ࡲࡓࡣᣑᩓ≉ᛶࢆ᭷ࡍࡿ⤖ᬗ඲య࡟ⴭࡋࡃᗈࡀࡾࠊ୍᪉ࠊỈ⣲↓⛛ᗎࡢị࡛ࡣࠊᩓ㐓࣮ࣔࢻ࡜࿧
ࡤࢀࡿ᣺ືࣂࣥࢻࡢ➃࡟ከࡃࡢᒁᅾ໬࣮ࣔࢻࡀ⌧ࢀࡿࠋᒁᅾ໬ࡢ⛬ᗘࡣࠊ㓟⣲ཎᏊࡢ↓⛛ᗎ໬ࡢࡓࡵ࡟ࠊప
ᐦᗘ࢔ࣔࣝࣇ࢓ࢫ࠾ࡼࡧ㧗ᐦᗘ࢔ࣔࣝࣇ࢓ࢫ࡛ᑡࡋ㢧ⴭ࡛࠶ࡗࡓࠋ
⾨ᫍࡢᫍ㛫✵㛫࡜Ỉᅪࡢ⾲㠃ࡢ⇕ຊᏛⓗ᮲௳ࢆ࢝ࣂ࣮ࡍࡿᗈ࠸ᅽຊ⠊ᅖ࡛ࠊ. 㝈⏺࠿ࡽ . ࡲ࡛ࡢᴟప
࡛ࡢໟ᥋Ỉ࿴≀ࡢ⇕ຊᏛⓗᏳᐃᛶࢆㄪ࡭ࡓࠋ఩┦ᣲືࡢホ౯ࡣࠊධຊ࡜ࡋ࡚ศᏊ㛫┦஫స⏝ࡢࡳࢆᚲせ࡜ࡍࡿཝᐦ࡞⤫ィຊᏛⓗ⌮ㄽ࡟ᇶ࡙࠸࡚ࠊྍኚᅽຊ࡛㔞Ꮚศ㓄㛵ᩘࢆタᐃࡍࡿࡇ࡜࡟ࡼࡗ࡚⾜ࡗࡓࠋᕼ࢞ࢫࠊ
Ⅳ໬Ỉ⣲ࠊ❅⣲ࠊ࠾ࡼࡧ㓟⣲ࢆࢤࢫࢺ✀࡜ࡋ࡚㑅ᢥࡋࡓࠋࡇࢀࡽࡣࠊࡑࡢࡼ࠺࡞⾨ᫍࡢ᥹Ⓨᛶ≀㉁ࡢ㔜せ࡞ᡂศ࡛࠶ࡿࠋị⾨ᫍࡢ⾲㠃ࡲࡓࡣᆅୗ࡛Ⓨ⏕ࡍࡿࠊỈࡀ㇏ᐩ࡞᮲௳࡛ࡢࡇࢀࡽࡢࢡࣛࢫ࣮ࣞࢺỈ࿴≀ࡢỈ࿴

- 180 -

≀Ỉ஧┦ቃ⏺࡜ࠊࢤࢫࢺࡀ㇏ᐩ࡞᮲௳࡛ࡢỈ࿴≀ࢤࢫࢺࡢ஧┦ቃ⏺࡟ὀ┠ࡋࡓࠋᚓࡽࢀࡓ≧ែᅗࡣࠊໟ᥋Ỉ࿴≀ࡀ୕┦ඹᏑ᮲௳࠿ࡽ㐲ࡃ㞳ࢀࡓᗈ࠸⠊ᅖ࡛Ỉࡲࡓࡣࢤࢫࢺ✀ࡢ࠸ࡎࢀ࠿࡜ᖹ⾮≧ែ࡟࠶ࡿྍ⬟ᛶࡀ࠶ࡾࠊ
ྛໟ᥋Ỉ࿴≀ࡢᏳᐃᅽຊࢰ࣮ࣥࡀ⃭ࡋ࠸෭༷࡛኱ᖜ࡟ᣑ኱ࡍࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋࢱ࢖ࢱࣥࡢᏳᐃࡋࡓỈࡢᙧែ࡟㛵ࡍࡿᡃࠎࡢⓎぢࡢព࿡ࡣࠊ⾲㠃ࡢỈࡣࢡࣛࢫࢺࡢὸ࠸㡿ᇦࡲ࡛኱Ẽ࡜࡜ࡶ࡟ࢡࣛࢫ࣮ࣞࢺࣁ࢖ࢻࣞ
࣮ࢺ࡜ࡋ࡚ࡢࡳᏑᅾࡍࡿࡀࠊࢡࣛࢫࢺࡢṧࡾࡢ㒊ศࡢࢡࣛࢫ࣮ࣞࢺࣁ࢖ࢻ࣮ࣞࢺࡣỈ࡜ඹᏑ࡛ࡁࡿ࡜࠸࠺ࡇ
࡜࡛࠶ࡿࠋịࠋࡇࢀࡣࠊⷧ࠸㓟⣲ࡢ✵Ẽࡀ⣧⢋࡞ị࡜᤼௚ⓗ࡟ඹᏑࡍࡿ࢚࢘ࣟࣃ࡜࢞ࢽ࣓ࢹࡢ⾲㠃࡜ࡣᑐ↷ⓗ࡞⤖ᯝ࡜࡞ࡗࡓࠋ ࣈࣛࢩ≧࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ㛫࡟⏕ࡌࡿ᪂ࡋ࠸ị᫖ᖺᗘࠊࢃࢀࢃࢀࡣ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡀᙧᡂࡍࡿࣈࣛࢩࡢࡍࡁࡲ࡟ࠊ᪂ࡋ࠸⤖ᬗᵓ㐀ࡢịࡀ⏕ࡌࠊࣈࣛࢩࡢ㛫㝸ࢆㄪᩚࡍࡿࡇ࡜࡛ࠊỈࡢ⼥Ⅼࢆ⮬ᅾ࡟ㄪ⠇ࡋ࠺ࡿࡇ࡜ࢆぢ௜ࡅࡓࠋ᭱㐺࡞㛫㝸࡛ࡣࠊ . ࡜࠸࠺㠀ᖖ࡟㧗࠸

ᗘ࡛⮬Ⓨⓗ࡟ GWF ࡜࠸࠺᪂ࡋ࠸⤖ᬗᵓ㐀ࡢịࡀ⏕ᡂࡋࡓࠋ௒ᖺᗘࡣࠊࣈࣛࢩࢆᵓᡂࡍࡿ࣮࢝

࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ┤ᚄࢆኚ໬ࡉࡏࡿࡇ࡜࡛≀ᛶ࡟࡝ࡢࡼ࠺࡞ᙳ㡪ࡀ࠶ࡿ࠿ࢆㄪ࡭ࡓࠋ
࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ࡜ࡋ࡚ࡣ᭱ᑠ┤ᚄࡢࡶࡢ࠿ࡽࡣࡌࡵࠊᚎࠎ࡟┤ᚄࢆኴࡃࡋ࡞ࡀࡽࠊࡑࡢ⼥ⅬࢆศᏊືຊᏛἲ࡛᥎ᐃࡋࡓࠋ௨๓ࡢ◊✲࠿ࡽࠊ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ㛫ࡢࢠࣕࢵࣉࡢ㛫㝸ࡣࠊỈศᏊࡀ  ಶධࡿᖜࡼࡾ኱ࡁࡃ࡚ࡶᑠࡉࡃ࡚ࡶᏳᐃ࡞ᵓ㐀ࡀ࡛ࡁ࡞࠸ࡇ࡜ࡀண᝿ࡉࢀࡓࡢ࡛ࠊࢠࣕࢵࣉࡣ  QP ୍࡛ᐃ࡜ࡋ
ࡓࠋࡑࡢ⤖ᯝࠊ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ┤ᚄ࡟౫Ꮡࡋ࡚ࠊịࡢ⼥Ⅼࡀ࠿࡞ࡾ኱ࡁࡃኚືࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞
ࡗࡓࠋ᭱ࡶ⼥Ⅼࡀ㧗ࡃ࡞ࡿࡢࡣࠊ๓ࡢ◊✲࡛Ⓨぢࡋࡓ GWF ịࡀ⏕ࡌࡿࢧ࢖ࢬࡢ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢሙྜ
࡛࠶ࡗࡓࡀࠊࡑࢀࡼࡾ⣽࠸ሙྜ࡛ࡶኴ࠸ሙྜ࡛ࡶࠊ≉ᐃࡢ┤ᚄ࡛⼥Ⅼࡀ㧗ࡃ࡞ࡿࠊ࠸ࢃࡺࡿ࣐ࢪࢵࢡࢼࣥࣂ
࣮ࡀᏑᅾࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
␗࡞ࡿ࣐ࢪࢵࢡࢼࣥࣂ࣮࡛ᚓࡽࢀࡿịࡢ⤖ᬗᵓ㐀ࡣࡑࢀࡒࢀ␗࡞ࡿࠋࡑࡢ࠸ࡃࡘ࠿ࡣࠊࢮ࢜ࣛ࢖ࢺࡢ᪤▱ࡢ⤖ᬗᵓ㐀࡜఩┦ྠᙧ࡛࠶ࡾࠊࡲࡓ࠸ࡃࡘ࠿ࡣࠊᐇᅾࡢ≀㉁࡜ࡋ࡚ࡣྜᡂࡉࢀ࡚࠸࡞࠸ࡀࠊࢿࢵࢺ࣮࣡ࢡࢺ
࣏ࣟࢪ࣮ࡢࢹ࣮ࢱ࣮࣋ࢫ࡟ࡍ࡛࡟Ⓩ㘓ࡉࢀ࡚࠸ࡿࡶࡢ࡛࠶ࡗࡓࠋࡲࡓࠊ᪂ወ࡞ࢿࢵࢺ࣮࣡ࢡᵓ㐀ࡶ᪂ࡓ࡟Ⓨぢࡉࢀࡓࠋࡇࢀࡽࡢịࡢ⤖ᬗࡣࠊ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ㍈᪉ྥࡢศᏊ㓄ิࡢ࿘ᮇ࡛  ࡘࡢࢢ࣮ࣝࣉ࡟ศ㢮࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ࡝ࡢ⤖ᬗᵓ㐀ࡶࠊ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࢆ୍ᒙࡢỈ ị ࢼࣀࢳ࣮ࣗࣈ࡛ໟࡴᵓ㐀࡟࡞ࡗ࡚࠸ࡿࠋከࡃࡢ⤖ᬗᵓ㐀࡛ࠊỈࢼࣀࢳ࣮ࣗࣈࡣࢪࢢࢨࢢᆺ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ࡜఩┦ྠᙧ࡛࠶ࡗࡓࡀࠊ
ࡑࢀ௨እ࡟࢔࣮࣒ࢳ࢙࢔ᆺ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ࡜఩┦ྠᙧ࡞ࡶࡢࡀⓎぢࡉࢀࡓࠋࡇࡢ  ✀㢮ࡣศᏊ㓄ิࡢ࿘ᮇࡀ␗࡞ࡿࡓࡵࠊྠ᫬࡟ฟ⌧ࡍࡿࡇ࡜ࡣ࡞࠸ࠋ

- 181 -ᅗ  ࣮࢝࣎ࣥࢼࣀࣈࣛࢩࡢࡍࡁࡲ࡟⏕ࡌࡓịࡢᵓ㐀ࠋ᭱ୖẁ࠿ࡽࠊ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ࢝࢖ࣛࣜࢸ࢕
ᣦᶆࠊịࡢ⼥Ⅼࠊ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ㍈᪉ྥࡢᢞᙳᅗࠊഃ㠃ᢞᙳᅗࠋⅣ໬Ỉ⣲ࣁ࢖ࢻ࣮ࣞࢺࡢࢣ࣮ࢪ༨᭷⋡࡜ゎ㞳࢚ࣥࢱࣝࣆ࣮
ᮏ◊✲࡛ࡣࠊࢡࣛࢫ࣮ࣞࢺỈ⣲໬≀ࡢ⤫ィຊᏛⓗ⌮ㄽࢆ⏝࠸࡚ࠊࡑࡢ┦ᖹ⾮࡜ゎ㞳࢚ࣥࢱࣝࣆ࣮ࢆㄪ࡭ࡓࠋ
࣓ࢱࣥࠊ࢚ࢱࣥࠊ࢔ࢭࢳࣞࣥࠊࣉࣟࣃࣥࡢྛࣁ࢖ࢻ࣮ࣞࢺࡢゎ㞳ᅽຊࡣࠊᡃࠎࡀᥦ᱌ࡋࡓ᪉ἲ࡟ࡼࡗ࡚ᐇ㦂ⓗ࡟ࡼࡃ෌⌧ࡉࢀࡓࠋ୕┦ᖹ⾮≧ែ࡟ຍ࠼࡚ࠊỈỈ࿴≀ࠊỈ࿴≀ࢤࢫࢺࡢ஧┦ඹᏑ≧ែࢆᗘ࣭ᅽຊ࣭⤌ᡂ✵㛫࡛᥎ᐃࡋࡓࠋ┦ᅗ࡟࠾ࡅࡿࢤࢫࢺศᏊࡢ༨᭷⋡࡜஧┦ቃ⏺ࡣࠊࡑࡢ኱ࡁࡉ࡟ᛂࡌ࡚ᩄឤ࡟ኚ໬ࡍࡿࡇ࡜
ࡀ♧ࡉࢀࡓࠋ࣍ࢫࢺ࡜ࢤࢫࢺࡢ┦஫స⏝࡟㉳ᅉࡍࡿ࢚ࣥࢱࣝࣆ࣮ᡂศࡣࠊᑐᛂࡍࡿ⮬⏤࢚ࢿࣝࢠ್࣮ࡢ

ᗘ౫Ꮡᛶ࠿ࡽಶู࡟ィ⟬ࡉࢀࡿࠋࡇࢀ࡟ࡼࡾࠊịࡢ⼥ゎࡢࡼ࠺࡞ඹᏑࡍࡿ┦ࡢ┦㌿⛣ࠊ≉࡟୕┦ᖹ⾮⥺࡟ἢࡗࡓ┦㌿⛣ࢆ⪃៖ࡋ࡚ࠊ࠶ࡽࡺࡿᏳᐃ࠾ࡼࡧ‽Ᏻᐃ࡞⇕ຊᏛⓗ≧ែ࡟࠾ࡅࡿゎ㞳࢚ࣥࢱࣝࣆ࣮ࢆホ౯ࡍࡿࡇ࡜
ࡀ࡛ࡁࡿࠋịࡢ⢏⏺࡟࠾ࡅࡿỈࡢᣑᩓ⮬↛⏺࡟Ꮡᅾࡍࡿịࡣከ⤖ᬗ࡛࠶ࡿࡇ࡜ࡀከ࠸ࠋịࡢヨᩱ୰ࡢ⢏⏺㡿ᇦࡢయ✚ศ⋡ࡣ㠀ᖖ࡟ᑠࡉࡃࠊ ࡘࡢ⤖ᬗ⢏ࡀฟ఍࠺୕ཫ㊰ 7ULSOH -XQFWLRQ 㡿ᇦࡢయ✚ศ⋡ࡣࡉࡽ࡟ᑠࡉ࠸ࠋ౛࠼ࡤࠊከ⤖ᬗయࡢ㟁Ẽఏᑟᗘࡣ༢⤖ᬗయࡼࡾࡶ㧗ࡃࠊࡇࢀࡣ⢏⏺ࡸ୕ཫ㊰࡟⵳✚ࡉࢀࡓ࢖࢜ࣥ✀࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ ༢⤖ᬗ࡜ከ⤖ᬗࡢịࡢ㛫࡟ࡣࠊᶵᲔⓗᛶ㉁ࡢ኱ࡁ࡞㐪࠸ࡀ࠶ࡿࠋ༢⤖ᬗࡢረᛶኚᙧࡣ୺࡟ᗏ㠃࡛ࡢࡍ࡭ࡾ࡟㉳ᅉࡍࡿࡀࠊ
ከ⤖ᬗị࡛ࡣࡇࡢ✀ࡢኚᙧࡣ௚ࡢ⤖ᬗ⢏࡟㜼ࡲࢀࡿࠋ ࡑࡢ௦ࢃࡾࠊከ⤖ᬗịࡢኚᙧ㐣⛬࡛ࡣࠊቃ⏺㠃ୖ࡛ࡢ⤖ᬗ⢏ྠኈࡢ⁥ࡾ࡜ࠊ⤖ᬗ⢏࠿ࡽ௚ࡢ⤖ᬗ⢏࡬ࡢỈศᏊࡢ⛣ືࢆక࠺⢏⏺ࡢ࣐࢖ࢢ࣮ࣞࢩࣙࣥࡀ㉳ࡇࡿࠋᴟᆅࡢ࢔࢖ࢫࢥ࢔࡟ྵࡲࢀࡿỈྠ఩యࠊ஧㓟໬Ⅳ⣲ࠊ◲㓟ሷ࡞࡝ࡢ໬Ꮫ✀ࡢ⃰ᗘࣉࣟࣇ࢓࢖ࣝࢆࡶ࡜࡟ࠊ
ẼೃኚືࡢṔྐࢆ᥈ࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡇࡢ⃰ᗘࣉࣟࣇ࢓࢖ࣝࡣࠊịࡢࢧࣥࣉࣝ୰ࡢ⢏Ꮚࡢᣑᩓࢆ⪃៖ࡋ࡚⿵ṇࡍࡿᚲせࡀ࠶ࡿࠋࡑࡢࡓࡵ࡟ࡣࠊ⢏⏺ࡸ୕ཫ㊰࡛ࡢᣑᩓಀᩘࡀ㔜せ࡞ࣃ࣓࣮ࣛࢱ࡜࡞ࡿࠋࡲࡓࠊ⢏⏺࡛ࡢỈศᏊࡢᣑᩓಀᩘࡣࠊ⢏⏺ࡢ⛣ືᛶ࡜㛵㐃ࡋ࡚࠸ࡿࠋ
ᡃࠎࡣࠊ7,33,FH ࣔࢹࣝࢆ⏝࠸࡚ࠊ. ࡟࠾ࡅࡿከ⤖ᬗịࡢྂ඾ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋከ⤖ᬗịࡢᵓ㐀ࡣࠊ㐣෭༷Ỉࡢ୰࡛ịࡢ⢏Ꮚࢆᡂ㛗ࡉࡏࡿࡇ࡜࡛సᡂࡋࡓࠋᾮయᾮయ┦㌿⛣ࢩࢼࣜ࢜ࡢほⅬ- 182 -

࠿ࡽᒁᡤᵓ㐀ࢆ≉ᚩ௜ࡅࡿࡓࡵ࡟᭱㏆㛤Ⓨࡉࢀࡓ⛛ᗎࣃ࣓࣮ࣛࢱࢆ౑⏝ࡋࡓ⤖ᯝࠊịࡢ⢏⏺࡜୕㔜⤖ྜࡣࠊ࡯࡜ࢇ࡝ࡢỈศᏊࡀ  ࡘࡢỈ⣲⤖ྜࢆᙧᡂࡋࠊ222 ゅࡀᅄ㠃యゅ r࠿ࡽࡎࢀ࡚࠸ࡿపᐦᗘᾮయỈ࡜ᵓ㐀ⓗ࡟㢮ఝࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡲࡓࠊ⢏⏺ࡢཌࡉࡣ⣙ QP ࡛࠶ࡗࡓࠋᮏ◊✲࡛ィ⟬ࡋࡓ⢏⏺࡟ἢࡗࡓỈศᏊࡢᣑᩓಀᩘࡣ PV ࡛ࠊᐇ㦂ࢹ࣮ࢱ࡜ࡼࡃ୍⮴ࡋ࡚࠸ࡿࠋ୕ཫ㊰࡟ἢࡗࡓᣑᩓࡣࠊ⢏⏺࡟ἢࡗࡓᣑᩓࡼࡾࡶ  ಸ㏿࠸ࠋࡇࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝࢆ⏝࠸࡚ࠊከ⤖ᬗị୰ࡢỈศᏊࡢᣑᩓ㏿ᗘࡢ⢏ᚄ౫Ꮡᛶࢆࣔࢹࣝ໬ࡋࡓ࡜ࡇࢁࠊ⢏ᚄࡀ࣑࣓࣮ࣜࢺ࣮ࣝ࢜ࢲ࣮ࡢ඾ᆺⓗ࡞ከ⤖ᬗịヨᩱ࡛ࡣࠊ⢏⏺࡜୕ཫ㊰ࡀᣑᩓ⋡࡟୚࠼ࡿᙳ㡪ࡣࡈࡃࢃࡎ࠿࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓ㸪ྠ୍ᗘࡢị⵨Ẽ⏺㠃࡜⢏⏺ࡢ≉ᛶࡀ኱ࡁࡃ␗࡞ࡿࡇ࡜ࡶ᫂ࡽ࠿࡟ࡋࡓࠋị⵨Ẽ⏺㠃ࡢ␲ఝᾮయᒙࡣ㧗ᐦᗘࡢᾮయỈ࡟ఝ࡚࠾ࡾ㸪ị⵨Ẽ⏺㠃࡟ἢࡗࡓᣑᩓಀᩘࡣ⢏⏺࡟ἢࡗࡓᣑᩓಀᩘࡼࡾࡶ  ᱆኱ࡁ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
xᯇᮏṇ࿴ ³Ỉ⣲↓⛛ᗎị࡟㞃ࡉࢀࡓ⛛ᗎ´≀ᛶ◊✲ᡤࢫࣃࢥࣥඹྠ฼⏝࣭&&06 ྜྠ◊✲఍ࠕィ⟬≀㉁⛉Ꮫࡢ᪂ᒎ㛤 ࠖ ࢜ࣥࣛ࢖ࣥ ᖺ  ᭶  ᪥࢜ࣥࣛ࢖ࣥ ᮾ኱≀ᛶ◊ xᯇᮏṇ࿴³Ỉࡢ୐୙ᛮ㆟´ ⮬↛⛉Ꮫ࢝ࣇ࢙ ࢜ࣥࣛ࢖ࣥ  ᖺ  ᭶  ᪥ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
x

մ0DVDND]X0DWVXPRWR7DNXPD<DJDVDNLDQG+LGHNL7DQDND³)RUPDWLRQRI+RW,FH&DXVHGE\&DUERQ
1DQREUXVKHV ,, 'HSHQGHQF\ RQ WKH 5DGLXV RI 1DQRWXEHV´ 7KH-RXUQDORI&KHPLFDO3K\VLFV 154    x

մ+LGHNL 7DQDND 7DNXPD <DJDVDNL DQG 0DVDND]X 0DWVXPRWR ³&DJH 2FFXSDQF\ DQG 'LVVRFLDWLRQ(QWKDOS\ RI +\GURFDUERQ +\GUDWHV´ $,&K(-RXUQDO$PHULFDQ,QVWLWXWHRI&KHPLFDO(QJLQHHUV 67  
HH  x

մ+LGHNL7DQDND7DNXPD<DJDVDNLDQG0DVDND]X0DWVXPRWR³2QWKH2FFXUUHQFHRI&ODWKUDWH+\GUDWHV
LQ ([WUHPH &RQGLWLRQV 'LVVRFLDWLRQ 3UHVVXUHV DQG 2FFXSDQFLHV DW &U\RJHQLF 7HPSHUDWXUHV ZLWK$SSOLFDWLRQWR3ODQHWDU\6\VWHPV´7KH3ODQHWDU\6FLHQFH-RXUQDO1    x

մ<DJDVDNL 7DNXPD 0DVDND]X 0DWVXPRWR DQG +LGHNL 7DQDND ³0ROHFXODU '\QDPLFV 6WXG\ RI *UDLQ%RXQGDULHVDQG7ULSOH-XQFWLRQVLQ,FH´7KH-RXUQDORI&KHPLFDO3K\VLFV153    - 183 -

㔞ᏊศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔ NTChem ࡟ࡼࡿࢼࣀࢧ࢖ࢬศᏊࡢศᏊᶵ⬟ࡢゎ࣭᫂タィ
Application of quantum molecular science simulation software NTChem forelucidation and design of molecular functionality of nanomolecules‫ۑ‬୰ᔱ 㝯ே㸪:LOOLDP'DZVRQ ᕝᔱ ⱥభ ⌮໬Ꮫ◊✲ᡤ  㸪㜿ஂ᰿ ᫀᙪ ⚄ᡞ኱Ꮫ  





◊✲┠ⓗ

 ศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔ 17&KHP ࡢ㛤Ⓨ17&KHP ࡣᮏࢢ࣮ࣝࣉࡀ㛤Ⓨࡋ࡚࠸ࡿ㸪኱つᶍ࠿ࡘ」㞧࡞ศᏊ⣔࡟ᑐࡍࡿ➨୍ཎ⌮㔞Ꮚ໬Ꮫィ⟬ࡢࡓࡵࡢໟ
ᣓⓗ࡞ࢯࣇࢺ࢙࢘࢔࡛࠶ࡿ >@㸬᪤Ꮡࢯࣇࢺ࢙࢘࢔ࡢᣢࡘከࡃࡢᶵ⬟ࢆ࢝ࣂ࣮ࡋࡘࡘ㸪௚ࡢࣉࣟࢢ࣒࡛ࣛ฼⏝ࡍࡿࡇ࡜ࡢ࡛ࡁ࡞࠸ከࡃࡢ㔞Ꮚ໬Ꮫィ⟬ἲࢆ฼⏝ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ㸬⮬↛⛉Ꮫ◊✲ᶵᵓィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡟࠾࠸࡚ࡣ 17&KHP ࣂ࣮ࢪࣙࣥ  ࡀබ㛤ࡉࢀ࡚࠸ࡿࡀ㸪ࡑࡢᚋࡶ㸪ᵝࠎ࡞᪂ᶵ⬟ᐇ⿦ࡸᨵⰋ㸪&0DNH
࡟ࡼࡿࣅࣝࢻᶵ⬟ࡢᙉ໬㸪ࢸࢫࢺࡢᣑ඘࡞࡝ࡢᵝࠎ࡞ࣜࣇ࢓ࢡࢱࣜࣥࢢࢆ⾜ࡗ࡚࠾ࡾ㸪᭱㏆㸪ࣂ࣮ࢪࣙࣥ 
ࢆ࣮ࣜࣜࢫࡋࡓ㸬ከࡃࡢ࣮ࣘࢨ࣮࡟฼⏝ࡋ࡚࠸ࡓࡔࡃࡓࡵ㸪⮬↛⛉Ꮫ◊✲ᶵᵓィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡟࠾࠸࡚ࡶ  ᖺᗘࡢ᪩࠸᫬ᮇ࡟ࡣ᭱᪂∧࡟᭦᪂ࡍࡿணᐃ࡛࠶ࡿ㸬 ࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụṇᏍ㍺㏦ᮦᩱࡢタィ࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụࡢṇᏍ㍺㏦ᮦᩱ 6SLUR20H7$' ࡣࡑࡢ㧗࠸࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡࡛▱ࡽࢀ࡚࠸ࡿ㸬)$3E,  0$3E%U  ࣌ࣟࣈࢫ࢝࢖ࢺ࡟ᑐࡍࡿ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࡣ ࡛࠶ࡿ>@㸬6SLUR20H7$' ࡢྜᡂ㈝⏝ࡣ࠾ࡼࡑJ ࡜᥎ᐃࡉࢀ࡚࠸ࡿ>@㸬ẚ㍑ⓗ㧗࠸࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡࡛ࡼࡾᏳ౯࡞ṇᏍ㍺㏦ᮦᩱࡶ
ぢࡘ࠿ࡗ࡚࠾ࡾ ; J 3\& J HWF 㸪ࡼࡾ㧗࠸࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆಖᣢࡋࡘࡘࡼࡾᏳ౯࡞ྜᡂ
ࢥࢫࢺࡀ᥎ᐃࡉࢀࡿᮦᩱࡢ᥈⣴ࡀᚲせ࡛࠶ࡿ㸬ࡑࡇ࡛㸪ᮏ◊✲࡛ࡣᶵᲔᏛ⩦ࢆ⏝࠸࡚ṇᏍ㍺㏦ᮦᩱࢆຠ⋡ⓗ࡟᥈⣴ࡍࡿࡇ࡜ࢆ┠ᣦࡍ㸬 ࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụࡢᅛయ㟁ゎ㉁ࡢ࢖࢜ࣥఏᑟᶵᵓࡢゎ᫂ࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụࡢ㟁ゎ㉁࡜ࡋ࡚㸪඲ᅛయᆺࡀᏳ඲ᛶ࡞࡝ࡢほⅬ࠿ࡽὀ┠ࢆ㞟ࡵ࡚࠸ࡿ㸬᭷ᶵᆺᅛయ
㟁ゎ㉁ࡣ࣏࣐࣮ࣜ࡜࢔ࣝ࢝ࣜ㔠ᒓሷ࠿ࡽᵓᡂࡉࢀ㸪ࡓ࡜࠼ࡤ᭷ᶵ◹⣲࣏࣐࣮ࣜࡀೃ⿵ᮦᩱ࡜ࡋ࡚ᥦ᱌ࡉࢀ࡚
࠾ࡾ>@㸪&RXORPE ┦஫స⏝ࡀᙅ࠸ࡓࡵ࡟ࣜࢳ࣒࢘࢖࢜ࣥࡢఏᑟᗘࡀ㧗࠸࡜ࡉࢀࡿ㸬ࡑࡇ࡛㸪ᮏ◊✲࡛ࡣ᭷ᶵ◹⣲࡛ಟ㣭ࡋࡓ࣏ࣜ࣋ࣥࢰ࢖࣑ࢲࢰ࣮ࣝࢆᑐ㇟࡟㸪࢖࢜ࣥ㟁ᑟࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚⌮ㄽⓗ࡟᫂ࡽ࠿࡟ࡍࡿ
ࡇ࡜ࢆ┠ⓗ࡜ࡍࡿ㸬

- 184 -

.HJJLQ ᆺ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺࡢ⌮ㄽⓗ◊✲, .HJJLQ ᆺ 320 >;02@]íࡣࣉࣟࢺࣥ⛣ື࡜ඹᙺࡋࡓከ㟁Ꮚ⛣ື཯ᛂࢆ௰௓ࡍࡿゐ፹࡜ࡋ࡚᭷ᮃ࡞ೃ⿵࡛
࠶ࡿ㸬ࡇࢀࡲ࡛ࡢᡃࠎࡢ◊✲ >@ ࡛࣊ࢸࣟཎᏊ ; ࡀ኱ࡁ࡞࢖࢜ࣥࢧ࢖ࢬ࡜ᑠࡉ࡞ṇ㟁Ⲵࢆᣢࡘ࡜ࡁ㸪ከ㟁Ꮚ⛣ືࡢⓎ⌧ࡢྍ⬟ࡀ㧗ࡃ࡞ࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿ㸬ከ㟁Ꮚ⛣ືࢆྍ⬟࡟ࡍࡿ࣊ࢸࣟཎᏊ ; ࢆᣢࡘ .HJJLQ ᆺ
320 ࡢ㛤Ⓨἲࢆ☜❧ࡍࡿࡓࡵ㸪$QGHUVRQ ᆺ 320 ࠿ࡽࡢ .HJJLQ ᆺ 320 ⏕ᡂ཯ᛂ࡟࠾࠸࡚୰᰾ࡢ཯ᛂ࡟࡞ࡿ
࡜⪃࠼ࡽࢀࡿභဨ⎔ ;02+ 㒊ࡢ㌿᥮཯ᛂࡢ⤒㊰᥈⣴࡜ࡑࡢ⤒㊰࡟ཬࡰࡍ࣊ࢸࣟཎᏊ ; ࡢ㟁Ⲵࡸࢧ࢖ࢬ㸪⁐፹ࡢㄏ㟁⋡ࡢᙳ㡪ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬,,.HJJLQ ᆺ࢖ࢯ࣏ࣜࢱࣥࢢࢫࢸࣥ㓟࢖࢜ࣥ >+Q:2@ íQ í ࡣከ㟁Ꮚ⛣ື཯ᛂࡢ᭷ᮃ࡞ೃ⿵࡛࠶ࡾ㸪ᢠ࢘࢖ࣝࢫࡸᢠ⭘⒆άᛶࢆ♧ࡍࡇ࡜ࡶᮇᚅࡉࢀࡿ㸬.HJJLQ ᆺ࢖ࢯ࣏ࣜࢱࣥࢢࢫࢸࣥ㓟࢖࢜ࣥ࡟࠾ࡅࡿࣉࣟࢺࣥ㌿⛣཯ᛂࡢゎ᫂ࡣ㸪ࡇࢀࡽࡢάᛶࡸ .HJJLQ ᆺ࢖ࢯ࣏ࣜࢱࣥࢢࢫࢸࣥ㓟࢖࢜ࣥࡢ✀ศ໬ࡢ㆟ㄽ࡟㔜せ࡛࠶ࡿ㸬.HJJLQᆺ࢖ࢯ࣏ࣜࢱࣥࢢࢫࢸࣥ㓟࢖࢜ࣥࡢእ㒊ࣉࣟࢺࣥࢧ࢖ࢺ࠿ࡽෆ㒊ࣉࣟࢺࣥࢧ࢖ࢺ࡬ࡢࣉࣟࢺࣥ㌿⛣཯ᛂ࡜ࡑࢀ࡟ᇶ࡙࠸ࡓ .HJJLQ ᆺ࢖ࢯ࣏ࣜࢱࣥࢢࢫࢸࣥ㓟࢖࢜ࣥࡢ✀ศ໬ࡢヲ⣽࡟ࡘ࠸࡚᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬,,, 㕲 ,,,  㘒య >)H D]S 0HTVDO @ ࡣ⤖ᬗ࡟࠾࠸࡚ࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮ࢆ♧ࡍ㸬ࡇࡢ⤖ᬗࡣ㧗ࢫࣆࣥ≧ែ࡛ືⓗ࡞ࢹ࢕ࢫ࣮࢜ࢲ࣮ࢆ♧ࡍࡢ࡟ᑐࡋ㸪పࢫࣆࣥ≧ែ࡛ࡣࡑࡢࡼ࠺࡞ࢹ࢕ࢫ࣮࢜ࢲ࣮ࡣㄆࡵࡽࢀ࡞࠸㸬ࡇࡢືⓗ࡞ࢹ࢕ࢫ࣮࢜ࢲ࣮࡟ࡣ㓄఩Ꮚ࣌ࢲࣝ㐠ືࡀ㛵ࢃࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀ㸪ࡇࡢ≀㉁ࡢ≀ᛶࡢ⌮ゎ࡟㓄఩Ꮚ࣌ࢲࣝ㐠ືࡢヲ⣽ࡢゎ᫂ࡀ୙ྍḞ࡛࠶ࡿ㸬୰ᚰ㕲 ,,, ࢖࢜ࣥࡢపࢫࣆࣥ≧ែ࡜㧗ࢫࣆࣥ≧ែ࡟࠾ࡅࡿ㓄఩Ꮚ࣌ࢲࣝ㐠ືࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆồࡵࡿࡓࡵ㓄఩Ꮚ࣌ࢲࣝ㐠ືࡢ㑄⛣≧ែࢆ᥈⣴ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬◊✲᪉ἲࠊィ⟬᪉ἲ ࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụṇᏍ㍺㏦ᮦᩱࡢタィᡃࠎࡣศᏊグ㏙Ꮚࢆධຊࢹ࣮ࢱ࡜ࡋࡓ῝ᒙࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࢆ⏝࠸࡚ṇᏍ㍺㏦ᮦᩱࡢ࢚ࢿࣝࢠ࣮ኚ᥮
ຠ⋡ࢆ᥎ࡍࡿࣔࢹࣝࢆᵓ⠏ࡋࡓ㸬ࡉࡽ࡟࢞࢘ࢫ㐣⛬ᅇᖐࣔࢹࣝࢆ⏝࠸࡚⋓ᚓ㛵ᩘࢆホ౯ࡋ࣋࢖ࢬ᭱㐺໬ࢆ⾜ࡗࡓ㸬⭾኱࡞ࢣ࣑࢝ࣝ✵㛫ࢆ᥈⣴ࡍࡿࡓࡵ࡟㞳ᩓ⢏Ꮚ⩌᭱㐺໬ࢆ᥇⏝ࡋࡓ㸬ṇᏍ㍺㏦ᮦᩱࡢศᏊᵓ㐀ࡢ⤌ࡳྜࢃࡏ࠿ࡽศᏊࢆ⏕ᡂࡋ㸪ࡑࡢ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆ᥎ࡍࡿᏛ⩦ࣔࢹࣝࢆᵓ⠏ࡋࡓ㸬Ꮫ⩦ࣔࢹࣝࡢカ⦎ࢹ࣮ࢱ࡟ࡣ㸪࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụࡢṇᏍ㍺㏦ᮦᩱࡢ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࡢᐇ㦂್ ィ   ࢆ⏝࠸ࡓ㸬ධຊࢹ࣮ࢱ࡜ࡋ࡚ṇᏍ㍺㏦ᮦᩱ  ศᏊ 㸪άᛶᒙ  ⤌ᡂ㸪ࣂࣥࢻࢠࣕࢵࣉ㸪9%0㸪&%0 㸪㟁Ꮚ㍺㏦ᮦᩱ
 ศᏊ㸪&%0 㸪ࢻ࣮ࣃࣥࢺ㸪ࢥࢻ࣮ࣃࣥࢺ㸪άᛶ㠃✚㸪࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ 3&(  ࢆ᥇⏝ࡋࡓ㸬 ศᏊࡢṇᏍ㍺㏦ᮦᩱࢆ  ࡘࡢࣇࣛࢢ࣓ࣥࢺ࡟ศゎࡋ㸪ࡇࢀࡽࡢࣇࣛࢢ࣓ࣥࢺ࠿ࡽೃ⿵ศᏊࢆᵓ⠏ࡍࡿ㸬0RUGUHG >@ࢆ⏝࠸࡚ࣇࣛࢢ࣓ࣥࢺẖ࡟ศᏊグ㏙Ꮚࢆィ⟬ࡋ㸪ឤᗘศᯒ࡛ୖ఩ ࡢࡶࡢࢆᏛ⩦ࣔࢹࣝࡢㄝ᫂ኚᩘ࡟ྵࡵ
ࡓ㸬ࡉࡽ࡟ 0RUGUHG ࡢ PDWUL[DJJUHJDWLQJPHWKRG ࢆ⏝࠸࡚ィ⟬ࡋࡓศᏊ඲య࡜ࣇࣛࢢ࣓ࣥࢺẖࡢࢡ࣮ࣟࣥ⾜ิ࡜ 17&KHP >@ ࢆ⏝࠸࡚ィ⟬ࡋࡓࣇࣛࢢ࣓ࣥࢺẖࡢ㔞Ꮚグ㏙Ꮚ +202 /802 ඲࢚ࢿࣝࢠ࣮㸪GLVSHUVLRQHQHUJ\ ඲㟁Ꮚ࢚ࢿࣝࢠ࣮㸪⏕ᡂ⇕㸪཮ᴟᏊ࣮࣓ࣔࣥࢺ  ࢆㄝ᫂ኚᩘ࡟ྵࡵࡓ㸬ᐇ㦂ࢹ࣮ࢱ㸪ศᏊグ㏙Ꮚ ศᏊ඲య࡜ࣇࣛࢢ࣓ࣥࢺ  㸪㔞Ꮚグ㏙Ꮚ ࣇࣛࢢ࣓ࣥࢺ  㸪ࢡ࣮ࣟࣥ⾜ิ ඲య࡜ࣇࣛࢢ࣓ࣥࢺ  ࢆㄝ᫂ኚᩘ࡜
ࡋ࡚㸪SDUWLDOOHDVWVTXDUHVUHJUHVVLRQ 3/65 VXSSRUWYHFWRUPDFKLQH 690 NQHDUHVWQHLJKERU N11 ࡢ 6WDFNLQJ ࣮࣋ࢫࣞ࢖࣮ࣖࡢᏛ⩦ࣔࢹࣝࢆᵓ⠏ࡋࡓ㸬ᵓ⠏ࡋࡓ 6WDFNLQJ ࣮࣋ࢫࣞ࢖࣮ࣖࡢண

3&( ࢆㄝ᫂ኚᩘ࡟ຍ࠼࡚㸪ࡉࡽ࡟ 6WDFNLQJ ࣮࣋ࢫࣞ࢖࣮ࣖࡢᏛ⩦ࣔࢹࣝࢆᵓ⠏ࡍࡿ㸬ࡇࢀࢆ⧞ࡾ㏉ࡋ㸪6WDFNLQJ ࣮࣋ࢫࣞ࢖࣮ࣖࢆ  ಶ

- 185 -

⏝ពࡋࡓ㸬6WDFNLQJ ࣮࣋ࢫࣞ࢖࣮ࣖࡢண

್ࢆㄝ᫂ኚᩘ࡟ຍ࠼࡚㸪῝ᒙࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࣔࢹࣝࢆᵓ

⠏ࡍࡿ㸬඾ᆺⓗ࡞ᐇ㦂᮲௳ࡢࡶ࡜ೃ⿵ศᏊࢆ࢞࢘ࢫ㐣⛬ᅇᖐࣔࢹࣝ࡟ࡼࡗ࡚㑅ᢥࡋࡓ㸬௬᝿ᐇ㦂࡜ࡋ࡚㸪῝ᒙࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࣔࢹࣝ࠿ࡽೃ⿵ศᏊࡢ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆ᥎ࡋࡓ㸬௬᝿ᐇ㦂ࢆ⧞ࡾ㏉ࡍࡇ࡜࡛㸪࢞࢘ࢫ㐣⛬ᅇᖐࣔࢹࣝࢆᨵၿࡋ㸪᭱㐺࡞ೃ⿵ศᏊࢆ᥈⣴ࡋࡓ㸬ೃ⿵ศᏊࡢ⤌ࡳྜࢃࡏࡣ࠾ࡼࡑ 
㏻ࡾ࡜࡞ࡾ㸪ࡇࡢࢣ࣑࢝ࣝ✵㛫ࢆ⥙⨶ⓗ࡟᥈⣴ࡍࡿࡇ࡜ࡣᅔ㞴࡟࡞ࡿ㸬㞳ᩓ⢏Ꮚ⩌᭱㐺໬ࢆ᥇⏝ࡋ㸪⭾኱࡞ࢣ࣑࢝ࣝ✵㛫ࢆ᥈⣴ࡍࡿ㸬ࡇࡢ᥎ࣔࢹࣝࡀ୚࠼ࡿ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆ┠ⓗ㛵ᩘ࡜ࡋ࡚㞳ᩓ⢏Ꮚ⩌᭱㐺໬ἲࢆ㐺⏝ࡋࡓ㸬ࣇࣛࢢ࣓ࣥࢺࡢᩘࢆ Q㸪ࣇࣛࢢ࣓ࣥࢺࢆ㓄⨨ࡍࡿ⟠ᡤࢆ 1 ࡜ࡋࡓ࡜ࡁ㸪⢏Ꮚࡢᗙᶆࢆ Qî1 ࣅ
ࢵࢺ⾜ิ࡜ࡋ࡚ᐃ⩏ࡋࡓ㸬ᗙᶆࡣ☜⋡ㄽⓗ࡟᭦᪂ࡉࢀ㸪 ⟠ᡤ࠶ࡓࡾ㸯ࡘࡢࣇࣛࢢ࣓ࣥࢺࡀ㑅ࡤࢀࡿࡼ࠺࡟
☜⋡㛵ᩘࡣࢯࣇࢺ࣐ࢵࢡࢫ㛵ᩘ࡛ホ౯ࡋࡓ㸬 ࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụࡢᅛయ㟁ゎ㉁ࡢ࢖࢜ࣥఏᑟᶵᵓࡢゎ᫂࣋ࣥࢰ࢖࣑ࢲࢰ࣮ࣞࢺ  㔞యࢆᑐ㇟࡟㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗࡓ㸬ࢺ࢚ࣜࢳ࡛ࣝ࣎ࣛࣥ࣋ࣥࢰ࢖࣑ࢲࢰ࣮ࣞࢺ ศᏊ඲య࡛㟁Ⲵí  ࡢ ƍ ࡲࡓࡣ ƍ఩ࡢ 1 ࢆಟ㣭ࡋࡓ㸬⣔ࡀศᴟࡋ࡚࠸ࡿࡓࡵ㸪ᐦᗘỗ㛵ᩘ࡟ࡣ㛗㊥㞳⿵ṇࡋࡓ /&Ȧ3%( ࢆ㸪ᇶᗏ㛵ᩘ࡟ࡣ *  /L   *  + % & 1  ࢆ⏝࠸ࡓ㸬ࡲࡓศᩓຊࢆ ')7'/&Ȧ3%(V V D D   ࡟ࡼࡾグ㏙ࡋࡓ㸬཯ᛂ⤒㊰᥈⣴ࢆ QXGJHGHODVWLF
EDQG 1(% ࡟ࡼࡾ⾜࠸㸪࢜ࣜࢦ࣐࣮࡟ἢࡗࡓࣜࢳ࣒࢘ᣑᩓ࡟࠾ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮ࢆホ౯ࡋࡓ㸬ィ⟬࡟ࡣ
17&KHP>@ ࡜ ')7'>±@ ࢆ⏝࠸ࡓ㸬.HJJLQ ᆺ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺࡢ⌮ㄽⓗ◊✲
17&KHP>@ ࡟ࡼࡾ㸪➨୍ཎ⌮㟁Ꮚ≧ែィ⟬࡜ QXGJHGHODVWLFEDQG 1(%  ἲ࡟ࡼࡿ᭱ᑠ࢚ࢿࣝࢠ࣮⤒㊰᥈⣴ࢆ⾜ࡗࡓ㸬, ࡟ࡘ࠸࡚ࡣ &2602 ἲࢆ⏝࠸࡚⁐፹ࡢㄏ㟁⋡ࡢຠᯝࢆ⧊ࡾ㎸ࢇࡔィ⟬ࡶ⾜ࡗࡓ㸬,$QGHUVRQ ᆺ ;02+ ࡜ .HJJLQJ ᆺ ;02+ 0 :; $O6L36&G 㸪࡞ࡽࡧ࡟ࡑࢀࡽࡢ㛫ࡢ཯ᛂ⤒㊰ࢆ Ȧ%;'GHI693 ࡛ィ⟬ࡋࡓ㸬&2602 ἲ࡛ࡣ࢔ࢭࢺࢽࢺࣜࣝ ㄏ㟁⋡  㸪Ỉ⇕᮲௳ୗࡢỈ  㸪Ỉ   ࢆ⁐፹࡜ࡋࡓ㸬
,,>+Q:2@ íQ  í࡜ +>+Qí:2@ íQ  í Q ± 㸪࡞ࡽࡧ࡟ࡑࢀࡽࡢ㛫ࡢ཯ᛂ⤒㊰ࢆ Ȧ%;'GHI693 ࡛ィ⟬ࡋࡓ㸬,,, >)H D]S 0HTVDO @ ࡢ㧗ࢫࣆࣥ࡜పࢫࣆࣥ≧ែࡑࢀࡒࢀ࡟࠾ࡅࡿ஧ࡘࡢࢹ࢕ࢫ࣮࢜ࢲ࣮ᵓ㐀࡜ࡑࢀࡽࡢ㛫ࡢ཯ᛂ⤒㊰ࢆ %/<3* G  &12 * GS  )H ࡛ィ⟬ࡋࡓ㸬




◊✲ᡂᯝ

 ࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụṇᏍ㍺㏦ᮦᩱࡢタィ ㏻ࡾࡢィ⟬ࢆ⾜࠸㸪ィ  ศᏊࢆೃ⿵࡜ࡋ࡚㑅ᢥࡋࡓ㸬ࢺࣜ࢔࣮ࣜࣝ࢔࣑ࣥ࡜㛗࠸࢔ࣝ࢟ࣝ㙐ࢆ᭷ࡍࡿᵓ㐀ࡢศᏊࡢ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࡀ㧗࠸ࡇ࡜ࡀ♧ࡉࢀࡓ ᅗ  㸬

- 186 -

ᅗ 1. ᮏィ⟬࡛ணࡉࢀࡓ㧗ຠ⋡ HTM

 ࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụࡢᅛయ㟁ゎ㉁ࡢ࢖࢜ࣥఏᑟᶵᵓࡢゎ᫂࣋ࣥࢰ࢖࣑ࢲࢰ࣮ࣞࢺ  㔞య࡟ἢࡗࡓࣜࢳ࣒࢘࢖࢜ࣥࡢᣑᩓࡢ཯ᛂࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࢆᅗ  ࡟♧ࡍ㸬ࣜࢳ࣒࢘࢖࢜ࣥࡀ  㔞యࡢ୧➃ 1 %]  ࡟㓄఩ࡋࡓᵓ㐀࡛ࡣ࣋ࣥࢰ࢖࣑ࢲ࣮ࣞࢺ㛫ࡢ஧㠃ゅࡀ ࡛࠶ࡗࡓ
ࡀ㸪᭱Ᏻᐃᵓ㐀 1ƍ  ࡛ࡣ ⛬ᗘ࡜࡞ࡾ㸪ᵓ㐀ࡀ኱ࡁࡃኚ໬ࡋࡓ㸬ࢺ࢚ࣜࢳ࡛ࣝ࣎ࣛࣥಟ㣭ࡋࡓ⣔࡟ࡶྠᵝࡢഴྥࡀࡳࡽࢀࡓ㸬ᅗ 2. NEB ࡛ᚓࡽࢀࡓࣜࢳ࣒࢘࢖࢜ࣥᣑᩓ཯ᛂࡢ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝ

.HJJLQ ᆺ࣏ࣜ࢜࢟ࢯ࣓ࢱ࣮ࣞࢺࡢ⌮ㄽⓗ◊✲,.HJJLQ ᆺ 320 ࡢᙧᡂ⤒㊰࡟࠾ࡅࡿභဨ⎔ࡢ㌿᥮཯ᛂࡢ཯ᛂ㞀ቨࡢ኱ࡁࡉࡣ୍⯡ⓗ࡞࣊ࢸࣟཎᏊ࡛࠶ࡿ 3ࡢ࡜ࡁ࡟᭱ࡶᑠࡉࡃ㸪ᡃࠎࡀྜᡂ┠ᶆ࡜ࡍࡿ &G࡛ࡣ .HJJLQ 㦵᱁࡟ྲྀࡾ㎸ࡲࢀࡸࡍ࠸࡜ࡉࢀࡿ 6L࡜ྠ⛬ᗘ- 187 -

࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬ࡲࡓ㸪཯ᛂ⤒㊰ࡢ㞀ቨࢆ᭱ᑠ࡟ࡍࡿㄏ㟁⋡ࡢ್ࡣ㸪࣊ࢸࣟཎᏊࡢ✀㢮࡟౫Ꮡࡋ࡚ኚ
ࢃࡿࡇ࡜ࡶ᫂ࡽ࠿࡟࡞ࡗࡓ㸬,, .HJJLQ ᆺ࢖ࢯ࣏ࣜࢱࣥࢢࢫࢸࣥ㓟࢖࢜ࣥࡢ✀ศ໬࡜እ㒊ࣉࣟࢺࣥࢧ࢖ࢺ࠿ࡽෆ㒊ࣉࣟࢺࣥࢧ࢖ࢺ࡬ࡢࣉࣟࢺࣥ㌿⛣཯ᛂ࡟ࡘ࠸࡚ࡢศᏊ◊࡛ࡢィ⟬࡛ᚓࡽࢀࡓ⤖ᯝࢆࡶ࡜࡟◊✲ࢆࡍࡍࡵ㸪ෆ㒊ࣉࣟࢺࣥࢧ࢖ࢺ࡬ࡢ
ࣉࣟࢺࣥ㌿⛣཯ᛂࡢᅛ᭷཯ᛂᗙᶆࢆ᫂ࡽ࠿࡟ࡍࡿ࡜࡜ࡶ࡟⇕໬Ꮫゎᯒࢆ⾜࠺ࡇ࡜ࡶ࡛ࡁࡓ㸬ࡇࢀ࡟ࡼࡾ㸪ࡇࢀࡲ࡛Ꮡᅾࡀ␲ࢃࢀ࡚࠸ࡓ >+:2@í ࡀᐊ࡛༑ศᏑᅾࡋ࠺ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸬,,, ୰ᚰ㕲 ,,, ࢖࢜ࣥࡢ㧗ࢫࣆࣥ≧ែ࡟࠾ࡅࡿ㓄఩Ꮚ࣌ࢲࣝ㐠ືࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆồࡵࡿࡓࡵ㓄఩Ꮚ࣌ࢲࣝ㐠ືࡢ㑄⛣≧ែࢆ 1(% ἲ࡟ࡼࡾ᥈⣴ࡋࡓ㸬ࡑࡢ⤖ᯝ࡟ᇶ࡙࠸࡚◊✲ࢆࡍࡍࡵࡿࡇ࡜࡟ࡼࡾ㸪ࡑࢀࡒࢀࡢ
㑄⛣≧ែࢆồࡵࡿࡇ࡜ࡀ࡛ࡁࡓ㸬άᛶ໬ࢠࣈࢫ࢚ࢿࣝࢠ࣮ࡣ㧗ࢫࣆ࡛ࣥ N-PRO㸪పࢫࣆ࡛ࣥ N-PRO ࡛࠶ࡾ㸪㧗ࢫࣆࣥ࡟࠾࠸࡚ࡢࡳ㓄఩Ꮚࡢ࣌ࢲࣝ㐠ືࡀ㉳ࡇࡾᚓࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃմ(LVXNH.DZDVKLPD7DNDKLWR1DNDMLPD7KHUG5&&6,QWHUQDWLRQDO6\PSRVLXPRQOLQH
մ.D]X\XNL7DNDKDVKL$WVXKLUR0L\DZDNL.D]XR(GD7RPR\XNL0RFKLGD7DNDKLUR6DNXUDL+LWRVKL2KWD7DNDKLWR
1DNDMLPD7KHVW$VLDQ&RQIHUHQFHRQ0ROHFXODU0DJQHWLVPRQOLQH
մ㜿ஂ᰿ ᫀᙪ㸪ᯞ ࿴⏨㸪኱ሜ ฼⾜㸪୰ᔱ 㝯ே㸪᪥ᮏ໬Ꮫ఍➨  ᫓Ꮨᖺ఍㸪RQOLQHฟ∧ᐇ⦼ࡲࡓࡣணᐃ

:'DZVRQ60RKU/(5DWFOL൵71DNDMLPDDQG/*HQRYHVH-&KHP7KHRU\&RPSXW16±  
GRLDFVMFWFE
0=DFFDULD:'DZVRQ9&ULVWLJOLR05HYHUEHUL/(5DWFOL൵71DNDMLPD/*HQRYHVHDQG%0RPHQL&XUU2SLQ%LRWHFKQRO62±  GRLMFRSELR
/ ( 5DWFOL൵ : 'DZVRQ * )LVLFDUR ' &DOLVWH 6 0RKU$ 'HJRPPH % 9LGHDX 9 &ULVWLJOLR 0 6WHOOD 0
'¶$OHVVDQGUR 6 *RHGHFNHU 7 1DNDMLPD 7 'HXWVFK DQG / *HQRYHVH - &KHP 3K\V 152   
GRL
մ.0L\DJDZD7.DZDNDPL<6X]XNL+,VREH06KRML6<DPDQDND02NXPXUD71DNDMLPDDQG.<DPDJXFKL
0RO3K\V118H  GRL
0=%UHOD2.OLPDV0%RF]DU71DNDMLPDDQG0-:yMFLN6SHFWURFKLP$FWD$0RO%LRPRO6SHFWURVF237  GRLMVDD
մ. <DPDJXFKL + ,VREH 0 6KRML . 0L\DJDZD 6 <DPDQDND 7 .DZDNDPL DQG 7 1DNDMLPD - 3KRWRFKHP
3KRWRELRO$&KHP402  GRLMMSKRWRFKHP
. +LUDR 7 1DNDMLPD % &KDQ -: 6RQJ DQG +6 %DH - 3K\V &KHP $ 124 ±  
GRLDFVMSFDF
մ.0L\DJDZD7.DZDNDPL<6X]XNL+,VREH06KRML6<DPDQDND02NXPXUD71DNDMLPDDQG.<DPDJXFKL-3KRWRFKHP3KRWRELRO$&KHP405  GRLMMSKRWRFKHP
($+DLGDU6$7DZ¿N&6WDPSÀ.+LUDR.<RVKL]DZD71DNDMLPD.$6ROLPDQDQG$0(O1DKDV$GY
7KHRU\6LPXO4  GRLDGWV

- 188 -

ཧ⪃ᩥ⊩
>@ 7 1DNDMLPD 0 .DWRXGD 0 .DPL\D DQG < 1DNDWVXND ,QW - 4XDQWXP &KHP 115 ±  
GRLTXD
>@--<RR6:LHJKROG0&6SRQVHOOHU05&KXD61%HUWUDP173+DUWRQR-67UHVEDFN(&+DQVHQ-3&RUUHD%DHQD9%XORYLü7%XRQDVVLVL666KLQDQG0*%DZHQGL(QHUJ\(QYLURQ6FL12±  
GRL&((%
>@&+7HK5'DLN(//LP&&<DS0$,EUDKLP1$/XGLQ.6RSLDQDDQG0$07HULGL-0DW&KHP
$4±  GRL&7$+>@$1DJ0$$OL$6LQJK59HGDUDMDQ10DWVXPLDQG7.DQHNR-0DWHU&KHP$7±  
GRL&7$- >@.1DNDMLPD.(GDDQG6+LPHQR,QRUJ&KHP49±  GRLLF
>@+0RULZDNL<67LDQ1.DZDVKLWDDQG77DNDJL-&KHPLQIRUP10  GRLV\>@(&DOGHZH\KHU&%DQQZDUWKDQG6*ULPPH-&KHP3K\V147  GRL
>@(&DOGHZH\KHU6(KOHUW$+DQVHQ+1HXJHEDXHU66SLFKHU&%DQQZDUWKDQG6*ULPPH-&KHP3K\V150
  GRL
>@ ( &DOGHZH\KHU -0 0HZHV 6 (KOHUW DQG 6 *ULPPH 3K\V &KHP &KHP 3K\V 22 ±  
GRL'&3$

- 189 -

⏕యศᏊࡢ࣐ࣝࢳࢥࣆ࣮࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ
Multicopy and multiscale simulation of biomolecules‫ۑ‬᳃ḟ ᆂ㸦ᶓ὾ᕷ኱㝔㸧1◊✲┠ⓗ◊✲௦⾲⪅ࡣࡇࢀࡲ࡛࡟ࠊḟୡ௦ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࡢィ⟬⬟ຊࢆ᭱኱㝈࡟ά⏝ࡋ⏕య㧗ศᏊࡢ❧యᵓ㐀ᙧᡂ࣭ᶵ⬟Ⓨ⌧࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆ㧗⢭ᗘ࠿ࡘຠ⋡ⓗ࡟⾜࠺ࡇ࡜ࡢ࡛ࡁࡿ᪂つ࢔ࣝࢦࣜࢬ࣒ࡢ㛤Ⓨ࡜ࠊࡇࢀࢆᐇ⿦ࡍࡿࣉࣛࢵࢺࣇ࢛࣮࣒࡜࡞ࡿ࣐ࣝࢳࢥࣆ࣮࣭࣐ࣝࢳࢫࢣ࣮ࣝศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ࢘
࢙࢔ࠕP2libࠖࡢ㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓ(http://www.csrp.riken.jp/application_j.html)ࠋࡲࡓࠊࡑࡢ࢔ࣉࣜࢣ࣮ࢩࣙࣥ࡜
ࡋ࡚ࠊ⮬⏤࢚ࢿࣝࢠ࣮᭱ᑠ⤒㊰᥈⣴ἲ㸦ࢫࢺࣜࣥࢢἲ㸧࡜ᵓ㐀᥈⣴ἲ㸦MSES ἲ㸧ࡢ◊✲㛤Ⓨࢆ⾜ࡗࡓࠋࢫࢺࣜࣥࢢἲ࡛ࡣࠊ඲ཎᏊࣔࢹࣝ࡜ప⮬⏤ᗘࡢ㞟ᅋᗙᶆ㸦collective variables: CVs㸧ࢆ㐃ᡂࡉࡏࡓ࣐ࣝࢳࢫࢣ࣮
ࣝᡭἲࢆ㐺⏝ࠊࡲࡓࠊከᩘࡢࢩࢫࢸ࣒ࡢࢥࣆ࣮ࢆࢱࣥࣃࢡ㉁ࡢᵓ㐀ኚ໬ࣃࢫୖ࡟㓄⨨ࡋࠊࡑࢀࡽ࣐ࣝࢳࢥࣆ
࣮ࢆᙅ㐃ᡂ࡛୪ิ࡟ィ⟬ࡍࡿࡇ࡜࡛ࠊ⮬⏤࢚ࢿࣝࢠ࣮᭱㐺⤒㊰ࢆຠ⋡ⓗ࡟ィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ௒ᖺᗘࡢ
◊✲࡛ࡣࠊ᫖ᖺᗘ࠿ࡽࡢ⥅⥆ㄢ㢟࡜ࡋ࡚ከ๣᤼ฟ ABC ࢺࣛࣥࢫ࣏࣮ࢱ࣮㸦ABCB1㸧࡟ᮏᡭἲࢆ㐺⏝ࡋࠊ⸆๣㠀⤖ྜ࠾ࡼࡧ Rhodamine 6G ⤖ྜ≧ែ࡛ࡢィ⟬ࡢ㏣ຍࠊཬࡧࠊVerapamil ⤖ྜ≧ែ࡛ࡢ᪂つィ⟬ࢆᐇ⾜ࡍࡿࡇ࡜࡛ࠊᵓ㐀ኚ໬ࣃࢫࡸ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࡀ⸆๣┦஫స⏝࡟ࡼࡾ࡝࠺ኚ໬ࡍࡿ࠿ࢆゎᯒࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ᑐ㇟࡜ࡋ࡚ࡣࠊ⸆๣ࡢయෆືែ࡟㛵ࢃࡿ ABC㸦ATP-binding cassette㸧ከ๣᤼ฟࢺࣛࣥࢫ࣏࣮ࢱ࣮ࡢ୍

ࡘ࡛࠶ࡿ CmABCB1 ࢆ㑅ࢇࡔࠋ⤖ᬗᵓ㐀ゎᯒ࡛ᚓࡽࢀࡓ CmABCB1 ࡢෆྥᆺࠊእྥᆺࡢ 2 ࡘࡢ≧ែ࡛ࡢ❧యᵓ㐀᝟ሗࢆ⏝࠸ࠊMD ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ౑⏝ࡍࡿࣔࢹࣝࡢసᡂࢆ⾜࡞ࡗࡓࠋ⬡㉁ศᏊ POPC378 ಶ࣭ỈศᏊ
TIP3 ࣔࢹࣝ⣙ 6 ୓ಶࢆ⏝࠸࡚సᡂࡋࡓ⬡㉁஧㔜⭷ࡢ㔜ᚰ࡟ࢱࣥࣃࢡ㉁⤖ᬗᵓ㐀ࡢ⭷㈏㏻㒊఩ࡢ㔜ᚰࢆ㔜ࡡྜࢃࡏࡿࡇ࡜࡛ࢱࣥࣃࢡ㉁ࢆᇙࡵ㎸ࢇࡔࠋࡑࡢ㝿ࠊእྥᆺࡢ⤖ᬗᵓ㐀࡛ࡣ⤖ᬗ໬Ᏻᐃࡢࡓࡵኚ␗ࢆ࠿ࡅ࡚࠸ࡓ
ࡢ࡛㸦Q147A/T381A㸧
ࠊ㔝⏕ᆺ࡟ᡠࡋࡓࠋ⁐ᾮࡢሷ⃰ᗘࡀ 150 mM ࡜࡞ࡿࡼ࠺࡟ࢼࢺ࣒ࣜ࢘࢖࢜ࣥ࠾ࡼࡧሷ⣲࢖࢜ࣥࢆຍ࠼ࠊྜィ⣙ 25 ୓ཎᏊ࠿ࡽ࡞ࡿ⣔ࢆᵓ⠏ࡋࡓࠋ௒ᖺᗘࡢ◊✲࡛ࡣࠊ⸆๣࡜ࡋ࡚ Rhodamine 6G ࡜
Verapamil ࢆ㑅ᢥࡋࠊ⸆๣┦஫స⏝࡟ࡼࡿ᭱ᑠ⮬⏤࢚ࢿࣝࢠ࣮ࣃࢫࡢ㐪࠸ࢆゎᯒࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ⸆๣
⤖ྜࡢ⣔ࡣࠊ⤖ᬗᵓ㐀࡟ᑐࡋ࡚ࢻࢵ࢟ࣥࢢࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ GOLD ࡟ࡼࡾ⸆๣ࢆ⤖ྜࡉࡏࠊ⸆๣㠀⤖ྜ⣔࡜ྠᵝ࡟ᵓ㐀ࣔࢹࣝࢆᵓ⠏ࡋࡓࠋຊሙ࡜ࡋ࡚ࡣ CHARMM36ࠊ㟼㟁ⓗ┦஫స⏝ࡢィ⟬࡟ࡣ Particle mesh
Ewald ἲࢆ⏝࠸ࠊNPT ࢔ࣥࢧࣥࣈ࡛ࣝ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋࢫࢺࣜࣥࢢἲ࡛ࡣࡲࡎࠊෆྥᆺ࠿ࡽእྥᆺᵓ㐀ࢆࡘ࡞ࡄࡼ࠺࡞㠀ᖹ⾮ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦Targeted MD㸧ࢆࡤࡡᐃᩘ࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫ࡢࣃ࣓ࣛࢱࢆኚ࠼࡞ࡀࡽ 10 ᮏࡎࡘᐇ⾜ࡋࠊ᭱㐺໬ࡍ࡭ࡁึᮇࣃࢫࢆᵓ⠏ࡋࡓࠋࢫࢺࣜࣥࢢἲࡢィ⟬ࡣࠊ⸆๣㠀⤖ྜ⣔࡛ 2 ᮏ(Apo1, Apo2)ࠊRhodamine 6G ⤖ྜ⣔࡛ 2 ᮏ(Rho1, Rho2)࡜
Verapamil ⤖ྜ⣔ 1 ᮏ(Ver1)ࡢィ⟬ࢆᐇ᪋ࡋࠊึᮇࣃࢫ࡜⸆๣┦஫స⏝࡟ࡼࡿ᭱ᑠ⮬⏤࢚ࢿࣝࢠ࣮ࣃࢫࡢ౫Ꮡ
ᛶࢆゎᯒࡋࡓࠋྛ⣔ࡢࢫࢺࣜࣥࢢἲ࡛ࡣࠊᚓࡽࢀࡓึᮇࣃࢫୖ࡛➼㛫㝸࡟࡞ࡿࡼ࠺࡟ 36 ಶࡢ࢖࣓࣮ࢪࢆ㑅ᢥ
ࡋࠊ30㸫50 ns ࡟ࢃࡓࡗ࡚༑ศ࡟ึᮇࣃࢫᖹ⾮໬ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ༑ศ࡟ࣃࢫୖࡢᵓ㐀ࡀ⦆࿴ࡋࡓࡇ࡜ࢆ☜ㄆࡋࡓᚋࠊ2 ḟᵓ㐀ࢆᙧᡂࡍࡿṧᇶࡢ CDཎᏊᗙᶆ㸦234 ಶ㸧ཬࡧ⸆๣໬ྜ≀ࡢ 2 ཎᏊ(Rho)/3 ཎᏊ(Ver)ࢆ཯ᛂᗙᶆ(CVs)࡜ࡋ࡚ࢫࢺࣜࣥࢢἲࢆ 20㸫40 ns ᐇ⾜ࡋࠊᵓ㐀ኚ໬ࣃࢫࡢ᭱㐺໬ࢆ༑ศ࡟⾜ࡗࡓࠋ᭱ᚋ

- 190 -

࡟ࠊྛ࢖࣓࣮ࢪࢆᖹ⾮఩⨨࡜ࡍࡿࣁ࣮ࣔࢽࢵࢡ࣏ࢸࣥࢩࣕࣝࢆ࠿ࡅࡓ 5 ns ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ 3 ᅇ⾜࠸ࠊ
multistate Bennett acceptance ratio (MBAR)ἲࢆ⏝࠸࡚⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆㄗᕪࢆྵࡵ࡚⢭ᐦ࡟ィ⟬ࡋࡓࠋィ⟬࡟ࡣࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࣉࣟࢢ࣒ࣛ GENESIS ࢆ⏝࠸ࡓࠋ3◊✲ᡂᯝ⸆๣⤖ྜ࡟ࡼࡿ᭱ᑠ⮬⏤࢚ࢿࣝࢠ࣮ࣃࢫ࡜⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࡢኚ໬ࢆゎᯒࡍࡿࡓࡵࠊ⸆๣㠀⤖ྜ≧ែ࠾ࡼࡧ Rhodamine 6G/Verapamil ࡀ⤖ྜࡋࡓ≧ែ࡛ࡢࢫࢺࣜࣥࢢἲィ⟬⤖ᯝࡢẚ㍑ࢆ⾜ࡗࡓࠋᵓ㐀ኚ໬ࣃࢫࢆぢࡿ࡜ࠊ⸆๣㠀⤖ྜ≧ែ࡛ࡣ Occluded ᵓ㐀࡟㏿ࡸ࠿࡟฿㐩ࡍࡿࡢ࡟ᑐࡋࠊ⸆๣⤖ྜ≧ែ(Rho)࡛ࡣ ABCB1 ෆ㒊࡛ࡢ⊃ࡲࡗࡓ✵㛫࡛ࡢ⸆๣┦஫స⏝࡟ࡼࡿᵓ㐀ࡦࡎࡳ࡟ࡼࡾ Occluded ᵓ㐀࡟࡞ࡾ࡟ࡃ࠸࡜࠸࠺ᕪ␗ࡀぢࡽࢀࡓ㸦ᅗ 1㸧
ࠋVerapamil ࡣᰂ㌾࡟ᵓ㐀ࢆኚ໬ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࡶࡢࡢࢧ࢖ࢬࡀ኱ࡁ࠸ࡓࡵࠊᵓ㐀ࡦࡎࡳ࡟ࡼࡾ
Occluded ᵓ㐀࡟ࡉࡽ࡟࡞ࡾ࡟ࡃ࠸ࡇ࡜ࡶ♧ࡉࢀࡓࠋ⮬⏤࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡍࡿ࡜ࠊ⸆๣㠀⤖ྜ≧ែ࡛ࡣOccluded ᵓ㐀࡛࠶ࡿࡢ࡟ᑐࡋࠊ⸆๣⤖ྜ≧ែ࡛ࡣᵓ㐀ࡦࡎࡳ࡟ࡼࡾ Occluded ᵓ㐀ࡀ୙Ᏻᐃ໬ࡍࡿࡇ࡜ࠊࡑࡢ
⤖ᯝ࡜ࡋ࡚ࠊ⸆๣ࡢ⭷㒑㏦࡟┤⤖ࡍࡿእྥᆺᵓ㐀ࡀ‽Ᏻᐃᵓ㐀࡟࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࡢࡼ࠺࡞⸆
๣┦஫స⏝࡟ࡼࡿᵓ㐀ኚ໬ࣃࢫ࡜⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࡢኚ໬ࡣࠊ⸆๣ࡀ ABCB1 ෆ㒊࡟ྲྀࡾ㎸ࡲࢀࡿࡇ࡜࡟
ࡼࡾෆྥᆺ࠿ࡽእྥᆺ࡬ࡢᵓ㐀ኚ໬ࡀ㉳ࡇࡾࡸࡍࡃ࡞ࡿࡇ࡜ࢆ♧ࡋ࡚࠾ࡾࠊRhodamine 6G ⃰ᗘ࡟ᑐࡋ࡚ ATPάᛶࡢୖ᪼ࢆ♧ࡍᐇ㦂⤖ᯝࢆᵓ㐀ࢲ࢖ࢼ࣑ࢡࢫ࠿ࡽ♧၀ࡍࡿ⤖ᯝ࡛࠶ࡿ࡜ゝ࠼ࡿࠋ
ᅗ 1. ⸆๣㠀⤖ྜ≧ែ㸦㟷࡜ࢩ࢔ࣥ㸧࡜ Rhodamine 6G㸦㉥㸧/Verapamil 㸦⥳㸧⤖ྜ≧ែ࡛ࡢ᭱ᑠ⮬⏤࢚ࢿࣝࢠ࣮ࣃࢫ
㸦ᕥ㸧࡜⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧ㸦ྑ㸧ࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ۻ‬1.

᳃ḟ ᆂ, ᒣᮏ ඾ྐ, ⡿⃝ ᗣ⁠, ᴙ ┿୍, ⸨ᓮ ᘯኈࠕ㔜ࡳ௜ࡁ࢔ࣥࢧࣥࣈࣝἲ࡟ࡼࡿ Pin1 ␗ᛶ໬ࡢࣃࢫࢧࣥࣉࣜࣥࢢࠖ
➨ 58 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ࠊ࢜ࣥࣛ࢖ࣥࠊ2020 ᖺ 9 ᭶

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫  ۻ‬.HL0RULWVXJX1RULIXPL<DPDPRWR<DVXVKLJH<RQH]DZD6KLQLFKL7DWHDQG+LURVKL)XMLVDNL³3DWKHQVHPEOHVIRU3LQFDWDO\]HGFLVWUDQVLVRPHUL]DWLRQRIDVXEVWUDWHFDOFXODWHGE\ZHLJKWHGHQVHPEOHVLPXODWLRQV´-RXUQDORI&KHPLFDO7KHRU\DQG&RPSXWDWLRQ  ±

- 191 -





A comparative study of interaction between antibodies to N-glycans byquantum chemical calculations considering desolvation effects
! &)
 ) ) '

%

"

(



ls8»ÀÃÙFÆ £6¸Ö9Þ(EB8¸Ö4-EFËÌ,DNbRJÎ×8¡?2Û©¬F
@1²im«7A02Þ»À×cq­¹8ËÌ7"2ÔÅ6wF ß+#+Þ-8©¬8Ê»9
B#76026ßSPq­grIH_MÜÝÃÙ8¸NbRJÎ79Þ£6  ¼¸Ö$¼+Þ l9-EB¸ÖFk+2  7¼,Dß l8¸Ö7,DÈ9Þl7A02%&¬6D(4$Ú¯7µ*E2"CÞn!:GWQÓÒv8²$Û Þ Þ l8 /ÞÛVbQdM¸Ö79  $@&ÞLG_ÓF>Ä¸Ö79  $@&¼,Dß´·9Þªls8q­¤¢7"'Dl8¸ÖËÌ©¬8ÉF±¯4+2Þ(8  l¾FÍ7
Â0.ß(E=37Þl8ÛVbQdM¸Ö<8È8Ð7Ø,D³ÇF.83Þj9Þ|¸Öh¶ÜÛVbQdM};Ä¸ÖÝ7,DÞf¶8l8ËÌÁ8Ð7§±+Þl$¸Ö
8ÐF58A 7ËÌ,D#FÉ+.ß )$  l$  °¸NbRJÎ7¼,DÄl8  ½¼¢ÏÜ  Ý8  p8ÛVbQd
M¸Ö8eÑFZO^bK7A02Ä7o¥+ÞlÑuF Þ Þ l7,D(47ACÞ l$¼,D¸NbRJÎ8Äl¢Ïf¶F.ß(EBFt®¢Ï4+2ÞUaK]X  F«2uzxLW[`dL\bFÂ0.ß¢ÏÜº  |Ý#BÞ±¯8¸Ö4-EB7¼,DlÑuF~Ct+.¢ÏÜº   |Ý712ÞGWQÓ¦ Þ{¸)47T]KYbPu
w+ÞUaK]X   F«2Þ¨y F¿+.Õ#?:ÜÝFÂÞl4¸Ö×8²im«É+.ß*B7ÞÄlÞlÑuÞ^bÑu712Þ
37ACp"7?:+22?._dF(+)%,D(47A02<¨8y F¿,DLMXÉFÂÞ@ Â´·8¸ÖÈ1CÚ¼ 41C+.ß 
Þ Þ l4ÛVbQdM¸Ö"A;Ä¸Ö×8²im«_d4Þ@ Â´·8¸ÖÈ1CÚ¼ F1C+.4(Þu¡D;lZO_7AD¨y F¿Ü
3Ý+.'39ÞÚ¼ F!5,D(4$3%6#0.ß+#+ÞLMXÉ7A
02<¨8y F¿,D4Þl¸Ö×²im«_d9ÞÚ¯7BED_d4
1C$Á6dd46CÞ¸ÖÈ1CÚ¼ 4=²Ø$ÇBEÞÕ¯6BA$$Á760.ß
(EB8¼ F=4?Þ9 39 %,¸Î"A;,#9  -'3®Ã+.ß5&Þ>
A+F*843 Dß

 #



1.

Á7EÞ <¨y F¿+.Õ#?:7ADl8¸ÖËÌ8Ð86A¯É ,#
9 101 -'Üb]HbÝ2021  3 .
2. Á7E HIV-1 ËÌ PGT l4LG_Ó/Ä¸Ö×8²im«É 9 39 %,¸ÎÜ0Ý2020  11 .

- 192 -

㌾ ; ⥺ග໬Ꮫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDO6WXGLHVRQVRIW;UD\3KRWRFKHPLFDO3KHQRPHQD‫ۑ‬㧗ᶫಟ㸪ᒣᮧᾴ௓㸪⛅ᘅ೺ᩯ㸪஧ཪᮃ㸦ᗈᓥ኱㝔⌮㸧㸯㸬◊✲┠ⓗ㸪ෆᐜᮏㄢ㢟࡛⾜ࡗࡓ◊✲ࡢ୰࠿ࡽ௨ୗࡢࢸ࣮࣐࡟ࡘ࠸࡚ࡑࡢ⤖ᯝࢆ⡆༢࡟㏙࡭ࡿࠋ  ᭷ᶵ⁐፹୰䛻䛚䛡䜛Ỉ䛾㌾ 㼄 ⥺ศග  ศᏊືຊᏛィ⟬࡟ࡼࡿ࢔ࣝࢥ࣮ࣝỈ⁐ᾮࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡゎᯒ㸰㸬◊✲᪉ἲ㸪ィ⟬᪉ἲ㸪◊✲ᡂᯝ  ᭷ᶵ⁐፹୰䛻䛚䛡䜛Ỉ䛾㌾ 㼄 ⥺ศගศᏊ࡟㌾ ; ⥺ࢆ↷ᑕࡍࡿࡇ࡜࡛ෆẆ㟁Ꮚࢆඖ⣲㑅ᢥⓗ࡟ບ㉳ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡑࡢ྾཰ ;$6 㸪Ⓨග;(6 ࢫ࣌ࢡࢺࣝࡣ㠀༨᭷㸪༨᭷ศᏊ㌶㐨ࢆ┤᥋཯ᫎࡍࡿࡇ࡜࠿ࡽ㸪୧ศගἲࢆ⤌ࡳྜࢃࡏࡿࡇ࡜࡛౯㟁Ꮚ㌶
㐨඲࡚ࢆᤸᥱ࡛ࡁࡿࠋ≉࡟Ỉ⁐ᾮ࡛ࡣ㸪Ỉࢆ୰ᚰ࡜ࡋࡓỈ⣲⤖ྜᵝᘧࢆᩄឤ࡟ᤊ࠼ࡿࡇ࡜ࡀ࡛ࡁࡿࠋᚨᓥࡽ
ࡣỈࡀᕼⷧ࡞࠸ࡃࡘ࠿ࡢ᭷ᶵ⁐ᾮ୰࡛ࡢ ;$6㸪;(6 ࢆᐃࡋࡓࠋ࢔ࢭࢺࢽࢺࣜࣝỈ⁐ᾮ $1 ࡜࢚ࢳࣞࣥࢪ࢔

࣑ࣥỈ⁐ᾮ ('$ ࡢ D ࡜ E ࡟ᖐᒓࡉࢀࡿࣆ࣮ࢡࢆẚ㍑ࡍࡿ࡜㸪$1 Ỉ⁐ᾮ࡛ࡣỈࡢ JDVOLNH㸪('$ Ỉ⁐ᾮ࡛ࡣỈࡢ OLTXLGOLNH ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡿࠋᮏ◊✲࡛ࡣ⌮ㄽィ⟬ࢆ⏝࠸࡚୧⪅ࡢࢫ࣌ࢡࢺࣝࢆ෌⌧ࡋ㸪ࡉࡽ࡟Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡゎᯒࢆ⾜࠺ࡇ࡜࡛㸪ྛ⁐፹࡟࠾ࡅࡿ⤖ྜᵝᘧࡢ㐪࠸ࢆ⪃ᐹࡋࡓࠋ
ศᏊືຊᏛἲࢥ࣮ࢻ *URPDFV ࢆ⏝࠸㸪$1('$ Ỉ⁐ᾮ࡟ᑐࡋ࡚ᐇ㦂ࡢࣔࣝศ⋡ࢆ෌⌧ࡍࡿࡓࡵ࡟ศᏊᩘࢆỈ  ศᏊ㸪$1('$ ศᏊ࡜ࡋ㸪197 ࢔ࣥࢧࣥࣈࣝ࡟ࡼࡗ࡚ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ QV ⾜ࡗࡓࠋ;$6;(6ࢫ࣌ࢡࢺࣝィ⟬ࡣᐦᗘỗ㛵ᩘἲࢥ࣮ࢻ GH0RQN ࢆ⏝࠸ࡓࠋ0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ᚓࡽࢀࡓࢫࢼࢵࣉ
ࢩࣙࢵࢺ࠿ࡽ  ศᏊࢧࣥࣉࣜࣥࢢࡋ㸪୰ᚰࡢỈศᏊࡢࡳᵓ㐀᭱㐺໬ࡋ㸪᣺ືᩘィ⟬ࢆ⾜ࡗࡓࠋ᣺ື࣮ࣔࢻࡣ ࡘࡢ 2+ ఙ⦰࣮ࣔࢻࢆྲྀࡾධࢀ㸪ྛ᣺ື࣮ࣔࢻ࡟ࡘࡁ఩⨨࡟ᑐࡋ࡚  ࡘ㸪㐠ື㔞࡟ᑐࡋ࡚  ࡘࢧࣥࣉࣜࣥ
ࢢࡋࡓࠋࡲࡓ㸪;(6 ࡟㛵ࡋ࡚ࡣึᮇᵓ㐀࡟ᑐࡋ࡚㸪IV 㛫㝸࡛ IV ࡲ࡛ࡢෆẆṇᏍ 0' ࢆィ⟬ࡋ㸪.UDPHUV+HLVHQEHUJ ࡢศᩓᘧ࡟ᚑࡗ࡚ࢫ࣌ࢡࢺࣝィ⟬ࢆ⾜ࡗࡓࠋ㻜㻚㻞$1ZDWHU㻜㻚㻠㻵㼚㼠㼑㼚㼟㼕㼠㼥㻌㻔㼍㼞㼎㻚㼡㼚㼕㼠㼟㻕㻵㼚㼠㼑㼚㼟㼕㼠㼥㻌㻔㼍㼞㼎㻚㻌㼡㼚㼕㼠㼟㻕

㻜㻚㻡

㻜㻚㻟
㻜㻚㻞
('$ZDWHU

㻜㻚㻝

㻜㻚㻝㻢

$1ZDWHU

㻜㻚㻝㻞
㻜㻚㻜㻤

('$ZDWHU

㻜㻚㻜㻠

㻜

㻜

㻡㻞㻜

㻡㻞㻞

㻡㻞㻠

㻡㻞㻢

㻡㻞㻤

㻱㼙㼕㼟㼟㼕㼛㼚㻌㼑㼚㼑㼞㼓㼥㻌㻔㼑㼂㻕

㻡㻟㻜

㻡㻟㻞

㻡㻟㻞

 

㻡㻟㻠

㻡㻟㻢

㻡㻟㻤

㻡㻠㻜

㻡㻠㻞

㻼㼔㼛㼠㼛㼚㻌㼑㼚㼑㼞㼓㼥㻌㻔㼑㼂㻕ᅗ  ྛỈ⁐ᾮ୰࡟࠾ࡅࡿỈࡢ ;(6        ᅗ  ྛỈ⁐ᾮ୰࡟࠾ࡅࡿỈࡢ ;$6

- 193 -ᅗ 㸪ᅗ  ࡟ィ⟬࡛ᚓࡽࢀࡓࡑࢀࡒࢀࡢỈ⁐ᾮ࡟࠾ࡅࡿ ;(6㸪;$6 ࢆ♧ࡍࠋ$1 Ỉ⁐ᾮࡢ E ࡢࣆ࣮ࢡࡣ
H9 ࡟㸪('$ Ỉ⁐ᾮࡣ H9 ௜㏆࡟⌧ࢀ࡚࠾ࡾ㸪$1 Ỉ⁐ᾮࡼࡾࡶࣈ࣮ࣟࢻࡋ࡚࠸ࡿࠋࡲࡓ㸪D ࡢࣆ࣮ࢡࡣ ('$ Ỉ⁐ᾮ࡛ࡣᇙࡶࢀ࡚࠸ࡿࡢ࡟ᑐࡋ࡚㸪$1 Ỉ⁐ᾮ࡛ࡣ H9 ࡛ࣈ࣮ࣟࢻࡋࡓࣆ࣮ࢡࡀぢࢀࡿࠋࡇࢀࡽࡢഴྥࡣᐇ㦂ࢆࡼࡃ෌⌧ࡋ࡚࠸ࡿࠋࡲࡓ )LJ ࡛ࡣ ('$ Ỉ⁐ᾮࡢ D ࡢࣆ࣮ࢡࡣ $1 Ỉ⁐ᾮ࡜ẚ࡭࡚ᙉᗘࡀᑠࡉࡃ㸪H9 ௜㏆ࡢ E ࡢࣆ࣮ࢡࡣ ('$ Ỉ⁐ᾮ࡛ࡣࣈ࣮ࣟࢻࡋ࡚࠸ࡿࠋࡇࢀࡽࡢⅬ࡟࠾࠸࡚ᐇ㦂ࡢ;$6㸪;(6 ࢆࡼࡃ෌⌧࡛ࡁࡓࠋ  ศᏊືຊᏛィ⟬࡟ࡼࡿ࢔ࣝࢥ࣮ࣝỈ⁐ᾮࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡゎᯒ㻌ᚑ᮶Ỉ䛻௦⾲䛥䜜䜛ᾮయ䛿䛹䛾ሙᡤ䜢䛸䛳䛶䜒ᆒ㉁䛷䛒䜛䛸䛔䜟䜜䛶䛝䛯䚹䛧䛛䛧䠈≉䛻௒ୡ⣖䛻ධ䜚㌾ ; ⥺ศගἲ䛻䜘䜚ᾮయ䛾ᚤどⓗᥥീ䛜䛸䜙䛘䜙䜜䠈䛭䛾ᒁᡤⓗ䛺୙ᆒ୍ᛶ䛜ᐇ㦂ⓗ⌮ㄽⓗ䛻䛒䛝䜙䛛䛻䛥䜜䛴䛴䛒䜛䚹ᮏ◊✲䛷䛿䝍䞊䝀䝑䝖䜢䛥䜙䛻┤㙐䜢ఙᙇ䛧䛯䜶䝍䝜䞊䝹䠈䠍䝥䝻䝟䝜䞊䝹䛻ᣑᙇ䛧䠈ྛ⃰ᗘ䛻䛚䛡䜛䜰䝹䝁䞊䝹Ỉ⁐ᾮ䛾ᵓ㐀䜢ศᏊືຊᏛἲ䛻䜘䜚ồ䜑䛯䚹䛥䜙䛻Ỉ⣲⤖ྜ䝛䝑䝖䝽䞊䜽ゎᯒ䛻䜘䜚Ỉ⁐ᾮ䛾ᵓ㐀䛻䛴䛔䛶㆟ㄽ䛧䛯䚹䝯䝍䝜䞊䝹 䜶䝍䝜䞊䝹䝥䝻䝟䝜䞊䝹Ỉ⁐ᾮ䛻䛴䛔䛶 ;  䛛䜙 ;  䜎䛷䛾ྛ⃰ᗘ䛷ศᏊືຊᏛィ⟬䜢⾜䛳
䛯䚹0' ィ⟬䛻䛿➨୍ཎ⌮ศᏊືຊᏛィ⟬䝋䝣䝖䜴䜵䜰䝟䝑䜿䞊䝆 *520$&6 䜢⏝䛔䛯䚹䜰䝹䝁䞊䝹䠈Ỉ䛾 IRUFHILHOG 䛿 23/6$$䠈7,33İ 䜢⏝䛔䛯䚹䝅䝭䝳䝺䞊䝅䝵䞁䝪䝑䜽䝇୰䛻  ศᏊタ⨨䛧䠈࿘ᮇቃ⏺᮲௳ୗ䛾䜒䛸  EDU
. ᮲௳䛻䛚䛔䛶 197137 䜰䞁䝃䞁䝤䝹䛻䜘䜚䝍䜲䝮䝇䝔䝑䝥 IV 䛷ィ QV ᐇ⾜䛧ᾮయ≧ែ䜢෌⌧䛧䛯䚹᭱⤊ⓗ䛻ᚓ䜙䜜䛯䝇䝘䝑䝥䝅䝵䝑䝖䛛䜙Ỉ⣲⤖ྜ䝛䝑䝖䝽䞊䜽ゎᯒ䜢⾜䛳䛯䚹䛺䛚Ỉ⣲⤖ྜ䛾᭷↓䛿 22+ ゅᗘߠ䜢ྵ䜣䛰
:HUQHW 䜙䛻䜘䜛ุᐃᘧ䜢᥇⏝䛧䛯䚹㻌 ࡲࡓỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡢゎᯒࢆࡑࢀࡒࢀࡢ࢔ࣝࢥ࣮ࣝỈ⁐ᾮ࡟ࡘ࠸࡚⾜ࡗࡓࠋᅗ  ࡟ ࣉࣟࣃࣀ࣮ࣝ
Ỉ⁐ᾮࡢ ࣉࣟࣃࣀ࣮ࣝྠኈࡢỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡢ๭ྜࢆ♧ࡍࠋỈ⣲⤖ྜࡣỈ⣲ࢻࢼ࣮㸪Ỉ⣲࢔ࢡࢭࣉࢱ࣮ࡢ㸰✀㢮࡟ศ㢮࡛ࡁ㸪ࡉࡽ࡟⤖ྜᩘ࡟ࡼࡗ࡚⣽ศ໬࡛ࡁࡿࠋ'$ ࡣࢻࢼ࣮࡜࢔ࢡࢭࣉࢱ࣮ࡀᏑᅾࡏࡎᏙ
❧ࡋ࡚࠸ࡿ≧ែ'$'$ ࡣ┤㙐≧ࢡࣛࢫࢱࡢ➃㸪'$ ࡣ┤㙐ୖࢡࣛࢫࢱࡢ୰ࡢ㒊ศ࡟ᑐᛂࡍࡿࠋ'$
࡜ '$ ࡣࢡࣛࢫࢱࡢศᒱⅬ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࡀᅗ  ࠿ࡽࢡࣛࢫࢱࡢศᒱⅬࡣ࡯ࡰᏑᅾࡋ࡞࠸ࠋ

ࡲࡓࣉࣟࣃࣀ࣮ࣝࡢ⃰ᗘࢆୖࡆࡿࡇ࡜࡛Ꮩ❧ࡋ

$FFHSWRU

ࡿࡀ;  ࠿ࡽࡣࢡࣛࢫࢱࡢᩘࡣ࠶ࡲࡾቑ࠼ࡎࢡ

ࣛࢫࢱࡢࢧ࢖ࢬࡀቑ኱ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ



5DWH

࡚࠸ࡿ ࣉࣟࣃࣀ࣮ࣝࡀῶᑡࡋࢡࣛࢫࢱࡣቑ኱ࡍ

㸱㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

U




㸲㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ



5<DPDPXUDHWDO&KHP3K\V/HWW738 




SDJHV   











0ROHIUDFWLRQRISURSDQRO$<DPDPXUDHWDO&RPPXQLFDWLRQV3K\VLFV3(1)

61DJDRNDHWDO&KHP3K\V 534 SDJHV 

ș

'$
'$
'$
'$
'$
'$



࡞ࡋ

 SDJHV   'RQQHUᅗ  ࣉࣟࣃࣀ࣮ࣝỈ⁐ᾮࡢỈ⣲⤖ྜࢿࢵࢺ࣡
࣮ࢡࡢ๭ྜ

 
+<DPDQHHWDO-3K\V&KHP&124(17)  $9HUQDHWDO1HZ-3K\V22(12) SDJHV   - 194 -

໬Ꮫ཯ᛂࡢ㔞Ꮚࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDO6WXG\RQWKH4XDQWXP'\QDPLFV3URFHVVHVRI&KHPLFDO
5HDFWLRQV‫ۑ‬ᒣୗ᫭୍㸪㔠Ꮚṇᚨ㸦ி኱ (6,&%㸧㸪୕ᔱㅬ஧㸦⟃Ἴ኱㸧




◊✲┠ⓗ

 1DQ ࢡࣛࢫࢱ࣮ࡢ 1D105 ࢫ࣌ࢡࢺࣝ࡟ࡘ࠸࡚ࡢᶵᲔᏛ⩦ ࣁ࣮ࢻ࣮࢝࣎ࣥ㸦+&㸧㈇ᴟࡢᛶ⬟ྥୖ࡟ྥࡅ࡚ࠊᅛయ 1D105 ໬Ꮫࢩࣇࢺࢆ⏝࠸࡚ +& ㈇ᴟ࡟ᤄධࡉࢀ
ࡓࢼࢺ࣒ࣜ࢘㔞࡟ᑐࡍࡿ +& సᡂ᮲௳ࡢᙳ㡪ࡀᐇ㦂ⓗ࡟ሗ࿌ࡉࢀ࡚࠸ࡿ >@ࠋࢼࢺ࣒ࣜ࢘ࢡࣛࢫࢱ࣮ࡢ 105໬Ꮫࢩࣇࢺ࡜⣽Ꮝࢧ࢖ࢬ࠾ࡼࡧᵓ㐀ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣࠊ+& ࠾ࡼࡧࡑࡢ௚ࡢ㠀⤖ᬗᛶⅣ⣲ᮦᩱࡢ㛢⣽Ꮝࡢࢧ࢖ࢬศᕸࢆホ౯ࡍࡿࡓࡵࡢ᪉ἲ࡜ࡋ࡚᭷⏝࡛࠶ࡿࠋࡋ࠿ࡋࠊィ⟬ࢥࢫࢺࡢほⅬ࠿ࡽࠊ')7 ィ⟬࡛ࡣ኱ࡁ࡞ࢧ࢖ࢬࡢࢼࢺ࣒ࣜ࢘ࢡࣛࢫࢱ࣮ࡢ 105 ໬Ꮫࢩࣇࢺࢆண

ࡍࡿࡇ࡜ࡣ㞴ࡋ࠸ࠋᮏ◊✲࡛ࡣࠊཎᏊ㛫ࡢ㊥㞳ࢆ฼⏝ࡍࡿࢹ࢕࣮ࣉ࣮ࣛࢽࣥࢢࣔࢹࣝ࡟ࡼࡾࠊࢼࢺ࣒ࣜ࢘ࢡࣛࢫࢱ࣮ࡢᵓ㐀࠿ࡽ 1D 105 ࢫ࣌ࢡࢺࣝ
ࡢணྍ⬟ᛶ࡟ࡘ࠸᳨࡚ウࡋࡓࠋ ᙉㄏ㟁ᛶ࣌ࣟࣈࢫ࢝࢖ࢺ≀㉁ࡢ㟁Ꮚ㸫ࣇ࢛ࣀࣥ┦஫స⏝࡜ࣇ࣮ࣞࣜࢵࣄ࣭࣏࣮ࣛࣟࣥఏᑟ  ᖺ࡟࣓ࢳࣝ࢔ࣥࣔࢽ࣒࢘㖄࣌ࣟࣈࢫ࢝࢖ࢺࡀኴ㝧㟁ụග྾཰ᮦᩱ࡜ࡋ࡚ᑟධࡉࢀࠊࡇࢀࢆ⏝࠸ࡓኴ㝧㟁ụࡣ  ᖺ ࡜࠸࠺㦫␗ⓗ࡞ኚ᥮ຠ⋡ྥୖࢆ㐩ᡂࡋࡓࠋ㧗ຠ⋡ࡢせᅉ࡜ࡋ࡚ࠊග⏕ᡂࡋࡓ࢟ࣕࣜ࢔㸦㟁ᏊࠊṇᏍ㸧ࡢᣑᩓ㊥㞳ࡀ㏻ᖖࡢ༙ᑟయ↓ᶵᮦᩱ࡜ẚ㍑ࡋ࡚ᴟࡵ࡚㛗࠸ࡇ࡜ࡀᣦ᦬ࡉࢀ࡚࠸ࡿࡀࠊ࢟ࣕࣜ࢔෌
⤖ྜᢚไࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࡣ౫↛᫂ࡽ࠿࡛ࡣ࡞࠸ࠋᮏ◊✲࡛ࡣࠊᙉㄏ㟁ᛶ࣌ࣟࣈࢫ࢝࢖ࢺ≀㉁࡟࠾ࡅࡿ
࢟ࣕࣜ࢔㸫ࣇ࢛ࣀࣥ┦஫స⏝ࡢ➨୍ཎ⌮ィ⟬࡟ᇶ࡙࠸࡚ࠊග⏕ᡂ࢟ࣕࣜ࢔࡜⦪ᆺගᏛࣇ࢛ࣀࣥࡢ┦஫స⏝࡟ࡼࡿࣇ࣮ࣞࣜࢵࣄ࣭࣏࣮ࣛࣟࣥᙧᡂࡢほⅬ࠿ࡽග⏕ᡂ࢟ࣕࣜ࢔ࡢ෌⤖ྜᢚไࡢ࣓࢝ࢽࢬ࣒ࢆ᳨ウࡋࡓࠋ ගゐ፹ %L92 ࡟ࡼࡿỈศゎ཯ᛂ࡜ሷ⣲࢖࢜ࣥ㓟໬཯ᛂࡢ⌮ㄽⓗ◊✲ ᭱㏆ࠊబᒣࡽࡣྍどගᛂ⟅ࡍࡿ㓟໬≀༙ᑟయࢆ⏝࠸ࡓග㟁ᴟ࡟ࡼࡾ㣗ሷỈࡸᾏỈ࡞࡝ࡢሷ໬≀࢖࢜ࣥ㸦&O㸧ࢆྵࡴỈ⁐ᾮ࠿ࡽప࠸㟁ゎ㟁ᅽ࡛Ỉ⣲࡜㓟⣲ࢆ㑅ᢥⓗ࡟〇㐀ࡍࡿேᕤගྜᡂᢏ⾡ࡢ㛤Ⓨ࡟ᡂຌࡋࡓ>@ࠋ≉࡟⯆࿡࠶ࡿࡇ࡜࡟ࠊ%L92 ࡸ :2 ࠿ࡽ࡞ࡿග㟁ᴟࡢ⾲㠃࡟࣐ࣥ࢞ࣥ㓟໬≀ࢆᢸᣢࡍࡿࡇ࡜࡟ࡼࡾࠊ๪཯ᛂ࡛࠶
ࡿሷ໬≀࢖࢜ࣥࡢ㓟໬࡟ࡼࡿḟளሷ⣲㓟ࡢ⏕ᡂࡀᢚไࡉࢀࡿࡇ࡜ࢆぢฟࡋࡓࠋࡇࢀࡽࡢᡂᯝࡣࠊග㟁ᴟࢆ⏝࠸ࡓேᕤගྜᡂᢏ⾡࡟ࡼࡿỈ⣲〇㐀ࢩࢫࢸ࣒ࡢᐇ⌧ࡢࡳ࡞ࡽࡎࠊኳ↛ගྜᡂ⣔ࡢ㓟⣲Ⓨ⏕୰ᚰࡢ㐍໬ࡢ㐣⛬࡛ࠕ࡞ࡐ࣐ࣥ࢞ࣥࡀ㑅ࡤࢀࡓࡢ࠿ࠖࢆゎࡃ࢝ࢠࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊ%L92 ⾲㠃࠾ࡼࡧ 0Q ࢻ࣮ࣉࡋࡓ⾲㠃࡛ࡢ㓟⣲Ⓨ⏕㐣⛬࡜ሷ⣲࢖࢜ࣥ㓟໬཯ᛂ࡟ࡘ࠸࡚ࠊࡑࢀࡽࡢ཯ᛂ㐣⛬ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡾゎᯒࡋࠊ0Q ཎᏊࡢᙳ㡪ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ  1DQ ࢡࣛࢫࢱ࣮ࡢ 1D105 ࢫ࣌ࢡࢺࣝ࡟ࡘ࠸࡚ࡢᶵᲔᏛ⩦ ࢹ࢕࣮ࣉ࣮ࣛࢽࣥࢢ࡟ࡣࠊ6FK1HW3DFN ࢆ⏝࠸ࡓࠋ6FK1HW ࡢࣃ࣓࣮ࣛࢱࡣࠊ(PEHGGLQJ ࣋ࢡࢺࣝࢧ࢖ࢬ

- 195 -

ࠊ㐃⥆ࣇ࢕ࣝࢱ␚㎸ࡳᒙࡢࣇ࢕ࣝࢱࠊ┦஫స⏝ࣈࣟࢵࢡࠊ࢝ࢵࢺ࢜ࣇ༙ᚄύύύ࡜ࡋࡓࠋࢹ
࣮ࢱࢭࢵࢺ࡜ࡋ࡚ࡣࠊ1DQ Q  ࣭࣭࣭ ࡢᵓ㐀ࡢ࠺ࡕࠊࢺ࣮ࣞࢽࣥࢢ  ᵓ㐀ࠊࣂࣜࢹ࣮ࢩࣙࣥ 
ᵓ㐀ࠊࢸࢫࢺ  ᵓ㐀࡜ࡋࡓࠋࡇࢀ࡜ࡣู࡟ࠊࢺ࣮ࣞࢽࣥࢢࢭࢵࢺ࡟ࡣྵࡲࢀ࡚࠸࡞࠸኱ࡁ࡞ࢡࣛࢫࢱ࣮
ࢧ࢖ࢬࡢࢸࢫࢺࢭࢵࢺ࡜ࡋ࡚ 1D ࡢ  ᵓ㐀ࢆ⏝࠸ࡓࠋ㐽ⶸᐃᩘࡀእࢀ್ࢆ♧ࡋ࡚࠸ࡿᵓ㐀ࢆྲྀࡾ㝖࠸ࡓࠋ*DXVVLDQ ࢆ⏝࠸࡚ࠊ')7 ィ⟬࡟ࡼࡾ㐽ⶸᐃᩘࢆồࡵࡓࠋỗ㛵ᩘ࠾ࡼࡧᇶᗏ㛵ᩘࡣࡑࢀࡒࢀ %/<3 ࡜ * G
ࢆ⏝࠸ࡓࠋ



ᙉㄏ㟁ᛶ࣌ࣟࣈࢫ࢝࢖ࢺ≀㉁ࡢ㟁Ꮚ㸫ࣇ࢛ࣀࣥ┦஫స⏝࡜ࣇ࣮ࣞࣜࢵࣄ࣭࣏࣮ࣛࣟࣥఏᑟ

➨୍ཎ⌮ィ⟬ࡣࠊ')73%(**$ ࡛ࣞ࣋ࣝࢯࣇࢺ࢙࢘࢔ 4XDQWXP (VSUHVVR ࢆ⏝࠸࡚⾜ࡗࡓࠋ㟁Ꮚ̿ࣇ࢛ࣀ
ࣥ┦஫స⏝ࡣࠊ㟁Ꮚ̿ࣇ࢛ࣀࣥ⤖ྜಀᩘࢆ➨୍ࣈࣜࣗ࢔ࣥ㡿ᇦ࡛ᖹᆒ໬ࡋࡓ୍⯡໬ (OLDVKEHUJ 㛵ᩘ࡛ホ౯ࡋࡓࠋఏᑟᖏୗ➃ࠊ౯㟁Ꮚᖏୖ➃㏆ഐ࡛ࡢ㟁Ꮚ̿ࣇ࢛ࣀࣥᩓ஘㐣⛬ࢆ⪃៖ࡍࡿࡇ࡜࡟ࡼࡾࠊග⏕ᡂࡋࡓ࢟ࣕࣜ
࢔࡜ࣇ࢛ࣀࣥࡢ┦஫స⏝࡜ࡋࡓࠋගゐ፹ %L92 ࡟ࡼࡿỈศゎ཯ᛂ࡜ሷ⣲࢖࢜ࣥ㓟໬཯ᛂࡢ⌮ㄽⓗ◊✲➨୍ཎ⌮ィ⟬ࡣᐦᗘỗ㛵ᩘἲ㸦3%(㸧࡟ࡼࡾࢯࣇࢺ࢙࢘࢔ 4XDQWXP (VSUHVVR ࢆ⏝࠸࡚⾜ࡗࡓࠋ࢘ࣝࢺࣛࢯ
ࣇࢺᆺᨃ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸ࠊᖹ㠃Ἴᇶᗏࡢ࢚ࢿࣝࢠ࣮࢝ࢵࢺ࢜ࣇࡣ H9 ࡜ࡋࡓࠋ %L92  㠃ࡣ [[ࢫ࣮ࣃ࣮ࢭࣝࢆ  ᒙ㔜ࡡࠊ┿✵㡿ᇦࢆྵࢇࡔࢫࣛࣈࣔࢹࣝ࡟ࡼࡾసᡂࡋࠊ0RQNKRUVW3DFN ἲ ࡟ࡼࡾ [[ ࡢN ࣓ࢵࢩࣗࢆసᡂࡋࡓࠋࡲࡓ 0Q ࢆ⾲㠃 %L ࢧ࢖ࢺ࡟ࢻ࣮ࣉࡍࡿࡇ࡜࡟ࡼࡾ %L[0Q[92  㠃ࢆࣔࢹࣝ໬
ࡋࡓࠋ



◊✲ᡂᯝ



1DQ ࢡࣛࢫࢱ࣮ࡢ 1D 105 ࢫ࣌ࢡࢺࣝ࡟ࡘ࠸࡚ࡢᶵᲔᏛ⩦ᅗ㸯ࡣࠊ6FK1HW ࢆ⏝࠸࡚ 1DQ Q ͐  ࠾ࡼࡧ
1D ࡢࢸࢫࢺࢭࢵࢺࡢ㐽ⶸᐃᩘࢆண

ࡋࡓࡶࡢ࡛࠶ࡿࠋ

1DQ Q ͐  ࡢࢸࢫࢺࢭࢵࢺ࡟ࡘ࠸࡚ࡣࠊ࢝ࢵࢺ࢜
ࣇ༙ᚄࡀ኱ࡁ࠸࡯࡝ࠊ')7 ࡛ᚓࡽࢀࡓศᕸ࡜ 6FK1HW ࡛ணࡉࢀࡓศᕸࡣⰋ࠸୍⮴ࢆ♧ࡋ࡚࠸ࡿࠋࡋ࠿ࡋࠊ1Dࡢࢸࢫࢺࢭࢵࢺ࡛ࡣ㏫࡟ࠊ࢝ࢵࢺ࢜ࣇ㊥㞳ࡀᑠࡉ࠸࡯࡝
ᛶ⬟ࡀⰋ࠸ࠋࡇࢀࡣࠊ6FK1HW ࡀ 㹼 ཎᏊࡢࢡࣛࢫࢱ࣮
࡟㐣๫࡟㐺ྜࡋ࡚ࡋࡲࡗࡓ࠿ࡽࡔ࡜ᛮࢃࢀࡿࠋࡲࡓࠊ࡝
ࡕࡽࡢࢸࢫࢺࢭࢵࢺ࡛ࡶ࢝ࢵࢺ࢜ࣇ༙ᚄࡀᑠࡉ࠸࡜⣙ SSP ௨ୗࡢ㐽ⶸᐃᩘࢆṇࡋࡃண࡛ࡁࡎࠊ')7 ࡜

6FK1HW ࡛ᚓࡽࢀࡓ㐽ⶸᐃᩘࡢศᕸࡀ␗࡞ࡗ࡚ࡋࡲ࠺ࠋࡘ
ࡲࡾࠊ࠶ࡿཎᏊࡢ㐽ⶸᐃᩘࢆᑠࡉ࠸࠿ุ᩿ࡍࡿ࡟ࡣࠊࡑ
ࡢཎᏊ࠿ࡽ㐲࠸ཎᏊࡢ᝟ሗࡀᚲせ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉᅗ㸯 ࢝ࢵࢺ࢜ࣇ༙ᚄ࡜ࢸࢫࢺࢭࢵࢺࡢ␗࡞ࡿࠊ
6FK1HW 11 ࡜ ')7 ࡛ண ࡉࢀࡓ㐽ⶸᐃᩘࡢẚ㍑
࡜ᖹᆒ⤯ᑐㄗᕪ 0$(- 196 -

ࢀࡿࠋ㐽ⶸᐃᩘࡣ࿘ࡾࡢཎᏊ࡟ᙉࡃ౫Ꮡࡋ࡚࠸ࡿࡀࠊࢡࣛࢫࢱ࣮ෆ㒊ࡢ໬Ꮫࢩࣇࢺࢆண

ࡍࡿࡓࡵ࡟ࡣࡼࡾ

㐲㊥㞳ࡢཎᏊࡢ᝟ሗࡀᚲせ࡜࡞ࡿ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋࠊ6FK1HW ࡢ࢝ࢵࢺ࢜ࣇ༙ᚄࢆ኱ࡁࡃࡋࡍࡂࡿ࡜ࡑࡢ
ࢺ࣮ࣞࢽࣥࢢ࡛⏝࠸ࡓࢡࣛࢫࢱ࣮ࢧ࢖ࢬ࡟㐣๫࡟㐺ྜࡋ࡚ࡋࡲ࠺ࡓࡵࠊ࢝ࢵࢺ࢜ࣇ༙ᚄࡣ㸵ύ⛬ᗘࡢ㐺ษ࡞್࡟タᐃࡍ࡭ࡁࡔ࡜⪃࠼ࡽࢀࡿࠋ

ᙉㄏ㟁ᛶ࣌ࣟࣈࢫ࢝࢖ࢺ≀㉁ࡢ㟁Ꮚ㸫ࣇ࢛ࣀࣥ┦஫స⏝࡜ࣇ࣮ࣞࣜࢵࣄ࣭࣏࣮ࣛࣟࣥఏᑟ

ᙉㄏ㟁ᛶ࣌ࣟࣈࢫ࢝࢖ࢺ≀㉁࡜
ࡋ࡚ &V3E, ࡜ &V3E%U ࢆྲྀࡾୖࡆࠊ
➨୍ཎ⌮ィ⟬ࡣࠊ')73%(**$ ࡛ࣞ࣋ࣝ 4XDQWXP (VSUHVVR ࢆ⏝࠸࡚⾜ࡗࡓࠋᅗ㸰࡟౯㟁Ꮚᖏ 9% ୖ➃ࠊఏᑟᖏ &% ୗ➃㏆ഐ࡟࠾ࡅࡿࠊ➨୍ࣈࣜࣗ࢔ࣥ㡿ᇦ࡛ᖹᆒࡋࡓ㟁ᏊࠊṇᏍ̿ࣇ࢛ࣀࣥ┦஫స⏝ࢆ♧ࡍࠋࡑࢀࡒࢀ⦪ᆺගᏛ /2 ࣇ࢛ࣀࣥ࡜
ࡢ┦஫స⏝ࡀ㢧ⴭ࡟ࡳࡽࢀࡿࠋ㟁ᏊࠊṇᏍࡣ /2 ࣇ࢛ࣀࣥ࡜ࡢ┦஫స⏝࡟ࡼࡾࠊࣇ࣮ࣞࣜࢵࣄ࣭࣏࣮ࣛ
ࣟࣥࢆᙧᡂࡍࡿࠋ࣏࣮ࣛࣟࣥࡢ⮬ᕫ࢚ࢿࣝࢠ࣮ (   D) ƫZ ࡣ D)㸦ୗᘧ㸧࡛࠶ࡽࢃࡉࢀࡿࠋࡇࡇ࡛Hࡣᅗ  &V3E, ࡜ &V3E%U ࡢ౯㟁Ꮚᖏࠊఏᑟᖏ㏆ഐ࡛ࡢ࢟ࣕࣜ࢔
࣮ࣇ࢛ࣀࣥ┦஫స⏝㸦୍⯡໬ (OLDVKEHUJ 㛵ᩘ㸧ගᏛㄏ㟁⋡ࠊH ࡣ㟼Ṇㄏ㟁⋡ࠊP ࡣࣂࣥࢻ᭷ຠ㉁㔞ࠊƫZࡣ /2 ࣇ࢛ࣀࣥࡢ᣺ືᩘࢆ࠶ࡽࢃࡍࠋ&V3E%U ࡟ࡘ࠸࡚ࡣග↷ᑕᚋ SV ࡟ࣇ࣮ࣞࣜࢵࣄ࣭࣏࣮ࣛࣟࣥࡢほࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ㟁Ꮚ࣏࣮ࣛࣟࣥ࡜

ṇᏍ࣏࣮ࣛࣟࣥࡢ┦஫స⏝ࡣࠊ㟁Ꮚ࡜ṇᏍࡢࢡ࣮ࣟࣥ┦஫స⏝ࡀᙉㄏ㟁ᛶ࣌ࣟࣈࢫ࢝࢖ࢺࡢ኱ࡁ࡞ㄏ㟁⋡࡟ࡼࡾ㐽ⶸࡉࢀ࡚࠸ࡿࡓࡵࠊ࣏࣮ࣛࣟࣥᙧᡂ࡟࡜ࡶ࡞࠺᱁Ꮚṍࡳࡀ኱ࡁ࠸ሙྜࠊ཯Ⓨⓗ࡟࡞ࡿ࡜ண᝿ࡉࢀ࡚࠸
ࡿࠋࡋࡀࡗ࡚㟁Ꮚ࣏࣮ࣛࣟࣥ࡜ṇᏍ࣏࣮ࣛࣟࣥࡢ཯Ⓨⓗ࡞┦஫స⏝ࡀࠊELPROHFXODU ࡞෌⤖ྜࢆᢚไࡋࠊ࢟ࣕ
ࣜ࢔ࡢ㛗㊥㞳ᣑᩓࢆྍ⬟࡟ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ

ගゐ፹ %L92 ࡟ࡼࡿỈศゎ཯ᛂ࡜ሷ⣲࢖࢜ࣥ㓟໬཯ᛂࡢ⌮ㄽⓗ◊✲%L92  㠃㸦 ࡛♧ࡍ㸧࡛ࡢගゐ፹㓟⣲Ⓨ⏕ᶵᵓ࡜ࡋ࡚ࠊ⾲㠃 %L ࢧ࢖ࢺ࡬ࡢỈศᏊ྾╔࠿ࡽࢫࢱ࣮ࢺࡉࡏࠊձ +2 !+2 + Hࠊղ +2 !2 + Hࠊճ +22 !+22 + Hࠊմ +22 !2  + Hࠊࡢ  㟁Ꮚ⛣ື཯ᛂ㐣⛬>@ࢆ⪃࠼ࠊࡑࢀࡒࢀࡢࢫࢸࢵࣉ࡛ࡢ཯ᛂ୰㛫≧ែࡢᵓ㐀ࢆ᭱㐺໬ࡋࠊ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋ%L92 ග㟁ᴟࡢ࢜ࣥࢭࢵࢺ࣏ࢸࣥ
ࢩࣕࣝࢆᶆ‽Ỉ⣲㟁ᴟ࡟ᑐࡋ࡚H9 ࡜タᐃࡋࠊ  㠃ࡢࣂࣥࢻࢠࣕࢵࣉࡢィ⟬್ H9㸦ࣂࣝࢡࡢィ⟬್㸸H9㸧࠿ࡽ㓟⣲Ⓨ⏕࢜ࣥࢭࢵࢺ࣏ࢸࣥࢩࣕࣝࢆ H9 ࡜ࡍࡿ࡜ࠊղࡀ཯ᛂ㏿ᗘỴᐃࢫࢸࢵࣉ㸦άᛶ㞀ቨ H9㸧࡜࡞ࡾࠊ- 197 -

ᅗ㸱㸬 2+ ࠾ࡼࡧ &O ྾╔ࡋࡓ %L92  ⾲㠃 㠃࡛ࡢ㓟⣲Ⓨ⏕㐣⛬ࡣ H9 ࡢⓎ⇕཯ᛂ࡜࡞ࡗࡓࠋሷ⣲࢖࢜ࣥࡢ㓟໬࡟ࡼࡿḟளሷ⣲㓟ࡢ⏕ᡂࡣࠊ&Oࡢ⾲㠃྾╔࠿ࡽࢫࢱ࣮ࢺࡉࡏ  㟁Ꮚ཯ᛂ㐣⛬࡜ࡋࡓࠋ཯ᛂᶵᵓ࡜ࡋ࡚ࠊձ &O !&O Hࠊղ &O &O !&Oࠊճ &O+2!+&O2+ࠊࡢ &O ⁐ゎ࡟ࡼࡿᶵᵓ࡜ࠊձ &O !&O Hࠊղ +2 !+2 +Hࠊճ &O +2 !+2&O ࠊ࡟ࡼࡿ +&O2 ⏕ᡂࡀ⪃࠼ࡽࢀࡿࡀࠊᚋ⪅࡜ࡋࡓࠋᅗ㸱࡟ሷ⣲࢖࢜ࣥࢆ⾲㠃%L ࢧ࢖ࢺ࡟྾╔ࡉࡏࠊḟ࡟ղ࡛ 2+ ࢆ⾲㠃 %L ࢧ࢖ࢺ࡟྾╔ࡉࡏࡓᵓ㐀ࢆ♧ࡍࠋ%L2 ㊥㞳ࡣ ύࠊ%L&O ㊥㞳ࡣ ύ࡜࡞ࡗࡓࠋ྾╔ࡉࢀࡓ 2+ ࡜ &O ཎᏊࢆ┦஫స⏝ࡉࡏࡿ࡜㓟⣲Ⓨ⏕཯ᛂ࡜➇ྜࡋ࠺ࡿ⣙ H9 ࡢάᛶ໬㞀ቨࢆ⤒࡚ +&O2 ࢆ⏕ᡂࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋḟ࡟ 0Q ࢆ %L ࢧ࢖ࢺ࡟ࢻ࣮ࣉࡋࡓ %L92  㠃࡟ྠᵝࡢィ⟬ࢆ⾜ࡗࡓࠋ⾲㠃 0Q ཎᏊࡣ㸲౯ࡢ G 㟁Ꮚ㓄⨨ࢆ࡜ࡾࢫࣆࣥศᴟࡋࡓࠋ0Q ࢻ࣮ࣉ %L92  㠃࡛ࡢ +&O2
⏕ᡂࡢάᛶ㞀ቨࡣ㓟⣲Ⓨ⏕ࡢࡑࢀࡼࡾ㧗ࡃᚓࡽࢀࡓࠋࡇࡢ⤖ᯝࡣ 0Q&O ⤖ྜ࢚ࢿࣝࢠ࣮ࡀ %L&O ⤖ྜ࢚ࢿࣝࢠ࣮ࡼࡾ኱ࡁ࠸ࡇ࡜࡟㉳ᅉࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

 ࣏ࢫࢱ࣮Ⓨ⾲>@ ‫ ۻ‬6WDWLVWLFVDQG0DFKLQH/HDUQLQJIRU'RXEOH3HURYVNLWH0DWHULDOV0.DQHNR++DWDQDND$0XUDRND.    <DPDVKLWD6SDLQ RQOLQH QDQR*H&RQIHUHQFH ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

>@   -1DJDNXER71LVKLKDVKL.0LVKLPD.<DPDVKLWD&KHP3K\V SDJHV   >@ ‫ۻ‬.0LVKLPD0.DQHNR-:6RQJ+.DZDL.<DPDVKLWD.+LUDR-RXUQDORI&KHPLFDO3K\VLFV            >@   03DOXPPR'9DUVDQR(%HUUtRV.<DPDVKLWD**LRUJL(QHUJLHV  >@   ,0DVXPRWR1:DVKLGD6,QRPDWD7,PDPXUD$0XUDRND.<DPDVKLWD-&KHP3K\V       >@ ‫ۻ‬.0LVKLPD76DNDL.<RNRWD07DQLJXFKL<$VR<,H.<DPDVKLWD-3KRWRFKHPLVWU\ 3KRWRELRORJ\     $&KHPLVWU\  >@ ‫ۻ‬5:DGD.7RQRNXUD6.RED7,PDPXUD.1DNDL+8VKL\DPD.<DPDVKLWD<0DWVXPL6(QDPL3:      6HDNLQV&KHP3K\V/HWW  >@   <XKDQ/L6KXZHL7DQJ-LQJSLQJ=KDQJ.RLFKL<DPDVKLWD/HL1L3K\V&KHP&KHP3K\V  >@   6DHLG$UDEQHMDG0HJXPL.RLMLPD.RLFKL<DPDVKLWD-0DWHULDOV6FLHQFH0DUFKRQOLQH  ཧ⪃ᩥ⊩>@50RULWDHWDO&DUERQ
>@50RULWDHWDO-0DWHU&KHP$
>@62NXQDND<0LVHNL.6D\DPDL6FLHQFH  - 198 -

- 199 -- 200 -- 201 -- 202 -- 203 -㑄⛣㔠ᒓ໬ྜ≀࠾ࡼࡧໟ᥋໬ྜ≀ࡢᵓ㐀࣭཯ᛂ࣭ศᏊ㛫┦஫స⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDO VWXG\ RQ VWUXFWXUHV UHDFWLRQV DQG LQWHUPROHFXODU
LQWHUDFWLRQV RI WUDQVLWLRQPHWDOFRPSRXQGV DQG FODWKUDWH FRPSRXQGV‫ ۑ‬㮚㔝 ᬒᏊࠊ኱ᶫ బ㬅Ꮚࠊ℈㔝 ⸛㸦࠾ⲔࡢỈዪᏊ኱Ꮫ኱Ꮫ㝔ே㛫ᩥ໬๰ᡂ⛉Ꮫ◊✲⛉㸧ࠊᅵ⏣ ᩔᏊ㸦ᇸ⋢་⛉኱Ꮫ㸧◊✲┠ⓗ㸪ෆᐜ
ᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣ㸪㸱ࡘࡢࢧࣈࢸ࣮࣐࡟ࡘ࠸࡚◊✲ࢆ⾜ࡗࡓࠋ  ࣁ࣮ࣇࢧࣥࢻ࢖ࢵࢳᆺ5X5K,U 㘒యࡢ཯ᛂᶵᵓࡢゎ᫂㸪  㞄᥋ࡋࡓ࢔ࢦࢫࢸ࢕ࢵࢡ┦஫స⏝ࢆࡶࡘ㘒యࡢ⤖ྜ≉ᛶࡢゎᯒ㸪  ࢡࢡࣝࣅࢵࢺ࢘
ࣜࣝࢆ࣍ࢫࢺ࡜ࡍࡿໟ᥋໬ྜ≀࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ࠋࡇࡇ࡛ࡣ  ࡢᡂᯝ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ
5X ,U5K ࡞࡝ࡢ㑄⛣㔠ᒓࢆྵࡴࢩࢡ࣓ࣟࢱࣝ໬㘒యࡣ㸪ࡑࡢ᭷⏝ᛶࡀᮇᚅࡉࢀ࡚࠸ࡿࠋࡲࡓ &+άᛶ໬ࢆ
క࠺ࢩࢡ࣓ࣟࢱࣝ໬཯ᛂ࡟࠾࠸࡚ࡣ㸪ᙉሷᇶࡸᙉ㓟࡞࡝ࡢᙉ࠸ヨ⸆ࢆᚲせ࡜ࡋ>@㸪࿴࡞᮲௳ୗ࡛ࡢ཯ᛂ

ࡣᅔ㞴࡛࠶ࡗࡓࠋ ᖺ㸪'DYLHV ࡽࡣ㓑㓟ሷࡀゐ፹࡜ሷᇶࡢ୧᪉ࡢᙺ๭ࢆࡍࡿࡇ࡜࡛&+άᛶ໬ࢆಁ㐍ࡍࡿࡇ࡜ࢆぢฟࡋ㸪ࢩࢡ࣓ࣟࢱࣝ໬㘒యࢆᐊ࡛ᚓࡿࡇ࡜࡟ᡂຌࡋࡓ>@ࠋࡑࡢᚋ㸪❅⣲ࡲࡓࡣࣜࣥྵ᭷㓄఩Ꮚ࡜

>&S 0&O @ 0 5K ,U ࡸ> SF\PHQH 5X&O @ ࡢࢩࢡ࣓ࣟࢱࣝ໬ࡢྜᡂ౛ࡀᩘከࡃሗ࿌ࡉࢀ࡚࠸ࡿࠋ








=KDQJ ࡽࡣ㸪 ᖺ࡟ࢪࢼࣇࢳࣝ࣍ࢫࣇ࢕ࣥ㸦1a 1b 5 3K %X㸧࡜>&S ,U&O @ ࡢࢩࢡ࣓ࣟࢱࣝ໬཯ᛂ࡟ࡼࡾ㸪
W





ࢩࣥࢢࣝཪࡣࢲࣈࣝࡢࢩࢡ࣓ࣟࢱࣝ໬㘒యࡀ⏕ᡂࡍࡿࡇ࡜ࢆぢฟࡋࡓ㸦6FKHPH㸧>@ࠋ1b ࢆ⏝࠸ࡓሙྜ㸪ࢩࣥࢢࣝࢩࢡ࣓ࣟࢱࣝ໬ᵓ㐀 Ir_3b ࡀᐊ ࡛ᚓࡽࢀ㸪ຍ⇕࡟ࡼࡾ 1a㸪1b ࠸ࡎࢀࡢሙྜ࡛ࡶࢲࣈࣝࢩࢡ࣓ࣟࢱࣝ
໬ᵓ㐀 Ir_4a㸪Ir_4b ࡀ⏕ࡌࡓࠋ㓑㓟ሷゐ፹Ꮡᅾୗ࡛ྠᵝࡢ཯ᛂࢆ⾜ࡗࡓ࡜ࡇࢁ㸪୍Ẽ࡟ࢲࣈࣝࢩࢡ࣓ࣟࢱࣝ
໬཯ᛂࡀ㐍⾜ࡋࡓࠋ୍᪉㸪୰ᚰ㔠ᒓࢆ 5K࡟ኚ࠼ࡓ>&S 5K&O @ ࡜ 1a ࡢ཯ᛂ࡛ࡣ㸪㓑㓟ሷゐ፹౑⏝᫬࡟ࢩࣥࢢࣝ
ࢩࢡ࣓ࣟࢱࣝ໬ᵓ㐀 Rh_ace_3a ࢆᚓࡓࡀ㸪ຍ⇕ࡋ࡚ࡶࢲࣈࣝࢩࢡ࣓ࣟࢱࣝ໬ࡣ㐍⾜ࡋ࡞࠿ࡗࡓࠋᮏ◊✲࡛ࡣ㸪㔞Ꮚ໬Ꮫⓗᡭἲ࡟ࡼࡗ࡚ 6FKHPH ࡢࢩࢡ࣓ࣟࢱࣝ໬཯ᛂࡢ⤒㊰ࢆ᫂ࡽ࠿࡟ࡋ㸪  ⨨᥮ᇶຠᯝ㸪  㓑㓟ሷゐ፹ࡢᙳ㡪㸪  ୰ᚰ㔠ᒓ౫Ꮡᛶࡢ Ⅼ࡟ࡘ࠸࡚⪃ᐹࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲᐦᗘỗ㛵ᩘἲ࡟ࡼࡿᵓ㐀᭱㐺໬㸪᣺ືᩘゎᯒ㸪㑄⛣≧ែ᥈⣴㸪,5& ィ⟬ࢆ⾜ࡗࡓࠋỗ㛵ᩘ࡜ࡋ࡚
6FKHPH 1a1b ࡜>&S ,U&O@ࡢ཯ᛂ >@0/㸪᭷ຠෆẆ࣏ࢸࣥࢩࣕࣝཬࡧᇶᗏ㛵ᩘ࡜ࡋ࡚㸪,U㸪5K ࡟ 6''㸪ࡑࡢ௚ࡢཎᏊ࡟ * GS ࢆ⏝࠸ࡓࠋィ⟬ࣉࣟࢢ࣒ࣛࡣ *DXVVLDQ㸪1%2 ࡛࠶ࡿࠋ◊✲ᡂᯝ
2a ࠿ࡽ 4a  ࠶ࡿ࠸ࡣ 2b ࠿ࡽ 4b ࡟⮳ࡿ⤒㊰࡛ࡣࢼࣇࢳࣝᇶࡢᅇ㌿ࢆక࠺ࠋ2a2b ࡢࢼࣇࢳࣝᇶࡢᅇ㌿ࡀࢩࢡ࣓ࣟࢱࣝ໬࡟ඛ⾜ࡍࡿ⤒㊰ࢆ SDWK㸦2a’2b’࡜ 3a’3b’ࢆ⤒ࡿ㸧㸪ࢩࣥࢢࣝࢩࢡ࣓ࣟࢱࣝ໬ࡢᚋ㸪3a3b ࠿ࡽࢼࣇࢳࣝᇶᅇ㌿ࡍࡿ⤒㊰ࢆ SDWK 㸦3a’3b’ࢆ⤒ࡿ㸧࡜ࡍࡿࠋࡇࡇ࡛㸪ࢼࣇࢳࣝᇶᅇ㌿ᚋࡢ㘒య␒ྕ࡟ࣉࣛ࢖࣒ࢆ
ࡘࡅ࡚࠸ࡿࠋ,U 㘒య㸪5K 㘒య࡟࠾ࡅࡿ཯ᛂࡢᚊ㏿ẁ㝵ࡢάᛶ໬㞀ቨࡢ್࠿ࡽ㸪㓑㓟ሷゐ፹ࡢ᭷↓࡟ࡼࡗ࡚ࠊ
SDWK㸦ゐ፹࡞ࡋ㸧࠶ࡿ࠸ࡣ SDWK㸦ゐ፹࠶ࡾ㸧ࡀ᭷฼࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

- 204 -

100

㸺⨨᥮ᇶຠᯝ 5 3K W%X 㸼 Ir_2a ࠿ࡽ Ir_4a ࠶ࡿ࠸ࡣ Ir_2b

ȴGkcal/mol90

࠿ࡽ Ir_4b ࡟⮳ࡿ཯ᛂࡢSDWKࡢࢠࣈࢫ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬

2ण৯३ॡটওॱঝ৲
ણਙ৲ग़ॿঝॠ‫ش‬+64.1580

ࢆᅗ ࡟♧ࡍࠋᚊ㏿ẁ㝵ࡢάᛶ໬㞀ቨࡣ㸪5 3K ࡜ 5  W%X

70࡛㸪ࡑࢀࡒࢀ   NFDOPRO ࡛࠶ࡾ኱ᕪ࡞࠸ࡀ㸪⏕ᡂ

60ࡋࡓࢩࣥࢢࣝࢩࢡ࣓ࣟࢱࣝ໬㘒య Ir_3b’ࡣ Ir_3a’࡟ẚ࡭࡚50 NFDOPRO ⇕ຊᏛⓗ࡟Ᏻᐃ࡛࠶ࡿࠋ=KDQJ ࡽ࡟ࡼࡿሗ࿌㸪40

ࡍ࡞ࢃࡕ5  W%X ࡟࠾࠸࡚ࡢࡳᐊ

30

Ir_3a’

࡛ࢩࣥࢢࣝࢩࢡ࣓ࣟࢱࣝ

໬㘒యࡀᚓࡽࢀࡓࡇ࡜ࡣ㸪ࡇࡢ⇕ຊᏛⓗᏳᐃᛶࡢ㐪࠸࡟㉳ᅉࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ

Ir_2a+37.7020

1ण৯३ॡটওॱঝ৲
ણਙ৲ग़ॿঝॠ‫ش‬+35.1310

Ir_3a’

ࡿ཯ᛂࡢࢠࣈࢫ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝ

᭷฼࡞ SDWK㸦ゐ፹࡞ࡋ࡛ SDWK 㸪ゐ፹࠶ࡾ࡛ SDWK 㸧ࢆ♧ࡋࡢẁ㝵࡛  NFDOPRO ࡛࠶ࡾ㸪≉࡟ᚋ⪅࡛పୗࡀ኱ࡁ࠸ࠋ
㸺୰ᚰ㔠ᒓ౫Ꮡᛶ㸼 㓑㓟ሷゐ፹౑⏝᫬ࡢ Ir_ace_2a ࠿ࡽ
Ir_ace_4a ࡟⮳ࡿ཯ᛂ࡜ Rh_ace_2a ࠿ࡽ Rh_ace_4a ࡬ࡢ཯ᛂ࡜ࢆẚ㍑ࡋࡓ࡜ࡇࢁ㸪୍ࡘ┠ࡢࢩࢡ࣓ࣟࢱࣝ໬ཬࡧࢼࣇ
ࢳࣝᇶࡢᅇ㌿ẁ㝵㸦M_ace_2a ĺM_ace_3a’㸧࡛ࡣ㸪୧㔠ᒓ

100

ȴG
kcal/mol902ण৯३ॡটওॱঝ৲
ણਙ৲ग़ॿঝॠ‫ش‬

80+64.1570

Ir_ace_3a60

Ir_ace_2a50 1ण৯
4३ॡটওॱঝ৲
ણਙ৲ग़ॿঝॠ‫ش‬30+28.721ण৯३ॡটওॱঝ৲
ણਙ৲ग़ॿঝॠ‫ش‬20
Ir_ace_3a+17.07

㘒య࡟࠾࠸࡚㏿ᗘㄽⓗᏳᐃᛶ㸪⇕ຊᏛⓗᏳᐃᛶࡣ࡯ࡰྠࡌ 10࡛࠶ࡗࡓࠋ஧ࡘ┠ࡢࢩࢡ࣓ࣟࢱࣝ໬ࡢάᛶ໬㞀ቨࡣ㸪5K 㘒+1.85

ᅗ   Ir_2aIr_2b㸦5 3KW%X㸧࠿ࡽ Ir_4aIr_4b ࡟⮳ࣈࢫ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࡢẚ㍑ࢆ♧ࡍࠋࡑࢀࡒࢀ

࣓ࢱࣝ໬ࡢẁ㝵࡛  NFDOPRO ஧ࡘ┠ࡢࢩࢡ࣓ࣟࢱࣝ໬

ણਙ৲ग़ॿঝॠ‫ش‬+62.30

Ir_3b’

Ir_2a
Ir_2b

㸺㓑㓟ሷゐ፹ࡢᙳ㡪㸼 ᅗ ࡟㓑㓟ሷゐ፹ࡢ᭷↓࡟ࡼࡿࢠ

Ir_4a
Ir_4a
+25.29Ir_4b+20.082ण৯३ॡটওॱঝ৲

+11.800࡚࠸ࡿࠋゐ፹࡟ࡼࡿάᛶ໬㞀ቨࡢపୗࡣ㸪୍ࡘ┠ࡢࢩࢡࣟ1ण৯३ॡটওॱঝ৲
ણਙ৲ग़ॿঝॠ‫ش‬+37.70

Ir_ace_4a

Ir_3a’+11.800
Ir_2a
Ir_ace_2aIr_4a+25.29Ir_ace_3a’+15.162ण৯
३ॡটওॱঝ৲
ણਙ৲ग़ॿঝॠ‫ش‬Ir_ace_4a+27.93+3.27

యࡢ᪉ࡀ  NFDOPRO 㧗࠿ࡗࡓࠋࡲࡓ㸪ฟⓎ≀㉁ M_ace_2a ᅗ Ir_2aIr_ace_2a 㸦 ゐ ፹ ࡞ ࡋ ࠶ ࡾ 㸧 ࠿ ࡽ࡟ᑐࡍࡿ᭱⤊⏕ᡂ≀ M_ace_4a ࡢ┦ᑐⓗᏳᐃᛶࡣ㸪5K㘒య

Ir_4aIr_ace_4a ࡟⮳ࡿ཯ᛂࡢࢠࣈࢫ⮬⏤࢚ࢿࣝࢠ࣮ࡢ᪉ࡀ  NFDOPRO ୙Ᏻᐃ࡛࠶ࡗࡓࠋ௨ୖࡢ⤖ᯝࡣ㸪5K ࡛ࢲࣈࣝࢩࢡ࣓ࣟࢱࣝ໬㘒య㸪ࡍ࡞ࢃࡕ Rh_ace_4a ࡟┦ᙜࡍࡿᵓ㐀ࡀᐇ㦂᳨࡛ฟࡉࢀ࡞࠿ࡗࡓ࡜࠸࠺ඛ⾜◊✲ࡢ⤖ᯝ࡜▩┪ࡋ࡞࠸ࠋᮏ◊✲ࢆ㏻ࡋ࡚㸪  ⨨᥮ᇶࢆኚ࠼ࡿࡇ࡜࡛⇕ຊᏛⓗ࡟Ᏻᐃ࡞⏕ᡂ≀ࢆࢥࣥࢺ࣮࡛ࣟࣝࡁࡿྍ⬟ᛶࡀ࠶ࡿࡇ࡜㸪   㓑㓟ሷゐ፹ࡀάᛶ໬㞀ቨࢆ㢧ⴭ࡟పୗࡉࡏࡿࡇ࡜㸪  5K 㘒య࡛ࢲࣈࣝࢩࢡ࣓ࣟࢱࣝ໬ࡀ㐍⾜ࡋ࡞࠿ࡗࡓせᅉࡀ஧ࡘ┠ࡢࢩࢡ࣓ࣟࢱࣝ໬཯ᛂࡢẁ㝵࡟࠶ࡾ ,U 㘒య࡟ẚ࡭࡚㏿ᗘㄽⓗ࡟ࡶ⇕ຊᏛⓗ࡟ࡶ୙฼࡛
࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ
࠙ᩥ⊩ࠚ>@ )HUQDQGH]6HW DO2UJDQRPHWDOOLFV 18>@ )RRW5-HW DO'DOWRQ 7UDQV2
 >@ 'DYLHV ' HW DO'DOWRQ 7UDQV   >@ =KDQJ 6 HW DO$&6 2PHJD  3



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫℈ۻ‬㔝㸪ᅵ⏣㸪㮚㔝 ᪥ᮏ໬Ꮫ఍ &6- ࣇ࢙ࢫࢱ 㸪 ᖺ  ᭶㸪࢜ࣥࣛ࢖ࣥ

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬7<RNDLFKL\D.7DNDQR %XOO&KHP6RF-SQᢞ✏ணᐃ‫ۻ‬17VXFKLGD.7DNDQR2UJDQRPHWDOOLFVᢞ✏ணᐃ< 8WDND * .DVKLZD]DNL 1 7VXFKLGD 0)XNXVKLPD , 7DNDKDVKL < .DZDL 7 .LWD\DPD- 2UJ &KHP 
 

- 205 -

ᾮయ࣭⏕యศᏊ࠾ࡼࡧ㛵㐃ศᏊ⣔ࡢᵓ㐀࣭ࢲ࢖ࢼ࣑ࢡࢫ࣭
ศᏊ㛫┦஫స⏝࡜᣺ືࢫ࣌ࢡࢺࣝ
Structures, Dynamics, Intermolecular Interactions, and Vibrational
Spectra of Liquids, Biomolecules, and Related Molecular Systems‫ۑ‬㫽ᒃ ⫕㸪ᩪ⸨೺ே㸪୕Ꮿ㞞㍤㸦㟼ᒸ኱࣭ᕤ㸧1ᗎᮏࣉࣟࢪ࢙ࢡࢺ࡛ࡣ㸪ᾮయ࣭⏕యศᏊ࠾ࡼࡧ㛵㐃ศᏊ⣔ࢆᑐ㇟࡟㸪ᵓ㐀࣭ࢲ࢖ࢼ࣑ࢡࢫ࣭ศᏊ㛫┦஫స⏝࡟ࡲࡘࢃࡿ⌮ㄽⓗㅖၥ㢟ࡢ࠺ࡕ㸪≉࡟㸦ᗈ⩏ࡢ㸧᣺ືࢫ࣌ࢡࢺࣝ࡟㛵ಀࡋࡓࡶࡢ࡟ࡘ࠸࡚㸪ศᏊືຊᏛἲ࣭
ࣔࣥࢸ࢝ࣝࣟἲ࡜⊂⮬㛤Ⓨᡭἲࡢ⤌ࡳྜࢃࡏࢆ୺࡞ᡭἲ࡜ࡋࡘࡘ㸪ศᏊ㌶㐨ἲࡶే⏝ࡋ࡞ࡀࡽ◊✲ࡋ࡚࠸ࡿࠋ
௧࿴㸰ᖺᗘ࡟ࡣ㸪௨ୗ࡟♧ࡍ◊✲ࢆ⾜ࡗࡓࠋỈࡢ OH ఙ⦰࣮ࣔࢻࡢỈ⣲⤖ྜᙧᡂ࡟ࡼࡿ᣺ືᩘࢩࣇࢺ࡟㛵ࡍࡿ㟼㟁┦஫స⏝ࣔࢹࣝ࡜㠀㟼㟁ⓗ࣓࢝ࢽࢬ࣒
Ỉࡢ OH ఙ⦰࣮ࣔࢻࡀỈ⣲⤖ྜᙧᡂ࡟ࡼࡾప᣺ືᩘࢩࣇࢺࡍࡿࡇ࡜ࡣ㸪௨๓࠿ࡽⰋࡃ▱ࡽࢀ࡚࠸ࡿࠋ᭱㏆࡛ࡣ㸪ࡇࢀࡀỈ⣲ཎᏊ࡟᥃࠿ࡿ㟁ሙࡢⰋ࠸㛵ᩘ࡛࠶ࡿࡇ࡜ࡶ᫂ࡽ࠿࡟ࡉࢀ࡚࠾ࡾ㸪frequency map ࡜ࡋ࡚▱ࡽࢀ࡚࠸ࡿࠋࡇࢀ⮬యࡣ㸪ྂ඾ MD ࡜ࡢ⤌ࡳྜࢃࡏ࡟ࡼࡿࢫ࣌ࢡࢺࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ࡞࡝࡟࠾࠸࡚ᐇ⏝ⓗ࡛࠶ࡿࡀ㸪ࡑࡢ୍⯡ᛶ࠶ࡿ࠸ࡣ㐺⏝ྍ⬟⠊ᅖࢆ㏣ồࡍࡿࡓࡵ࡟ࡣ㸪࣓࢝ࢽࢬ࣒ࢆ▱ࡿᚲせࡀ࠶ࡿࠋᮏ◊✲࡛ࡣ
ࡇࡢⅬ࡟ࡘ࠸࡚㸪Ỉ 90 㔞య࡞࡝ࢆᑐ㇟࡜ࡋࡓィ⟬࡟ࡼࡾゎᯒࢆ࠾ࡇ࡞ࡗࡓࠋ
⤖ᯝ࡜⪃ᐹᾮయỈࡢ MD ィ⟬ࡢ snapshots ࠿ࡽ 90 㔞యࢆษࡾฟࡋࡓࡶࡢ 13 ㏻ࡾࢆึᮇ㓄⨨࡜ࡋ࡚㸪᭱㐺໬ᵓ㐀ࢆᚓࡓࡢࡕ㸪(HDO)(D2O)89 ࡢ OH ఙ⦰ࡢ᣺ືᩘ࣭཮ᴟᏊᚤศ࡜ᵓ㐀ⓗ࣭㟼㟁ⓗ≉ᚩࡢ┦㛵ࢆ᳨ウࡋࡓࠋࡑࡢ⤖ᯝ㸪OH ఙ⦰᣺ືᩘࡣᙜヱ H ཎᏊ࡟᥃࠿ࡿ㟁ሙ࠾ࡼࡧ OH ⤖ྜ㛗࡜Ⰻ࠸┦㛵㛵ಀ࡟࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡋ࠿
ࡋ㸪࿘ᅖࡢศᏊࢆཎᏊୖⅬ㟁Ⲵࡢ㞟ྜయ࡛⨨᥮ࡍࡿ࡜㸪㟁ሙ࡜ࡢ┦㛵㛵ಀ࡟࠾࠸࡚ࡣ㠀⥺ᙧᛶࡀ㢧ⴭ࡟ῶᑡࡋ㸪OH ⤖ྜ㛗࡜ࡢ┦㛵㛵ಀ࡟࠾࠸࡚ࡶഴࡁࡀపῶࡍࡿࠋࡋࡓࡀࡗ࡚㸪᣺ືᩘኚ໬ࡣ࿘ᅖศᏊ⏤᮶ࡢ㟁ሙࡢ㛵ᩘ࡜ࡋ࡚Ⰻࡃ⾲⌧࡛ࡁࡿࡶࡢࡢ㸪⣧⢋࡞㟼㟁┦஫స⏝௨እ࡟ࡼࡿࡶࡢࡀ↓ど࡛ࡁ࡞࠸⛬ᗘ࡟ྵࡲࢀ࡚࠸ࡿ
ࡇ࡜ࡀศ࠿ࡿࠋ ࡇࡢཎᅉࢆ᥈ࡿࡓࡵ㸪Ỉࡢ⎔≧㸲㔞య㸦S4 ᑐ⛠㸧ࢆᑐ㇟࡟㸪㟁Ꮚᐦᗘࢆ OH ఙ⦰ᗙᶆ࡛㸯ᅇ࠾ࡼࡧ㸰ᅇᚤศࡋࡓ㔞ࢆィ⟬ࡋࡓࠋ⤖ᯝࢆᅗ㸯࡟♧ࡍࠋ௨๓࡟♧ࡋࡓ࡜࠾ࡾ [1]㸪㟁Ꮚᐦᗘ㸯ḟᚤศࡢ᣺ᖜࡀ኱ࡁ࠸㒊ศࡀ㸪Ỉ⣲⤖ྜཷᐜศᏊࡢ✵㛫㡿ᇦ࡟ཬࢇ࡛࠸ࡿ㸦ศᏊ㛫㟁Ⲵ᮰㸧ࠋࡇࢀ࡟ࡼࡾ཮ᴟᏊᚤศࡀቑᙉࡉࢀ㸪᣺ືᩘࡢ㟁ሙ౫Ꮡᛶ࡟࠾࠸࡚㠀⥺ᙧᛶࡀቑ኱ࡍࡿࠋ㟁Ꮚᐦᗘ㸰ḟᚤศ࡟ࡘ࠸࡚ࡶ㸪᣺ᖜࡀ኱ࡁ࠸㒊ศࡀỈ⣲⤖ྜཷᐜศᏊࡢ✵㛫㡿ᇦ࡟ཬࢇ࡛࠸ࡿࠋࡇࢀࡣ㸪࿘ᅖศᏊ⏤᮶ࡢ㟁ሙࡀ OH ⤖ྜ㛗ኚ໬ࢆ௓ࡉࡎ┤᥋ⓗ࡟᣺ືᩘኚ
໬ࢆ㉳ࡇࡍ㒊ศ࡟࠾࠸࡚㸪ᐇ㝿࡟ࡣ㠀㟼㟁ⓗ࡞࣓࢝ࢽࢬ࣒ࡀྵࡲࢀ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ

[1] H. Torii, J. Phys. Chem. B 114, 13403–13409 (2010).

- 206 -

(a)
-4

-3

(b)
-5

-1/2

× 10 a0 me
6

2

3

1

0

0

-3

-1

-6

-2
-3

-2

-1/2

× 10 a0 me
-3

× 10

-4

-1

-5

-3

-5

-2
-1
a0 me

× 10 a0 me

3
2
1
0
-1

-1

× 10 a0 me

-1
-1/2
a0 me

× 10
10
5
0
-5

ᅗ㸯㸸Ỉ⎔≧㸲㔞యࡢỈ⣲⤖ྜ౪୚ OH ࡢఙ⦰᣺ື࡟㛵ࢃࡿ㟁Ꮚᐦᗘࡢ (a) 㸯ḟᚤศ࠾ࡼࡧ (b)㸰ḟᚤศࡢ㸪Ỉ⣲⤖ྜᙧᡂ࡟ࡼࡗ࡚㉳ࡇࡿኚ໬ࡢ㸯ḟඖ࣭㸰ḟඖࣉࣟࢵࢺࠋ

3

ฟ∧࣭Ⓨ⾲ᐇ⦼㸦௧࿴㸰ᖺᗘ㸧 Yuki Nojima, Yuki Shioya, Hajime Torii, and Shoichi Yamaguchi, Chem. Commun. 56, 4563–4566 (2020).
‫ ۻ‬Kento Saito, Ryoma Izumi, and Hajime Torii, J. Chem. Phys. 153, 174302/1–10 (2020).
C. R. Baiz, B. Błasiak, J. Bredenbeck, M. Cho, J.-H. Choi, S. A. Corcelli, A. G. Dijkstra, C.-J. Feng, S.
Garrett-Roe, N.-H. Ge, M. W. D. Hanson-Heine, J. D. Hirst, T. L. C. Jansen, K. Kwac, K. J. Kubarych, C. H.
Londergan, H. Maekawa, M. Reppert, S. Saito, S. Roy, J. L. Skinner, G. Stock, J. E. Straub, M. C. Thielges, K.
Tominaga, A. Tokmakoff, H. Torii, L. Wang, L. J. Webb, and M. T. Zanni, Chem. Rev. 120, 7152–7218 (2020).
‫ ۻ‬Hajime Torii and Ryota Ukawa, J. Phys. Chem. B 125, 1468–1475 (2021).
‫୕ ۻ‬Ꮿ㸪㫽ᒃ㸪ศᏊ⛉Ꮫ఍ ࢜ࣥࣛ࢖ࣥウㄽ఍㸪2020 ᖺ 9 ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸬‫ ۻ‬㰻⸨㸪㫽ᒃ㸪ศᏊ⛉Ꮫ఍ ࢜ࣥࣛ࢖ࣥウㄽ఍㸪2020 ᖺ 9 ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸬‫୕ ۻ‬Ꮿ㸪㫽ᒃ㸪➨ 34 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸪2020 ᖺ 12 ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸬‫ ۻ‬㰻⸨㸪㫽ᒃ㸪➨ 34 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸪2020 ᖺ 12 ᭶㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸬- 207 -

 5
Simulation of Molecular Assemblies 5


 

   







  

 É»Þf;PQU ;RW$É~­#»¶}ª2xULTc¡0ÖÙ!ÌÍ /9WI
Q >l#Ë"Ä p$x  Ò2]s"®+|^Ù1 0#*kÀÖk´É#~s"0xULT#?5DP7=6S:O ,NSO #z~}ª#c¡."$ÓkiÅ"0ÂÑraµ#y! #uvm&#·Ù`À!/ 0Ðvm$#- !n±!É~­#ÈÛ_f¶y#cÔ"/¦)2Õ¶ " '-,-&ÏÉ}1EO@A7\³"8=BÉt{¥É2C K0Ü»2ÊÃ{Ý¼.10#- !~\s" 8=BÉ\ØÁ³o­2r
0 0 $É°" 02w#(Ô."0$¾ 0b$sº¶"É}ªX!0Ã{É#\ØÁ³#0Æ $ #- "! 0'1.wg 
1 0Èß %Øc!  #- !§hhq 02Ûc0*¤xÉ»Þf;PQ
U ;RW2Ù vm2¹d 

 $+ &

MK@C#z~_"-/r10HCV8T$Î#¢²,×¨É_©2«Î¬Ý#¹dj¯10³DFJ35G 2r0¸£4PF#(.!0MK@C"
ZÇ#4PF2}ª0DFJ35G #r,U6V< ½"Y  0e¿1 0#Ú[$'É ! #MK@C2³")W?&"És"®¤x'#TÉ»Þf;PQU ;RW2G MK@C#4PFz #- "DFJ35G
r"-=0" h %(0 .!/ 3 *0 21 #0-)&

­É¿PÇ+ux1YÁÉr0eÉÑ$½X¶">W$7Q9²
0w;PQU ;RW#.e*.1 0Ðyo$Ñp#É#»°"gÕ½"6;»" c¡2*#^# ­YÝ"®+t#c¡2G ¼.1fD
2º~¶"70Ý# ­Y#»°#h" CU2*





¤#vm3c" É#}ª·_-ZmN"W;(T#u$    '$   2Ù GÉ»Þf;PQU ;RW"$ ZÇ$2NÙ'zF}ª"h0j¶!c¡! "$v#KV!)&2Ù 

 





vm3c  " $u®É#}ª·_ZmN"W;(T2¼!;PQU;RW'#T"®CU2G +`q!'#T2k*H°"0B)<7BS "®7)=>SW!c¡2Ù 0É~°#V2h0- 208 -

vm3c  $#4PF.}1 >Z!i[r! NSMK@C" #4PFzz~_"-/r10DFJ35G #r,U6V< ½"§h 0
W"É
'vm3c  $eÉÑ#>W$7Q9²J  GT7Ñp$É#6
"±!LD.10É' ­Y#JÉ%);" +t#A2¼.1

 

n KÉ;PQU ;RWcÔ\#|O¶~\cÔÈvmS=$9W<tÙ  ~tvm4uÈQ1f#W¹d 6W)5W  y  B T¯I/n KÉ;PQU ;RWcÔÖkÝ#É~\b  5  9V &6W)5W
 y  B T¯I/*R:DWDQDEH7DNX\RVKL0DQGDL0LWVXR+DUD-XQ<RVKLGD³(OXFLGDWLQJ+HOLFDO6WUXFWXUHRI&ROXPQDU/LTXLG
&U\VWDOV)RUPHGE\&KLUDO2FWDKHGUDO0HWDOORPHVRJHQV8VLQJ0ROHFXODU'\QDPLFV6LPXODWLRQV´WK6\PSRVLXPRQ
0DFURPROHFXOHV2QOLQH 6HS 2UDO3UHVHQWDWLRQrp.±:0±,Ôn KÉ»Þfu"-0EO@A7\³"0t{É#Z¶}ª»¶;»#c¡ ywÐ\f46W)5WvmÃ}46W)5W  y  B EsÃ}
ad 8lX_8l Rx { nK{­@?]M­ÉÃy0)&D \#
É»Þf;PQU ;RW ywÐ\f46W)5WvmÃ}46W)5W  y  B EsÃ}
 

6KLJHWDND<RQHGD7DNDPL6DLWR'DLVXNH1DNDMLPD*R:DWDQDEH³3RWHQWLDORIPHDQIRUFHDQGXPEUHOODVDPSOLQJVLPXODWLRQIRUWKHWUDQVSRUWRIဨR[D]ROLGLQRQHLQKHWHURWHWUDPHULFVDUFRVLQHR[LGDVH´3URWHLQV LQSUHVV 
6R6KLNLWD*R:DWDQDEH'DL.DQRXFKL-XQ\D6DLWR7DNXPD<DVXGD³$OWHUQDWLQJ'RQRU±$FFHSWRUʌဨ&RQMXJDWHG
0DFURF\FOH([KLELWLQJ(IILFLHQW7KHUPDOO\$FWLYDWHG'HOD\HG)OXRUHVFHQFHDQG6SRQWDQHRXV+RUL]RQWDO0ROHFXODU2ULHQWDWLRQ´$GY3KRWRQLFV5HV LQSUHVV 
.D]XWR1DNDPXUD6KLQ\D6XJLXUD)XPLWR$UDRND6DWRVKL$\D<RLFKL7DNDQLVKL*R:DWDQDEH5\XPD
6DWR<DVXWHUX6KLJHWDDQG+LURPLWVX0DHGD &RQIRUPDWLRQ&KDQJHDEOHʌ(OHFWURQLF6\VWHPVZLWK0HWDVWDEOH
%HQW&RUH&RQIRUPDWLRQVDQG/LTXLG&U\VWDOOLQH6WDWH(OHFWULF)LHOG5HVSRQVLYH3URSHUWLHV´2UJ/HWW
 
*R:DWDQDEH+LURNL(LPXUD1LFKRODV/$EERWWDQG7DNDVKL.DWR ³%LRPROHFXODU%LQGLQJDW$TXHRXV,QWHUIDFHV
RI/DQJPXLU0RQROD\HUVRI%LRFRQMXJDWHG$PSKLSKLOLF0HVRJHQLF0ROHFXOHV$0ROHFXODU'\QDPLFV6WXG\´/DQJPXLU  
6XEDUX.RQLVKL<X.DVKLZDJL*R:DWDQDEH0RWRIXPL2VDNL7DNX\D.DWDVKLPD2VDPX8UDNDZD7DGDVKL,QRXH+LUR\DVX<DPDJXFKL$NLUD+DUDGDDQG<RVKLQRUL7DNDVKLPD³'HVLJQDQGPHFKDQLFDOSURSHUWLHVRIVXSUDPROHFXODUSRO\PHULFPDWHULDOVEDVHGRQKRVW±JXHVWLQWHUDFWLRQVWKHUHODWLRQEHWZHHQUHOD[DWLRQWLPHDQGIUDFWXUHHQHUJ\´3RO\P&KHP  *R:DWDQDEH+LGH\R:DWDQDEH.RWD6X]XNL+LGHWDND<XJH6KLQWDUR<RVKLGD7DNX\RVKL0DQGDL6KLJHWDND
<RQHGD+LVDNR6DWR0LWVXR+DUD DQG-XQ<RVKLGD 9LVXDOL]LQJWKHKHOLFDOVWDFNLQJRIRFWDKHGUDOPHWDOORPHVRJHQVZLWKDFKLUDOFRUH´&KHP&RPPXQ  
<RVKLDNL8FKLGD*R:DWDQDEH7DNX\D$NLWDDQG1RULND]X1LVKL\DPD³7KHUPDO0ROHFXODU0RWLRQ&DQ$PSOLI\,QWHUPROHFXODU0DJQHWLF,QWHUDFWLRQV´-3K\V&KHP%±  - 209 -

ࢼࣀ࣐ࢸࣜ࢔ࣝཬࡧ⏕యศᏊࡢᶵ⬟࣭≀ᛶ࣭཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDO6WXGLHVRQ)XQFWLRQV3URSHUWLHVDQG5HDFWLYLWLHVRI
1DQRPDWHULDOVDQG%LRORJLFDO0ROHFXOHV‫ۑ‬୰஭ ᾈᕭࠊΎ㔝 ῟ྖࠊ஬༑ᖭ ᗣᘯࠊすᮧ ዲྐࠊྜྷᕝ Ṋྖࠊᑠ㔝 ⣧୍ࠊ࿘ᘓᩩࠊࢧࢡࢸ࢕ ࢔ࢹ࢕ࢳࣕ ࢘࢕ࣂ࣡ࠊ⸨Ἴ ⨾㉳Ⓩࠊᶡぢ ᮃ㒔ࠊᾆ㇂ ᾈ㍤ࠊ㧗ᓥ༓Ἴࠊ୰ᮧ ᓫ⋪ࠊ⸨௦ ኳ♸ࠊ➉ᮧ ಇ᫭ࠊ⸨⃝ 㑈ࠊᅵᒇ భኴࠊ⏣ᔱ ୍㍤ࠊ㧗᲍೔ဢࠊΎỈ ఀ⧊ࠊబ⸨ ⛱ஓ㸦᪩኱ඛ㐍⌮ᕤ㸧 ◊✲┠ⓗຌ‫Ͳڂݜ‬ͺɼψόϜτϨΠϩΏਫ਼ର෾ࢢ͗‫ͤܐؖ‬Ζझʓ͹‫ݳ‬েΝྖࢢԿָ‫ࢋܯ‬ͶΓΕखΕѽ͏ɼͨ͹‫ؽ‬೵ʀ෼੓ʀൕԢ੓͹൅‫ߑؽݳ‬Νཀྵ࿨దͶմ໎ͤΖ͞ͳΝ໪ࢨͪ͢ɽΉͪɼͨ͹ͪΌͶචགྷͳ͵Ζཀྵ࿨͹֋൅͕Γ;ϕϫήϧϞ͹ࣰૹ΍ߨͮͪɽҐԾͶ͞͹໪దͶॊͮͱߨͮͪ‫ڂݜ‬͹͑ͬɼ  ‫ؽ‬փָस‫ܗ‬ుࢢ૮‫ؖ‬Ϡυϩ͹րྒྷɼ   '&')7%0' ϕϫήϧϞ͹֌૜దด྽Կɼ   &2 յफͶనͪ͢Πϝϱ෾ࢢ͹୵ࡩɼ   ϘϫϔηΩ΢φଢཇుஓࡒྋͶ͕͜Ζޭྯًয়ସξ΢ψϝέηεϝϣϪʖεϥϱ Ͷͯ͏ͱ
ๅࠄͤΖɽ ◊✲᪉ἲࠊィ⟬᪉ἲҲ࿊͹‫ڂݜ‬Ͷ͍ͪΕɼྖࢢԿָ‫ࢋܯ‬Ϗρίʖζ *$0(66ɼ9$63 ͍Ζ͏ͺಢࣙͶ֋൅ͪ͢ϕϫήϧϞ
'&')7%0' Νཤ༽͢ͱ਼஍‫ࢋܯ‬Νߨͮͪɽ ◊✲ᡂᯝ
3-1.ML-EC Ϡυϩ΃͹౜಼݃֬ۛࣇ͹న༽ ԿָൕԢ͹ఈྖద͵٠࿨ͶͺɼΦϋϩάʖΝ NFDOPRO Ґ಼͹‫ࠫޣ‬ɼͤ͵ΚͬԿָద੠ౕͲ‫੷ݡ‬Ζචགྷ͍͗
Ζɽ౲‫Ͳ࣪ڂݜ‬ͺɼ‫ؽ‬փָसΝ༽͏ͱɼԿָద੠ౕΝຮͪͤ &&6' 7 ๑͹‫׮‬સ‫خ‬ఊʤ&%6ʥ‫ݸۅ‬Ϫϗϩ͹૮‫ؖ‬ΦϋϩάʖືౕΝ༩଎ͤΖɼ‫ؽ‬փָस‫ܗ‬ుࢢ૮‫ؖ‬ʤ0/(&ʥϠυϩΝߑ஛ͪ͢ɽ͖͢͢ɼ&&6' 7 Ϫϗϩ͹‫ࢋܯ‬ͺଡ୉͵‫ࢋܯ‬αηφΝགྷͤΖͪΌɼָसυʖν͹‫͗ؔ࣎ࢋܯ‬ௗ͏ɽຌ‫Ͳڂݜ‬ͺɼ໪దร਼‫ࢋܯ‬Ͷ౜಼݃֬ۛࣇʤ)&$ʥΝన༽ͤΖ͞ͳͶΓΕɼָसυʖν͹‫ࢋܯ‬Ν߶ଐԿ͢ɼ͞ΗͶ‫ ͘Ͱخ‬0/(& ϠυϩΝߑ஛ͪ͢ɽ ຌघ๑Ͳͺɼ‫ى‬फ़ࢢͶՃుࢢ͹ుࢢືౕ U ుࢢືౕ‫ޱ‬ഓѭU ӣಊΦϋϩάʖືౕ W+DUWUHH±)RFN ި‫׷‬Φϋϩάʖືౕ H+); Ν༽͏ͪɽ໪దร਼Ͷ )&$ Ͳ‫&& ͪ͢ࢋܯ‬6' 7 &%6 Ϫϗϩ͹૮‫ؖ‬ΦϋϩάʖືౕΝ༽͏ͪɽָसυʖνͶͺɼ+&12)6&O Ν‫؜‬΋  ෾ࢢ͹৚ๅΝ༽͏ͪɽ)LJ ͶɼϠυϩΝ༽͏ͱ‫  ͪ͢ࢋܯ‬झ͹ൕԢ͹ൕԢΦϋϩάʖΝ ')7 ͹஍ͳർֳͪ݃͢ՎΝࣖͤɽॐ࣢ͺɼ&&6' 7 &%6 Ϫϗϩ͹‫ࢋܯ‬஍͖Δ͹ฑ‫ۋ‬ઊଲ‫͍Ͳࠫޣ‬Ζɽ0/(& Ϡυϩͺɼ')7 ΓΕ΍੠ౕΓ͚ൕԢΦϋϩάʖΝ‫ͪ͢ࢋܯ‬ɽ࣏Ͷɼ໪దร਼‫ࢋܯ‬͹Ϛφϩϋρέͳ͵Ζɼ&&6' 7 ๑͹ઃಊ  ుࢢྯًߴ͹‫ؔ࣎ࢋܯ‬Ν )LJ  Ͷࣖͤɽ‫ࢋܯ‬Ͷͺ FFS9'= ‫خ‬ఊ‫਼ؖ‬Ν༽͏ͪɽ)&$ Ν༽͏Ζ͞ͳͲɼસుࢢ $OOHOHFWURQ  ͹‫ͳࢋܯ‬ർֳ͢ͱ‫ؔ࣎ࢋܯ‬Ν୉෱Ͷ୻क़Ͳͪ͘ɽ
Ήͪɼ߶ब‫ݫغ‬ોΝ‫؜‬΋෾ࢢͶଲ͢ͱͺɼಝͶͨ͹ްՎ͗୉͚͘͵ͮͪɽ- 210 -)LJ  5HDFWLRQ HQHUJ\ GLIIHUHQFH
IURP&&6' 7 &%6FDOFXODWLRQ)LJ  &RPSXWDWLRQDO WLPH RI WKHSHUWXUEDWLYH WULSOHV FRUUHODWLRQHQHUJ\3-2. DCDFTBMD ϕϫήϧϞ͹֌૜దด྽Կ
౲‫֋Ͳ࣪ڂݜ‬൅ͪ͢ '&')7%0' ϕϫήϧϞͺɼ෾ׄ౹࣑‫ౕືܗ‬൜‫ک਼ؖ‬଍ള '&')7% ๑͹ด྽ࣰૹͶΓΕɼ਼એ‫ࢢݬ‬Ґ৏͖Δ͵Ζ‫ܧ‬સରΝྖࢢదͶखΕѽͮͪ෾ࢢಊྙָ 0' ʀϟνξ΢ψϝέη 07' ‫ʹ͵ࢋܯ‬ΝࣰߨՆ೵Ͳ͍ΖɽγϱϕϨϱήްིΏࣙ༟Φϋϩάʖ͹फ଍੓րવͶࣁͤΖ֨௃‫ؽ‬೵͹಍೘ͶΓΕɼ'&
')7%0'07' ‫ࢋܯ‬͹ࣰ༽੓͹͠Δ͵Ζ޴৏͗‫غ‬ଶ͠ΗΖɽຌ‫Ͳڂݜ‬ͺɼಋͣ‫ܧ‬͹ҡ͵ΖߑଆͶଲͤΖ '&
')7%0'07' ‫ࢋܯ‬Νಋ࣎Ͷߨ͑ͪΌ͹࢕ૌΊΝߑ஛ͪ͢ɽ۫ରదͶͺɼ03, ϕϫιηΝϪϕϨΩด྽Ͳචགྷͳ͵Ζ‫ࢋܯ‬ΠϩβϨθϞΝॴཀྵͤΖ PDVWHU ͳ֦ϪϕϨΩ͹ '&')7%0'07' ‫ࢋܯ‬Ν୴͑ ZRUNHU Ͷ෾ׄͪ͢ɽ͞͹֌૜దด྽ԿͶΓΕɼͤͲͶด྽Կ͠Ηͪ '&')7% ‫ࢋܯ‬෨෾Νरਜ਼ͤΖ͞ͳ͵͚ɼPXOWLSOHZDONHUV
07' ๑ɼϪϕϨΩި‫ ׷‬0' 5(0' ๑ɼSDUDOOHOWHPSHULQJ07' 3707' ๑͵ʹ͹෾ࢢεϝϣϪʖεϥϱ๑ͳૌΊ߻ΚͦΖ͞ͳ͗Ն೵ͳ͵ͮͪɽ‫ـ‬૮஦͹ DODQLQHGLSHSWLGH Νଲেͳͪ͢εϝϣϪʖεϥϱ݃ՎΝ )LJ Ͷ
ࣖͤɽ5(0' 3707' ‫Ͳࢋܯ‬ͺ௪৙͹ 0' ‫ࢋܯ‬ΓΕްིΓ͚ߑଆγϱϕϨϱήͲ͘ͱ͏Ζ͞ͳ )LJ  D Ώɼ3707' ๑Ͳͺॊཔ͹ 07' ‫ࢋܯ‬ΓΕηϞʖθͶࣙ༟Φϋϩάʖ‫ۄ‬໚͗फ଍ͤΖ͞ͳ )LJ  E ֮͗೟͠ΗͪɽϪϕϨΩด྽ͳ '&')7% ด྽‫ࢋܯ‬͹ྈཱིͺɼ௔ด྽‫ؽࢋܯ‬͹༙ްཤ༽ͳ͏͑؏఼Ͷ͕͏ͱ΍༙༽͵‫خ‬൭ͳ
͏͓Ζɽ

)LJ  ')7%0' ')7%07' ')7%5(0' DQG ')7%3707' VLPXODWLRQ UHVXOWV RI DODQLQHGLSHSWLGHLQJDVSKDVH D 3UREDELOLW\GLVWULEXWLRQVRIEDFNERQHGLKHGUDODQJOHVDQG E WLPHHYROXWLRQRIIUHHHQHUJ\VXUIDFHDVDIXQFWLRQRIFROOHFWLYHYDULDEOH

- 211 -

3-3. DFTB-MD/MTD ๑ͶΓΖ CCU ࠠ߻Πϝϱ͹ૌ߻ͦͳՖಉড়݇͹୵ࡩ
&DUERQ&DSWXUHDQG8WLOLWLHV &&8  Ͷ͕͏ͱɼഋΪη஦͹ &2 Ν‫ٷ‬फͤΖΠϝϱ༻ӹ͹֋൅͗੟ΞͶߨΚΗͱ͏ΖɽಝͶɼࠠ߻ΠϝϱͶ͕͏ͱͺɼ&2 ‫ٷ‬फްི͗߶ΉΖ͞ͳ͗எΔΗͱ͕ΕɼΠϝϱ͹ૌ߻ͦΏೳౕɼԻౕͶ‫ͤؖ‬Ζ࠹నড়݇͹୵ࡩ͗ߨΚΗͱ͏Ζɽຌ‫Ͳڂݜ‬ͺɼΠϝϱ&2 ൕԢ͹೦ྙָྖ͹‫ͳࢋܯ‬ɼ౲‫Ͳ࣪ڂݜ‬֋൅ͪ͢ฑߩ࿨Ͷ‫͚Ͱخ‬ൕԢεϝϣϪʖνΝ༽͏ͱɼ೦ྙָదͶ༙ཤ͵ࠠ߻Πϝϱ͹ૌͳͨ͹ড়݇Ν୵ࡩͪ͢ɽ۫ରదͶͺɼ झ͹ΠϝϱͶͯ͏ͱɼΠϝϱ&2 ൕԢ͹೦ྙָྖͳ͢ͱൕԢࣙ༟Φϋϩάʖ'* ͳൕԢΦϱνϩϒʖ'+ Νࢋड़ͪ͢ɽ͞ΗͶͺɼ')7%0' ๑ͳ 07' ๑ΝૌΊ߻Κͦͪɼ')7%0'07' ๑Ν༽͏ͪɽಚΔΗͪ೦ྙָྖΝ༽͏ͱɼΠϝϱ͹ૌɼೳౕɼԻౕɼΠϝϱ͗‫ٷ‬फͤΖ &2 ͹ׄ߻ΝනͤϫʖυΡϱή͹ড়݇Ͷͯ͏ͱ೦αηφΝ඲Ճͪ͢ɽ
)LJ Ͷɼ
7ULV K\GUR[\PHWK\O DPLQRPHWKDQH 7+0$0  ͳ  SLSHULGLQ\O HWKDQRO +(33  ͹ૌͶ͕͜Ζɼ೦αηφ 4 ͹ೳౕғଚ੓Νࣖͤɽԥ࣢ͳॐ࣢ͺɼͨΗͩΗ 7+0$0ͳ +(33 ͹ॵ‫غ‬ೳౕΝන͢ɼ੪৯͹྘Үͺɼ೦αηφ͗ঘ͠͵஍Ͳ͍Ζ͞ͳΝන͢ͱ͏Ζɽ͞͹Γ͑Ͷ ຬҐ৏͹ড়݇͹ૌ߻ͦͶͯ͏ͱɼ೦αηφΝࢋड़͢ɼ࠹నড়݇Ν‫ݡ‬ड़ͪ͢ɽ)LJ,QLWLDOFRQFHQWUDWLRQVGHSHQGHQF\RIWKHUPDOFRVWVIRU7+0$0DQG+(33
3-4. ϘϫϔηΩ΢φଢཇుஓࡒྋ͹ඉஇ೦ྯًয়ସ෾ࢢಊྙָεϝϣϪʖεϥϱԘύϧ΢χϘϫϔηΩ΢φʤ/+3ʥͺɼଢཇుஓ΃͹Ԣ༽͹ࢾΊΝ௪ͣɼௗथໍ͵ϙρφΫϡϨΠ͹ଚࡑΏఁ͏ుࢢਜ਼޺࠸݃߻ଐౕ͵ʹࡏཱིͮͱಝ௅ద͵ޭుࢢ෼੓Ν࣍ͯ͞ͳ͗໎Δ͖Ͷ͠Ηͱͪ͘ɽ͑ͪ͢͞෼੓ͺɼޭྯًয়ସͶ͕͜Ζుࢢξ΢ψϝέηͳߑଆξ΢ψϝέη͗‫͏ޕ‬ͶӪ‫ڻ‬Ν༫͓߻͑͞ͳͶΓͮͱ΍ͪΔ͠ΗΖͳߡ͓ΔΗΖɽ͖͢͢ɼుࢢʀߑଆξ΢ψϝέη͹ྈंΝ‫ݨ‬Ͷߡྂͪ͢εϝϣϪʖεϥϱΝࣰࢬͤΖ͞ͳͺ‫ؔ࣎ࢋܯ‬͹؏఼͖Δ༲ҝͲͺ͵͚ɼ͏ͥΗ͖Ҳ๏ͫ͜Ͷ஭໪ͪ͢‫͠͵͗ڂݜ‬Ηͱͪ͘ɽຌ‫Ͳڂݜ‬ͺɼ')7% Ͷ‫ًྯ͚Ͱخ‬য়ସ‫ࢋܯ‬घ๑Ͳ͍Ζ࣎ؔғଚʤ7'ʥ')7% ๑Ν΍ͳͶɼඉஇ೦෾ࢢಊྙָ
๑͹ҲझͲ͍Ζ IHZHVWVZLWFKHVVXUIDFHKRSSLQJʤ)66+ʥ๑Ν '&')7%0' ϕϫήϧϞͶࣰૹͪ͢ɽΉͪɼ͞ΗΝԢ༽͢ɼుࢢʀߑଆξ΢ψϝέη͹૮‫༽ࡠޕ‬Νߡྂͪ͢‫ Ͳܙ‬/+3 ͹ޭྯًয়ସξ΢ψϝέηεϝϣϪʖεϥϱΝࣰࢬͪ͢ɽ)LJ ͺ 0XOOLNHQ ϛϒϣϪʖεϥϱմੵͶΓΕಚΔΗͪుࢢʤ੪ʥͳਜ਼޺ʤ੼ʥ͹‫ؔۯ‬ద෾ාΝࣖͤɽεϝϣϪʖεϥϱ֋࢟࣎ʤW ʥͶർ΄ɼ࣎ؔ‫ܨ‬գ‫ޛ‬ʤW IVʥͲͺΓΕుࢢͳਜ਼޺͹‫ؔۯ‬ద॑͵Ε͗ঘ͚͠ɼు՛෾཯͗਒ߨͪ͢͞ͳ͗Κ͖ΖɽΉͪɼ)LJ ͺ 3E², ؔ͹݃߻‫཯ړ‬Νන͢ͱ͕ΕɼుࢢΏਜ਼޺͹ଚࡑͶ൒ͮͱ݃߻‫ݨ͗཯ړ‬ஸͶรԿͪ͢͞ͳΝࣖͤɽҐ৏ΓΕɼࣰૹͪ͢ 7'')7%)66+ ๑ͶΓͮͱు- 212 -

ࢢʀߑଆξ΢ψϝέη͹ྈंΝߡྂͪ͢ /+3 ͹ޭྯًয়ସξ΢ψϝέηεϝϣϪʖεϥϱΝࣰ‫͢ݳ‬ɼྈξ΢ψϝέη͹૮‫༽ࡠޕ‬͹॑གྷ੓Νࣖͪ͢ɽ)LJ6SDWLDOGLVWULEXWLRQRIDQHOHFWURQ EOXH DQGKROH UHG )LJ7LPHFRXUVHFKDQJHRI3E²,GLVWDQFHⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ

>@ ੜ໼५࢚ɼnԿָͶ͕͜Ζਕ޽எ೵ٗढ़ͳ͹༧߻͹‫ݩࣰͳેخ‬ʀ‫ࢋܯ‬Կָ΃͹Ԣ༽ࣆྭ|ɼৰഖ΢ϱϓΧϜτΡέηιϝψʖɼΨϱϧ΢ϱ֋࠷ɼ ೧  ݆ʤডଶߪԍʥ>@ ੜ໼५࢚ɼnԿָ‫ͳڂݜ‬ਕ޽எ೵ٗढ़͹༧߻Ͷ‫ͤؖ‬Ζ‫ͳેخ‬Ԣ༽|ɼ&0& ϨγʖοιϝψʖɼΨϱϧ΢ϱ֋࠷ɼ ೧  ݆ʤডଶߪԍʥ>@-XQLFKL2QRn0LFURVFRSLFPHFKDQLVPVRISURWRQWUDQVIHUVLQEDFWHULRUKRGRSVLQUHYHDOHGE\TXDQWXPPROHFXODUG\QDPLFVPHWKRGEDVHGRQPROHFXODUPRYLHV| ୊  յೖຌਫ਼෼෼ཀྵָճ೧ճɼΨϱϧ΢ϱ
֋࠷ɼ ೧  ݆ʤডଶߪԍʥ>@ +LURPL 1DNDL DQG <RVKLIXPL 1LVKLPXUD n'&')7%0' 'LYLGHDQGFRQTXHU GHQVLW\ IXQFWLRQDOWLJKWELQGLQJ SURJUDP IRU KXJHV\VWHP TXDQWXP PHFKDQLFDO PROHFXODU G\QDPLFV VLPXODWLRQV| 1HZ+RUL]RQVLQ6FLHQWLILF6RIWZDUH)URP/HJDF\&RGHVWR0RGXODU(QYLURQPHQWV 1+,66 RQOLQH
1RY LQYLWHG>@ ౽ഀඔًౌɼnӣಊΦϋϩάʖ൜‫਼ؖ‬͹֋൅ɼൕԢ༩଎ɼൕԢড়݇࠹నԿͶଲͤΖྖࢢԿָ‫ؽͳࢋܯ‬փָस͹Ԣ༽|ɼ‫ࢋܯ‬Ռָ‫ڂݜ‬ιϱνʖʀψότέόϫζʖϕϧρφϓΧʖϞࣆ‫߻ۂ‬ಋϭʖέεϥρϕɼΨϱϧ΢ϱ֋࠷ɼ ೧  ݆ʤডଶߪԍʥʤଠɼࠅ಼ָճ  ݇ʥ- 213 -

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

մ>@0,QDPRUL<,NDEDWD7<RVKLNDZDDQG+1DNDL³8QYHLOLQJFRQWUROOLQJIDFWRUVRIWKH6
6PLQLPXPHQHUJ\FRQLFDOLQWHUVHFWLRQ  $SSOLFDWLRQWRSHQDOW\IXQFWLRQPHWKRG´-&KHP3K\V152
  SDJHV 
մ>@ 0 )XMLQDPL 5 .DJH\DPD - 6HLQR < ,NDEDWD DQG + 1DNDL ³2UELWDOIUHH GHQVLW\ IXQFWLRQDO WKHRU\FDOFXODWLRQ DSSO\LQJ VHPLORFDOPDFKLQHOHDUQHG NLQHWLF HQHUJ\ GHQVLW\ IXQFWLRQDO DQG NLQHWLF SRWHQWLDO´ &KHP
3K\V/HWW748   SDJHV 
մ>@ - 2QR DQG + 1DNDL ³:HLJKWHG KLVWRJUDP DQDO\VLV PHWKRG IRU PXOWLSOH VKRUWWLPH PHWDG\QDPLFVVLPXODWLRQV´&KHP3K\V/HWW751   SDJHV 
˔>@0)XMLQDPL+0DHNDZDUD5,VVKLNL-6HLQR-<DPDJXFKLDQG+1DNDL³6ROYHQW6HOHFWLRQ6FKHPH
8VLQJ 0DFKLQH /HDUQLQJ %DVHG RQ 3K\VLFRFKHPLFDO 'HVFULSWLRQ RI 6ROYHQW 0ROHFXOHV$SSOLFDWLRQ WR &\FOLF
2UJDQRPHWDOOLF5HDFWLRQ´%XOO&KHP6RF-SQ93²  
˔>@< 1LVKLPXUD DQG + 1DNDL ³+LHUDUFKLFDO SDUDOOHOL]DWLRQ RI GLYLGHDQGFRQTXHU GHQVLW\ IXQFWLRQDO WLJKWELQGLQJPROHFXODUG\QDPLFVDQGPHWDG\QDPLFVVLPXODWLRQV´-&RPSXW&KHP41²  
 >@.7RNR.,WR+6DLWR<+RVRQR.0XUDNDPL60LVDNL7+LJR62JR+7VXQHNL60DHGD.
+DVKLPRWR+1DNDLDQG<6HNLQH³&DWDO\WLF'HK\GURJHQDWLRQRI(WKDQHRYHU'RSHG3HURYVNLWHYLDWKH
0DUVíYDQ.UHYHOHQ0HFKDQLVP´-3K\V&KHP&124²  
 >@700DLHU<,NDEDWDDQG+1DNDL³5HODWLYLVWLFORFDOK\EULGIXQFWLRQDOVDQGWKHLULPSDFWRQVFRUHRUELWDOHQHUJLHV´-&KHP3K\V152   SDJHV 
˔>@ +8UDWDQL DQG+1DNDL ³6LPXODWLQJ WKH &RXSOHG 6WUXFWXUDO±(OHFWURQLF'\QDPLFV RI 3KRWRH[FLWHG /HDG
,RGLGH3HURYVNLWHV´-3K\V&KHP/HWW11²  
˔>@ + 8UDWDQL DQG + 1DNDL ³1RQDGLDEDWLF PROHFXODU G\QDPLFV ZLWK GLYLGHDQGFRQTXHU W\SH ODUJHVFDOH
H[FLWHGVWDWHFDOFXODWLRQV´-&KHP3K\V152   SDJHV 
˔>@7<RVKLNDZD7'RLDQG+1DNDL³)LQLWHWHPSHUDWXUHEDVHGWLPHGHSHQGHQWGHQVLW\IXQFWLRQDOWKHRU\PHWKRGIRUVWDWLFHOHFWURQFRUUHODWLRQV\VWHPV´-&KHP3K\V152   SDJHV 
˔>@-2QR0,PDL<1LVKLPXUDDQG+1DNDL³+\GUR[LGH,RQ&DUULHUIRU3URWRQ3XPSVLQ%DFWHULRUKRGRSVLQ
3ULPDU\3URWRQ7UDQVIHU´-3K\V&KHP%124²  (Supplementary Journal Cover)
˔>@<,NDEDWD5)XMLVDZD-6HLQR7<RVKLNDZDDQG+1DNDL³0DFKLQHOHDUQHGHOHFWURQFRUUHODWLRQPRGHOEDVHGRQIUR]HQFRUHDSSUR[LPDWLRQ´-&KHP3K\V153   SDJHV 
 >@):DQJ6/DQJIRUGDQG+1DNDL³5REXVWGHVLJQRI'S$PRGHOFRPSRXQGVXVLQJGLJLWDOVWUXFWXUHVIRU
RUJDQLF'66&DSSOLFDWLRQV´-0RO*UDSK0RGHO102   SDJHV 
˔>@+8UDWDQL70RULRND7<RVKLNDZDDQG+1DNDL³)DVW1RQDGLDEDWLF0ROHFXODU'\QDPLFVYLD6SLQ)OLS
7LPH'HSHQGHQW 'HQVLW\)XQFWLRQDO 7LJKW%LQGLQJ $SSURDFK $SSOLFDWLRQ WR 1RQUDGLDWLYH 5HOD[DWLRQ RI
7HWUDSKHQ\OHWK\OHQH ZLWK /RFNHG $URPDWLF 5LQJV´ - &KHP 7KHRU\ &RPSXW 16 ²  (Supplementary Journal Cover)
- 214 -

 >@.0XUDNDPL<0L]XWDQL+6DPSHL$,VKLNDZD<7DQDND6+D\DVKL6'RL7+LJR+7VXQHNL+
1DNDLDQG<6HNLQH³7KHRUHWLFDOSUHGLFWLRQE\')7DQGH[SHULPHQWDOREVHUYDWLRQRIKHWHURFDWLRQGRSLQJHIIHFWVRQ K\GURJHQ DGVRUSWLRQ DQG PLJUDWLRQ RYHU WKH &H2   VXUIDFH´ 3K\V&KHP&KHP3K\V23²
  (Journal Cover) >@<7DQDND.0XUDNDPL6'RL.,WR.6DHJXVD<0L]XWDQL6+D\DVKL7+LJR+7VXQHNL+1DNDL
DQG<6HNLQH³(IIHFWVRI$VLWHFRPSRVLWLRQRISHURYVNLWH 6Uí[%D[=U2 R[LGHVRQ+DWRPDGVRUSWLRQPLJUDWLRQDQGUHDFWLRQ´56&$GY11²  
˔>@ + 8UDWDQL 7 <RVKLNDZD DQG + 1DNDL ³7UDMHFWRU\ 6XUIDFH +RSSLQJ$SSURDFK WR &RQGHQVHG3KDVH
1RQUDGLDWLYH 5HOD[DWLRQ '\QDPLFV 8VLQJ 'LYLGHDQG&RQTXHU 6SLQ)OLS 7LPH'HSHQGHQW 'HQVLW\)XQFWLRQDO
7LJKW%LQGLQJ´-&KHP7KHRU\&RPSXW17²  
˔>@&7DNDVKLPD-6HLQRDQG+1DNDL³,PSOHPHQWDWLRQRI3LFWXUH&KDQJH&RUUHFWHG'HQVLW\ )XQFWLRQDO
7KHRU\%DVHGRQ,QILQLWH2UGHU7ZR&RPSRQHQW0HWKRGWR*$0(663URJUDP´-&RPSXW&KHP-SQ19²  - 215 -







Development of a coarse-grained model for protein-protein interaction
and its application for electron transport1 ('



!

)

!
^n wÖ%^-=K/O*pkhz-=K/Ot³¶`c' ^-=K/O%hz-=K/Ot6J2,:·RØx*WÍ' »)('ØxWÍ_Y]% #ØxWÍÈª$v¢&iq Á(390MD b6f ½nY³¶·Ryrm lØx*390MD fÞCyt fß*Ç@J493+<NÞPcßm Cyt f ADÑ*o!C ­Ús ³¶·`(' vÏb³¶·uÙa'Pc Ò,.N*#5N?0Å³¶·u*¸ Ëg' ØxWÍÌ©³¶·u»)(^n _YØxWÍÈ~'}Q v   ª Cyt f  Pc ØxWÍ½nYÉ %' ( 5N?0Å½nY f¤3CHLO3IN*|'"5N?0ÅÔ¦TZ§¥¿±ÀhF8KhÓ£*Ê" [1-4] ( ¨¬%_ixbxgd
z3CHLO3INdz«b*¸ -=K/OÂ¯$R+C>Ð+;M1bxÔ±ÀhF8KB7N3GKÕ$?JEO5*{Ý® Cyt f % Pc ØxWÍÈj{*¾«#'  e'[3] F8K*^n ØxWÍ² ' Cyt f % Pc ØxWÍÌ©'¡Ä¨¬^n ØxWÍ²R390MD fÞCyt fß%@J493+<NÞPcßØxWÍªÎ$'ØxWÍ½nY Î§¥'

2!&"ÃÛ¨¬¡Äµ Ó£*Ê" 3CHLO3IN*'[1, 2]+C>ÐP\*P±Àh°xF8Kh'5N?0Å`¦TZ Go-like F8K*['5
N?0ÅÔ¦TZ Ó£ F8K*'±Àh°xÔÆ×!Õ´F8K*' Â¯249Xf¤3CHLO3IN*|' *
Cyt f  Pc

×(ÞÁ
¼ 1. 3CHLO3INª PDB ID

×ß%½nY* ÞVnß'3CHLO3IN*

3F

&\WI

»SªÜÝ®PªÜKLJKHUSODQWV

6ROHUDFHD 3&) 

B. rapa (2PCF)

ºÜSªÜ³¹ÂUªÜKLJKHUSODQWV

3RSXOXVQLJUD 7.: %UDSD 7.: 3CHLO3IN*»

JUHHQDOJDH&UHLQKDUGWLL 3/7 &UHLQKDUGWLL &)0 

Þ¼ 1ß
%(½nYÉF\DQREDFWHULD

3ODPLQRVXP 4% 

3ODPLQRVXP &, &'F\DQREDFWHULD

1RVWRF 78 

1RVWRF 78 - 216 -

3

!
3CHLO3IN"% Pc Ò,.N Cyt f Ñ,.NÔÆ×~'gbÕ*"Þ

1 ßª$½nY{É v

×Þr = 1.2 nmÞ¢'  )'2PLT-1CFM 'Æ'ßv O0 &ØxWÍc'´%(',.NÔÆ×

1 Rß 2.4 nmÞ

1ß ' ¼¤É* Cyt fÞ

1.3 nm

1 R %ß~PcÞ

1R $ß½Vn'  )'½nY*#'Ô#ª$v¢ (%"%Cyt f  Pc ØxWÍ ('½nYª$v¢'  )' (%"%ØxWÍÈ*¾«#&|(ØxWÍÈ¦Õ*¾ '  ÃÛ'$
[1] K. Kawaguchi, et al., Mol. Phys. 2017, 115, 587-597.
[2] K. Kawaguchi, et al., Mol. Phys. 2018, 116, 649-657.
[3] S. Nakagawa, et al., Mol. Phys. 2018, 116, 666-677.
[4] K. Kawaguchi, et al., Mol. Phys. 2019, 117, 2355-2361.

4

%#

 K. Kawaguchi, H. Nagao, ‘Theoretical study of electron transport between cytochrome f and plastocyanin by using acoarse-grained simulation’ ! 58

5zVV 9  16 18  .NJ,N

#

K. Kawaguchi, K. M. Nakagawa, S. Nakagawa, H. Shindou, H. Nagao, H, Noguchi, ‘Conformation of ultra-long-chain
fatty acid in lipid bilayer: Molecular dynamics study’, J. Chem. Phys. 2020, 153, 165101.

1. ÞßÒ-Ñ,.NÔÆ×~'gbÕÞRßr = 1.3 nm  '4;@3I9
Þ ßr = 2.4 nm  '4;@3I9%- 217 -

Cyt f$Pc *¼ゐ፹ࢆ⏝࠸ࡓ໬Ꮫ཯ᛂᶵᵓࡢ⌮ㄽⓗゎ᫂Theoretical Studies on Mechanisms of Catalytic Reactions‫ۑ‬᳃ ⪷἞ࠊᕝᓥᜤᖹࠊ୕ࢶἨᏹ᫭ࠊᓥᓮ ඃ୍ࠊ㕥ᮌ ᓫࠊᗉᮧ ᗣேࠊ㓇஭┤ᶞࠊᒸᮏඃᝅࠊ⸨஭⛸㤿ࠊఀ⸨ᣅᮍࠊAttila Taborosi㸦Ⲉᇛ኱Ꮫ㸧

1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲࡛ࡣ,(1)⌮ㄽ໬Ꮫࢆᇶ┙࡜ࡋࡓ࡞ࡿ࡭ࡃ↓㥏࡞ヨ⸆ࢆ౑⏝ࡋ࡞࠸,࠿ࡘ↓㥏࡞๪⏕ᡂ≀ࢆฟࡉ࡞࠸(ࡍ࡞ࢃࡕ⎔ቃ࡟ඃࡋ࠸)㧗ຠ⋡ⓗゐ፹཯ᛂࡢ㛤Ⓨ(2)⎔ቃ⛉Ꮫⓗ࠶ࡿ࠸ࡣ⏕໬Ꮫⓗ࡟⯆࿡῝࠸ゐ፹཯ᛂᶵᵓࡢゎ᫂ࢆ⾜ࡗ࡚࠸ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬ࡸศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣ Gaussian 09 Rev. E 01ࠊ
Gaussian 16 Rev B.01 ࠾ࡼࡧ AMBER

18 ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋィ⟬ࡣ୺࡟ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢ₇⟬ࢧ࣮ࣂ࣮࠾ࡼࡧᙜ◊✲ᐊࡢࢥࣥࣆ࣮ࣗࢱୖ
࡛⾜ࡗࡓࠋࡉࡽ࡟ࠊ㠀ඹ᭷⤖ྜᛶ(NCI)┦஫స⏝ࡢ⾲♧࡟ࡣࠊNCI Plot Version 3.0 ࣉࣟࢢ࣒ࣛ࠾ࡼࡧ VMD,
Multiwfn 3.8 ࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ



㓝⣲ゐ፹㑏ඖ཯ᛂ࡟࠾ࡅࡿ㠀ඹ᭷⤖ྜᛶ┦஫స⏝ࡢ㔜せᛶᛶ

5D -ࢪࣄࢻࣟࢸࢫࢺࢫࢸࣟࣥ(5D -DHT)ࡣே㛫࡟࡜ࡗ࡚᭱ࡶᙉຊ࡞࢔ࣥࢻࣟࢤ࡛ࣥ࠶ࡾࠊ๓❧⭢ࡀࢇࢆᘬࡁ
㉳ࡇࡍཎᅉ࡜࡞ࡿ໬ྜ≀࡛࠶ࡿࠋ࢔ࣝࢻ-ࢣࢺ㑏ඖ㓝⣲ࢫ࣮ࣃ࣮ࣇ࢓࣑࣮ࣜ࡟ᒓࡍࡿ 3D-ࣄࢻࣟ࢟ࢩࢫࢸࣟ࢖
ࢻࢹࣄࢻࣟࢤࢼ࣮ࢮ(3D -HSD)ࡣࠊ㑏ඖᆺ NADP Ꮡᅾୗ࡟࠾࠸࡚ࠊ5D -DHT ࢆேయ࡟↓ᐖ࡞ 3D-࢔ࣥࢻࣟࢫࢱ
ࣥࢪ࣮࢜ࣝ࡬࡜ࣄࢻࣜࢻ㑏ඖࡍࡿ㸦ᅗ㸯㸧ࠋࡇࡢ㓝⣲ࡣࠊ⮫ᗋ᳨ᰝ࡟࠾࠸࡚⫹Ồ㓟ࡢᐃ࡛⏝࠸ࡽࢀࡿ࡯࠿ࠊ

ࡇࡢ㓝⣲ࡀḞᦆࡋࡓሙྜࠊ๪⭈୙඲ཬࡧእᛶჾ␗ᖖࢆ㉳ࡇࡍ࡜ࡉࢀ࡚࠸ࡿࠋࣄࢺ 3D-HSD3 ᆺ࡟࠾ࡅࡿẚάᛶཬࡧ X ⥺⤖ᬗᵓ㐀ࡣࡍ࡛࡟ሗ࿌ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊゐ፹ᶵᵓཬࡧάᛶ㒊఩࿘㎶⎔ቃࡢཎᏊ࡛ࣞ࣋ࣝࡢヲ⣽ࡣᮍࡔ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋ

ᅗ㸯.ࢸࢫࢺࢫࢸࣟࣥ࠿ࡽࠊ5α-androstane-3α,17β-diol ࢆ⏕ᡂࡍࡿ㑏ඖ཯ᛂ⤒㊰ࡇࡢ㓝⣲཯ᛂ࡛ࡣࠊ㑏ඖ๣࡜ࡋ࡚ാࡃ⿵㓝⣲࡛࠶ࡿ NADPH ࡢࡑࡤ࡟ࠊTyr216 ࡣᏑᅾࡋࠊS-Sࢫࢱࢵ࢟ࣥࢢ࡛
┦஫స⏝ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡿࡀࠊࡑࡢᙺ๭ࡶࡣࡗࡁࡾࡋ࡚࠸࡞࠸ࠋࡲࡓࠊ⤖ᬗỈ࡞࡝ࡢỈࡢᙺ๭ࡶࡣࡗࡁࡾࡋ࡚࠸࡞࠿ࡗࡓࠋᮏ◊✲࡟࠾࠸࡚ࠊᡃࠎࡣάᛶ㒊఩࿘㎶࡟࠾ࡅࡿྛṧᇶࡢᙺ๭ࢆヲ㏙ࡍࡿࡓࡵ࡟

- 218 -MD ࢩ࣑࣮ࣗࣞࢩࣙࣥཬࡧ ONIOM ἲࢆ⏝࠸ࡓ QM/MM ィ⟬ࢆ⾜ࡗࡓࠋAMBER ff14SB/TIP3P ຊሙࢆ⏝࠸ࡓ
100 ns MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ᳨ウࡋࡓ࡜ࡇࢁࠊ⤖ᬗᵓ㐀ࡢẁ㝵࡛ࡣࠊᇶ㉁ࡢ 5D -DHT ͳɼTyr55 ͕Γ;
His117 ࢔‫ͳخ‬͹ؔͶͺ૮‫͚͵͗༽ࡠޕ‬ɼᇶ㉁ࡣ෈‫׈‬੓Ͳ͍ΖҲ๏ɼεϝϣϪʖεϥϱ͹౏஦Ͳɼ‫࣯͗خ‬յ఺ɼϓϨρϕ͢ɼ͞ΗΔ͹ Tyr55 ͕Γ; His117 ࢔‫ ͳخ‬5D -DHT ΩϩϚωϩ࢐ો͹ؔͶਭો݃߻͗‫ݡ‬ΔΗΖΓ͑Ͷ͵ͮͪɽ೨͹ͪΌ΍͑Ҳౕ MD εϝϣϪʖεϥϱΝߨͮͪ͗ɼ‫࣯خ‬͹յ఺ͳϓϨρϕ͹‫ݳ‬েͺ࠸;ًͮͪ͞ɽ
NADPH ͶΓΖؒ‫ݫ‬ൕԢͺ͞ΗΔ͹ਭો݃߻ͶΓͮͱɼ‫࣯خ‬͹ΩϩϚωϩ࢐ો͗‫׈‬੓Կ͠ΗΖ‫ޛ‬Ͷً͘Ζ͞
ͳ͗ࣖࠨ͠ΗͪɽONIOM ‫ࢋܯ‬Ͷͺɼ̑झྪ͹ QM ྘ҮΝร͓ͪϠυϩΝߡ͓ͪɽ‫࣯خ‬ɼNADPH ͕Γ;बҕ͹࢔‫خ‬ɼ‫࣯خ‬͹ϐχϫΫε‫ͳخ‬૮‫ͤ༽ࡠޕ‬Ζ̓ͯ͹ਭ෾ࢢΝͺͣΌɼ233 ‫ࢢݬ‬Ν QM ྘ҮͶ‫؜‬Όͪ ONIOMME(M06-2X/def-2SVP:Amber)Ͳ͹‫݃ࢋܯ‬Վ͖Δɼৰഖ‫ߑؽ‬ͺؒ‫ ܗݫ‬NADP ͶΓΖ‫΃࣯خ‬͹௜ંద͵ϐχϨχ
ؒ‫͍Ͳݫ‬Εɼ‫΃࣯خ‬͹ϕϫφϱ͹ण͜ో͢ͺɼ‫࣯خ‬͹ۛ๥Ͷ͍Ζ Tyr55 ͶΓͮͱߨΚΗΖ͞ͳ͗໎Δ͖ͳ͵ͮͪʤਦ̐ʥ
ɽ࠹΍୉͘͵ QM ྘ҮΝ༽͏ͪ৖߻͹‫׈‬੓ԿΦϋϩάʖͺɼ18. 7 kcal/mol Ͳ͍ΕɼରԻͲً͘ΖൕԢͳ͢ͱͺॉ෾Ͷ਒ߨͤΖɽਫ਼੔෼ͳ߮ોɼNADP+෵߻ର͹ΦϋϩάʖͺɼൕԢ઴ۨରͶർ΄ͱ 9.4 kcal/molఁ͏͞ͳ͗Κ͖ͮͪɽඉ‫߻༙݃ڠ‬੓૮‫(༽ࡠޕ‬NCI)‫ ;ٶ‬Quantum Theory of Atoms in Molecules (QTAIM)մੵͶΓΕɼؒ‫࢐;ٶܗݫ‬Կ‫ ܗ‬NADP ͹ωαοϱΠϝχ‫ ͳ؂‬Tyr21 ͹ଈ࠱ؔͶSS૮‫֮͗༽ࡠޕ‬೟͠ΗͪɽTyr216
ͺൕԢ͹਒ߨΝঁ͜ɼਫ਼੔෼͹҈ఈԿͶ‫ر‬༫ͤΖͳ͏͑॑གྷ͵ༀׄΝ࣍ͯͳࣖࠨ͠ΗͪɽΉͪɼGlu127 ͳ‫خ‬࣯‫ͨ;ٶ‬͹ؔͶଚࡑͤΖਭ෾ࢢͺ‫͏ޕ‬Ͷਭો݃߻ϋρφϭʖέΝ‫ܙ‬੔ͤΖ͞ͳͲɼ‫࣯خ‬͹‫׈‬੓෨Ғ΃͹ഓ஖
Νঁ͜Ζಉ͍͗͘Ζͳ͏͑͞ͳ͗ࣖࠨ͠Ηͪɽᅗ㸰 QM/MM ィ⟬⤖ᯝ࠿ࡽணゝࡉࢀࡿ㑏ඖ཯ᛂ⤒㊰࢖ࣜࢪ࣒࢘ゐ፹୙ᩧỈ⣲໬཯ᛂ࡟࠾ࡅࡿ㠀ඹ᭷⤖ྜᛶ┦஫స⏝ࡢ㔜せᛶᛶ΢ϨζΤϞͳ஢ો͕Γ;ϨϱഓҒࢢΝ‫؜‬΋෈੬ϕϫϨόʖϩʖϙηϓΡϱ༢಍ରͳ͹‫ڢ‬ಋৰഖͶΓΖίφϱ
͹ΦψϱοΨમ୔దؒ‫ݫ‬ൕԢΝๅࠄͪ͢ʤਦ̐ʥɽ͞͹‫Ͳڂݜ‬ͺɼt-ϔοϩϓΥωϩίφϱ͹Γ͑͵ɼ͖͠߶͏ίφϱͲ΍߶ཱིରમ୔ద( >99 %ee)ͶൕԢ͗਒ߨͤΖ͞ͳ͗໎Δ͖Ͷ͵ͮͪΆ͖ɼΦψϱοΨમ୔੓͹ઈ໎ͶɼϕϫϨόʖϩʖϙηϓΡϱ༢಍ର͹ OtHwwwO/sp3-CtHwwwO ΏϒϫϨζϱ‫؂‬͹ CtH ݃߻͕Γ;‫࣯خ‬͹ϓΥωϩ‫ͳخ‬͹ CtH/S૮‫ʹ͵༽ࡠޕ‬ඉ‫߻༙݃ڠ‬੓૮‫॑͗༽ࡠޕ‬གྷͲ͍Ζ͞ͳΝɼDFT ‫ࢋܯ‬ʤB3LYP+D3(BJ)PCM/def2TZVPP//B3LYP+D3(BJ)/def2SVP Ϫϗϩʥ͕Γ;ͨ͹ుࢢືౕմੵͶΓͮͱ΍໎Δ͖Ͷͪ͢ɽયҢয়ସ͹ߑଆ࠹నԿͲͺɼϒϫϨζϱ‫؂‬͹ཱིରഓ࠴͗ଡ͚ଚࡑͤΖͳߡ͓ΔΗΖ͗ɼ2013 ೧Ͷըʓ͗ๅࠄͪ͢ྪ
ࣇ͹ഓҒࢢͳಖʤIʥΝৰഖͳͤΖΩϩϚωϩԿ߻෼͹ΠϩΫωϩԿൕԢ͹યҢয়ସ͹ཱིରഓ࠴մੵͲ‫ݗ‬౾ͪ͢எ‫ݡ‬Ν༽͏ͱߨͮͪɽ

- 219 -

ਦ̑ ΢ϨζΤϞʖϕϫϨόʖϩ༢಍ରৰഖͶΓΖίφϱ͹ؒ‫ݫ‬ൕԢɼ͕Γ;ͨ͹ؒ‫ݫ‬ൕԢ͹યҢয়ସͶ͕͜Ζඉ‫߻༙݃ڠ‬੓૮‫༽ࡠޕ‬कਫ਼੔෼ͶࢺΖયҢয়ସ͕Γ;෯ΦψϱοΨϜʖਫ਼੔෼ͶࢺΖયҢয়ସΝ‫ٽ‬Όͪͳ͞Θɼ઴ं͗ 9.1 kJ/mol ‫ޛ‬ंͶർ΄ͱ Gibbs ΦϋϩάʖదͶఁ͏͞ͳ͗෾͖ͮͪɽ͞Ηͺɼࣰ‫ݩ‬͹߶ΦψϱοΨમ୔੓Νઈ໎Ͳ͘ΖɽΦϋϩάʖ͹߶͏‫ंޛ‬͹યҢয়ସ͹๏͗ɼऑ‫ܧݬױ‬ΓΕͲ͍Εɼ઴ंͲͺϒϫϨζϱ‫؂‬͹ CtH ݃߻͕Γ;‫خ‬࣯͹ϓΥωϩ‫ͳخ‬͹ CtH/S૮‫ݡ͗༽ࡠޕ‬ΔΗͱ͏Ζ͗ɼ‫Ͳंޛ‬ͺ‫ݡ‬ΔΗ͵͏ɽʤਦ̒ʥਦ̒ ΢ϨζΤϞʖϕϫϨόʖϩ༢಍ରৰഖͶΓΖίφϱ͹ؒ‫ݫ‬ൕԢ͹(a)कਫ਼੔෼ͶࢺΖયҢয়ସ͕Γ;(b)෯ΦψϱοΨϜʖਫ਼੔෼ͶࢺΖયҢয়ସͶ͕͜Ζඉ‫߻༙݃ڠ‬੓૮‫༽ࡠޕ‬͹ NCI ϕϫρφᮌᮦ⭉ᮙᢸᏊ⳦࠿ࡽ༢㞳ࡉࢀࡓኳ↛≀ JDQRFRORVVXVLQQ$ ࠾ࡼࡧ ' ࡢ㟁Ꮚ෇஧Ⰽᛶࢫ࣌ࢡࢺࣝ
ࣝᮌᮦ⭉ᮙᢸᏊ⳦ Ganoderma ࠿ࡽ༢㞳ࡉࢀࡓኳ↛≀ࡢከࡃࡣࠊࣛࣀࢫࢱࣥࢺࣜ࣌ࣉࢳࢻ࡟ᒓࡋࠊ⏕⌮άᛶࡀ᳨ウࡉࢀ࡚࠸ࡿࠋࢱ࢖⋤ᅜ༡㒊ࢡࣛࣅ┴ࡢᮌᮦ⭉ᮙᢸᏊ⳦ Ganoderma colossus ࠿ࡽኳ↛≀࡛࠶ࡿࣛࣀࢫࢱࣥࢺ
ࣜ࣌ࣉࢳࢻࡀᢳฟࡉࢀࠊ㸯㸱✀㢮ࡀ᪂ࡋ࠸໬ྜ≀࡛࠶ࡗࡓࠋࡑࡢ୰࡛ࠊganocolossusin A ࠾ࡼࡧ D㸦ᵓ㐀ᘧࢆᅗ㸳࡟♧ࡍ㸧ࡀ༢㞳ࡉࢀࡓࠋganocolossusin D ࡣࠊᙉຊ࡞ᢠ࣐ࣛࣜ࢔άᛶࢆᣢࡘࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࠋ

ࡇࢀࡽࡢศᏊᘧࡣࡑࢀࡒࢀ C32C44O6 ࠾ࡼࡧ C30C42O5 ࡛࠶ࡾࠊ┦ᑐ❧య㓄⨨࡟ࡘ࠸࡚ࡣ 1D ࠾ࡼࡧ 2D
NMR ࢫ࣌ࢡࢺࣝゎᯒ㸦C-H COSY(COrrelation SpectroscopY)࠾ࡼࡧ HMBC(1H-detected Multi-Bond heteronuclear
multiple quantum Coherence spectrum)㸧࡛Ỵࡵࡓࠋganocolossusin A ࠾ࡼࡧ D ࡢ⤯ᑐ❧య㓄⨨࡟ࡘ࠸࡚ࡣࠊMeCN⁐ᾮࡢ㟁Ꮚ෇஧Ⰽᛶ(ECD)ࢫ࣌ࢡࢺࣝ࡜ࠊGFN2-xTB ᣑᙇᙉ᮰⦡⤖ྜ༙⤒㦂ⓗ᪉ἲ࡟ࡼࡿ❧య㓄ᗙ᳨⣴࠾ࡼࡧ
DFT ἲ࡟ࡼࡿ᭱㐺໬ᵓ㐀࡟ᇶ࡙ࡃ TD-DFT ィ⟬(TD-ZB97X-D(SMD)/def2-TZVPP//B3LYP-D3BJ(SMD)/def2SVP)ࡢ⤖ᯝ࡜ẚ㍑ࡋ࡚ࠊࡑࡢ⤯ᑐ❧య㓄⨨ࢆỴࡵࡓࠋ- 220 -

OAc

21

20

18

19

9

1

3

O

O

8
7

10

2

5
4

17

13

24

H 23

12
11

22

14

16

27

25

OAc

26

O

OH

H
O

15
30

6

H

3
2

29

O

O

19
1
4

AcO

OH

10
5

H
28

29
28

ganocolossusin A

ganocolossusin Dᅗ㸳JDQRFRORVVXVLQ$ ࠾ࡼࡧ ' ࡢᵓ㐀ᘧ

4 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫⸨ۻ‬஭⛸㤿࣭ᕝᓥᜤᖹ࣭᳃⪷἞࣭6X<X&KHQJ࣭/X&KLD+DR࣭/LHQ&KLHQ,࣭6DJDU5DPX࣭&KHQ
&KLHQ7LHQࣂࢼࢪ࣒࢘ゐ፹࡟ࡼࡿ࢜ࣞࣇ࢕ࣥࡢ 㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬཯ᛂ࡟࠾ࡅࡿᐇ㦂ⓗ࣭⌮ㄽⓗ◊✲➨  ᅇ &6- ໬Ꮫࣇ࢙ࢫࢱ  ᖺ  ᭶ 㸫 ᪥ࠊ3㸦࢜ࣥࣛ࢖ࣥ㛤ദ㸧
մ2. ᳃ ⪷἞ࠊComputational Insights into Chemical Reactions related to Coordination Chemistryࠊ㘒య໬Ꮫ఍➨㸵㸮ᅇウㄽ఍ࠊ2020 ᖺ 9 ᭶ 28㸫30 ᪥,࢜ࣥࣛ࢖ࣥ㸦౫㢗ㅮ₇㸧
մ3. Attila Taborosi, Takahide Yamaguchi, Seiji Mori, Takamitsu Kohzuma, “The unfolding mechanism of Pseudoazurin
determined by Small Angle Neutron Scattering and Molecular Dynamics simulation”, 101st CSJ Annual Meeting, March
19-22 2021, Online

5 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
մ1. Hiroaki Mitsuizumi, Seiji Mori, Combined MD and QM/MM Investigations of Hydride Reduction of 5αDihydrotestosterone Catalyzed by Human 3α-Hydroxysteroid Dehydrogenase Type 3:Importance of Non-covalentInteractions, J. Phys. Chem. B, in press. DOI: 10.1021/acs.jpcb.1c01751
մ2. Hiroaki Murayama, Yoshito Heike, Kosuke Higashida, Yohei Shimizu, Nuttapon Yodsin, Yutthana Wongnongwa,
Siriporn Jungsuttiwong, Seiji Mori, Masaya Sawamura, Iridium̺Catalyzed Enantioselective Transfer Hydrogenation of
Ketones Controlled by Alcohol Hydrogen̺Bonding and sp3̺C-H Noncovalent Interactions, Advanced Synthesis &Catalysis, 2020, 362, 4655-4661. (VIP; Front Cover)մ3. Masahiko Isaka, Panida Chinthanom, Rattaket Choeyklin, Tuksaporn Thummarukcharoen, Pranee Rachtawee,
Malipan Sappan, Kitlada Srichomthong, Ryoma Fujii, Kyohei Kawashima, and Seiji Mori, Highly Modified Lanostane
Triterpenes from the Wood-Rot Basidiomycete Ganoderma colossus: Comparative Chemical Investigations of Naturaland Artificially Cultivated Fruiting Bodies and Mycelial Cultures, J. Nat. Prod. 2020, 83, 2066-2075.

- 221 -

  

Theoretical Studies on Electronic Propertiesof Functional Materials
SÉªÀÞeMä{ÛNÞ³z~j³[æPsá|ç ¹¾¶µ]xÎ¿ÃL-/452H@.I!r¥âÜcãt`}&7?I`}·Ù')ãt¯-a+*`tÂ*¹¾! Y"  Y¿ÃL;Åi
1

2,7-<@8GIgÈ)hÜc¥â
*

²

O

O

£D=:

N

N

N

N

N

/452H@.I*`t'" 2 -i+((¤È¤`t½O'

*rX190I½`tkf
NN

7B2;F¬vJãt7?I\å7B2;F¬v
O-ÊL¯'"Üc¯

O

*7?I

ãt¯Õ#*%ßtcuÒÁ
-w±Öµ¡ÓO

m 1. 2,7–<@8GI
52H@.I   .

O



£D=:;+*/4

 ¹¾©ÒÁ©
Ð/452H@.I`t   
-»

,

b

$Üc½

ã¦cu¬v-wÜcãU-¬v++è¥âãÑkf7B2;F¬v-whÜc½

ãt¯p-«gqãt7?I\å (ESR) 7B2;F¬v&^Å ESR ¬v')Üc½?Iãt¯Õ#y§à© 8%/<3*  o®½

ÜcØ¼¸Ï-RK

7

ÜcT7?Iãt¯qc

ÒÁ! *DXVVLDQ  AH3EC-W²Ê

 ¹¾
`t

E61F190I½

8%/<3* E61F190I½

Úc`t¢×

dÅVÍ-°nwL);Æ¢×ÑÄµ¢×-¨v*Ov*Üc½
QlßtcuÒÁ!o¯

7(65©')`tZÌ-*

(657B2;F¬v!º7?IrÝ

ä7?I¯*-*Å

rX190I½o¯. ´ËwÇ
Ô _­wÇÔ- 222 -

Å-%¨v

(+Q

>F

*7?IrÝ-¨v*Ov*ከඖ⣲ࢡࣛࢫࢱ࣮ࡢ㉥እゎ㞳ศගࡢࡓࡵࡢ㉥እࢫ࣌ࢡࢺࣝࡢண
Prediction of infrared spectra of multi-element clusters
for infrared photodissociation spectroscopy‫ۑ‬ᕤ⸨ ⪽㸪ᒣཱྀ 㞞ே㸦ᮾி኱Ꮫ㝔⥲ྜᩥ໬㸧1◊✲┠ⓗ㔠ᒓࢡࣛࢫࢱ࣮ୖ࡛ࡢゐ፹཯ᛂࡢ཯ᛂᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚ࠊ᪼

⬺㞳ᐇ㦂ࠊ㉥እゎ㞳ศගᐇ㦂࡞࡝ࡢᐇ㦂࡜㔞Ꮚ໬Ꮫィ⟬ࢆే⏝ࡋ࡚◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ㔠ᒓࢡࣛࢫࢱ࣮࡜⿕ゐ፹ศᏊࡢ」ྜయࡢᵓ㐀ࢆỴᐃࡍࡿࡓࡵ࡟ࠊ㉥እゎ㞳ศගᐇ㦂࡛㉥እࢫ࣌ࢡࢺࣝࢆ

ᐃࡋࠊGaussian09 ࡟ࡼࡿ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ண

ࡉࢀࡓࢫ࣌ࢡࢺࣝࣃࢱ࣮ࣥ࡜ẚ㍑ࡍࡿࡇ࡜࡛ᵓ㐀ࡢỴᐃࢆ࠾ࡇ࡞ࡗࡓࠋ

3◊✲ᡂᯝ௒ᮇࡣࠊග໬Ꮫ⣔ϩࡢ୰ᚰᵓ㐀࡜ྠ୍⤌ᡂࢆᣢࡘ CaMnO5 ࢡࣛࢫࢱ࣮࢝ࢳ࢜ࣥ࡟ỈศᏊࡀ྾╔ࡋࡓ

CaMnO5(H2O)n+ (n = 1- 4)࡞࡝ࡢᵓ㐀᥈⣴ࢆ࠾ࡇ࡞ࡗ࡚ࠊᚓࡽࢀࡓᏳᐃᵓ㐀࡟ࡘ࠸࡚᣺ືᩘィ⟬ࡋ㉥እࢫ࣌ࢡࢺࣝࣃࢱ࣮ࣥࢆసᡂࡋ࡚ᐇ㦂⤖ᯝ࡜ẚ㍑ࡋࡓࠋ୍౛࡜ࡋ࡚ CaMnO5(H2O)+࡛ࡣࠊ㉥እゎ㞳ࢫ࣌ࢡࢺࣝ࡜㉥እࢫ࣌ࢡࢺࣝࣃࢱ࣮ࣥࢆẚ㍑ࡋࡓ࡜ࡇࢁࠊỈศᏊࡀゎ㞳྾╔ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡉࡽ࡟ࠊࢡࣛࢫࢱ࣮ୖ࡛
ࡢỈศᏊࡢ OH ⤖ྜࡢゎ㞳ࡢ࢚ࢿࣝࢠ࣮㞀ቨࢆィ⟬ࡋࡓ࡜ࡇࢁศᏊ྾╔≧ែ࡟ᑐࡋ+7.7 J mol-1 ࡛࠶ࡗࡓࠋࡇ
ࢀࡣ⇕࢚ࢿࣝࢠ࣮࡛ᐜ᫆࡟஌ࡾ㉺࠼ࡽࢀࡿ࡜ண᝿ࡉࢀࡿࡢ࡛ࠊ㉥እゎ㞳ศගᐇ㦂ࡢ⤖ᯝࢆㄝ࡛᫂ࡁࡿࡇ࡜ࡀ
ࢃ࠿ࡗࡓࠋ

4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
x‫ۻ‬Zhou et al., Adsorption forms of Water on Manganese Oxide Clusters investigated by Infrared
Photodissociation Spectroscopy㸦 ᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍㸪࢜ࣥࣛ࢖ࣥ㸪2021 ᖺ 3 ᭶㸧xZhang et al., Adsorption forms of NO on Rh5Ir cationic clusters investigated by the infrared multiple
photon dissociation spectroscopy 㸦᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍㸪࢜ࣥࣛ࢖ࣥ㸪2021 ᖺ 3 ᭶㸧x5‫ۻ‬ᒣཱྀ࡯࠿, IX ᪘ࢡࣛࢫࢱ࣮ࡢ NO ゎ㞳⬟(᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍㸪࢜ࣥࣛ࢖ࣥ㸪2021 ᖺ 3 ᭶㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
x‫ۻ‬Yamaguchi et al., , Oxophilicity as a Descriptor for NO Cleavage Efficiency over Group IX Metal
Clusters, J. Phys. Chem. Lett., 11(11), 4408-4412 (2020).

x‫ۻ‬Mafuné et al., Substitution of O with a Single Au Atom as an Electron Acceptor in Al Oxide Clusters, J.
Phys. Chem. A, 124(37), 7511-7517 (2020).

x‫ۻ‬Zhou et al., , Dissociative Adsorption of Water on CaMn4O5 Cationic Clusters, in preparation.

- 223 -

㔜ཎᏊࢆྵࡴ໬ྜ≀ࡢᇶᗏ࣭ບ㉳㟁Ꮚ≧ែ࡜ศᏊ≀ᛶ࡟㛵ࡍࡿ㔞Ꮚ໬Ꮫィ⟬
4XDQWXP&KHPLFDO&DOFXODWLRQIRU*URXQGDQG([FLWHG(OHFWURQLF
6WDWHVDQG0ROHFXODU3URSHUWLHVRI0ROHFXOHV&RQWDLQLQJ+HDY\(OHPHQWVżἼ⏣ 㞞ᙪࠊ୰㇂ ┤㍤ࠊ㜿㒊 ✨㔛ࠊ௒ᮧ ✨ࠊከ⏣ ᐓࠊ∵ᑿ ஧㑻ࠊ<L-XQࠊᐑᮏ ඃᘺࠊ6DOPDKDPLQDWLࠊ0D=KLIHQJࠊబ⸨ ᭷ử␃ࠊྜྷ⏣ ⋹ࠊ㐨᫂ Ṋಙࠊ஭ୖ ᝆ㈗ࠊᮌୗ ⓡྐࠊᐩ⏣ ኱ᶞ㸦ᮾி㒔❧኱Ꮫ㸧 ◊✲┠ⓗࠊෆᐜ┦ᑐㄽࢆ⪃៖ࡋࡓ㟁Ꮚ≧ែࡢ㧗⢭ᗘ࣭኱つᶍィ⟬ࣉࣟࢢ࣒ࣛࡢ㛤Ⓨཬࡧࠊࡑࢀࡽ࡟㛵㐃ࡍࡿୗ㏙ࡢ◊✲ࢸ࣮࣐ࢆ㐍ࡵࡓࠋ 㟼 㟁 ሙ ୗ ࡟ ࠾ ࡅ ࡿ 㕲 ࢜ ࢟ ࢯ ࣏ ࣝ ࣇ ࢕ ࣜ ࣥ ࡟ ࡼ ࡿ ࢜ ࣞ ࣇ ࢕ ࣥ ࡢ ࢚ ࣏ ࢟ ࢩ ໬ ཯ ᛂ ࡢ ィ ⟬ ゎᯒ ⨨ ᥮ ࣋ ࣥ ࢮ ࣥ ࡢ   &105 ໬ Ꮫ ࢩ ࣇ ࢺ ࡢ ⮬ ↛ ᦤ ື ㌶ 㐨 ࡟ ࡼ ࡿ ゎ ᯒ  ⮬ ↛ ㌶ 㐨 ᦤ ື ἲ ࡟ ࡼ ࡿ 㔠 ᒓ ⾲ 㠃 ࡛ ࡢ ࣛ ࣐ ࣥ ྾ ཰ ᙉ ᗘ ࡢ ቑ ኱ ࡟ 㛵 ࡍ ࡿ ⌮ ㄽ ◊ ✲  㟁 ᅽ ༳ ຍ ࡟ ࡼ ࡿ ศ Ꮚ ෆ &7 ≧ ែ ࡢ ฟ ⌧ ࡜ ࠊࡑ ࢀ ࡟ ⏤ ᮶ ࡍ ࡿ ኱ ࡁ ࡞ 㟼 ⓗ 㟁 Ꮚ ┦ 㛵 ຠ ᯝ ࢆ ᣢࡘศᏊ⣔ࡢ⌮ㄽ◊✲  ᡂ ศ ┦ ᑐ ㄽ ἲ ࢆ ⏝ ࠸ ࡓ ࢘ ࣛ ࣥ 㘒 య ࡢ ྠ ఩ య ศ ู ࡟ 㛵 ࡍ ࡿ ⌮ ㄽ ◊ ✲  ,U5X3G ࢆ ྵ ࡴ ᭷ ᶵ 㔠 ᒓ ゐ ፹ ࡢ ග 㔜 ྜ ཯ ᛂ ࡢ ィ ⟬ ゎ ᯒ  ࢳ ࢱ ࣥ 㘒 య ࠊ ࣂ ࢼ ࢪ ࢘ ࣒ 㘒 య ࡟ ࡼ ࡿ 㔜 ྜ ཯ ᛂ ࡢ ィ ⟬ ゎ ᯒ  㑄 ⛣ 㔠 ᒓ ࢼ ࣀ ࢡ ࣛ ࢫ ࢱ ࣮ ࡢ ᵓ 㐀 ࠊ ࠾ ࡼ ࡧ 㟁 Ꮚ ≧ ែ ࡢ ⌮ ㄽ ◊ ✲  ᫍ 㛫 ị ⾲ 㠃 ࡟ ࠾ ࡅ ࡿ ໬ Ꮫ 㐍 ໬ ࡟ 㛵 ࡍ ࡿ ➨ ୍ ཎ ⌮ ࢩ ࣑ ࣗ ࣞ ࣮ ࢩ ࣙ ࣥ  ◊✲᪉ἲࠊィ⟬᪉ἲࢸ࣮࣐  ࡟ࡘ࠸࡚ࡣ +21'2 ࢆ࣮࣋ࢫ࡟ᨵⰋࡋࡓᮏ◊✲ᐊࡢࣉࣟࢢ࣒ࣛࠊࢸ࣮࣐  ࡟ࡘ࠸࡚ࡣ
1:&KHPࠊࢸ࣮࣐  ࡟ࡘ࠸࡚ࡣ 9$63 ࡜ᮏ◊✲ᐊࡢᶵᲔᏛ⩦ࣉࣟࢢ࣒ࣛࠊࢸ࣮࣐  ࡟ࡘ࠸࡚ࡣ ',5$&ࠊࡑࡢ௚ࡢࢸ࣮࣐࡟ࡘ࠸࡚ࡣ *DXVVLDQࠊ*DXVVLDQ ࢆ฼⏝ࡋ࡚◊✲ࢆ⾜ࡗࡓࠋ   ◊✲ᡂᯝୖグ◊✲࡟ᑐࡋࠊ୺࡟  ᖺᗘ࡟◊✲㐍ᤖࡀ࠶ࡗࡓࢸ࣮࣐ ࠊࠊࠊ ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ
⨨᥮࣋ࣥࢮࣥࡢ &±105 ໬Ꮫࢩࣇࢺࡣࠊࡑࡢ⨨᥮ᇶࡢ㐪࠸ࢆ཯ᫎࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᐇ㝿࡟ࠊ㟁Ꮚ౪୚ᛶࡢ࢔࣑ࣀᇶࡀ⨨᥮ࡋࡓ࢔ࢽ࡛ࣜࣥࡣࠊ㟁Ꮚ㇏ᐩ࡞࢜ࣝࢺࠊࣃࣛ఩ࡢⅣ⣲ࡢ໬Ꮫࢩࣇࢺࡣ↓⨨᥮࣋ࣥࢮࣥࢆᇶ‽࡟ࡋ࡚㧗☢ሙࢩࣇࢺࡍࡿࠋྠᵝ࡟ࠊ㟁Ꮚồᘬᛶࡢࢽࢺࣟᇶࡀ⨨᥮ࡋࡓࢽࢺࣟ࣋ࣥࢮࣥ
࡛ࡣࠊ㟁Ꮚ୙㊊࡞࢜ࣝࢺࠊࣃࣛ఩ࡢⅣ⣲ࡢ໬Ꮫࢩࣇࢺࡣప☢ሙࢩࣇࢺࡍࡿࡇ࡜ࡀண᝿ࡉࢀࡿࡀࠊ࢜ࣝࢺ
఩ࡢⅣ⣲࡛ࡣ㏫ࡢഴྥࢆ♧ࡍ㸦)LJ㸧ࠋࢸ࣮࣐  ࡛ࡣࠊࡇࡢഴྥࢆゎᯒࡋࡓࠋ

- 224 -

ゎᯒࡢ⤖ᯝࠊᚓࡽࢀࡓ⮬↛ᦤື㌶㐨ࡢഴྥࡣ࡝ࡢศᏊ࡛ࡶ㢮ఝࡋ࡚࠾ࡾࠊ໬Ꮫࢩࣇࢺ࡟ᐤ୚ࡍࡿࡢࡣ
)LJ ࡟♧ࡍ  ࡘࡢ㌶㐨ᑐ㸦 V [ ± S [  V \ ± S \ 㸧ࡢࡳ࡜࠸࠺ࡇ࡜ࡀศ࠿ࡗࡓࠋࡉࡽ࡟ࠊ⨨᥮ᇶ࡟ࡼࡿ໬Ꮫ
ࢩࣇࢺࡢኚ໬ࡣࠊྛ㌶㐨ࡢඹ㬆᰾㏆ഐࡢ㟁Ꮚࡢከᐻ࡜㌶㐨ᑐࡢ㌶㐨࢚ࢿࣝࢠ࣮ᕪ࡟౫Ꮡࡋࠊ๓⪅ࡣ⨨᥮ᇶࡢ㟁Ꮚ౪୚ᛶ࠾ࡼࡧ㟁Ꮚồᘬᛶࡢഴྥ࡜୍⮴ࡋࡓࠋ⤖ᯝ࡜ࡋ࡚ࠊࢽࢺࣟ࣋ࣥࢮࣥࡢ࢜ࣝࢺ఩ࡢⅣ⣲ࡢప☢ሙࢩࣇࢺࡣࠊ V [ ± S [ ㌶㐨ᑐࡢ㌶㐨࢚ࢿࣝࢠ࣮ᕪࡢῶᑡ࡟⏤᮶ࡍࡿࠋ








)LJ ↓⨨᥮࣋ࣥࢮࣥࢆᇶ‽࡟ࡋࡓ⨨᥮࣋ࣥࢮࣥࡢ &±105 ໬Ꮫࢩࣇࢺ



)LJ ࣋ࣥࢮࣥࡢ⮬↛ᦤື㌶㐨㸸༨᭷㌶㐨㸦ᕥ㸧࡜௬᝿㌶㐨㸦ྑ㸧㔠ᒓࢼࣀ⢏Ꮚ࡟྾╔ࡋࡓศᏊࡢ ,5 ࢫ࣌ࢡࢺࣝࡣࡑࡢ྾╔ࢧ࢖ࢺࡢ㐪࠸ࢆ཯ᫎࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ)LJ ࡟♧ࡍ 3G ࢼࣀ⢏Ꮚ࡟྾╔ࡋࡓ &2 ࡛ࡣࠊᚓࡽࢀࡿ &2 ఙ⦰ࡢ᣺ືᩘࡣྠ⛬ᗘ࡛࠶ࡿࡀࠊ྾཰
ᙉᗘࡀⴭࡋࡃ␗࡞ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࢸ࣮࣐  ࡛ࡣࠊ3G ࢼࣀ⢏Ꮚ࡟྾╔ࡋࡓ㉥እ྾཰ࢫ࣌ࢡࢺࣝࡢ
ゎᯒࢆ⾜࠸ࠊࡑࡢ⤖ᯝࠊ୧ࣔࢹࣝ࡜ࡶ࡟  ࡘࡢ㌶㐨ᑐ㸦 V ± V  S ± S 㸧ࡀ྾཰ᙉᗘ࡟኱ࡁࡃᐤ୚ࡋ࡚
࠸ࡿࡀࠊDWRS ࣔࢹ࡛ࣝࡣ &2 ㏆ഐ࡟㟁Ꮚࡀᒁᅾ໬ࡋ࡚࠸ࡿࡢ࡟ᑐࡋࠊORZFRRUGLQDWH ࣔࢹ࡛ࣝࡣ 3G ࢡࣛࢫࢱ࣮඲య࡟㟁Ꮚࡀ㠀ᒁᅾ໬ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸦)LJ㸧ࠋࡇࡢഴྥࡣ &2 ఙ⦰࡟ᑐࡍࡿ඲㟁Ꮚࡢᕪ㟁Ꮚᐦᗘ࡟ࡶ⾲ࢀࠊ୧⪅ࡢ㐪࠸ࡣ &2 ఙ⦰࡟ࡼࡗ࡚⏕ࡌࡿ㟼㟁࣏ࢸࣥࢩࣕࣝࡢኚ໬ࡀ 3G ⾲㠃࡟୚࠼ࡿᙳ㡪ࡢ㐪࠸࡟⏤᮶ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ






)LJ3G ࢼࣀ⢏Ꮚ࡟྾╔ࡋࡓ &2)LJ&2RQ3G ࢡࣛࢫࢱ࣮ࡢ⮬↛ᦤື㌶㐨㸸
DWRS㸦ୖ㸧࡜ ORZFRRUGLQDWH㸦ୗ㸧ࣔࢹࣝࢸ࣮࣐  ࡛ࡣࠊ㛝࢘ࣛࣥ㖔࡟࠾ࡅࡿྠ఩యศูࡢᶵᵓࢆࠊ➨୍ཎ⌮ィ⟬ࢆ⏝࠸࡚ゎᯒࡋࡓࠋࣂࢡࢸࣜ࢔ࡀ௓ࡍࡿ  ౯࢘ࣛࣥ 8 9, ࡢ  ౯࢘ࣛࣥ 8 ,9 ࡬ࡢ⏕≀ᛶ㑏ඖ࡛ࡣࠊ8 ,9 ࡟㔜࠸ྠ఩య 8 ࡀศูࡉࢀࡿࡀࠊ
㠀⏕≀ᛶ㑏ඖ࡛ࡣྠ఩యศูࡢഴྥࡀ␗࡞ࡿࠋࡇࡢ஦ᐇࢆ⏝࠸࡚ࠊྂ௦࡟ሁ✚ࡋࡓᆅ㉁୰ࡢ࢘ࣛࣥྠ఩యẚ࠿ࡽᙜ᫬ࡢ⏕≀άືࢆ⌮ゎࡍࡿࡇ࡜ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ⏕≀ᛶ࡜㠀⏕≀ᛶࡢ㑏ඖ࡛ྠ఩యศูࡢഴ
ྥࡀ␗࡞ࡿཎᅉࡣゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋ⏕≀ᛶ㑏ඖ࡛ࡣ㠀ᬗ㉁ 8 ,9 ࠊ㠀⏕≀ᛶ㑏ඖ࡛ࡣ㛝࢘ࣛࣥ㖔 82 ⤖ᬗࡀ⏕ᡂࡍࡿࡓࡵࠊࡇࡢ⏕ᡂ≀ࡢ㐪࠸ࡀྠ఩యศูࡢഴྥ࡟ᙳ㡪ࢆ୚࠼࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ㠀⏕≀ᛶ㑏ඖ࡟↔Ⅼࢆᙜ࡚ࠊ཯ᛂ≀ࡢ 82 &2 ࡜⏕ᡂ≀ࡢ 82 ⤖ᬗ㛫࡛ࡢ⇕ⓗᖹ⾮ࢆ௬ᐃࡋ࡚ྠ఩య

- 225 -

ศูಀᩘH ࢆィ⟬ࡋࠊศูᶵᵓࢆ㆟ㄽࡋࡓࠋH ࡣ᰾య✚㡯 OQ.QY ࡜᰾㉁㔞㡯 OQ.QP ࡢ࿴࡜ࡋ࡚㏆ఝ࡛ࡁࠊH ࡀṇࡢ್ࢆࡶࡘ᫬ 8 ࡀ 8 ,9 ࡟ศูࡉࢀࡿࡇ࡜ࢆព࿡ࡍࡿࠋᮏ◊✲࡛ࡣ OQ.QP ࡣ 9$63 ࢆ⏝࠸࡚ㄪ࿴᣺ື
ᩘࢆồࡵ࡚ィ⟬ࡋࡓࠋ୍᪉ࠊOQ.QY ࡢィ⟬࡛ࡣཎᏊ᰾㏆ഐࡢ㟁Ꮚ≧ែࡀ㔜せ࡜࡞ࡿࡓࡵࠊ┦ᑐㄽຠᯝࡀ㢧ⴭ࡜࡞ࡿࠋࡋ࠿ࡋࠊ⌧≧࡛ࡣ㧗⢭ᗘ࡟┦ᑐㄽຠᯝࢆྲྀࡾ㎸ࢇࡔ࿘ᮇቃ⏺⣔ࡢィ⟬ᡭἲࡣ☜❧ࡉࢀ࡚࠸࡞࠸ࠋࡑࡇ
࡛ࠊඛ⾜◊✲࡛ᥦ᱌ࡉࢀࡓࠊ࿘ᮇቃ⏺ィ⟬࠾ࡼࡧ┦ᑐㄽィ⟬࡟ࡼࡾồࡵࡓཎᏊ᰾ୖࡢ㟁ᏊᐦᗘU  ࡢ┦㛵㛵ಀ࠿ࡽ OQ.QY ࢆ⟬ฟࡍࡿ᪉ἲࢆ᥇⏝ࡋࡓࠋ࡞࠾ࠊᮏ◊✲࡟࠾ࡅࡿ OQ.QY ࡢィ⟬࡛ࡣࠊ࿘ᮇቃ⏺ィ⟬ࡣ $%,1,7ࠊ
┦ᑐㄽィ⟬ࡣ ',5$& ࢆ⏝࠸࡚⾜ࡗࡓࠋU  ࡢ┦㛵㛵ಀࢆᚓࡿࡓࡵ࡟ࠊ ✀ࡢ࢘ࣛࣥศᏊ࡟ᑐࡋ࡚U  ࢆィ⟬ࡋࡓࠋᚓࡽࢀࡓ┦㛵㛵ಀ࠾ࡼࡧࣇ࢕ࢵࢸ࢕ࣥࢢ࡟⏝࠸ࡓศᏊ✀ࢆ )LJ ࡟♧ࡍࠋ








)LJ$%,1,7 ࡜ ',5$& ࡛ồࡵࡓ ȡ  ࡢ┦㛵㛵ಀ ᕥ ࡜ࣇ࢕ࢵࢸ࢕ࣥࢢ࡛⏝࠸ࡓ໬Ꮫ✀ ྑ $%,1,7 ࡜ ',5$& ࡛ồࡵࡓU  㛫ࡢ┦㛵ಀᩘࡣ  ࡛࠶ࡗࡓࠋࡇࡢ┦㛵ࢆ⏝࠸࡚ࠊ$%,1,7 ࡛ồࡵࡓ 82 ⤖ᬗࡢU  ࢆ OQ.QY ࡟᥮⟬ࡍࡿ࡜ࠊÅ࡜ồࡲࡗࡓࠋ୍᪉ࠊㄪ࿴᣺ືᩘࢆࡶ࡜࡟ OQ.QP ࢆィ⟬ࡍࡿ࡜ࠊÅ࡜ồࡲࡗࡓࠋᚓࡽࢀࡓ OQ.QY ࡜ OQ.QP ࡢ࿴࡜ࡋ࡚H ࢆィ⟬ࡍࡿ࡜ࠊÅ࡜ồࡲࡗࡓࠋࡇࢀࡣ⏕ᡂ≀ࢆ㠀ᬗ㉁ 8 ,9 ࡜ࡋ࡚ィ⟬ࡋࡓ⏕≀ᛶ㑏ඖ࡟࠾ࡅࡿH ࡢィ⟬್ H Å ࡜ྠ⛬ᗘ࡛࠶ࡿࠋࡋࡓࡀࡗ࡚ࠊ
⏕≀ᛶ࡜㠀⏕≀ᛶ㑏ඖࡢྠ఩యศูࡢᶵᵓࡢ㐪࠸ࡣࠊ⏕ᡂ≀ࡢ㟁Ꮚ≧ែ࡛ࡣㄝ࡛᫂ࡁ࡞࠸ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࢸ࣮࣐  ࡛ࡣࠊඹྠ◊✲⪅ࡢࢢ࣮ࣝࣉ࡛ྜᡂࡉࢀࡓࢳࢱࣥࠊࣂࢼࢪ࣒࢘ࠊࢽ࢜ࣈ㘒య࡟ࡼࡗ࡚ゐ፹ࡉࢀࡿ㔜ྜ཯ᛂ࡟ࡘ࠸࡚ࠊ⁐ᾮ୰άᛶ✀ࡢ ;$1(6 ࢫ࣌ࢡࢺࣝ࡜཯ᛂᶵᵓࡢィ⟬ゎᯒࢆ⾜ࡗࡓࠋࡇࢀࡽࡢ㘒యゐ፹ࡣࠊ⁐ᾮ୰࡛ຓゐ፹࡜ࡋ࡚ຍ࠼ࡽࢀࡓ࢔࣑ࣝࢽ࣒࢘໬ྜ≀࡜」ྜయࢆᙧᡂࡋࠊάᛶ࡞๓㥑㘒యࡀ⏕ᡂࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋඹྠ◊✲⪅ࡢ㒔❧኱࣭㔝ᮧࢢ࣮ࣝࣉ࡛ࡣࠊ; ⥺྾཰ศගἲࢆ฼⏝ࡋ࡚཯ᛂάᛶ✀ࡢほほࢆ⾜ࡗ࡚࠸ࡿࡀࠊ྾཰➃ࡢ❧ࡕୖࡀࡾ㒊ศ࡟ほࡉࢀࡿ⫪ࣆ࣮ࢡࡸ๓྾཰➃㡿ᇦ࡟ࡉࢀࡿ」㞧࡞ᚤ⣽ᵓ㐀㸦;$1(6㸧ࡢᖐᒓࡀၥ㢟࡜࡞ࡗ࡚࠸ࡓࠋ







)LJ ✀ࠎࡢࣂࢼࢪ࣒࢘㘒యࡢ . ➃྾཰ࢫ࣌ࢡࢺࣝ㸦ᕥ㸸ᐇ㦂ࠊ୰ኸ㸸ィ⟬ࠊྑ㸸ࣆ࣮ࢡ఩⨨ࡢ┦㛵㸧- 226 -

ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ7'')7 ィ⟬ࢆ౑ࡗ࡚✀ࠎࡢࢳࢱࣥࠊࣂࢼࢪ࣒࢘ࠊࢽ࢜ࣈ㘒యࡢ . ➃྾཰ࢫ࣌ࢡ
ࢺࣝࡢィ⟬ゎᯒࢆ⾜࠸ࠊ⁐ᾮ୰ࡢ ;$1(6 ࢫ࣌ࢡࢺࣝࡢᖐᒓࢆ⾜ࡗࡓࠋ7'')7 ィ⟬࡛ࡣෆẆ㌶㐨ࡢグ㏙ࡀ୙༑ศ࡛࠶ࡿࡓࡵࠊィ⟬ࢫ࣌ࢡࢺࣝࡢࣆ࣮ࢡ఩⨨࡟ࡣ኱ࡁ࡞⣔⤫ㄗᕪ㸦⣙  H9㸧ࡀ⌧ࢀࡿࡀࠊࡇࢀ
ࢆ༢⣧࡞࢚ࢿࣝࢠ࣮ࢩࣇࢺ࡟ࡼࡗ࡚⿵ṇࡍࡿࡇ࡜࡛ࠊィ⟬ࢫ࣌ࢡࢺࣝࡣᐇ㦂ࢫ࣌ࢡࢺࣝ࡜㠀ᖖ࡟Ⰻࡃ୍⮴ࡋࡓ㸦)LJ 㸧ࠋࡉࡽ࡟ࠊ཯ᛂゎᯒ࡟ࡼࡗ࡚ᚓࡽࢀࡓάᛶ✀ࡢೃ⿵ᵓ㐀࡟ࡘ࠸࡚ ;$1(6 ࢫ࣌ࢡࢺࣝࢆ
ィ⟬ࡋࠊゐ፹㸫ຓゐ፹ࡢ」ྜయᵓ㐀ࡀゐ፹άᛶ✀࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ  Ⓨ⾲ᐇ⦼㐨᫂Ṋಙ HWDO ศᏊ⛉Ꮫ఍࢜ࣥࣛ࢖ࣥウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥ࠊ࢜ࣥࣛ࢖ࣥ  ᮌୗⓡྐ HWDO ศᏊ⛉Ꮫ఍࢜ࣥࣛ࢖ࣥウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥ࠊ࢜ࣥࣛ࢖ࣥ  ᐩ⏣኱ᶞ HWDO ศᏊ⛉Ꮫ఍࢜ࣥࣛ࢖ࣥウㄽ఍ࠊ ᖺ  ᭶  ᪥ ᪥ࠊ࢜ࣥࣛ࢖ࣥ =0DHWDO ศᏊ⛉Ꮫ఍࢜ࣥࣛ࢖ࣥウㄽ఍ࠊ ᖺ ᭶  ᪥ ᪥ࠊ࢜ࣥࣛ࢖ࣥ  Ἴ⏣㞞ᙪ ,4&( 㔞Ꮚ໬Ꮫ᥈⣴ㅮ₇఍ ࠕ㔞Ꮚ໬Ꮫ࡛᥈ࡿ໬Ꮫࡢ᭱ඛ
➃ࠖࠊ ᖺ  ᭶  ᪥ࠊ࢜ࣥࣛ࢖ࣥ  㜿㒊✨㔛 HW DO  ᖺᗘ᪥ᮏᆅ⌫໬Ꮫ఍ᖺ఍ࠊ ᖺ  ᭶ ᪥ ᪥ࠊ࢜ࣥࣛ࢖ࣥ  బ⸨᭷ử␃ HW DO ⇃ྲྀ◊✲఍ࠕ࢔ࢡࢳࣀ࢖ࢻ≀ᛶ໬Ꮫ࡜ࡑࡢᛂ⏝ࠖࠊ ᖺ ᭶  ᪥ࠊ࢜ࣥࣛ࢖ࣥ  㜿㒊✨㔛 HWDO ➨  ᅇྠ఩య⛉Ꮫ◊✲఍ࠊ ᖺ  ᭶  ᪥ࠊ࢜ࣥࣛ࢖ࣥ  బ⸨᭷ử␃ HWDO ➨  ᅇྠ఩య⛉Ꮫ◊✲఍ࠊ ᖺ  ᭶  ᪥ࠊ࢜ࣥࣛ࢖ࣥ  బ⸨᭷ử␃ HWDO ᪥ᮏ໬Ꮫ఍➨  ᅇ᫓Ꮨᖺ఍ࠊ ᖺ  ᭶  ᪥ ᪥ࠊ࢜ࣥࣛ࢖ࣥ  ᕷᕝ⤮⌮ HWDO ᪥ᮏ໬Ꮫ఍➨  ᅇ᫓Ꮨᖺ఍ࠊ ᖺ  ᭶  ᪥ ᪥ࠊ࢜ࣥࣛ࢖ࣥ  ྜྷ⏣⋹ HW DO ᪥ᮏ໬Ꮫ఍➨  ᅇ᫓Ꮨᖺ఍ࠊ ᖺ  ᭶ ᪥ ᪥ࠊ࢜ࣥࣛ࢖ࣥ $6DWRHWDO*ROGVFKPLGWYLUWXDO-XQ2QOLQH11DNDWDQLHWDO-DSDQ1RUZD\%LODWHUDO6\PSRVLXPIURP)XQGDPHQWDO&KHPLVWU\WR3RURXV0DWHULDOV7KHRU\DQG([SHULPHQW
$XJ2QOLQH0$EH)XQGDPHQWDO6FLHQFHV 4XDQWXP7HFKQRORJLHVXVLQJ$WRPLF6\VWHPV
6HS2FW2QOLQH0$EH<DPDGD&RQIHUHQFH/;;,,7KHWK$VLD3DFLILFFRQIHUHQFHRQ)HZ%RG\SUREOHPVLQ3K\VLFV $3)% 0DU.DQD]DZDEXQNDKDOO.DQD]DZD-DSDQ    ฟ∧ᐇ⦼մ-<LHWDO3K\V&KHP&KHP3K\V  
մ=0DHWDO%XOO&KHP6RF-SQ    +6X]XNLHWDO&KHP0DWHULDOV    
0$EHHWDO0RO3K\V  H  
մ6DOPDKDPLQDWLHWDO$&62PHJD  ±  
06DLWRHWDO2UJDQRPHWDOOLFV    մ-<LHWDO2UJDQRPHWDOOLFV    մ00L\DPRWRHWDO&RPSXW&KHP    մ00L\DPRWRHWDO0RO3K\V  H  0)XNXL,QRUJ&KHP     ͤἼ⏣ඛ⏕
0.DMLWDHWDO-3K\V%$W0RO2SW3K\V    
963UDVDQQDDHWDO6\PPHWU\%DVHO    
մ..RLGHHWDO2UJDQRPHWDOOLFV    մ/=KDRHWDO-&KHP3K\V    - 227 -

⏕య㉸ศᏊࡢ❧యᵓ㐀ኚ໬࡜ᶵ⬟
&RQIRUPDWLRQDOFKDQJHRIELRORJLFDOVXSUDPROHFXOHVDQG
LWVUHODWLRQWRIXQFWLRQV‫ۑ‬໭ᑿ ᙲᮁࠊ➉ᮧ ࿴ᾈࠊ75$13KXRF'X\ࠊ㮚⩚ ೺୍㑻ࠊ62%(+0RKDPHG0DU]RXNࠊᐑ⃝ ెᕼࠊᮌෆ 㱟அ௓ࠊ7HJDU1XUZDK\X:LMD\Dࠊᑿᕝ ᣅᕭࠊᖹ ᝆኴࠊ୕ᰨ ᾴ㞞㸦ᮾᕤ኱⏕࿨⌮ᕤ㸧◊✲┠ⓗࠊෆᐜ
ࢼࣀ࣓࣮ࢺࣝࢧ࢖ࢬࡢศᏊᶵᲔ࡛࠶ࡿ⺮ⓑ㉁ࡸࡑࢀࡽࡢ㞟ྜయ࡛࠶ࡿ⏕య㉸ศᏊࡣࠊ⏕యෆ࡛❧యᵓ㐀ኚ໬ࢆᕦࡳ࡟฼⏝ࡋ࡚ᶵ⬟ࡍࡿࠋᮏ⏦ㄳㄢ㢟࡛ࡣࠊ⺮ⓑ㉁ࡸ⺮ⓑ㉁」ྜయ⣔ࡢ❧యᵓ㐀ኚ໬࡜ᶵ⬟࡜ࡢ㛵ಀࢆศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾゎᯒࡋࠊ⏕࿨⌧㇟ࡢ⣲㐣⛬ࢆྖࡿ⏕య㉸ศᏊࡢศᏊ⛉Ꮫⓗ࡞ືసཎ⌮ࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ᣦࡋ࡚࠸ࡿࠋ ᖺᗘࡣୗグࡢ  ࡘࡢࢸ࣮࣐ࢆ୰ᚰ࡟ィ⟬ࢆ⾜ࡗࡓࠋ  ࡘ┠ࡢㄢ㢟࡛࠶ࡿࠕ3D&60'060 ἲࢆ⏝࠸ࡓ⺮ⓑ㉁㸫⺮ⓑ㉁」ྜయࡢ㏿ᗘᐃᩘホ౯࡛ࠖࡣࠊᡃࠎࡢ
ࢢ࣮ࣝࣉ࡛㛤Ⓨࡋࡓ୪ิ࢝ࢫࢣ࣮ࢻ㑅ᢥศᏊືຊᏛἲ㸦3DUDOOHO &DVFDGH 6HOHFWLRQ 0ROHFXODU '\QDPLFV
3D&60'㸧࠾ࡼࡧ࣐ࣝࢥࣇ≧ែࣔࢹࣝ㸦0DUNRY6WDWH0RGHO060㸧ࢆ⤌ࡳྜࢃࡏࡓ 3D&60'060 ἲࢆ⏝࠸࡚ࠊ⺮ⓑ㉁㸫⺮ⓑ㉁」ྜయࡢ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮࠾ࡼࡧゎ㞳㏿ᗘᐃᩘࡢホ౯ࢆ㐍ࡵ࡚࠸ࡿࠋ ᖺᗘࡣࠊࢡ
ࢸࣜ࢔ࡢࣜ࣎᰾㓟ศゎ㓝⣲ %DUQDVH ࡜㜼ᐖ๣࡛࠶ࡿ %DUVWDU ࡢ」ྜయࠊ๰⸆ᶆⓗ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿ 3'
3URJUDPPHGGHDWK&' ࠾ࡼࡧࡑࡢࣜ࢞ࣥࢻ⺮ⓑ㉁࡜ࡋ࡚▱ࡽࢀࡿ 3'/ 3'OLJDQG ࡀᙧᡂࡍࡿ」ྜ
యࢆᑐ㇟࡜ࡋ࡚ィ⟬ࡋࡓࠋ ࡘ┠ࡢㄢ㢟࡛࠶ࡿࠕ㧗⃰ᗘ᮲௳ࢆ฼⏝ࡋࡓ⺮ⓑ㉁」ྜయࡢ⤖ྜࢲ࢖ࢼ࣑ࢡࢫゎᯒ࡛ࠖ⏝࠸ࡿ &RO'RFN ἲ࡛ࡣࠊᑐ㇟⺮ⓑ㉁ࡢ࿘㎶࡟ࣜ࢞ࣥࢻࢆ㧗⃰ᗘ࡛㓄⨨ࡋࠊࣜ࢞ࣥࢻࡢจ㞟ࢆ㜵ࡄࡓࡵ࡟ࣜ࢞ࣥࢻ㛫࡟཯Ⓨຊࢆධࢀࡓ≧ែ࡛ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࠋ⺮ⓑ㉁࡟⤖ྜࡋ࡚࠸ࡿࣜ࢞ࣥࢻࢆᢳฟࡋ㸪ࢡࣛࢫࢱࣜࣥࢢࢆ⾜࠺ࡇ࡜࡛ࠊ」ྜయᵓ㐀ࡢணࢆ⾜࠺ࠋࡇࡢࡼ࠺࡞༢⣧࡞᪉ἲ࡞ࡀࡽ」ᩘࡢ」ྜయᵓ㐀࡟ᑐࡋ࡚㧗⢭ᗘࡢண࡟ᡂຌࡋ࡚࠸ࡿࠋ ᖺᗘࡣࠊ⺮ⓑ㉁㸫ࣜ࢞ࣥࢻ」ྜయࢆຍ࠼ࡿ࡜࡜ࡶ࡟ࠊ⺮ⓑ㉁̺⺮ⓑ㉁」ྜయ࡬ࡢ㐺⏝ࢆ⾜ࡗࡓࠋ  ࡘ┠ࡢㄢ㢟࡛࠶ࡿࠕS㸫'1$ 」ྜయࡢ⤖ྜ࣭ゎ㞳㐣⛬࡛ࠖᑐ㇟࡜ࡍࡿ S ࡣ 1 ᮎ➃ഃ࠿ࡽ㌿෗άᛶ໬ࢻ࣓࢖ࣥࠊࣉࣟࣜࣥࣜࢵࢳ࣭ࢻ࣓࢖ࣥࠊ'1$ ⤖ྜࢻ࣓࢖ࣥࠊᅄ㔞యᙧᡂࢻ࣓࢖ࣥࠊ& ᮎ➃ࢻ࣓࢖ࣥ࡞࡝࠿
ࡽᵓᡂࡉࢀࠊ1 ➃࡜ & ➃ࡢࢻ࣓࢖ࣥࡣኳ↛ኚᛶ㡿ᇦ࡜ࡋ࡚▱ࡽࢀࡿ࡞࡝㠀ᖖ࡟ᰂ㌾ᛶ࡟ᐩࡴ⺮ⓑ㉁࡛࠶ࡿࠋ
S ࡣࡀࢇᢚไ⺮ⓑ㉁࡜ࡋ࡚ᗈࡃ◊✲ࡉࢀ࡚࠾ࡾࠊᵝࠎ࡞ศᏊ࡜ࡢ┦஫స⏝ࢆ㏻ࡌ࡚ࠊ⩻ヂࠊቑṪࠊ࣮࢜ࢺࣇ࢓ࢪ࣮࡞࡝ᵝࠎ࡞ᶵ⬟࡟㛵ࢃࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ౛࡜ࡋ࡚ࠊ ᖺᗘࡲ࡛࡟ᑐ㇟࡜ࡋࡓ 0'0 ࡣ S࡟⤖ྜࡋࠊࣘࣅ࢟ࢳࣥ」ྜయࢆ௓ࡋ࡚ࠊS ࢆࣘࣅ࢟ࢳࣥ໬ࡍࡿࡇ࡜࡟ࡼࡾศゎࢆᘬࡁ㉳ࡇࡍࡇ࡜࡛▱ࡽࢀ࡚࠸ࡿࠋ ᖺᗘࡣࠊ3D&60'060 ἲࡢ᪂ࡓ࡞ᣮᡓⓗ࡞ㄢ㢟࡜ࡋ࡚ࠊ඲㛗 S ࡜ᶆⓗ '1$ ࢆᑐ㇟࡜ࡋࡓࠊ
⤖ྜ࣭ゎ㞳ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋᮏᖺᗘࡣࠊ኱ࡁ࡞ᡂᯝࡀᚓࡽࢀࡓࠕ3D&60'060 ἲࢆ⏝࠸ࡓ⺮ⓑ㉁㸫⺮ⓑ㉁」ྜయࡢ㏿ᗘᐃᩘホ౯ࠖ࡟㛵ࡍࡿ⤖ᯝࢆ୰ᚰ࡟ሗ࿌ࡍࡿࠋ

- 228 -

◊✲᪉ἲࠊィ⟬᪉ἲ」ྜయࡢゎ㞳ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟⏝࠸ࡿ 3D&60' ࡣࠊձࢫࢸࢵࣉᩘࡢẚ㍑ⓗ▷࠸ศᏊືຊᏛィ⟬ࢆྠ᫬ᐇ⾜ࠊղࢱ࣮ࢤࢵࢺ࡟㏆࠸ᵓ㐀ࢆ㑅ᢥࠊճࡑࢀࡽࢆึᮇᵓ㐀࡜ࡋ࡚ศᏊືຊᏛィ⟬ࢆࣜࢫࢱ࣮ࢺࠊ࡜࠸࠺ࢧ࢖
ࢡࣝࢆ⧞ࡾ㏉ࡍᡭἲ࡛ࠊศᏊࡢ኱ࡁ࡞ᵓ㐀ኚ໬ࡸ」ྜయࡢ⤖ྜ࣭ゎ㞳ࢆຠ⋡ⓗ࡟ࢧࣥࣉࣜࣥࢢ࡛ࡁࡿࠋࢧ࢖
ࢡࣝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫ࢆ  SV ࡜ࡋ࡚ࠊ ୪ิྠ᫬ᐇ⾜ࡋࡓࠋࢧ࢖ࢡࣝ᭦᪂᫬ࡢᵓ㐀㑅ᢥࡣศᏊࡢ
⏺㠃ṧᇶࡢ㔜ᚰ㛫㊥㞳㸦௨ୗ⏺㠃㊥㞳㸧ࡀ኱ࡁ࠸ᵓ㐀ࢆ㑅ᢥࡋࠊ⏺㠃ṧᇶࡢ᭱ᑠཎᏊ㛫㊥㞳ࡀ QP ࡟࡞ࡿࡲ࡛⧞ࡾ㏉ࡋࡓࠋ0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࡣ *520$&6  ࠾ࡼࡧ *520$&6  ࢆ⏝࠸ࠊຊሙࡣ $0%(5II6%ࠊỈࣔࢹࣝࡣ 63&(E ࣔࢹࣝࢆ౑⏝ࡋࡓࠋ
3D&60' ࡟ࡼࡗ࡚ᚓࡽࢀࡓゎ㞳㐣⛬ࡢࢺࣛࢪ࢙ࢡࢺࣜࢆ࣐ࣝࢥࣇ≧ែࣔࢹࣝ㸦060㸧࡟ࡼࡾゎᯒࡋࠊᶆ‽⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࠊ⤖ྜ࣭ゎ㞳㏿ᗘᐃᩘࢆィ⟬ࡋࡓࠋ060 ゎᯒ࡟ࡣ 060%XLOGHU  ࠾ࡼࡧ 3\(00$ ࢆ౑⏝ࡋࡓࠋ◊✲ᡂᯝᅗ  ࡟ゎ㞳౛ࢆ♧ࡋࡓࡼ࠺࡟ࠊ3D&60' ࢆ⏝࠸࡚⺮ⓑ㉁⺮ⓑ㉁」ྜయࡢゎ㞳ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ%DUQDVH%DUVWDU 」ྜయ࡟㛵ࡋ࡚ࡣࠊ ヨ⾜⾜࠸ࠊᚋ㏙ࡍࡿࡼ࠺࡟඲࡚ࡢヨ⾜࡛ຠ⋡ⓗ࡞」ྜయࡢゎ㞳࡟ᡂຌࡋ࡚࠸ࡿࠋ3'3'/ 」ྜయ࡟㛵ࡋ࡚ࡶࠊヨ⾜ᅇᩘࡣ  ᅇ⛬ᗘ࡛࠶ࡿࡀࠊຠ⋡ⓗ࡞」ྜయࡢゎ㞳࡟ᡂຌࡋ࡚
࠾ࡾࠊ⌧ᅾヨ⾜ᅇᩘ㏣ຍࡢィ⟬ࢆ⾜ࡗ࡚࠸ࡿࠋ௨ୗࠊ ᅇヨ⾜῭ࡳ࡛࠶ࡿ %DUQDVH%DUVWDU 」ྜయࡢ⤖ᯝ࡟㛵ࡋ࡚ሗ࿌ࡍࡿࠋ

ᅗ

3D&60' ࢆ⏝࠸ࡓ $ %DUQDVH%DUVWDU 」ྜయ % 3'3'/ 」ྜయࡢゎ㞳౛ᅗ 3D&60' ࡢྛࢧ࢖ࢡࣝ࡟࠾ࡅࡿ⏺㠃㊥㞳- 229 -

%DUQDVH%DUVWDU 」ྜయࡢゎ㞳ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ  ᅇ⾜ࡗࡓ⤖ᯝࠊᅗ  ࡟♧ࡋࡓࡼ࠺࡟ࠊ」ྜయࡢゎ㞳࡟ᚲせ࡞ࢧ࢖ࢡࣝᩘࡣヨ⾜ࡈ࡜࡟␗࡞ࡾࠊ᭱኱  ࢧ࢖ࢡࣝࠊᖹᆒ  ࢧ࢖ࢡࣝせࡋࡓࠋ᭱኱࡛࠶ࡿ  ࢧ࢖ࢡࣝࡢሙྜ࡛ࡶࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫ࡣ  QV㸦 ୪ิ [SV[ ࢧ࢖ࢡࣝ㸧࡛࠶ࡾࠊ」ྜయࡢゎ㞳㏿ᗘᐃᩘࡀ [V ࡛࠶ࡿࡇ࡜ࢆ⪃៖ࡍࡿ࡜ຠ⋡ࡀⰋ࠸ࡇ࡜ࡀศ࠿ࡿࠋ௨ୖࡢࡼ࠺࡟ 3D&60' ࡣ⺮ⓑ㉁̺⺮ⓑ㉁」ྜయࡢゎ㞳ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡶ᭷ຠ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋᅗ  $ ࡟♧ࡋࡓ %DUVWDU ⏺㠃ṧᇶ㔜ᚰࡢ㌶㊧࠿ࡽศ࠿ࡿࡼ࠺࡟ࠊヨ⾜ࡈ࡜࡟␗࡞ࡿᵝࠎ࡞ゎ㞳⤒㊰㸦ࣃࢫ࢙࢘࢖㸧ࡢ⏕ᡂ࡟ᡂຌࡋࡓࠋ⏕ᡂࡋࡓࣃࢫ࢙࢘࢖ࡣᅗ  % ࡟♧ࡋࡓࡼ࠺࡟ࠊ$5* ഃ ࣃࢫ࢙࢘࢖  ࡜ 6(5 ഃ㸦ࣃࢫ࢙࢘࢖ 㸧࡟኱ࡁࡃ஧ࡘ࡟ศ㢮࡛ࡁࡿࠋ඲  ヨ⾜ࡢ࠺ࡕࠊ ヨ⾜࡟࠾࠸࡚ࣃࢫ࢙࢘࢖ ࠊ ヨ⾜࡟࠾࠸࡚ࣃࢫ࢙࢘࢖  ࢆ⤒⏤ࡋ࡚࠾ࡾࠊ3D&60'࡟ࡼࡿゎ㞳ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣࠊࣃࢫ࢙࢘࢖  ࡢ᪉ࡀከࡃほࡉࢀࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊᚓࡽࢀࡓࢺࣛࢪ࢙

ࢡࢺࣜ࡟࠾ࡅࡿ⏺㠃㛫ࡢ┦ᑐ఩⨨ࢆ⏝࠸࡚ 060 '060 ゎᯒࢆ⾜ࡗࡓ⤖ᯝࠊࣃࢫ࢙࢘࢖  ࡜ࣃࢫ࢙࢘࢖ ࡢẚࡣ  ࡛ࣃࢫ࢙࢘࢖  ࢆྲྀࡾࡸࡍ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢ⤖ᯝࡣࠊࣃࢫ࢙࢘࢖  ࡀ୺࡞ゎ㞳⤒㊰࡜ࡉࢀ࡚࠸ࡿඛ⾜◊✲ࡢ⤖ᯝ࡜୍⮴ࡋ࡚࠾ࡾࠊ3D&60' ࡟ࡼࡾ೫ࡗࡓࢺࣛࢪ࢙ࢡࢺࣜࢆ⏕ᡂࡋࡓሙྜ࡛ࡶࠊࡑࡢᚋ
ࡢ 060 ゎᯒ࡟ࡼࡾࠊᵓ㐀㑅ᢥ᫬ࡢࣂ࢖࢔ࢫࡢᙳ㡪ࢆཷࡅࡎ࡟ࣃࢫ࢙࢘࢖ࡢゎᯒࡀྍ⬟࡜࡞ࡿࡇ࡜ࡀศ࠿ࡗ
ࡓࠋᅗ  $ ヨ⾜ࡈ࡜ % ࣃࢫ࢙࢘࢖ࡈ࡜࡟␗࡞ࡿⰍ࡛♧ࡋࡓゎ㞳㐣⛬࡟࠾ࡅࡿ %DUVWDU ࡢ⏺㠃ṧᇶ㔜ᚰࡢ㌶㊧060 ゎᯒࡼࡾホ౯ࡋࡓᖹᆒຊ࣏ࢸࣥࢩࣕࣝࢆᅗ  $ ࡟♧ࡋࡓࠋ⏺㠃㊥㞳ࡀ QP ௨ୖ࡛ࡣᖹᆠ࡟࡞ࡗ࡚࠸
ࡿ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࡀᚓࡽࢀࡓࡇ࡜࠿ࡽࠊ⏺㠃㊥㞳 QP ௨ୖࢆ㠀⤖ྜ≧ែ࡜ᐃ⩏ࡋࡓࠋ060 ゎᯒࢆ⾜࠺ୖ࡛ࡢࢡࣛࢫࢱ࣮ᩘࢆ ࠊ ࡜ࡋࡓሙྜᶆ‽⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࡣࠊࡑࢀࡒࢀNFDOPRO ࡛࠶ࡾᐇ㦂್࡛࠶ࡿ NFDOPRO ࡟㠀ᖖ࡟㏆࠸್ࡀᚓࡽࢀࡓࠋゎ㞳㏿ᗘᐃᩘ NRII ࠊ⤖ྜ㏿ᗘᐃᩘ NRQ ࡣᅗ  % ࡟♧ࡋࡓࡼ࠺࡟ࠊ060 ゎᯒࢆ⾜࠺㝿ࡢࢡࣛࢫࢱ࣮ᩘࡸ ODJWLPH ࡟౫Ꮡࡋࠊゎ㞳㏿ᗘᐃᩘ࡟㛵ࡋ࡚ࡣࠊࢡࣛࢫࢱ࣮ᩘ ࠊODJWLPHSV ࡜ࡋࡓሙྜ࡟ẚ㍑ⓗᐇ㦂್㸦ᅗ୰⅊Ⰽࡢᐇ⥺㸧࡟㏆࠸್ࡀᚓࡽࢀࡓࠋ⺮ⓑ㉁㸫࣌ࣉࢳࢻ」ྜయࢆᑐ㇟࡟ࡋࡓ㝿ࡢ⤒㦂࠿ࡽࠊࡼࡾ㧗ḟඖࡢ 060 ゎᯒࡼࡾᨵၿࡉࢀࡿࡇ࡜ࡀண᝿ࡉࢀࠊゎᯒ࡟⏝࠸ࡿ㐺ษ࡞ࣃ࣓࣮ࣛࢱ࡟㛵ࡋ࡚ࡣ᳨ウ୰࡛࠶ࡿࠋ
௨ୖࡢࡼ࠺࡟ࠊ3D&60' ࡣ⺮ⓑ㉁̿⺮ⓑ㉁」ྜయࡢゎ㞳㐣⛬ࢆຠ⋡ࡼࡃゎᯒࡍࡿୖ࡛㠀ᖖ࡟᭷ຠ࡞᪉ἲ࡛
࠶ࡾࠊ060 ࢆ⏝࠸ࡿࡇ࡜࡛ṇ☜࡞⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࢆホ౯ࡍࡿࡇ࡜࡟ࡶᡂຌࡋ࡚࠸ࡿࠋ௒ᚋࡣࠊᑐ㇟」ྜ
యࢆ㏣ຍࡍࡿ࡜࡜ࡶ࡟ࠊ㏿ᗘᐃᩘホ౯᫬ࡢ᭱㐺࡞ࣃ࣓࣮ࣛࢱࡢ᳨ウࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ

- 230 -

ᅗ060 ゎᯒࡼࡾᚓࡽࢀࡓ $ ᖹᆒຊ࣏ࢸࣥࢩࣕࣝ࡜ % ⤖ྜ࣭ゎ㞳㏿ᗘᐃᩘⓎ⾲ᐇ⦼ࡲࡓࡣணᐃx‫ ۻ‬-&KDQ.7DNHPXUD+5/LQ.&&KDQJ<<&KDQJ<-RWL$.LWDRDQG/:<DQJ$Q(IILFLHQW7LPHU
DQG6L]HURI%LRPDFURPROHFXODU0RWLRQV6WUXFWXUHH  x‫ ۻ‬$*XVPLUD.7DNHPXUD6</HH7,QDED.+DQDZD6XHWVXJX.2RQR<DNXUD.<DVXKDUD$.LWDR
DQG66XHWVXJX5HJXODWLRQRIFDYHRODHWKURXJKFKROHVWHUROGHSOHWLRQGHSHQGHQWWXEXODWLRQPHGLDWHGE\3$&6,1
-&HOO6FL  x‫ ۻ‬++DWD<1LVKLKDUD01LVKL\DPD<6RZD,.DZDJLVKLDQG$.LWDR+LJKSUHVVXUHLQKLELWVVLJQDOLQJ
SURWHLQELQGLQJWRWKHIODJHOODUPRWRUDQGEDFWHULDOFKHPRWD[LVWKURXJKHQKDQFHGK\GUDWLRQ6FL5HS
 x‫ ۻ‬++DWD01LVKL\DPDDQG$.LWDR0ROHFXODUG\QDPLFVVLPXODWLRQRISURWHLQVXQGHUKLJKSUHVVXUH
6WUXFWXUHIXQFWLRQDQGWKHUPRG\QDPLFV%LRFKLP%LRSK\V$FWD*HQ6XEM  x‫ ۻ‬.7DNDED'37UDQDQG$.LWDR(GJHH[SDQVLRQSDUDOOHOFDVFDGHVHOHFWLRQPROHFXODUG\QDPLFVVLPXODWLRQ
IRULQYHVWLJDWLQJODUJHDPSOLWXGHFROOHFWLYHPRWLRQVRISURWHLQV-&KHP3K\V  x‫' ۻ‬37UDQDQG$.LWDR.LQHWLF6HOHFWLRQDQG5HOD[DWLRQRIWKH,QWULQVLFDOO\'LVRUGHUHG5HJLRQRID3URWHLQ
XSRQ%LQGLQJ-&KHP7KHRU\&RPSXW  x‫ ۻ‬.+DQDZD6XHWVXJXHWDO3KDJRF\WRVLVLVPHGLDWHG E\WZRGLPHQVLRQDODVVHPEOLHVRIWKH)%$5SURWHLQ
*$61DW&RPPXQ  x‫ ۻ‬6+D\ZDUGDQG$.LWDR0XOWLVWUDQGEHWDVKHHWRI$O]KHLPHU$EHWD  IROGVWREHWDVWULSKHOL[LPSOLFDWLRQIRUSURWRILODPHQWIRUPDWLRQ-%LRPRO6WUXFW'\Q  x‫< ۻ‬2QRXH0,ZDNL$6KLQREX<1LVKLKDUD+,ZDWVXNL+7HUDVKLPD$.LWDR+.DQGRULDQG0+RPPD(VVHQWLDOLRQELQGLQJUHVLGXHVIRU1D  IORZLQVWDWRUFRPSOH[RIWKH9LEULRIODJHOODUPRWRU6FL5HS  x‫' ۻ‬37UDQDQG$.LWDR'LVVRFLDWLRQ3URFHVVRID0'0S&RPSOH[,QYHVWLJDWHGE\3DUDOOHO&DVFDGH
6HOHFWLRQ0ROHFXODU'\QDPLFVDQGWKH0DUNRY6WDWH0RGHO-3K\V&KHP%  x‫<< ۻ‬RNRFKL.6XJLXUD.7DNHPXUD.<RVKLGD6+DUD.,:DNDED\DVKL$.LWDRDQG7+LVDERUL,PSDFW
RINH\UHVLGXHVZLWKLQFKORURSODVWWKLRUHGR[LQIRQUHFRJQLWLRQIRUUHGXFWLRQDQGR[LGDWLRQRIWDUJHWSURWHLQV-%LRO
&KHP  - 231 -

➨୍ཎ⌮ィ⟬࠾ࡼࡧ࣐ࢸࣜ࢔ࣝࢬ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿࢼࣀᵓ㐀࠾ࡼࡧཎᏊᒙ≀㉁ࡢᙧᡂ࡜ᶵ⬟Ⓨ⌧࡟㛵ࡍࡿ◊✲)LUVWSULQFLSOHVDQGPDWHULDOVLQIRUPDWLFVVWXGLHVIRUIRUPDWLRQDQG
QRYHOIXQFWLRQVRIQDQRVWUXFWXUHVDQGOD\HUHGVWUXFWXUHV‫⛅ۑ‬ᒣ ஽ࠊΎỈ⣖ᚿࠊỌ஭຾ஓࠊோᮌඞⱥࠊ᪥ᰘ႐ᩥ᫛㸦୕㔜኱㝔ᕤ㸧  
1 ◊✲┠ⓗ࠾ࡼࡧෆᐜ
ᮏ◊✲࡛ࡣࢼࣀᵓ㐀ᙧᡂᶵᵓࡢゎ᫂࠾ࡼࡧ᪂つ≀ᛶ᥈⣴ࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ ᖺᗘࡣ༙ᑟయ
ࢼࣀᵓ㐀࠾ࡼࡧཎᏊᒙ≀㉁࡟㛵ࡍࡿ◊✲ࢆ㐙⾜ࡋࡓࠋලయⓗ࡟ࡣࠊ❅໬≀༙ᑟయ *D1 ࠾ࡼࡧ $O1 ࢼࣀᵓ㐀ᙧᡂ᫬ࡢẼ┦࠿ࡽࡢཎᏊ࠾ࡼࡧศᏊࡢ⾲㠃࡬ࡢ྾╔࠾ࡼࡧ⬺㞳㐣⛬ࠊࡇࢀࡽཎᏊ࠾ࡼࡧศᏊࡢ⾲㠃࡛ࡢ ࣐࢖ࢢ࣮ࣞࢩࣙࣥ➼ࡢ ᣲືࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊཎᏊᒙ≀㉁ࡢᵓ㐀࡜㟁Ꮚ≧ែ࡟㛵ࡍࡿ◊✲࡜ࡋ࡚ࠊ໬ྜ༙ᑟ
య࡟࠾ࡅࡿཎᏊᒙ≀㉁࡟࠾ࡅࡿ YG: ࣊ࢸࣟᵓ㐀ᙧᡂྍ⬟ᛶࡢ᳨ウࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊ༙ᑟయࢼࣀᵓ㐀ᙧᡂ࡟㛵ࡍࡿ◊✲࡜ࡋ࡚ 6L26L& ⏺㠃࠾ࡅࡿ཯ᛂ㐣⛬࡟㛵ࡍࡿ᳨ウࡶᐇ⾜ࡋࡓࠋ2 ◊✲᪉ἲ࠾ࡼࡧィ⟬᪉ἲィ⟬ࡣ୺࡟ᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃ඲࢚ࢿࣝࢠ࣮㟁Ꮚ≧ែィ⟬࡟ࡼࡗ࡚ᐇ⾜ࡋࡓࠋཎᏊ᰾࡜ෆẆ㟁Ꮚࡣᨃ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸࡚ᶍࡋࠊ౯㟁Ꮚࡢ┦஫స⏝࡟ᑐࡋ࡚ࡣ୍⯡໬໙㓄㏆ఝ **$3%( ࠶ࡿ࠸ࡣࣁ࢖ࣈࣜࢵ
ࢻᐦᗘỗ㛵ᩘ 3%( ࠾ࡼࡧ +6( ࢆ㐺⏝ࡋࡓࠋἼື㛵ᩘࡣᖹ㠃Ἴᇶᗏ࡟ࡼࡗ࡚ᒎ㛤ࡋࠊ㟁Ꮚ≧ែ࠾ࡼࡧᵓ㐀ࡢ᭱㐺໬ࡣඹᙺ໙㓄ἲ࡟ࡼࡗ࡚⾜ࡗࡓࠋ௨ୖࡢィ⟬ࡣࠊᒣෆ῟෸ᩍᤵ ៞ᛂ኱Ꮫ ࡽࢆ୰ᚰ࡜ࡍࡿ࣓ࣥࣂ࣮࡛సᡂ
ࡉࢀࡓ 7RN\R$ELQLWLR3URJUDP3DFNDJH 7$33 ࡟ࡼࡗ࡚ᐇ⾜ࡋࡓࠋࡲࡓ➨୍ཎ⌮ィ⟬ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪ࡜
ࡋ࡚ 4XDQWXP(VSUHVVR ࢆ㐺ᐅ฼⏝ࡋࡓࠋࡇࢀࡽࡢ㟁Ꮚ≧ែィ⟬࡟ຍ࠼ࠊỴᐃᮌศᯒ࡟ࡼࡿ㟁Ꮚ≧ែ ࣂࣥࢻࢠࣕࢵࣉ ࡟ᑐࡍࡿᶵᲔᏛ⩦ࡶ⾜ࡗࡓࠋ3 ◊✲ᡂᯝ
 ࢼࣀᵓ㐀࢚ࣆࢱ࢟ࢩࣕࣝ⤖ᬗᡂ㛗᫬ࡢ⣲㐣⛬࡟㛵ࡍࡿ◊✲ࢼࣀᵓ㐀࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ᶵᵓ࡟㛵ࡍࡿ◊✲࡜ࡋ࡚ࠊࡇࢀࡲ࡛ࡢᖹ⾮≧ែ࡟࠾ࡅࡿࢼࣀᵓ㐀ᙧ≧ࡢゎᯒ࡟ຍ࠼ࠊᡂ㛗ࣉࣟࢭࢫ࡟ᑐࡍࡿ᳨ウࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣࠊ*D1 ࡟࠾ࡅࡿࢩࣕࣝᡂ㛗᫬ࡢẼ┦࠿ࡽࡢཎᏊ࠾
ࡼࡧศᏊࡢ⾲㠃࡬ࡢ྾╔࠾ࡼࡧ⬺㞳㐣⛬ࠊࡇࢀࡽཎᏊ࠾ࡼࡧศᏊࡢ⾲㠃࡛ࡢ ࣐࢖ࢢ࣮ࣞࢩࣙࣥ➼ࡢ  ᣲືࢆ᫂ࡽ࠿࡟ࡋࡓࠋᅗ  ࡟♧ࡍࡼ࠺࡞␗࡞ࡿ㠃᪉఩࠿ࡽ࡞ࡿ⾲㠃 」ྜࣇ࢓ࢭࢵࢺ ࡟࠾࠸࡚᭷ᶵ㔠ᒓ࢚ࣆࢱࢩࣕࣝ
ᡂ㛗࡛ࡢ࢟ࣕࣜ࢔࢞ࢫ౫Ꮡᛶ࡟ᑐࡍࡿ᳨ウࢆ⾜࠸ࠊᡂ㛗 ᗘ࠾ࡼࡧᅽຊ࡟౫Ꮡᛶࡋ࡚ኚ໬ࡍࡿ⾲㠃ᵓ㐀࡟㉳ᅉࡋ࡚ࠊࡇࢀࡽࡢᣲືࡀ኱ࡁࡃኚ໬ࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡲࡓࠊࡇࢀࡽᣲືࡢ㐪࠸࡟ࡼࡾ *D1 ࡟࠾࠸࡚ᙧᡂ
ࡍࡿࢼࣀ࣡࢖ࣖࡢᡂ㛗ᵝᘧࡀ኱ࡁࡃኚ໬ࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡇࢀࡽࡢィ⟬⤖ᯝࡣᐇ㦂⤖ᯝ࡜ࡶᐃᛶⓗ࡟୍⮴ࡋ࡚࠸ࡿࠋ
 ཎᏊᒙ≀㉁ࡢᵓ㐀࡜㟁Ꮚ≧ែࡇࢀࡲ࡛࡟ᑐ㇟࡜ࡋ࡚ࡁࡓ໬ྜ༙ᑟయ࡟࠾ࡅࡿཎ
Ꮚᒙ≀㉁ࡢᙧᡂྍ⬟ᛶ࡟ຍ࠼ࠊࡇࢀࡽཎᏊᒙ≀㉁࡜ࡢ
࣊ࢸࣟᵓ㐀࡟㛵ࡍࡿ᳨ウࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣࠊ ✀㢮ࡢ ,,,9 ᪘໬ྜ≀༙ᑟయ $O$V$O6E*D$V*D6E,Q3
,Q$V ࡜ࢢࣛࣇ࢙ࣥ࠾ࡼࡧ %1 ࡛ᵓᡂࡉࢀࡿ㉸᱁Ꮚ࡛ࡢᏳᐃᛶࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚᫂ࡽ࠿࡟ࡋࡓࠋࡇࡢ
⣔࡟࠾࠸࡚ ,,,9 ᪘໬ྜ≀༙ᑟయࡣཎᏊᒙᵓ㐀࡜ࡋ࡚ ᒙࣁࢽ࣒࢝ '/+& ᵓ㐀ࢆ࡜ࡾࠊࡑࡢ⤖ྜ࢚ࢿࣝࢠ࣮
ࡢ್࠿ࡽࢢࣛࣇ࢙ࣥࡸ %1 ࡢሙྜ࡜ྠ➼ࡢᏳᐃᛶ࡛࣊
ࢸࣟᵓ㐀ࢆᙧᡂࡋᚓࡿࡇ࡜ࢆぢฟࡋࡓࠋࡲࡓࠊࡇࢀࡽ
࣊ࢸࣟᵓ㐀࡟࠾ࡅࡿᑐ⛠ᛶࡢపୗ࡟ࡼࡾࠊࢢࣛࣇ࢙ࣥ
ࢆྵࡴ⣔࡟࠾࠸࡚ࡣࢹ࢕ࣛࢵࢡࢥ࣮ࣥࡀᾘኻࡋ࡚࢚
ࢿࣝࢠ࣮ࢠࣕࢵࣉࡀᙧᡂࡍࡿࡇ࡜ࠊ'/+& ᵓ㐀ࢆ࡜ࡿ,,,9 ᪘༙ᑟయ࡟㉳ᅉࡍࡿ≉␗࡞㟁Ꮚ≧ែࡀฟ⌧ࡍࡿྍ⬟ᛶࡀ࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
6L& ⷧ⭷ࡢ㓟໬㐣⛬࡟㛵ࡍࡿ⌮ㄽ᳨ウ༙ᑟయࢼࣀᵓ㐀ᙧᡂ㐣⛬࡟㛵ࡍࡿ◊✲࡜ࡋ࡚ 6L& ⷧᅗ *D1 ࡟࠾ࡅࡿ␗࡞ࡿ㠃᪉఩࠿ࡽ࡞ࡿ⾲㠃 」ྜࣇ࢓ࢭࢵࢺ ࡢᶍᘧᅗࠋ⥳Ⰽࠊ㟷Ⰽࠊ࠾ࡼࡧ᱈Ⰽࡢ㡿ᇦࡣࡑࢀࡒࢀ^`^`࠾ࡼࡧ^`㠃ࢆ♧ࡍࠋࡇࢀࡽ」ྜࣇ࢓ࢭࢵࢺ࠾ࡼࡧྛ㠃࡟࠾ࡅࡿィ⟬ࣔࢹࣝࢆᵓ⠏ࡋ࡚ࠊࡑࡇ࡛ࡢཎᏊ࠾ࡼࡧศᏊࡢᣲື࡟ᑐࡍࡿ➨୍ཎ⌮ィ⟬ࢆ⾜ࡗࡓࠋ

- 232 -

⭷ࡢ㓟໬㐣⛬࡟㛵ࡍࡿ◊✲ࢆ⾜ࡗࡓࠋ௒ᖺᗘࡣ㓟໬཯ᛂᚋࡢࢹࣂ࢖ࢫࣉࣟࢭࢫ࡟࠾࠸࡚⾜ࢃࢀࡿ 12 ศᏊ࡟ࡼࡿ࢔ࢽ࣮ࣝ㐣⛬࡟㛵ࡍࡿ᳨ウࢆ⾜ࡗࡓࠋ12 ศᏊࡀᏑᅾࡍࡿሙྜ࡛ࡢ 6L26L& ⏺㠃࠾ࡅࡿ཯ᛂ㐣⛬ࢆ 1(%ἲ࡟ࡼࡿ཯ᛂ⤒㊰᥈⣴ࢆ⏝࠸࡚᫂ࡽ࠿࡟ࡋࡓࠋ6L ཎᏊࡀ᭱ୖᒙ࡜࡞ࡿ 6L 㠃࡟࠾࠸࡚ࡣ  ಶࡢ 12 ศᏊࡀ⏺㠃࡟ᏑᅾࡍࡿⅣ⣲㛵㐃Ḟ㝗࡜཯ᛂࡋ࡚ 6L1 ⤖ྜࢆᙧᡂࡋࠊḞ㝗‽఩ࡢ㉳ᅉ࡜࡞ࡿ㟁Ꮚ≧ែࡀᾘኻࡍࡿࡢ࡟ᑐࡋࠊ
& ཎᏊࡀ᭱ୖᒙ࡜࡞ࡿ & 㠃࡟࠾࠸࡚ࡣ  ಶࡢ 12 ศᏊࡀ⏺㠃࡟ᏑᅾࡍࡿⅣ⣲㛵㐃Ḟ㝗࡜཯ᛂࡋ࡚㟁Ꮚ≧ែࡀᾘኻࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡇࢀࡽⅣ⣲㛵㐃Ḟ㝗࡜཯ᛂࡍࡿ 12 ศᏊࡢಶᩘࡢ㐪࠸࡟ࡼࡗ࡚ࠊᐇ㝿ࡢࢹࣂ࢖ࢫస〇᫬࡟࠾ࡅࡿ⏺㠃Ḟ㝗ࡢపῶຠᯝ࡟࠾࠸࡚㠃᪉఩౫ᏑᛶࡀⓎ⏕ࡍࡿࡇ࡜ࢆண ࡋࡓࠋ ❅໬≀༙ᑟయ࡟࠾ࡅࡿ≀ᛶไᚚࡢࡓࡵࡢࢹ࣮ࢱゎᯒ❅໬≀༙ᑟయ࡟࠾ࡅࡿ≀ᛶไᚚ࡟㛵ࡍࡿ◊✲࡜ࡋ࡚ࠊࡇࢀࡲ࡛ࡢィ⟬࡛ᚓࡽࢀࡓ ,Q1$O1 ࠾ࡼࡧ ,Q1*D1㉸᱁Ꮚ࡟࠾ࡅࡿࣂࣥࢻࢠࣕࢵࣉ್࡟ᑐࡋ࡚ᶵᲔᏛ⩦ࢆ⏝࠸ࡓゎᯒࢆ⾜ࡗࡓࠋ$O1 ᇶᯈࢆ᝿ᐃࡋࡓሙྜ࡛ࡢ
P,Q1Q$O1 ㉸᱁Ꮚ P ࠾ࡼࡧ Q ࡣࡑࢀࡒࢀ ,Q1 ࠾ࡼࡧ $O1 ࡢᒙᩘ ࡟࠾ࡅࡿࣂࣥࢻࢠࣕࢵࣉࡢ ,Q ⤌ᡂ [ ࡟ᑐࡍࡿኚ໬ࢆࠊྛ✀ࣃ࣓࣮ࣛࢱ ᱁Ꮚᐃᩘࠊ⤌ᡂࠊ㉸᱁Ꮚ࿘ᮇ➼ ࢆධຊ࡜ࡋ࡚Ỵᐃᮌศᯒ࡟ࡼࡿࣂࣥࢻࢠࣕࢵࣉࡢண ࢆヨࡳࡓࠋ෌⌧ᛶࡢࡼ࠸ࢹ࣮ࢱ⠊ᅖࡶ࠶ࡗࡓࡀࠊᶵᲔᏛ⩦ࡣ୍⯡ⓗ࡟እᤄࡀ㞴ࡋ࠸ࡓࡵⴭࡋࡃ෌⌧ᛶࡢప࠸ࢹ࣮ࢱ⠊ᅖࡶ࠶ࡗࡓࠋ

4 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
>@ ‫ۻ‬76KLPL]X7$NL\DPD.1DNDPXUD7,WR+.DJHVKLPD08HPDWVXDQG.6KLUDLVKL³5HDFWLRQRI12PROHFXOHDW
+6L&6L2LQWHUIDFHDQDELQLWLRVWXG\IRUWKHHIIHFWRI12DQQHDOLQJDIWHUGU\R[LGDWLRQ´,QWHUQDWLRQDO&RQIHUHQFHRQ
6ROLG6WDWH'HYLFHVDQG0DWHULDOV  ᖺ  ᭶  ᪥ 
>@ ‫ۻ‬7$NL\DPD.1DNDPXUD7,WR³&RPSXWDWLRQDOSUHGLFWLRQIRUVWDEOHVWUXFWXUHVRIJUDSKHQHYDQGHU:DDOVKHWHURVWUXFWXUHVFRPSRVHGRIJURXS,,,9FRPSRXQGV´3DFLILF5LP0HHWLQJRQ(OHFWURFKHPLFDODQG6ROLG6WDWH6FLHQFH  ᖺ  ᭶  ᪥ 
>@ ‫ۻ‬76KLPL]X7$NL\DPD.1DNDPXUD7,WR³(IIHFWVRIZHWDPELHQWRQGU\R[LGDWLRQSURFHVVHVDW+6L&6L2LQWHUIDFHDQDELQLWLRVWXG\´3DFLILF5LP0HHWLQJRQ(OHFWURFKHPLFDODQG6ROLG6WDWH6FLHQFH  ᖺ  ᭶  ᪥ 
>@ ‫ۻ‬ΎỈ⣖ᚿ ⛅ᒣ஽ $ 0 3UDGLSWR ୰ᮧᾈḟ ఀ⸨ᬛᚨ ᙳᓥ༤அ ᳜ᯇ┿ྖ ⓑ▼㈼஧ ³➨୍ཎ⌮ィ⟬ࢆ⏝࠸ࡓ+6L&6L2 ⏺㠃࡛ࡢ㓟໬㐣⛬ࡢ᳨ウ㸸࢙࢘ࢵࢺ㓟໬ࡢᙳ㡪´ ᖺ➨  ᅇᛂ⏝≀⌮Ꮫ఍⛅ᏘᏛ⾡ㅮ₇఍S=
 ᖺ  ᭶  ᪥ 
>@ ‫ۻ‬ΎỈ⣖ᚿ ⛅ᒣ஽ ఀ⸨ᬛᚨ ᙳᓥ༤அ ᳜ᯇ┿ྖ ⓑ▼㈼஧ ³ࢻࣛ࢖࠾ࡼࡧ࢙࢘ࢵࢺ㓟໬✀ࡀඹᏑࡍࡿ +6L&6L2 ⏺
㠃࡛ࡢ཯ᛂᶵᵓࡢ⌮ㄽⓗ᳨ウ´ ᖺ➨  ᅇᛂ⏝≀⌮Ꮫ఍᫓ᏘᏛ⾡ㅮ₇఍S=  ᖺ  ᭶  ᪥ 
>@ ‫⛅ۻ‬ᒣ஽ Ἑᮧ㈗ᏹ ఀ⸨ᬛᚨ ³➨୍ཎ⌮ィ⟬࡟ࡼࡿ ,,,9 ᪘໬ྜ≀ࢢࣛࣇ࢙ࣥ㉸᱁Ꮚࡢᵓ㐀࠾ࡼࡧ㟁Ꮚ≧ែゎᯒ´ ᖺ➨  ᅇᛂ⏝≀⌮Ꮫ఍᫓ᏘᏛ⾡ㅮ₇఍S3  ᖺ  ᭶  ᪥  ௚  ௳5 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
>@ ‫ۻ‬³(IIHFWVRIZHWDPELHQWRQGU\R[LGDWLRQ3URFHVVHVDW+6L&6L2LQWHUIDFHDQDELQLWLRVWXG\´76KLPL]X7$NL\DPD.
1DNDPXUD7,WR+.DJHVKLPD08HPDWVXDQG.6KLUDLVKL(&67UDQV 98  >@ ‫ۻ‬³$ VLPSOH DSSURDFK WR JURZWK PRGH RI ,Q1 DQG ,Q*D1 WKLQ ILOPV RQ *D1   VXEVWUDWH . 1DJDL 7 $NL\DPD .
1DNDPXUDDQG7,WR(&67UDQV98  >@ ‫ۻ‬³(IIHFWRIILOPWKLFNQHVVRQVWUXFWXUDOVWDELOLW\IRU%$O1DQG%*D1DOOR\VERQGRUGHULQWHUDWRPLFSRWHQWLDOFDOFXODWLRQV´<+DVHJDZD7$NL\DPD$03UDGLSWR.1DNDPXUDDQG7,WR3K\V6WDWXV6ROLGL%257  >@ ‫ۻ‬³(TXLOLEULXP PRUSKRORJLHV RI IDFHWHG *D1 XQGHU WKH PHWDORUJDQLF YDSRUSKDVH HSLWD[\ FRQGLWLRQ :XOII FRQVWUXFWLRQ XVLQJ
DEVROXWHVXUIDFHHQHUJLHV´<6HWD$03UDGLSWR7$NL\DPD.1DNDPXUDDQG7,WR3K\V6WDWXV6ROLGL%257  >@ ‫ۻ‬³$E LQLWLR FDOFXODWLRQV IRU WKH HIIHFW RI ZHW R[LGDWLRQ FRQGLWLRQ RQ WKH UHDFWLRQ PHFKDQLVP DW +̽6L&6L2 LQWHUIDFH´ 7 
6KLPL]X7$NL\DPD$03UDGLSWR.1DNDPXUD7,WR+.DJHVKLPD08HPDWVXDQG.HQML6KLUDLVKL-SQ-$SSO3K\V
59600'  >@ ‫ۻ‬³5ROHVRIJURZWKNLQHWLFVRQ*D1QRQSODQDUIDFHWVXQGHUPHWDORUJDQLFYDSRUSKDVHHSLWD[\FRQGLWLRQ´<6HWD7$NL\DPD$03UDGLSWR.1DNDPXUDDQG7,WR$SSO3K\V([SUHVV13  >@ ‫ۻ‬³(IIHFWRIVWHSHGJHVRQDGVRUSWLRQEHKDYLRUIRU*D1  VXUIDFHVGXULQJPHWDORUJDQLFYDSRUSKDVHHSLWD[\DQDE,QLWLRVWXG\´72KND7$NL\DPD$03UDGLSWR.1DNDPXUDDQG7,WR&U\VW*URZWK 'HVLJQ20  >@ ‫ۻ‬³&RPSXWDWLRQDO GLVFRYHU\ RIVWDEOH SKDVHV RI JUDSKHQH DQGK%1 YDQ GHU :DDOV KHWHURVWUXFWXUHV FRPSRVHG RI JURXS,,,9
ELQDU\FRPSRXQGV´7$NL\DPD7.DUDPXUDDQG7,WR$SSO3K\V/HWW118  >@ ‫ۻ‬³5HDFWLRQRI12PROHFXOHDW+6L&6L2LQWHUIDFHDQDELQLWLRVWXG\IRUWKHHIIHFWRI12DQQHDOLQJDIWHUGU\R[LGDWLRQ´76KLPL]X
7$NL\DPD.1DNDPXUD7,WR+.DJHVKLPD08HPDWVXDQG.6KLUDLVKL-DS-$SSO3K\V606%%'   
>@ ‫ۻ‬³$E LQLWLR DSSURDFK IRU R[LGDWLRQ PHFKDQLVPV DW +6L&6L2 LQWHUIDFH LQWHUSOD\ RI 2 DQG +2 GXULQJ LQWHUIDFLDO UHDFWLRQ´ 7
6KLPL]X7$NL\DPD.1DNDPXUD7,WR+.DJHVKLPD08HPDWVXDQG.6KLUDLVKL3K\V5HY0DWHULDOVVXEPLWWHG ௚  ௳

- 233 -

ࢡࣛࢫࢱ࣮࢖࢜ࣥࡢᗄఱᵓ㐀ࠊ཯ᛂᛶ࠾ࡼࡧ⾪✺᩿㠃✚ࡢィ⟬Calculations of geometrical structures, reactivities and collision crosssections of cluster ions‫ۑ‬኱ୗ ៞ḟ㑻ࠊᓊᮏ ┤ᶞࠊୖ㔝 ⿱ࠊ୰ᓥ ♸ྖࠊఀ⸨ ᝆྣࠊ㛛ཱྀ ┿அࠊSu Changࠊ᭹㒊 ᆂ࿃ࠊHuang Tingࠊᑠ‖ ⍞ኸࠊబ⸨ Ⰻுࠊ୕➎ ὒኴᮁ㸦ᮾ໭኱㝔⌮㸧1◊✲┠ⓗᮏ◊✲࡛ࡣ㉁㔞ศᯒ࡜࢖࢜ࣥࣔࣅࣜࢸ࢕ศᯒ㸦࢖࢜ࣥ⛣ືᗘศᯒ㸧ࢆ⤌ࡳྜࢃࡏࡓ

ᗘྍኚప

࢖࢜ࣥࣔ

ࣅࣜࢸ࢕㉁㔞ศᯒ㸦IM-MS㸧ࡢ⮬స⿦⨨ࢆ⏝࠸࡚ࠊ㔠ᒓ㓟໬≀ࢡࣛࢫࢱ࣮ࡸ࣍ࢫࢺ㸫ࢤࢫࢺ໬ྜ≀࡞࡝࢖࢜ࣥࡢᵓ㐀࠾ࡼࡧ཯ᛂࢆほࡋࡓࠋIM-MS ࡢᐇ㦂࡛ࡣ㉁㔞㑅ูࡉࢀࡓ࢖࢜ࣥ࡜⦆⾪Ẽయ㸦He㸧࡜ࡢ⾪✺᩿㠃✚

㸦CCS㸧ࡀồࡵࡽࢀࡿࠋ୍᪉ࠊࢺࣛࢪ࢙ࢡࢺࣜἲ࡞࡝ࢆ⏝࠸ࡓィ⟬࡟ࡼࡾࠊ⦆⾪Ẽయ࡜࢖࢜ࣥ࡜ࡢ CCS ࢆィ⟬࡛ࡁࡿࠋᮏ◊✲࡛ࡣࠊᵝࠎ࡞ᵓ㐀ࢆ௬ᐃࡋ࡚ CCS ࢆィ⟬ࡋࠊᐇࡿࡇ࡜࡛ࠊ࢖࢜ࣥࡢᵓ㐀ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ2020 ᖺᗘࡣప

ࡢ CCS ࡜Ⰻ࠸୍⮴ࢆ♧ࡍᵓ㐀ࢆ᥈⣴ࡍ

IM-MS ࢆ࢔ࣝ࢝ࣜ㔠ᒓ࢖࢜ࣥ㸦Na+, K+㸧࡜ࢡ࢚࣮ࣛ࢘ࣥࢸࣝ࠿ࡽ࡞ࡿ㘒య࡟㐺⏝ࡋࠊ␗ᛶయศ㞳࡜ᵓ㐀ᖐᒓࢆ⾜ࡗࡓࠋࢡ࢚࣮ࣛ࢘ࣥࢸࣝ࡜ࡋ࡚ࠊࢪ࣋ࣥࢰ
-18-ࢡࣛ࢘ࣥ-6㸦DB18C6㸧
ࠊDB21C7ࠊDB24C8ࠊDB30C10 ࡜࠸ࡗࡓ⎔ࡢࢧ࢖ࢬࡀ␗࡞ࡿ 4 ✀ࡢศᏊࢆ⏝࠸ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
MMFF94s ຊሙ࡟ࡼࡿ㓄ᗙ᥈⣴࡜ᐦᗘỗ㛵ᩘἲࢆ⏝࠸ࡓᵓ㐀᭱㐺໬ィ⟬࡟ࡼࡾࠊM+ࢪ࣋ࣥࢰࢡ࢚࣮ࣛ࢘ࣥࢸࣝ (M = Na, K)㘒
య࢖࢜ࣥࡢᏳᐃᵓ㐀ࢆồࡵࡓᚋࠊ࢖࢜ࣥ࡜
He ࡜ࡢ⾪✺᩿㠃✚ࢆィ⟬ࡋࡓࠋ㓄ᗙ᥈⣴ィ⟬࡟ࡣ CONFLEX ࢆ⏝࠸ࠊᵓ㐀᭱㐺໬ィ⟬࡟ࡣ Gaussian 16 ࢆ฼⏝ࡋࡓࠋ⾪✺᩿㠃✚ࡢィ⟬࡟ࡣ MOBCAL ࣉࣟࢢ࣒ࣛࡢࢺࣛࢪ࢙
ࢡࢺࣜィ⟬ࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

Fig.1. CCS distributions of M+(DB24C8) and M+(DB30C10)(M = Na, K) complexes at 86 K. Curves are Gaussian functions
for fitting the experimental plots (circles).

ᅗ 1 ࡟ Na+, K+࡜ 2 ✀ࡢࢪ࣋ࣥࢰࢡ࢚࣮ࣛ࢘ࣥࢸࣝ㸦DB24C8, DB30C10㸧࠿ ࡽ ࡞ ࡿ 㘒 య ࡢ IM-MS ࡟ ࡼ ࡾ ᚓ ࡽ ࢀ ࡓ 86 K ࡟ ࠾ ࡅ ࡿ ⾪ ✺ ᩿ 㠃 ✚(DTCCSHe,86)ศᕸࢆ♧ࡍࠋNa+ࢆྵࡴ㘒య࡜ K+(DB24C8)࡛ࡣ 2 ᮏ࡟ศ㞳ࡉࢀࡓศᕸࡀほࡉࢀࡓ㸦ᅗ 1a-c㸧ࠋゎᯒࡢ⤖ᯝࠊࡇࢀࡽࡢ㘒య࢖࢜ࣥࡢᵓ㐀ࢆ

DB24C8, DB30C10 ࡢ 2 ࡘࡢ࣋ࣥࢮࣥ⎔㛫ࡢ㊥㞳ࡀ␗࡞ࡿ 2 ✀ࡢࢥࣥࣇFig.2. Conformers of K+(DB24C8).

࢛࣐࣮࡟ᖐᒓࡋࡓ㸦ᅗ 2 ࡢ Closed ࡜ Open ᵓ㐀㸧ࠋ ᗘྍኚ IM-MS ࡢᐇ㦂࡟ࡼࡾࠊ300 K ࡛ࡣࡇࢀࡽ 2 ✀ࡢࢥࣥࣇ࢛࣐࣮㛫࡛␗ᛶ໬ࡀ㉳ࡁ࡚࠸ࡿࡀࠊ86 K ࡛ࡣ␗ᛶ໬ࡀ㉳ࡁ࡞࠸ࡇ࡜ࢆぢฟࡋࡓ[1]ࠋ୍᪉ࠊK+(DB30C10)࡛ࡣࣆ࣮ࢡ 1 ᮏࡢࡳࡀほࡉࢀࠊゎᯒࡢ⤖ᯝ Closed ᵓ㐀࡟ᖐᒓࡋࡓ[2]ࠋK+(DB30C10)ࡢ Closed ᵓ㐀ࡣࠊX ⥺⤖ᬗᵓ㐀ゎᯒࡸ NMR ࢆ⏝࠸ࡓ◊✲࡛ᥦၐࡉࢀࡓ”wrap around”ᵓ㐀[3,4]࡜㢮ఝࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

- 234 -

4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬ᐑ㷂⯗㸪᭹㒊ᆂ࿃㸪ࠐ኱ୗ៞ḟ㑻㸪⨾㰺ὠᩥ඾ࠊ➨ 68 ᅇ㉁㔞ศᯒ⥲ྜウㄽ఍ 2020‫ۻ‬ᇼ⏣ຊ㸪Ọ⏣฼᫂㸪୰㔝ඖၿ㸪኱ୗ៞ḟ㑻㸪ࠐ⨾㰺ὠᩥ඾ࠊ➨ 68 ᅇ㉁㔞ศᯒ⥲ྜウㄽ఍ 2020‫➎୕ࠐۻ‬ὒኴᮁ, ୰㔝ඖၿ, Ọ⏣฼᫂, ⨾㰺ὠᩥ඾ࠊศᏊ⛉Ꮫ఍࢜ࣥࣛ࢖ࣥウㄽ఍‫ࠐۻ‬᭹㒊ᆂ࿃, బ⸨Ⰻு, ኱ୗ៞ḟ㑻, ⨾㰺ὠᩥ඾ࠊศᏊ⛉Ꮫ఍࢜ࣥࣛ࢖ࣥウㄽ఍‫ࠐۻ‬ఀ⸨ᝆྣ, ୰ᓥ♸ྖ, ዟὠ㈼୍, ୰㔝ඖၿ, ⨾㰺ὠᩥ඾ࠊศᏊ⛉Ꮫ఍࢜ࣥࣛ࢖ࣥウㄽ఍‫ࠐۻ‬኱ୗ៞ḟ㑻ࠊIQCE 㔞Ꮚ໬Ꮫ᥈⣴ㅮ₇఍ 2020㸦౫㢗ㅮ₇㸧‫ࠐۻ‬୰ᓥඃᩯࠊỌ⏣฼᫂ࠊ⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍ ➨ 101 ᫓Ꮨᖺ఍‫➎୕ࠐۻ‬ὒኴᮁࠊỌ⏣฼᫂ࠊ኱ୗ៞ḟ㑻ࠊ⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍ ➨ 101 ᫓Ꮨᖺ఍‫ࠐۻ‬Ting HuangࠊỌ⏣฼᫂ࠊ⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍ ➨ 101 ᫓Ꮨᖺ఍‫ࠐۻ‬ᑠ‖⍞ኸࠊఀ⸨ᝆྣࠊ୰ᓥ♸ྖࠊ⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍ ➨ 101 ᫓Ꮨᖺ఍‫ࠐۻ‬࿴⏣ள㔛ᩯࠊ኱ୗ៞ḟ㑻ࠊ⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍ ➨ 101 ᫓Ꮨᖺ఍‫ࠐۻ‬Xi Heࠊ኱ୗ៞ḟ㑻ࠊ⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍ ➨ 101 ᫓Ꮨᖺ఍‫ࠐۻ‬ఀ⸨ᝆྣࠊᑠ‖⍞ኸࠊ୰ᓥ♸ྖࠊ⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍ ➨ 101 ᫓Ꮨᖺ఍5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Keijiro Ohshimo, Xi He, Ryosuke Ito, and Fuminori Misaizu, J. Phys. Chem. A, 125, 3718 (2021).
࣭Yuji Nakashima, Yuri Ito, Mizuhiro Kominato, Keijiro Ohshimo, and Fuminori Misaizu, J. Chem. Phys. 154,174301 (2021).
‫ۻ‬Sota Tainaka, Tomoyuki Ujihira, Mayuko Kubo, Motoki Kida, Daisuke Shimoyama, Satoru Muramatsu, Manabu
Abe, Takeharu Haino, Takayuki Ebata, Fuminori Misaizu, Keijiro Ohshimo, and Yoshiya Inokuchi, J. Phys. Chem. A,
124, 9980 (2020).
‫ۻ‬Keijiro Ohshimo, Ryosuke Sato, and Fuminori Misaizu, J. Phys. Chem. A, 124, 7999-8004 (2020).
‫ۻ‬Kiichirou Koyasu, Ryohei Tomihara, Toshiaki Nagata, Jenna W. J. Wu, Motoyoshi Nakano, Keijiro Ohshimo,
Fuminori Misaizu, and Tatsuya Tsukuda, Phys. Chem. Chem. Phys., 22, 17842 (2020).
‫ۻ‬Yuji Nakashima, Yuri Ito, Kenichi Okutsu, Motoyoshi Nakano, and Fuminori Misaizu, Phys. Chem. Chem. Phys.,
22, 16926 (2020).
‫ۻ‬M. Abdul Latif, Toshiaki Nagata, Motoyoshi Nakano, Keijiro Ohshimo, and Fuminori Misaizu, J. Phys. Chem. C,
124, 9604 (2020).
࣭Keizo Tsukamoto, Tetsuro Tamura, Hiromi Matsusaki, Masahide Tona, Hiroaki Yamamoto, Yuki Nakagomi, Hiroshi
Nishida, Yoshihiro Hirai, Nobuo Nishimiya, Masaomi Sanekata, Keijiro Ohshimo, Kiichirou Koyasu, and Fuminori
Misaizu, Jpn. J. Appl. Phys., 59, SHHB05 (2020).

ཧ⪃ᩥ⊩[1] S. Tainaka, F. Misaizu, K. Ohshimo, Y. Inokuchi et al., J. Phys. Chem. A 124, 9980 (2020).
[2] K. Ohshimo, X. He, R. Ito, F. Misaizu, J. Phys. Chem. A 125, 3718 (2021).
[3] M.A. Bush, M.R. Truter, Chem. Commun. 1439 (1970).
[4] D. Live, S. I. Chan, J. Am. Chem. Soc. 98, 3769 (1976).

- 235 -

ࢱࣥࣃࢡ㉁ࡢᵓ㐀࡜ᶵ⬟Ⓨ⌧ࡢ㛵㐃ᛶ
Relation between functional expression and structure in protein‫ࢺ࢜ࣝࢗࢺࣥࣜۑ‬ṇ⨾ (ி㒔ᗓ❧኱Ꮫ኱Ꮫ㝔⏕࿨⎔ቃ⛉Ꮫ◊✲⛉)1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ㄢ㢟࡛ࡣࢱࣥࣃࢡ㉁ࡢᵓ㐀ኚ໬࡜ᶵ⬟ࡢኚ໬࡟ࡘ࠸࡚ศᏊ࡛ࣞ࣋ࣝ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚௨ୗࡢࢸ࣮࣐࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ

CD44 ࡟࠾ࡅࡿእຊ࡟ࡼࡿᵓ㐀ኚ໬࡜⢾⤖ྜぶ࿴ᛶኚ໬
&' ࡣ⣽⬊᥋╔ࡸ⣽⬊㐟㉮࡟㛵୚ࡍࡿࢱࣥࣃࢡ㉁࡛ࣄ࢔ࣝࣟࣥ㓟 +$ ࡜୍㐣ⓗ࡞᥋╔࡜⬺╔ࢆ⧞ࡾ㏉
ࡍࡇ࡜࡛⣽⬊ࡢ࣮ࣟࣜࣥࢢࢆᢸ࠺ࠋ&' ࣄ࢔ࣝࣟࣥ㓟⤖ྜࢻ࣓࢖ࣥ㸦+$%'㸧ࡣᐃᖖ≧ែ࡛ࡣ &ᮎ➃ࡀ୍ᐃࡢᵓ㐀ࢆࡶࡘ 2UGHUHG 2  ᵓ㐀࡛ࠊእຊ࡟ࡼࡗ࡚ & ᮎ➃ࡢ୍㒊㸦GLVRUGHU 㡿ᇦ㸧ࡀ࡯࡝ࡅࡓ 3DUWLDOO\'LVRUGHUHG
3'  ᵓ㐀࡟㑄⛣ࡍࡿᶵᵓࡀᐇ㦂⤖ᯝ࠿ࡽᥦ᱌ࡉࢀ࡚࠸ࡿࠋᮏ◊✲ㄢ㢟࡛ࡣ⾑ὶ࡞࡝ࡢእຊ࡟ࡼࡗ࡚㉳ࡇࡿࢱ
ࣥࣃࢡ㉁ࡢᵓ㐀ኚ໬ࡀᇶ㉁⤖ྜᛶࢆไᚚࡋ࡚࠸ࡿྍ⬟ᛶ࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵࡓࠋ&X=Q62' ࡟࠾ࡅࡿⅬኚ␗ᑟධ࡟ࡼࡿ㓝⣲άᛶኚ໬
3 ✀Ꮡᅾࡍࡿࣄࢺࡢ SOD㸦superoxide dismutase㸧ࡢ୍ࡘ࡛࠶ࡿ SOD1 ࡣ⣽⬊ෆ࡟Ꮡᅾࡋ࡚࠾ࡾࠊᐙ᪘ᛶ
➽ⴎ⦰ᛶഃ⣴◳໬⑕(FALS: Familial Amyotrophic Lateral Sclerosis㸧࡞࡝ࡢ⚄⤒⑌ᝈ࡜㛵ಀࡋ࡚࠸ࡿࠋᮏ◊✲࡛ࡣ  㔞య⏺㠃௜㏆࡟࠾ࡅࡿⅬኚ␗࡟ࡼࡿ཯ᛂάᛶࢧ࢖ࢺ࿘㎶ࡢ⁐፹⎔ቃࡢኚ໬࡜㓝⣲άᛶኚ໬ண

ࡢྍ⬟ᛶ࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵࡓࠋ ࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ NDOOLNUHLQ ࣇ࢓࣑࣮ࣜࡢᇶ㉁ࡢศᏊㄆ㆑ᶵᵓ
ࢱࣥࣃࢡ㉁ศゎ㓝⣲ ./. ࣇ࢓࣑࣮ࣜ࡟ᒓࡋ࡚࠸ࡿࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ࡛࠶ࡿࢽ࣮ࣗࣟࣉࢩࣥ KLK8 ࡣࠊ኱⬻㎶⦕⣔࡛Ⓨ⌧ࡉࢀࠊࡇࡢࢱࣥࣃࢡ㉁ࡢᶵ⬟㞀ᐖࡣ⢭⚄⑌ᝈࡢཎᅉ࡜࡞ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀ
ࡽศᏊㄆ㆑ᶵᵓࡢヲ⣽ࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋᩘ✀ࡢᑠࡉ࡞࣌ࣉࢳࢻࣔࢹࣝࢆᇶ㉁࡜ࡍࡿ KLK8-࣌ࣉࢳࢻ」ྜయࣔࢹࣝࢆ⏝࠸࡚ࠊ཯ᛂ㏿ᗘㄽⓗ࡞ᐇ㦂⤖ᯝ࡜ࡢẚ㍑࠿ࡽศᏊㄆ㆑ᶵᵓࡢゎ᫂ࢆ┠ᣦࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
CD44 ࠾ࡼࡧ SOD㸯ࡢ MD ィ⟬࡟ࡣ Gromacs2019 ࢆ⏝࠸ࡓࠋึᮇᵓ㐀࡟ࡣ㹖⥺⤖ᬗᵓ㐀ࡸ NMR ᵓ㐀ࢆ⏝࠸ࡓࠋ୍᪉ࠊKLK ࡢ MD ィ⟬࡟ࡣ myPresto ࢆ⏝࠸ࡓࠋ」ྜయࣔࢹࣝࡢึᮇᵓ㐀ࡣ sievgene ()XNXQLVKL<etal.   - 0RO *UDSK 0RGHO  )ࢆ⏝࠸ࢻࢵ࢟ࣥࢢࢆ⾜ࡗ࡚ࣔࢹࣝ໬ࢆ⾜࠸ MD ィ⟬࡟ࡣ cosgene()XNXQLVK<HWDO  -3K\V&KHP%)ࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

3-1. CD44 ࡟࠾ࡅࡿእຊ࡟ࡼࡿᵓ㐀ኚ໬࡜⢾⤖ྜぶ࿴ᛶኚ໬ࡇࡢ◊✲࡟࠾࠸࡚ࠊ&' ࡟ᑐࡋ࡚ࡣ 2ࠊ3' ᵓ㐀ࢆࠊ+$ ⤖ྜ࣮ࣔࢻ࡜ࡋ࡚ࡣ㸰ࡘࡢ࣮ࣔࢻࢆ௬ᐃࡋࠊィ  ࣔࢹࣝࢆ⏝࠸࡚ࡑࢀࡒࢀ QV ࡢ 137 ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ3' ᵓ㐀ࡣ 2 ᵓ㐀ࡼࡾࡶぶ࿴ᛶࡀ㧗ࡃࠊDSRࠊKROR㸫ࡍ࡭࡚ࡢࣔࢹࣝ࡟࠾࠸࡚ & ᮎ➃ࡢ 3' 㡿ᇦࡢࡳ࡞ࡽࡎ㐲㝸࡟఩⨨ࡍࡿ +$ ⤖ྜࢧ࢖ࢺ࡟࠶ࡿ
ȕࠊȕ ࢫࢺࣛࣥࢻ࡟ࡶᵓ㐀ኚ໬ࡀぢࡽࢀࡓࠋ2 ᵓ㐀࡛ࡣ /\V ࡸ $UJ ࡞࡝ࡢᴟᛶࡢᙉ࠸ᩘ✀ࡢ࢔࣑ࣀ㓟ṧᇶࡢࡳ࡜┦஫స⏝ࡋ࡚࠸ࡿࡀࠊ3' ᵓ㐀࡛ࡣከᵝ࡞࢔࣑ࣀ㓟ṧᇶ࡜ࡼࡾᗈ⠊ᅖ࡟ࢃࡓࡾ┦஫స⏝ࡋ࡚࠸ࡿࡇ࡜
ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ2 ᵓ㐀࡟࠾ࡅࡿ +$ ⤖ྜࡀ㹍ᵓ㐀࠿ࡽ㹎㹂ᵓ㐀࡬ࡢᵓ㐀㑄⛣ࢆຓࡅࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

- 236 -

ᖹ⾮≧ែ࡛ࡼࡾᏳᐃ࡛࠶ࡿ 2 ᵓ㐀࡛ +$ ⤖ྜ࡜⦆ࡃ⤖ྜࡋࡓ &' ࡣ⾑ὶୗࠊእຊ࡟ࡼࡗ࡚ 2 ᵓ㐀࠿ࡽ 3'ᵓ㐀࡬㑄⛣ࡍࡿࡇ࡜࡛࢔ࣟࢫࢸࣜࢵࢡ࡟⤖ྜࢧ࢖ࢺࡢᵓ㐀ࡀኚ໬ࡋ +$ ⤖ྜぶ࿴ᛶࢆୖ᪼ࡉࡏࡿᶵᵓࢆᨭᣢ
ࡍࡿ⤖ᯝ࡜࡞ࡗࡓࠋ⌧ᅾࠊ3' 㡿ᇦ࡟࠾ࡅࡿⅬኚ␗ࡢࡼࡿ㹆$ ⤖ྜぶ࿴ᛶࡢไᚚ࡟ࡘ࠸᳨࡚ウ୰࡛࠶ࡿࠋ

Cu,Zn-SOD1 ࡟࠾ࡅࡿⅬኚ␗ᑟධ࡟ࡼࡿ㓝⣲άᛶኚ໬
SOD㸯ࡢ fALS ࡬ࡢ㛵㐃ᛶࡀሗ࿌ࡉࢀ࡚࠸ࡿⅬኚ␗యࡢ࠺ࡕ 2 㔞య⏺㠃࡟ኚ␗ࡀᏑᅾࡍࡿ 3 ✀࡜㔝⏕ᆺ࡟ࡘ࠸࡚ࡑࢀࡒࢀ NPT ィ⟬ࢆ⾜࠸ࠊኚ␗Ⅼ࡜ࡣ㐲㝸ࡢ཯ᛂάᛶ㒊఩ࡢ⁐፹࿴⎔ቃࡢኚ໬࡟ࡘ࠸࡚ゎᯒࢆ⾜ࡗ
ࡓࠋSOD1 ࡣ Cu ࡜㹘n ཎᏊࢆᇶ㉁⤖ྜ࣏ࢣࢵࢺࡢᗏ࡟᭷ࡋࠊCu ཎᏊࡀᇶ㉁࡛࠶ࡿ O2-ࢆ㐣㓟໬Ỉ⣲࡟ኚ᥮ࡍࡿࠋࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࠊ㔝⏕ᆺ࡛ࡣ Cu ୖ 3~3.5  ௜㏆࡟ỈࡀᏑᅾࡋ࡚࠸ࡿࡀࠊኚ␗య࡛ࡣ୍ࡘ୍ࡘࡢ
ỈศᏊࡢ⁫ᅾ᫬㛫▷ࡃࡼࡾ㐲ࡃ࡟ᏑᅾࡍࡿࠋCu ࡣᇶ㉁⤖ྜ࣏ࢣࢵࢺࡢᗏ࡟Ꮡᅾࡋ࡚࠸ࡿࡀࠊኚ␗ᑟධ࡟ࡼࡗ
࡚ Cu ཎᏊ࡬ࡢᇶ㉁ࡢ࢔ࢡࢭࢫ⤒㊰࡟ኚ໬ࡀ⌧ࢀࡓ࡜௬ᐃࡋࠊO2-ࢆῧຍࡋࡓ co-solvent MD ィ⟬ࢆ⾜ࡗࡓࠋࡇࢀࡲ࡛ࡢᐇ㦂⤖ᯝ࡟ࡼࡾ Arg143 ࡜ Thr137 ࡀᇶ㉁⤖ྜ࣏ࢣࢵࢺୖ㒊࡟Ꮡᅾࡋࠊ㈇㟁Ⲵࢆ᭷ࡍࡿᇶ㉁ࢆ࣏ࢣࢵ
ࢺࡢᗏ࡟࠶ࡿ Cu ࡬࡜㟼㟁ⓗ࡟ㄏᑟࡍࡿ࡜⪃࠼ࡽࢀ࡚ࡁࡓࠋco-solvent MD ィ⟬ࡢ⤖ᯝࠊ㔝⏕ᆺ࡛ࡣ O2-ࡣ Arg143
࡟ᤕᤊࡉࢀ᩿⥆ⓗ࡟ Cu ୖ㒊࡟Ꮡᅾࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋኚ␗య࡛ࡣࡇࡢ Arg143 ࡟ࡼࡿᇶ㉁࢔ࢽ࢜ࣥࡢ
ᤕᤊ⬟ຊ࡟ᕪࡀ⌧ࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊᇶ㉁࢔ࢡࢭࢫ⤒㊰ධࡾཱྀࢧ࢖ࢬ࡟ࡶኚ఩ࡣᙳ㡪ࢆ୚࠼ࡿࠋࡇ
ࡢࡼ࠺࡟ Cu ୖ㒊ࡢ⁐፹࿴⎔ቃࡸᇶ㉁࢔ࢡࢭࢫ⤒㊰࡟Ⅼኚ␗ࡀ࢔ࣟࢫࢸࣜࢵࢡ࡟ᙳ㡪ࢆ୚࠼ࡿࡇ࡜࡟ࡼࡾࠊኚ
␗య࡟࠾ࡅࡿ㓝⣲άᛶ࡟ᙳ㡪ࡍࡿྍ⬟ᛶࢆぢฟࡋࡓࠋ ࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ NDOOLNUHLQ ࣇ࢓࣑࣮ࣜࡢᇶ㉁ࡢศᏊㄆ㆑ᶵᵓ
ࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ࡛ࡣᇶ㉁ࡢษ᩿㒊఩ࡢ๓᪉࡟࠶ࡿ࢔࣑ࣀ㓟ṧᇶࡢ㓄ิࡢ㔜せᛶ࡟ࡘ࠸࡚㆟ㄽࡉࢀࡿࡇ࡜ࡀከ࠸ࠋKLK8 ࡟࠾࠸࡚ࡶษ᩿㒊఩ࡢ๓᪉ 3 ࡘࡢ࢔࣑ࣀ㓟ṧᇶࡢ㓄ิࡢ㐪࠸ࡀᇶ㉁≉␗ᛶࢆᕥྑࡍࡿࡇ
࡜ࡀᐇ㦂ⓗ࡟ሗ࿌ࡉࢀ࡚࠸ࡿࠋ௒ᅇࠊ3 ࡘࡢ࢔࣑ࣀ㓟ṧᇶ࠿ࡽ࡞ࡿᑠࡉ࡞࣌ࣉࢳࢻࣔࢹࣝࢆ⏝࠸ KLK8-࣌ࣉ
ࢳࢻ」ྜయࣔࢹࣝ 5 ✀࡟ࡘ࠸࡚ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ᐇ㦂⤖ᯝ࡜ࡢẚ㍑ࢆ⾜ࡗࡓࠋᇶ㉁ࡢ⤖ྜぶ࿴ᛶ࡜ゐ፹ 3 ṧᇶࡸ࢜࢟ࢩ࢔ࢽ࣮࢜ࣥ࣍ࣝࢆᙧᡂࡍࡿṧᇶ࡟ᑐࡍࡿ㓄ྥᛶࡀᐇ㦂࡟࠾ࡅࡿᇶ㉁≉␗ᛶ࡜㛵㐃ࡋ࡚࠸ࡿࡇ࡜ࢆぢฟࡋࡓࠋ⌧ᅾࠊᇶ㉁ࡢษ᩿㒊఩ࡢᚋ᪉ࡶ࢔࣑ࣀ㓟ṧᇶࡢ㓄ิࡢ㔜せᛶ࡟ࡘ࠸࡚ࡶ᳨ウ୰࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬

SOD1 ࡟࠾ࡅࡿⅬኚ␗ᑟධࡼࡿ㓝⣲άᛶኚ໬ண

ࠊࣜࣥࢺࢗࣝ࢜ࢺṇ⨾ࠊࣜࣥࢺࢗࣝ࢜ࢺࣘࣁࠊ⚟すᛌᩥ(2019: ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2021 ᫓Ꮨᖺ఍)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ ۻ‬Lintuluoto, M., Horioka, Y., Hongo, S., Lintuluoto, J. M., & Fukunishi, Y. (2021). Molecular Dynamics
Simulation Study on Allosteric Regulation of CD44-Hyaluronan Binding as a Force Sensing Mechanism. ACS
omega, 6(12), 8045-8055.

- 237 -













Development of functions of liquid crystals utilizing dynamic
intermolecular interactions based on molecular motion !

"1 
ÌmQµz¥DKwDÊwD»k¶¸¨cÙ\Ï³!±!Â -p Úd7=C2{
ÛÔjQµ27=C8E7/r¬wL ©0gØ \x0  È!¬w2Ò/!"7=CÖ!¬ªIM¤/ ¬wL

/7=CÖ!¬ªIM¤"¬wL!

0"%*! -&qgØ¬wL!r¬wË¯"KÞ< 17 Kß!(É/!) ¬w"Ñ¯ÔjQµ+l`ÝQµ!ÓY +\Ô!_L ¡! w.
 "·!ea/®f¨Îv /F!H*¦wXw2N{"Êw2{xSd!Ù^ÐX ,»k¶¸¨ Ï sx0/y"!,!¡t2{¬wL'.ÛÔj¬w/<:B45;@63AÞNRß!¬w «²2¾ UÍ!,e!
r¬wL"¦.NR "ªJG!nÜbÞ300~450 K °nßr¬w¨SdÖªIM¤Þ¬Wß2­ ¡t/¢a!1r¬wË¯2­ NR "§Á0 ¬W!É2 -0#r¬wË¯2­Û]Ôj!\x|Õ Á /Zºw /«²"¬W!É2 -/2T!©~02SdÖ}ÄpOe/ w8>:?9EH!X¨Ï!×P F¼Y/_L 8>
:?9E¡!ÚD¬DRf¡w2­KSd2V¿/) uÀSdÆÅ$½
¹ /!) 2019 mn' in×£ÇÞDFTßÅ´ ,/ÒoÃ2¾[Òo!¬W$!h+ ¹P/* H

/R3jeX!Å´*¾ 2020 mn"Q2SdF¼ dDFT Å´DSdX@fÞMDß5#&)E5'C2¶(\ SdÆÅb2}/2©¨«²2¾

2 
SdÏDSdÖªIM¤DSdÒFLDR3jeX!0 0 p!!Å´b ,.5#&)E5'C2¾\/SdX@f ,.ª!SdÒFL2Sd) A<¢Ra¨SdÖ}Ä!n¢!SV2q)/!Ø "*520$&6 25¤/')7 Å´ 15 
Sd!7=CinSV2Å´SdÖªIM¤2q)/!Ø*DXVVLDQÅ´2¾/iªIM¤2Á*.g¦, ')7,/F/¬ªIM¤!É2h/0"> OºK

2 i 15 Sd!ÒoÃ2¾g¦

/Ë¯n³! w/[ w2§¢/) uÀSd!ÏG!É2h/mÖOe *LQ]EXUJ/DQGDX °p K )OXLG3DUWLFOH'\QDPLFVÞ)3'ß2¤!ÒFL2?B Å´/Þ&ßµ!§R2])mÖÜbUSÞ$'()'7'ß)7(Þ&/&ß?B3A+ &/& s!)E- 238 -

E§f/"§R7!:AR3jeX!5#&)E5'C2¾Þ&ß

3 
GROMACS,/ MD 5#&)E5'C ,SdÒoDSdÒ! CCA2q)!H!S

dÖªIM¤!SV2 Gaussian 09 2¤q)/b2}02Q C!£¨7=C@7!¬¡w2£Ã/) ¤-0p2X¨YJLÌ4 d\G!Å´! -g¦2/2Á=Þß:L¨"SdÇ¨%3<$2£Ã/)

')7 Å´ 0' 5#&)E5'C2¤SdÖªIM¤! CCA -¬m -0mn'¨Yv2q)/(2¾  mn -  mn g*JFwSdÖªIM¤2{ ªIM¤Q!¨¶(i,c!SdÖ!ªIM¤E³!W26{/ /

X¨SdÖªIM¤¹  .{ 02  m'!Å´ ¤/g¦E92  /

-



X¨SdÖªIM¤!¹ "7=CÖªIM¤SdÒoDSdÒFDÚDAÉu_D
7=Ccn *¤ [I!Sd!¡w!%87EA!É2Ã  /o]«²2)  mn -  mn

0' 5#&)E5'C ,[u_/SdÒo CCA2q)/b2¡§ :L¨ "*F¼¨ ¤-0/?
/ &\DQR SHQW\OELSKHQ\OÞ&%ß! 0' 5#&)E5'C2¾zH!  Sd  0' 5#&)E5'C2¾L\ª2§¢/u_"SdÒo CCA ¦/ Á /Þß


4 



 kfÜb«²

d! w®f$w8B«²4>#E C ;xZ ³W¬w

$!7=C7 ,/kºV=´ D¥§2QOLQH =RRP mnl .HdE$ ,/¤y¤!Rºh²«²2 ;xZ ³;0&'3((0 ,/ÂP^q¬ªIM¤!%E6C´ D¥§2QOLQH =RRP mnl lf2C@C«²§2 ;xZ

 r ~xc- S`G³SdÐX ,/¬ª

IM¤!MX´ D¥§2QOLQH =RRP mnl kfÜb«²

d! w®f1G§mn Üb«²2<8FKLGD³3URSDJDWLRQRI,QWHUPROHFXODU,QWHUDFWLRQVLQ/LTXLG&U\VWDOV´ D¥§2QOLQH =RRP mnl ,TNf,0,9E?¤D|o9E«² 8¡t2ºw!hF:"B6Eb ;xZ ³!SdÆÅ!)!SdÇ´ D¥§2QOLQH =RRP mnl

5





 ³7KHUPDO PROHFXODU PRWLRQ FDQ DPSOLI\ LQWHUPROHFXODU LQWHUDFWLRQV´ < 8FKLGD  * :DWDQDEH 7 $NLWD 1

1LVKL\DPD-3K\V&KHP%  - 239 -

ศᏊᛶᑟ㟁࣭☢ᛶᮦᩱ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical study on molecular conducting and magnetic materials‫ۑ‬୰㔝 ⩏᫂ࠊᒸᮏ ᑦ኱ࠊ⚟Ọ ኱႐ࠊᑠᕝ ෽ᖹࠊΎỈ ࡉࡽࡽ㸦ி㒔኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉໬Ꮫᑓᨷࠊி㒔኱Ꮫ⎔ቃᏳ඲ಖ೺ᶵᵓ㸧1◊✲┠ⓗᶵ⬟ᛶศᏊᅛయࡣࠊᵓᡂศᏊࡑࡢࡶࡢࡢ≉ᛶ࡟ຍ࠼࡚ࠊศᏊࡢ㓄ิᵝᘧ࡟ࡼࡗ࡚≀ᛶࡀ኱ࡁࡃኚ໬ࡍࡿࡇ

࡜࠿ࡽࠊᡤᮃࡢ≀ᛶࢆⓎ⌧ࡉࡏࡿୖ࡛ࠊศᏊ㛫࡟ാࡃ㠀ඹ᭷⤖ྜᛶ┦஫స⏝ࢆไᚚࡍࡿࡇ࡜ࡀ㔜せ࡞ㄢ㢟࡜࡞ࡗ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ㟁Ꮚ࢔ࢡࢭࣉࢱ࣮࡛࠶ࡾࠊྠ᫬࡟Ỉ⣲⤖ྜࡸࣁࣟࢤࣥ⤖ྜ➼ࡢศᏊ㛫┦஫స⏝㸦㉸ศᏊ┦஫స⏝㸧ࡢཷᐜ㒊఩࡜ࡋ࡚ᶵ⬟ࡍࡿࣆࣜࢪࣝᇶࢆ᭷ࡍࡿ࣌ࣜࣞࣥࢪ࢖࣑ࢻ㸦PDI㸧ㄏᑟయࢆ⏝࠸ࡓᶵ⬟ᛶศᏊᅛయࡢ㛤Ⓨࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲᐦᗘỗ㛵ᩘ㸦DFT㸧ἲ࡟ࡼࡿ⌮ㄽⓗゎᯒࡣࠊGaussian 09㸦Rev. E.01㸧ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋᇶᗏ㛵ᩘ࡜ࡋ࡚ cc-pVDZ ࢆ౑⏝ࡋࠊCAM-B3LYP ἲ࡟ࡼࡾồࡵࡓࠋບ㉳≧ែࡢィ⟬ࡣࠊTD-DFT ἲ࡟ࡼࡾ⾜ࡗࡓࠋ⁐፹ຠᯝࡣࠊ✚ศ᪉⛬ᘧ⾲ᘧ໬ศᴟ㐃⥆యࣔࢹࣝ㸦IEFPCM㸧࡟ࡼࡾྲྀࡾධࢀࡓࠋ

3◊✲ᡂᯝ࣌ࣜࣞࣥࢪ࢖࣑ࢻ㸦PDI㸧㢮ࡣࠊ㧗࠸⇕࣭ගᏳᐃᛶࢆ᭷ࡋࠊගᏛᮦ

ᩱࡸ FET ᮦᩱ➼࡟฼⏝ࡉࢀࡿ n ᆺ༙ᑟయ࡛࠶ࡿࡀࠊ㞴⁐ᛶ࡛࠶ࡿࡇ࡜ࡀ≀㉁㛤Ⓨୖࡢၥ㢟࡜࡞ࡗ࡚࠸ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ⁐ゎᛶ࡜㟁Ꮚ
3\&Q &O3',; &O5 3\ &+ Q
3\& 3',; +5 3\ &+ & &O3',; &O5 &+& 3',; +5 &+& &O3',; &O5 &+
3\ S\ULG\O ཷᐜᛶࡢྥୖࡢࡓࡵࢸࢺࣛࢡࣟࣟయ࡟ࣆࣜࢪࣝᇶࢆᑟධࡋࡓ
(PyCn)2Cl4PDI (n = 0, 1, 2)࡟ࡘ࠸᳨࡚ウࡋࡓࠋ(PyCn)2Cl4PDI ࡣࠊ4-࢔࣑ࣀࣆࣜࢪࣥࠊ4-࢔࣑ࣀ࣓ࢳࣝࣆࣜࢪࣥࠊ4-࢔࣑ࣀ࢚ࢳࣝࣆࣜࢪࣥࢆ཯
ᛂࡉࡏࡿࡇ࡜࡟ࡼࡾࠊ㉥Ⰽ⢊ᮎ࡜ࡋ࡚ᚓࡓ[1]ࠋ(PyCn)2Cl4PDI ࡣࠊ⁐ᾮ୰࡛ UV ගࢆ↷ᑕࡍࡿࡇ࡜࡟ࡼࡾⓎගࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋD

ᅗ 1 ࡟ RCAM-B3LYP/cc-pVDZ ࡛ࣞ࣋ࣝィ⟬ࡋࡓ(PyC2)2Cl4PDI ࡢࣇࣟࣥࢸ࢕࢔㌶㐨ࢆ♧ࡍࠋHOMOࠊLUMO ࡜ࡶ࡟࣌ࣜࣞࣥ㦵᱁ୖ࡟ศᕸ
ࡋ࡚࠾ࡾࠊ࢖࣑ࢻ㒊఩ࡢ❅⣲ୖࡣἼື㛵ᩘࡢ⠇࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀศ
࠿ࡿࠋࡋࡓࡀࡗ࡚ࠊHOMOࠊLUMO ࡟ᑐࡍࡿ࣌ࣜࣞࣥ㦵᱁࡬ࡢ໬Ꮫಟ

E㣭ࡢᙳ㡪ࡣ኱ࡁ࠸ࡀࠊ࢖࣑ࢻ㒊఩࡬ࡢ⨨᥮ᇶᑟධࡢᙳ㡪ࡣᑠࡉ࠸࡜⪃࠼ࡽࢀࡿࠋᅗ 2 ࡟(PyC2)2Cl4PDI ࡢ DMF ⁐ᾮ㸦~2×10−5 M㸧ࡢ⣸እྍど㏆㉥እ྾཰ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋDMF ୰ࠊTD-CAM-B3LYP/cc-pVDZ ࣞ
࡛࣋ࣝ(PyC2)2Cl4PDI0ࠊ(PyC2)2Cl4PDI•−ࡢ྾཰ࢫ࣌ࢡࢺࣝࡢィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊ(PyC2)2Cl4PDI0 ࡢ HO → LU 㑄⛣࡟ᖐᒓࡉࢀࡿ྾཰ᖏࡀ 2.591- 240 -

ᅗ 1. RCAM-B3LYP/cc-pVDZ ࡛ࣞ࣋ࣝ ィ ⟬ ࡋ ࡓ (PyC2)2Cl4PDI ࡢ (a)LUMO ࡜(b) HOMOࠋeVࠊ(PyC2)2Cl4PDI•−ࡢ α-HO → α-LUࠊȕ-HO → ȕ-LUࠊα-HO→ α-LU+1 㑄⛣࡟ᖐᒓࡉࢀࡿ྾཰ᖏࡀࠊ1.5~1.9 eV ࡟⌧ࢀࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡲࡓࠊ㢮ఝ໬ྜ≀࡛࠶ࡿ& &O3',•− [2]ࠊ & &O3', >@ࡢࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࡶ
ྠᵝࡢ྾཰ᖏࡀほࡉࢀ࡚ࡇ࡜࠿ࡽࠊᅗ 2 ࡢ 1~2 eV ࡢ྾཰ᖏࡣࣛࢪ࢝ࣝ࢔ࢽ࢜ࣥࡢ(PyC2)2Cl4PDI•−ࠊ2.3 eV ௜㏆ࡢ྾཰ᖏࡣ୰ᛶࡢ(PyC2)2Cl4PDI0 ࡟ᖐᒓࡉࢀࠊண᝿ࡉࢀࡓࡼ
࠺࡟ HOMOࠊLUMO ࡟ᑐࡍࡿ࢖࣑ࢻ㒊఩࡬ࡢ⨨᥮ᇶᑟධࡢᙳ㡪ࡣᑠࡉ࠸ࠋ(C5)2PDIࠊ(C5)2Cl4PDI ࡢ➨ 1 㑏ඖ㟁఩ࡣࠊ
−1.04ࠊ−0.82 V vs. Fc/Fc+࡜ࢡࣟࣟ໬࡟ࡼࡿ㟁Ꮚཷᐜᛶࡢྥ

ᅗ 2. (PyC2)2Cl4PDI ࡢ DMF ⁐ᾮ㸦~2×10−5 M㸧ࡢ⣸እྍど㏆㉥እ྾཰ࢫ࣌ࢡࢺࣝࠋ

ୖࡀሗ࿌ࡉࢀ࡚࠾ࡾ[3]ࠊ(PyCn)2Cl4PDI ࡶྠࡌࡃ−0.8 V
㸦ELUMO = −4 eV㸧⛬ᗘࡢ㟁Ꮚཷᐜᛶࢆ᭷ࡍࡿ࡜ᮇᚅࡉࢀࡿࠋ
(PyC2)2Cl4PDI ࡢࣛࢪ࢝ࣝ࢔ࢽ࢜ࣥሷࢆస〇ࡍࡿࡓࡵࠊo-ࢪࢡࣟࣟ࣋ࣥࢮࣥ㸦Cl2Bz㸧୰࡛ Zn ⢊ᮎࠊࡲࡓࡣ
ࢸࢺࣛ࢟ࢫ㸦ࢪ࣓ࢳࣝ࢔࣑ࣀ㸧࢚ࢳࣞࣥࢆ㑏ඖ๣࡜ࡋ࡚(PyC2)2Cl4PDI ࡟స⏝ࡉࡏࡓ࡜ࡇࢁࠊ⃰⥳Ⰽ⁐ᾮࡀᚓࡽࢀࡓࠋࡉࡽ࡟ࡇࡢ⁐ᾮࡼࡾࠊᬯ⥳Ⰽࡢ⢊ᮎ࡜࡜ࡶ࡟ࠊᶳⰍᯈ≧⤖ᬗࢆᚓࡓࠋᚋ⪅ࡣ X ⥺ᵓ㐀ゎᯒ࡟ࡼࡾࠊ
Cl2Bz ศᏊࢆྵࡴ(PyC2)2Cl4PDI·2Cl2Bz ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ(PyC2)2PDI ศᏊ[4]࡛ࡣ࣌ࣜࣞࣥ㦵᱁ࡣᖹ㠃ⓗ࡛࠶ࡿࡀࠊ(PyC2)2Cl4PDI ࡛ࡣࠊሷ⣲㛫ࡢ❧య㞀ᐖࡢࡓࡵ࡟ࠊ࣌ࣜࣞࣥ㦵᱁୰ࡢࢼࣇࢱࣞࣥ㒊఩㛫ࡢ 2 㠃ゅ࡛
30 ᗘ⛬ᗘศᏊࡀࡡࡌࢀ࡚࠾ࡾࠊࣆࣜࢪ࢚ࣝࢳࣝᇶࡣࢩࢫᆺ࡜࡞ࡗ࡚࠸ࡓࠋࡲࡓࠊࣆࣜࢪࣥ⎔ྠኈࡣ ʌʌ ✚ᒙ࣒࢝ࣛࢆᙧᡂࡋࠊ࣌ࣜࣞࣥ㦵᱁ࡢ㛫࡟ Cl2Bz ศᏊࡀᤄධࡍࡿᙧ࡛✚ᒙࡋ࡚࠸ࡓࠋࣆࣜࢪࣥ⎔ୖࡢ❅⣲ཎᏊࡸ࢝ࣝ࣎ࢽࣝᇶࡢ㓟⣲ཎᏊ࡜௚ࡢศᏊࡢ࣓ࢳࣞࣥ఩Ỉ⣲ཎᏊ࡜ࡢ㛫࡛▷㊥㞳᥋ゐࡀぢࡽࢀࡓࠋZn ⢊ᮎ࡟ࡼࡿ㑏ඖ࡛ᚓࡽࢀࡓᬯ⥳Ⰽ⢊ᮎࡢຍᅽᡂᆺヨᩱ࡟ࡘ࠸࡚㟁Ẽఏᑟᗘࢆᐃࡋࡓ࡜ࡇࢁࠊ
ᐊ

ఏᑟᗘ 1.7î10−8 S cm−1ࠊάᛶ໬࢚ࢿࣝࢠ࣮0.36 eV ࡢ༙ᑟయⓗᣲືࢆ♧ࡋࡓࠋ௒ᅇࡣࣛࢪ࢝ࣝ࢔ࢽ࢜ࣥሷࡢ⢊ᮎࡋ࠿ᚓࡽࢀ࡞࠿ࡗࡓࡀࠊ
ࡉࡽ࡟ࣛࢪ࢝ࣝ࢔ࢽ࢜ࣥሷࡢ༢⤖ᬗస〇᮲௳ࢆ᳨ウࡍࡿࡇ࡜࡟ࡼࡾࠊᵓ㐀࡜≀ᛶ࡟ࡘ࠸᳨࡚ウࡋ࡚࠸ࡃணᐃ
࡛࠶ࡿࠋ
⾲ 1. DMF ୰ࠊTD-CAM-B3LYP/cc-pVDZ ࡛ࣞ࣋ࣝィ⟬ࡋࡓ(PyC2)2Cl4PDI0ࠊ(PyC2)2Cl4PDI•−ࡢప࢚ࢿࣝࢠ࣮ບ
㉳≧ែࡢບ㉳࢚ࢿࣝࢠ࣮㸦ΔE㸧ࠊ᣺ືᏊᙉᗘ㸦f㸧ࠊ<S2>ࠊᖐᒓࠋ
ΔE / eVf<S2>
Assignment(PyC2)2Cl4PDI0
1
2.591
0.961
0
HO → LU (98%)
2
3.454
0.387
0
HO−1 → LU (88%)(PyC2)2Cl4PDI•−
1
2
3
4

4

1.513
1.600
1.882
2.697

0.253
0.791
0.114
0.000

0.773
0.995
0.831
1.531

α-HO → α-LU (86%)ȕ-HO → ȕ-LU (80%)α-HO → α-LU+1 (96%)α-HO → α-LU+5 (31%)Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] ͆N-࢔ࣝ࢟ࣝ໬ DABCO ࢆᑐ࢝ࢳ࢜ࣥ࡜ࡍࡿ TCNQ ㄏᑟయࡢࣛࢪ࢝ࣝ࢔ࢽ࢜ࣥሷࡢᵓ㐀࡜≀ᛶ͇㸪ࠐᑠᕝ෽ᖹ㸪▼⏣⪔኱㸪▼ᕝᏛ㸪ᒸᮏᑦ኱㸪୰㔝⩏᫂㸪኱ሯ᫭ᘯ㸪▮ᣢ⚽㉳㸪᪥ᮏ໬Ꮫ఍➨ 101 ᫓Ꮨᖺ఍(2021)㸪

- 241 -

P03-1am-09㸪࣏ࢫࢱ࣮㸪2021 ᖺ 3 ᭶ 19㹼22 ᪥㸪࢜ࣥࣛ࢖ࣥ㛤ദ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ࡞ࡋཧ⪃ᩥ⊩[1] H. J. Park et al., ACS Appl. Mater. Interfaces, 2016, 8, 24983.
[2] D. Schmidt et al., Angew. Chem. Int. Ed., 2015, 54, 3611.
[3] L. Perrin et al., Eur. J. Org. Chem., 2011, 28, 5427.
[4] J. Mizuguchi et al., Z. Kristallogr. NCS, 2002, 217, 247.

- 242 -











        

   Ǜ ǝǷÒǣÒÚÒÚǥÊżëÚŸƅſǸƤ ǩǷķ«ÒÚǛçĴĥŸƅďǸ{ĵ ÎǷŧĿĐƫƗµŸƅďǸèw ē¾ǷÒÒÚťëÚǖǸêé Ţ³Ƿ·²åÒÚÒÚǥťÚŸƅſǸƦǉ ­ŲǷÒǣÒÚÒÚǥÊżëÚŸƅſǸÒǟ ƜÓǷÒǣÒÚÒÚǥÊżëÚŸƅſǸþƨ ǱÓǷÒǣÒÚÒÚǥÊżëÚŸƅſǸƈĳ »ǷÒǣÒÚÒÚǥÊżëÚŸƅſǸ ŸƅŮŭÞǌïœ;°7$ƕĮÅ$&7ć2xƐş(ŕµ&%(Ķ'4"ƕĮªǤÝ87$ 7($œ)ǒ°šċ$&65'°7$#ElMšċ,$ǇƁ7 .
6ElMǇƁ$)Ʃśw(ŗõ#×2±×&$%Ŝƀô&Ǘƚ(..Œ©Ĉ;Ô Åª7Ťǂ
# 6ElM$)œ(4 'lrRf&ŀǎ;" 7Å(4 'źŒ8& şǃ# 7$
ƴ 7Ƕ×ElM×ĈElMǛçElM&%(Ĵĥ(Ŭæ(uħ#ElMǇƁ'Ǣ7ÊżŭťƳ')ģÑ(ƽǳĲÑģň8" 7Ūƿƞ5)|'×©¦ÚKejotKkr'47Ÿƅ;& Ł&ElMûčşǃ'Ǣ7´ǀŭ&Ÿƅ;Ŵ 7ŶưƖµ;ǌÀǳƳŌ;Ůė
" 7ĳòõ)   ǒ°Ŋ'7ŊƑƕµR@YeGM$dnJ`šċhVnƳĹ   ElM(ę©šċàõ$`lLmU?(ŰǢƳī  Ƕ×ElM(bPr_tG(MItmrHĈ$ùĈxÈu'47ťƳ
'Ǣ7Ÿƅ;ÜĨ ŸƅħŎƵƋħŎ ǒ°Ŋ'7ŊƑƕµR@YeGM$dnJ`šċhVnƳĹ Ŋ×ǡ(ŊƑƕµŹĦ)Ŋ×  ǡ(®ƾŭǐ©'4"öǄ87$ī5'8"
7 . (ƐŊ{#)ŊƑƕµ>GNaQt×Ė ņǦŀǎ ŊƑƕµ s ĳ ğ7û#ŊƑƕµ6İ:7(6İ ǐ©' XYt×)ÒÂǇǐ©;ƪ (0Ŋ×  ǡ(ǅǫ$Ʋõ;Ïģ$"Ĝ87ƟũC[nFtįǭv')Ʋõ;Ì§7ħ¸'ŊƑƕµǬƕµšċ;ǫ7ǔƁšċ$&7ǮśØÇ7ŗõ(w$$1'ƟũC[nFtįǭv#ǮśØÇ& zǏħ¸,(ŹĦapNMǴƧ'&7$;Ď(ƪŸƅ'4"ī5'ÂǇǐ©; ŊƑƕµŹĦ$)ū&6zǏǐ©; ŊƑƕµŹĦ)¼Ä(ŀǎÏªs®¶ŭǐ©'")¬&Ŷư)Ā58" & #ĳŸƅ#)dnJ`šċhVn;Ũ"ŊƑƕµ>GNaQtM@TSrH'"ƳĹ;&8.#1dnJ`šċhVnƳĹ)ŊƑƕµR@YeGM'ǓŨ8Ÿƅ 7ĳŸƅ)ŗõØĈ(ƻƒ;ƳĹ7Š'ŊƑƕµ>GNaQt6İ ǐ©;öǄ>GNaQt×(ŊƑƕµģ'ŐŮǒ°šċ#)ÁǭŀǎǴƧ$&6ŊƑƕµƓ/Ğ (Ǆś$&7ņǦŀǎ(ģćŚ'Ŗã7#>GNaQt×(Ė ŊƑƕµģ'ųŮ"ĂƱŭšċ;¥ǔƁƔǆƳĹ;Üƪ7$#ŗõw' Ì§7Ɣǆ;Ē7- 243 -

 ElM(ę©šċàõ$`lLmU?(ŰǢƳī ElMǇƁǊ#Ƙ½Ĭǡ2ƏĈţ(ŗõØĈ')>oZAM¹'4"Ò.'  ƃǵ'ǵ87 .6őĈªC[nFtşǃ'46ū&68)`lLmU?$

ėł'4"Ĥť8"ElM(×MItn5ìƱŭ&ƏĈĘ©;Ō07ťǀļƓ)ŻƇ8" &$5`lLmU?(ĳǃŭťƳ')Ơ" & #ĳŸƅ#)`lLmU?;ŌÛ!7×ǀŭ&ġǗÃ×;ī5'7$;Ůł$" 7Š' č /HQQDUG-RQHV cUrKin;Ũ ">hn`=MKmD'â"ĝĽ8 &RVORYLFK3DVWRUH &3 hVn;ĕøuƢª &3 hVn;ĚŨ(hVn#)ūčǡ')5ö¦(Ò;^lgtQ & '4"ƾĤ7$#`lLmU?
ā#7$Ŷ58" 7`lLmU?(ġǗÃ×;ī5'70'w(ƳĹ;&Ɖ ' VKRYLQJ hVn$(ŉǈ;&VKRYLQJ hVn$)ŀǎƘ½Ĭǡτα;ƾ½ę©×% (cUrKinǧÍí#y 71(# 7Š'cUrKinC[nFt<ĦùĈţ *3 '4"y 587$$ ;Ûģ$"ταH[S $*3N%7 $ :5hVn# 7ƴ Ğ 8*VKRYLQJ hVn'ÿ *`l
LmU?)<ĦùĈţ *3 '4"ŌÛ87$;Ž¿7Ɖ  'VKRYLQJ hVn(¢ĝ$&7El
M(Å$"(Ĉǃ;Šă!70'ę©šċàõƳĹ;&ElM' ")(ǬĮĈ5ę©šċàõ'V]@¡461ǒ¤&ę©htX# 7bPr_tGŤ87$Ŷ58" 7C[nFtƊǗ¡46Ǩěƍ×'4"587ItL#(ŝę©ęð(~ñÈ# 7V]@sqltÃ
×[!;ę©šċàõ5ƺ7$#7 .6VKRYLQJ hVn;bPr_tG(`lLmU?
ØĈ5ľƹ7$#ĳŸƅ#8;& ElM(ę©šċàõ$`lLmU?(ŰǢƳī >hn`=MÅ)ǒ¤&ę©ģ¨Ǆ# 7 :37ę©šċàõ(V]@¡5}ǫbOr_tG&%(Šū&ę©ŭŠĈ;ŽǶ×ElM(Ëµŀč7Ƕ×Ǟ(į£Ĉ'üǰ87$
Ɲ 58" 7Ď(ƪŸƅ#bPr_tG$ùĈŠĈ(ĭǑĈ;ī5'.(ƕĻ)
ùĈxÈuťǀ'48*äďŭ&<ĦùĈţ(ƆǡŭxÈuĈį£Ĉ(Ïª'â"ǜĊ# 7
$;Ž" 7#äďŭ&<ĦùĈţî;ůěŘÛ5'Ńħ¸(ǯŏ(ğ'
1ƾ-ǯǍ$Ŗƭţ(V]@¼ŏģ'47MItmrHĈ'""1ľƶ ŸƅčĻ ǒ°Ŋ'7ŊƑƕµR@YeGM$dnJ`šċhVnƳĹ ŊƑƕµǲÉ +% )22 ǅǫ 5QP22+ Ʋõ ȕ$Ûƛ#75'ŊƑƕµŹĦ${ǡšċ$"÷ ŊƑƕµšċ Z 5QPȕ 4+ (ŊƑsǘƑ±×#ŊƑƕµ" 7šċ D 85Ð(Ǭƕµšċ Q+% ( (šċ;ƸÛ75'>GNaQt×(ŊƑƕµĳģ 

ĳw ĳ ĳv(  ƃǵ'7$# Ŋ×  ǡ(ŀǎ;(ĂƱŭšċ'¥6ú"7$# (šċǡ(dnJ`šċhVn;ŀƌ75'ǔƁƔǆƳĹ;ƪ >GNaQt6İǐ©' " +D ǔƁƔǆ$&7Ǖđţ(ŗõØĈ;ŋ0 ŗõw' >GNaQt×ŊƑƕµ  ĳ;Ė ǔƁƔǆ(Ǖđţ)vĪ8Ð(Ǖđţ)Ŗã+D )ƟũC[nFtįǭ5)ĉÛ#& ŹĦƔǆ# 6Ŕ ǒ°šċ#) +D ;Ɣũ7ŹĦ')Š'ŊƑƕµ[TWqtG'ō®ŭǐ©ǙƯ# 7$;Ž¿7ƕĻ;Ā- 244 -

 ElM(ę©šċàõ$`lLmU?(ŰǢƳī IUDJLOH œ#) VKRYLQJ hVn;ĕøταH[S $*3N%7 *3N%7  'MItn8uħ#VWURQJ ElM)MItn8& $:&:<ĦùĈţ#)`lLmU?)Ƽī8& ƕ
Ļ;Ā¶Ł'τα)V]@sqltÃ×[!'4"1MItn8&5'bPr_tG¼
ŏģ)`lLmU?'4"Ïª7<ĦùĈţ(ǯŏĠ(/#)MItmrH8" & $
:($)VKRYLQJ hVn`lLmU?'4"MItmrH8& ƕĻ$ŵű& 
v46ElMûčœ(R@YeGM$ùĈţ;ƕ+ 7 VKRYLQJ hVn;ľƹ$9`lLm
U?;y 7Ã×)<ĦùĈţ#)& $:Š' VWURQJ ElM#)ƄùĈţ(ßy;º046ƮǪ&ę©¨Ǆ;ƝČ7ąƯ 7$;Ž¿71(# 7 ElM(ę©šċàõ$`lLmU?(ŰǢƳīäďŭ&<ĦùĈţî(xÈuĈ(Ƃõ)į£Ĉ(Ïª'üǰ8& $:ùĈxÈuťǀ'48*ùĈ(ƆǡxÈuĈÏª& ËµǬĮǃşǃ(ę©sǯǰŠĈ)ÒÉŭ&ùĈţ'4"(/ ā87ĳŸƅ#)(ťǀŭŘ$uơ74 'Ńħ¸(ǯŏ¨Ǆ$bPr_t
G 81<ĦùĈţ'4"(/¯Ɛ'MItn87$;Üƹ(ƕĻ)>hn`=MÅ(¦Úŭsę©ŭŠĈ;Ʒǋ70({Ąŭ&ťǀ(u # 7ùĈxÈuťǀ;ľƹ7ƣ ÜƹŸƅ$&" 7.ǹ©ŭĢÃ×5Ńħ¸(ǯǍ$Ŗƭţ;¼ŏģ(Ǣģ$"ŋ0$9V]@¼ŏģ'47MItmrHĈč6Ƈ" 7$;ư"6<ĦùĈţ(xÈuĈ'4"Ƽī87 ŬƬÜƙ.)Û Ʀǉ ­Ų Ǜ ǝ ĸĺ ó ³ŊƑƕµ[TWqtG'Ê!ItLsLirahVn(ǠŬ$(ǒ°Ŋ'7ĕĢR@YeGM,(ĆŨ´ ªÚëÚƉ  ò ò  ı Ʀǉ ­Ų Ǜ ǝ)UDQFHVFR5XVLDQR5DIIDHOH3DVWRUH)UDQFHVFR*UHFR ĸĺ ó³ItLsLira#
hVnª87ĕĢģ$ŀǎƘ½Ĭǡ´ ĩĳşťÚƉ  ÂòŇÒ ò  ı ƈĳ » ŷ ƣń Ǜ ǝ ĸĺ ó ³&% œĮ([dSTGŰǇƁ(×©¦ÚƳĹ'7
oamDĞŎ(ǓŨ´ ĩĳşťÚƉ  ÂòŇÒ ò  ı þƨ ǱÓ Ŋǚ ƥÖ Ǜ ǝ ĸĺ ó ³ŦšǶ×ElM(ę©šċàõƳĹ´ ĩĳşťÚƉ ÂòŇÒ ò  ı Òǟ ƜÓ Ŋǚ ƥÖ Ǜ ǝ ĸĺ ó ³ElMûčœ(`lLmU?$bPr_tG'47M
ItmrHĈ(ľƶ´ ĩĳşťÚƉ  ÂòŇÒ ò  ı Ʀǉ ­Ų Ǜ ǝ ĸĺ ó ³ǒ°Ŋ{#(ŊƑƕµŹĦ' ÑŀǎÏªǺdnJ`apNM#Ʒǋ7ǔƁ[TWqtG´ Ɖ  Â×KejotKkrƶǀ ò  ı Òǟ ƜÓ Ŋǚ ƥÖ Ǜ ǝ ĸĺ ó ³ElMûčœ(`lLmU?$bPr_tG'47M
ItmrHĈ(ľƶ´ Ɖ  Â×KejotKkrƶǀ ò  ı ƈĳ » ŷ ƣń Ǜ ǝ ĸĺ ó ³&% œĮ([dSTGŰǇƁ'7ƀôª(×©¦ÚƳĹ´ Ɖ  Â×KejotKkrƶǀ ò  ı þƨ ǱÓ Ŋǚ ƥÖ Ǜ ǝ ĸĺ ó ³ŦšǶ×gnW(ę©šċ4+R@YeGM(ƎƱª×©¦ÚKejotKkr'47ƳĹ´ Ɖ  Â×KejotKkrƶǀ ò  ı- 245 - þƨ ǱÓ Ŋǚ ƥÖ Ǜ ǝ ĸĺ ó ³ŦšǶ×gnW(ę©šċ4+R@YeGM(ƎƱª×©¦ÚKejotKkr'47ƳĹ´ òõǶ×ÊżşĈŸƅsǶ×ƵƋŅſÚŸƅ
sǶ×Y\UG\pLtŸƅ µ¶ƶǀ ò  ı Ǜ ǝ³ŊÆ' "Ñģ(Ŋ×®Õ"öǄ87ŊƑƕµR@YeGM´ Ɖ  Â &6- ªÚ`BMQ  ò  ıĔýǁř  Ʀǉ ­Ų Ǜ ǝ ĸĺ ó ³ǒ°Ŋ{#(ŊƑƕµŹĦ' ÑŀǎÏªǺdnJ`apNM#Ʒǋ7ǔƁ[TWqtG´ ĩĳşťÚ  òžÙÒ ò  ı ƈĳ » ŷ ƣń Ǜ ǝ ĸĺ ó ³&% œĮ([dSTGŰǇƁ'7ƀôª(×©¦ÚƳĹ´ ĩĳşťÚ  òžÙÒ ò  ı þƨ ǱÓ Ǜ ǝ ĸĺ ó ³ƎƱª×©¦ÚKejotKkr;Ũ Ŧš4+ůǞǶ×g
nW'7lAMhtXƳĹ´ ĩĳşťÚ  òžÙÒ ò  ı Òǟ ƜÓ Ŋǚ ƥÖ Ǜ ǝ ĸĺ ó ³ElMûčœ(`lLmU?$MItmrHǢ(Ɲá´ ĩĳşťÚ  òžÙÒ ò  ı ŞÜƙ.)Û
 5DIIDHOH 3DVWRUH 7DNXPD .LNXWVXML )UDQFHVFR 5XVFLDQR 1REX\XNL 0DWXED\DVL .DQJ .LP DQG )UDQFHVFR
*UHFR³%UHDNGRZQRIWKH6WRNHV(LQVWHLQUHODWLRQLQVXSHUFRROHGOLTXLGV$FDJHMXPSSHUVSHFWLYH´VXEPLWWHG
 7DNXPD.LNXWVXML.DQJ.LPDQG1REX\XNL0DWXED\DVL³7UDQVLWLRQSDWKZD\RIK\GURJHQERQGVZLWFKLQJLQVXSHUFRROHGZDWHUDQDO\]HGE\WKH0DUNRYVWDWHPRGHO´VXEPLWWHG
 1DR\D 7RPRVKLJH 6KRWD *RWR +LGH\XNL 0L]XQR 7DWVX\D 0RUL .DQJ .LP DQG 1REX\XNL 0DWXED\DVL
³8QGHUVWDQGLQJ WKH VFDOLQJ RI ERVRQ SHDN WKURXJK LQVHQVLWLYLW\ RI HODVWLF KHWHURJHQHLW\ WR EHQGLQJ ULJLGLW\ LQ
SRO\PHUJODVVHV´-RXUQDORI3K\VLFV&RQGHQVHG0DWWHULQSUHVV   <XVXNH 0RUL .HLLFKL 2ND]DNL 7RVKLIXPL 0RUL .DQJ .LP DQG 1REX\XNL 0DWXED\DVL ³/HDUQLQJ UHDFWLRQFRRUGLQDWHVYLDFURVVHQWURS\PLQLPL]DWLRQ$SSOLFDWLRQWRDODQLQHGLSHSWLGH´-RXUQDORI&KHPLFDO3K\VLFV
  - 246 -





Role of water on the structural transformation of macromolecules"#1 
 LbQHÌ:Üy6£5h0¢À@°«(=££5·¯£³ip­£¼½325
uÙ <Üy¢À¡Ï1£5Ös4-/´¹!Â?>/"*!)5¬Å6y+16Æ3®É¿6wË¨} 4¤²'/Üy5¡Ï4$=£¨5z@y`V_0<4(=´¹@Â,*W^ÝRN_FUa]HLYÞÝ Þ6BKUaQPc_5£¨¥h06wË¨} @¶(!ZLPc_h06wË¨} @¶&3%5  -5w¨!W^Xc5IbTDZc
J\b4f=Ú6o35 ß´¹06ZLPc_£;7BKUaQPc_£5¦¨
4¨Å'*   ;7[PXc5y~{Çº@Â,*)5½ d5 [PXcÕ5}{5A_Ic_©r6d5   5IbTDZcJ\b:Û±4Ä§&>*Ó5~1;#m/=%1!? ,*8*wË¨5t06[PXcÕ5{!¨5yØÎØ@Í*Ô»0v#%19? ,*)'/%5ÔÎØ{6[PXcÕ4Á¸&>*Ü5A_Ic_©5x«1ÖÐ'/=%1!? ,*&<4CO_Gc±3Q]ZcL@¾'*88A_Ic_5"&@jª±4È(=%10@µ4¶'*ke5%1 <[PXc5wË¨@EbET0"=%1

W^Xc5w¨46¨5gÑCbMaSc5 |@lA_Ic_h5×n¸} 5"&!ÒÃ0=1½Ê.$*
2 !
 y~{Çº4  @q­'* Ý 1 Þ6   £6 A_I

c_6  {n@­/[«'*²5A_Ic_©0XBHa¨5
bU^b81 Çº1Ab?`]9

@ª3?-/ 5{l{W=bJA_   @Çº'*3 
ÝÈÞA_Ic_1£5¦¥h05ALH;<H PVCL 50-mer 5 Rg @´3 MD J@B`cJ\b4;,/Çº'*A_Ic_5[_y¢@ 0< 20 mol%80&-*ZLPc_-£¦¥h5 PVCL

50-mer 5{l Rg 6ZLPc_ 0 mol% < 5 mol%80?, 4v(=!)>keÜ#3=1ZLPc_©4¿43=%1@¶'*dÆBKUaQPc_@ 5 mol%80|(=1{l Rg 6NE'&<
4 5 mol% < 20 mol%80|(=1{l Rg 6º4 |(=%1@¶'*%5IB_-8aRBc_-IB_¡Ï6wË¨5~133(%1!0"=´¹0Ät&>*d5 PVCL 50-mer 4(=
¤3=A_Ic_5Ú6À©5 PVCL Ó5£¨¥4Ö(=Û±Ät½ 1d®'/=- 247 -

ÝÉÞuÓÕ5{!A_Ic_5|4;,/25;4Ú&>= @È1*A_Ic_1£5¦¥4¨Å'*d5 [PXc5   @Çº'*  «6 -5¶ut@- ±3¡@/)5M¬6A_Ic_©4r'3%1@¶'*  Xn5¡6A_Ic_©4;,/2162'3!¶ut6È4e(=*4©|4l[PXc[PXcÕ5µÝ¶½Þ6|#3=1Æ= ¸y0·O'*XÃm4$=[PXc[PXcÕ5{9c+Td@¶'*
ÝÊÞZLPc_16¤35ÆBKUaQPc_5|6   ¡@< 4&-=%1@¶'*¶ut6?, 4  5"4JTM'*¨dx@6+ut!   4x«'*  5©
r680¶ut!d?, 4NE'[PXc1[PXc5¥½!PÑ&>=!
)>ke5©06  5¶ut!e'[PXc1[PXc5½!|#3=%1@¶'*%5
Td6  ¸y0³=1&<4Ä¯43=8*BKUaQPc_¨¥5n¨0yØ&>*³ip­
5!

[PXcÕ5Xn±3L4"#sf'/=%1@¶'*©r4¤²(=1BKUaQPc_06hÕ5A_Ic_©0[PXcÕ5{!~8=%1!Ä§&>*(3?/wË¨~13=%>6Û½ 1W5ÝËÞÇº4;=  5~1d®(=%1@¶'*

5¨¡Ï![PXc[PXcÕ5ÎØ A_Ic_5©Å;7)5©4+/25;4(= @y`V_0¬Å(=*44A_Ic_¼a5w @Xn50´'*¾@È1*i  6UaQPc_ 05  -5K°±3  4$= {lA_Ic_¼5Z¡5yz@¶'/=i  06 ÝBKUaQPc_Þ!Ü#ld4yz'/= -5 [PXc¹S5[PXc5f55A_Ic_¼[PXc!¹(=1BKUaQPc_

5¼±3e¦!PÑ&>  06¨Y5A_Ic_¼6>_H5 * Q43=ÝiÞ¨J7_Y5yz!d03#35yÕÃm!qu;59~#BKUaQPc_@"s-=%1!y ,*  06A_Ic_¼!  -5 [PXcÕ5]3Ãm4Ü©4k(=Ýi Þ
8*  4j'/©@=1BKUaQPc_5 : ;59 5!Ä¯0=%1!y ,*Ýi Þ
Ic_5UW±e¦5 |6

05¼±e¦6

e0Ät&>*;5ÜA_

1   ¨¥5Û½ 1d®'/=ÝÌÞ5ZLPc_£¦¥h5A_Ic_¼5yz@È1*i  6BKUaQPc_
0Ät&>*;4[PXc6£;59ZLPc_1UW±4³ip­(=%1@¶'/=''¨¡Ï6;5F§4³¨Y5A_Ic_¼  6BKUaQPc_;59
u&#3,/=[PXcÕ5Ä¯3A_Ic_e¦6ZLPc_ 06BKUaQPc_

: 1c4«>3%1@¶'*¨¡Ï1   ;7  ¸yÅ@ª3?-=%10[PXcÕ5}{![PXcÕ5A_Ic_©5Ü855x«14ÖÐ'/=%1@¶'*

- 248 -

(a) P5%, r=1.9nm(d) P2%, r=1.5nm

1

1
2
1

2
0.5

1.5
2
0.5

2
1

0

2.5

1.5

1

1.5

0
-1

0

1

2

-1

(b) P5%, r=1.5nm

0

1

2

(e) P20%, r=1.5nm
1R (nm)

1
1.5

2.5

-1

1.5
1.5
0.5

2
0.5

0

1

2

-1

0

(c) P5%, r=0.7nm(f) M5%, r=1.5nm

1

1

1

0
-1

0

1

2

-1

1

1

1.5
0.5

1.5

0

2

1

1.5

1

1.5

3.5

1

1

2 1.5
3

4

2.5
0.5

1

0

3

0

3

2.5

2.5
1

0

1

2

Z (nm)


iÈÇ'LVWULEXWLRQRIQRUPDOL]HGDOFRKROFDUERQGHQVLW\LQWKHYLFLQLW\RIWZR39&/PRQRPHUVDWSURSDQROPROD ZLWKWKHLQWHUPROHFXODUGLVWDQFHUEHLQJIL[HGWR QP E U QPDQG F U QPZLWKU QPDW G 
PRO H PRODQG I PHWKDQROPRO7KH=DQG5D[HVDUHKRUL]RQWDODQGYHUWLFDOUHVSHFWLYHO\WRDVWUDLJKW
OLQHEHWZHHQWKHFHQWHUVRIPDVVRIWKHWZRPRQRPHUVRQHRIZKLFKLVDWWKHRULJLQ7KHFRQWRXUYDOXHRIUHSUHVHQWVWKHEXONDOFRKROFDUERQGHQVLW\ÝÍÞZLPc_1BKUaQPc_525;3Ã¼! _1£5¦¥h5 

5yo4Ú@f=5 BKUaQPc[PXc4Ä§&>*wË¨} !BKUaQPc_5a5"&!u&#3=1r(=%1@³-$*BKUaQPc_59B:! v(=1© 4$= [PXcÕ5   !_±4(=%1@¶'*Ñ¶ut!e'¨0yØ'*ut!r'
c+n 4u&35G!«>=
(u&3)BKUaQPc_0<>*   6ÆZLPc_5   1;#
m/=I@< 4'* ¸y6V5BKUaQPc_16±4(u&3)BKUaQPc_
5|4;,/X»4?*=[PXc[PXc½!?, 4' '3%1@µ4¶'*%
5;4BKUaQPc_5CO_Gc±Q]ZcL@¾'*889B:@u&#(=%10

[PXc5wË¨5°£@^(=%1!0"*ÝÎÞº4ZLPc_59B:@"#(=1ZLPc_£¦¥h5 [PXc5wË¨!Ä

k(=I9¶'*ZLPc_5ba@  Q4(=15   4"3Ú@f=%1@¶'*Ñ¶ut6?, 4E!5¨yØut!«>=
(")ZLPc_5   «6
BKUaQPc_5   «1m/=I!y ,*ÝÏÞw¨0=A_Ic_5a9B:@&-=%10Æ¨5J7_¡Ï!25;4(= @È1*i  6BKUaQPc_y! [PXc4UW±4e¦' 4yÕÃm4e¦'/=%1@¶'/=dBKUaQPc_59B:!u&#3=1

[PXc05UW±3e¦!|85yÕÃm05~wk!r(=I!y ,*c4

[PXc6ZLPc_- 249 -

;59(")ZLPc_1;5~#³ip­'/=%1!y ,*&<4[PXccp5Õ

06­}'*ZLPc_!~#\Á'/=%1!? =%><5½ 6A_Ic_1W^Xc5L
5"&!wË¨5~@¶(½±3Ãh05[PXcÕ5ÔÎØ}{![PXcÕ5~&>*A_Ic_5x«14ÖÐ'/=%1@±J$/=ÝÐÞ´¹06A_Ic_1£5¦¨4¨Å'*   1[PXc4-/Çº@Â,*½   6BKUaQPc_1£5¦¨06A_Ic_©5 |4lIB_D8ac?D
IB_5;3¡Ï@¶(!ÆZLPc_1£5¦¨06¶&3%1!? ,*%><5 
6[PXcÕ5   54;,/;#[«&>=%1 < W^Xc5wË¨6H4[PXc

CN<MÕ5³ip­4¸h(=%1@¶g'*wË¨!t13=yÕÎØ  06[PXcÕ4wk(=A_Ic_y5`$@R5/[PXcÕ5{!~8=%1!? ,*&<4Z
LPc_1BKUaQPc_59B:@È(=%10CO_GcÖÐ5Q]ZcL@¾'*88 [PXc5wÂ¨Å5°£@^0"=%1@µ4¶'*%><5½ 6)>.>5A_Ic_4f<>*×n¸5»![PXc5\Á4$=¤3=wË¨5°Æ@'/=I@¶'/=


4 





5





    !$&  &$& "  " %"#!  # &! "#&  '#  #  &! !"&   
- 250 -

"


!





Development of multicomponent quantum mechanics-nudged elastic
band method to analyze chemical reactions including nuclear quantum
nature

1



!#"

$


«Çd{¦ %åd{¦)d{¦Îäò{a¥ ûÔ*ò{a¥ «Ç/ð«Ç

ýH/DþjSTa¥P×+*¨Ïm®c|³ß-âBorn-Oppenheimer éRtLÑ¸´ÞÙÄ­ ¨c|³ßØà²  l»ë)* ø{ª"ûÔd{¦íb Ì$H/D jSTa¥' d{¦ò{âp*³ß-f)
  L ô·*wZÆ´ÞýMulticomponent quantum mechanics: MC_QM­þ «Çd{¦' åd{¦-ø{j¨ò{_|¸f) d{¦ò{a¥¹f)è.ÙÄ gÍ*é Climbing-image-nudged elastic band (CI-NEB)­ '! CI-String­-µMC_QM ­'*c|eØ¤­%ô·¡ TDDFT ­-µ MC_QM ÙÄ')ø{`â° *@I;JÀbeØ¤f)È.#ü4GK@Xj½ÁÜú% f)È.

2





MC_QM ÙÄ ±Î GAUSSIAN09, GAUSSIAN16 -µCI-NEB'! CI-String ÙÄÎ]ô·5K<-µÖø{°ÙÄHAG ωB97XD/6-31+G**ò{_|¸f) «Çd{¦1s s307ö-tµü4GK@Xj½ÁÜú GRRM @I4FD-µ3Reactant

TS

Product

r 1. 8-HQ M@I;JÀbe * Reactant, TS, Product §ì

8-hydroxyquinoline ý8-HQþ *@I;JÀbeØ¤É¥¾ø{`â° @I;JÀb Ûâ+*e '»(+* Z{ />2J°- 251 -

*`â°j' øÓV) â)@I;JÀb Ûâ+* uk+*ýW.
Wang, et al., Nat. Commun., 10, 1170 (2019)þ
× 1. h° *«ÇÉilqd{õã÷[Å]Reactant, O-H Éió

Reactant, H...N ã÷

MC_QM(H)MC_QM(D)£­MC_QM(H)MC_QM(D)£­Mÿt°

0.996

0.989

0.972

2.059

2.068

2.100

Mÿ`â°

1.043

1.028

0.998

1.737

1.780

1.865

/>2J

1.008

1.000

0.981

1.893

1.913

1.952

Product, N-H Éió

Product, H...O ã÷

MC_QM(H)MC_QM(D)£­MC_QM(H)MC_QM(D)£­Mÿt°

1.038

1.031

1.014

1.968

1.992

2.050

Mÿ`â°

1.062

1.053

1.031

2.273

2.279

2.295

/>2J

1.032

1.025

1.009

2.124

2.139

2.174

 × 1  MC_QM ­ '!£­ÙÄ Reactant'! Product M«ÇÉilqd{õã÷-¾ MC_QM ­ Àb*«Çd{-ð«Çd{Ëð«ÇËT%ÙÄ×')/>2J'!ø{`â°

%Mt°j¨XÉióý«ÇÉióþ

MC_QM(H)%%óý¼þ£­%%¼ýóþ* , *#)+(ø{° %MC_QM ­-µ«Çd{¦ò{a¥-Ì*B:J6EGùÝn&ø{§ìvc'*«ÇÉiºNUµvc-î[Úê * , 

4 (1) ¯ñ^ÿ}¶yïÿ¬¢zÊ{ÿ~Õÿ¶M¿\ÿ¡çÒc|Q 2021 xQÿ2021  3
Ā(2) T. Udagawa, T. Ishimoto, U. Nagashima, T. Hirano, N. Nakayama, M. Tachikawa, M. Baba, The 5th Asian
Workshop on Molecular Spectroscopy (AWMS-2021), 2021  3 . (3) }¶yïÿÙÄZ{ZW|8C=K
2021ÿ2021  1 Ā(4) }¶yïÿÃ 1 o Deut-Switch 8C=Kÿ2020  12 Ā(5) ¯ñ^ÿ}¶yïÿ¬¢zÊ{ÿ~Õÿ¶M¿\ÿÃ 39 o¡Åá|QQÿ2020  11 Ā(6) Ð©æÿÂOYÿ}¶yïÿÃ 10 o CSJ c|?179 2020ÿ2020  10 Ā

5

(1) Y. Ishida, H. Funahashi, M. Tachikawa, T. Udagawa, Chem. Lett., 49, 745 (2020). (2) A, Kawafuchi, S. Kutsumizu,
Y. Kawase, I. Tokiwa, T. Udagawa, Y. Miwa, Phys. Chem. Chem. Phys., 22, 10132 (2020). (3) A. D. Sonawane, A.
Shimozuma, T. Udagawa, M. Ninomiya, M. Koketsu, Org. Biomol. Chem., 18, 4063 (2020). (4) H. Hagiwara, R.
Minoura, T. Udagawa, K. Mibu, J. Okabayashi, Inorg. Chem., 59, 9866 (2020). (5) Y. Ono, M. Ninomiya, D. Kaneko, A.
D. Sonawane, T. Udagawa, K. Tanaka, A. Nishina, M. Koketsu, Bioorg. Chem., 104, 104245 (2020). (6) H.
Funahashi, M. Tachikawa, T. Udagawa, Org. Lett., 22, 9439 (2020). (7) N. Yodsin, H. Sakagami, T. Udagawa, T.
Ishimoto, S. Jungsuttiwong, M. Tachikawa, Mol. Catal., 504, 111486 (2021).

- 252 -

㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜ࡑࡢ཯ᛂᛶ
Theoretical investigation on structures of metal clusters andtheir reactivity‫ۑ‬ᑠᏳ ႐୍㑻 1,2㸪㧘㔝 ៅ஧㑻 1㸪ỤᏲ ᐀ḟ㑻 1㸪㛗㇂ᕝ ៅ࿃ 1㸪୰ᮧ ຾அ௓ 1㸪
ఀ⸨ 㥴 1㸪᝴㇂ ᘓ௓ 1㸪⏣ᆏ ♸㔛Ꮚ 1㸪⚟⏣ ᾈ⏕ 1㸦1 ᮾ኱㝔⌮㸪2 ி኱ ESICB㸧
1◊✲┠ⓗᩘಶ࠿ࡽᩘⓒಶࡢ㔠ᒓཎᏊ࡛ᵓᡂࡉࢀࡿ㔠ᒓࢡࣛࢫࢱ࣮ࡣ㸪ࣂࣝࢡࡢ㔠ᒓࡸࢼࣀ⢏Ꮚ࡟ࡣぢࡽࢀ࡞࠸㸪≉␗ⓗ࡞ᗄఱᵓ㐀ࡸ㞳ᩓⓗ࡞㟁Ꮚᵓ㐀ࢆᣢࡕ㸪ࡑࢀࡽ࡟⏤᮶ࡍࡿࣘࢽ࣮ࢡ࡞≀ᛶࢆⓎ⌧ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ౛࠼ࡤ㸪Ỉ⁐ᛶ㧗ศᏊ࣏ࣜࣅࢽࣝࣆࣟࣜࢻࣥ㸦PVP㸧࡟ࡼࡗ࡚ಖㆤࡉࢀࡓ㔠ࢡࣛࢫࢱ࣮㸦Au:PVP㸧ࡣࢧ࢖ࢬ≉␗ⓗ࡟㧗࠸✵Ẽ㓟໬ゐ፹άᛶࢆ♧ࡍࠋ᭱㏆ࡢ◊✲࡟࠾࠸࡚ᡃࠎࡣ㸪࣐࢖ࢡ࣑ࣟ࢟ࢧ࣮࡟ࡼࡿᆒ୍࡞⁐ᾮΰྜ࡜኱㐣๫ࡢ PVP ࢆ฼⏝ࡋ࡚ࢡࣛࢫࢱ࣮ࡢᙧᡂ㐣⛬ࢆ㏿ᗘㄽⓗ࡟ไᚚࡍࡿࡇ࡜࡟ࡼࡾ㸪᪂つ࡞㨱ἲᩘ㔠ࢡࣛࢫࢱ࣮Au24:PVP ࡢ㑅ᢥྜᡂࢆ㐩ᡂࡋࡓࠋ࣐ࢺࣜࢵࢡࢫᨭ᥼࣮ࣞࢨ࣮⬺㞳࢖࢜ࣥ໬㸦MALDI㸧㉁㔞ศᯒ࡛ࡣሷ⣲྾╔య㸦Au24Cln, n = 0–3㸧࡜ࡋ࡚ほ ࡉࢀࡓ㸦ᅗ 1㸧ࠋAu24:PVP ࡟ᑐࡋ࡚㸪⣸እྍど྾ගศᯒ࣭⢊ᮎ X⥺ᅇᢡ࣭Au-L3 ྾཰➃ X ⥺྾཰ᚤ⣽ᵓ㐀㸦XAFS㸧ゎᯒ࣭㏱㐣㟁Ꮚ㢧ᚤ㙾㸦TEM㸧ほᐹࢆ⾜࠸㸪Au24 ࡟ᑐᛂࡍࡿ⢏Ꮚࢧ࢖ࢬ࡛࠶ࡿࡇ࡜ࢆ☜࠿ࡵࡓࠋࡲࡓ㸪྾╔ CO ࡢࣇ࣮࢚ࣜኚ᥮㉥እศග㸦FT-IR㸧࠿ࡽ Au24:PVP ࡢ㔠ᒓࢥ࢔ୖࡢ㟁Ⲵࢆㄪ࡭ࡓࠋᮏ◊✲࡛ࡣ㸪ᐦᗘỗ㛵ᩘ⌮ㄽ
㸦DFT㸧࡟ᇶ࡙࠸࡚ Au24 ࡢᵓ㐀␗ᛶయࢆィ⟬ࡋ㸪ཎᏊศゎ⬟ࡢ TEM ほᐹ࡜⤌ࡳྜࢃࡏ࡚ᵓ㐀ࢆゎᯒࡋࡓࠋࡲ
ࡓ㸪Au24 ࡢ CO ྾╔య࡟ࡘ࠸࡚ࡶࣔࢹࣝᵓ㐀ࢆィ⟬ࡋ㸪
ᅗ 1 Au24:PVP ࡢ㉁㔞ࢫ࣌ࢡࢺࣝ

FT-IR ࡢ⤖ᯝ࡟ࡘ࠸࡚⪃ᐹࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
DFT ィ⟬ࡣ Gaussian 09 ࣃࢵࢣ࣮ࢪ࡟ࡼࡗ࡚ᐇ⾜ࡋࡓࠋỗ㛵ᩘ࡜ࡋ࡚ B3LYP ࢆ౑⏝ࡋࡓࠋᇶᗏ㛵ᩘ࡜ࡋ࡚,Au ࡟ᑐࡋ࡚ࡣ LANL2DZ ࢆ㸪C, O ࡟ᑐࡋ࡚ࡣ 6-31+G(d)ࢆ㐺⏝ࡋࡓࠋඛ⾜◊✲࡟࠾࠸࡚ሗ࿌ࡉࢀ࡚࠸ࡿᵓ㐀ࢆึᮇᵓ㐀࡜ࡋ࡚ Au240 ࡢᵓ㐀᭱㐺໬ࢆ⾜࠸, 」ᩘࡢᵓ㐀␗ᛶయࢆᚓࡓࠋࡇࢀࡽࡢᵓ㐀␗ᛶయ࡟ࡘ࠸࡚, ほᐹ᪉ྥࢆ⣔⤫ⓗ࡟ኚ໬ࡉࡏ࡞ࡀࡽ TEM ീࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸, ᐇ ࡢ㧗ศゎ⬟ TEM ീ࡜ࡢẚ㍑ࢆ⾜࡞ࡗࡓࠋ୍㓟໬Ⅳ⣲྾╔యࡢࣔࢹࣝᵓ㐀࡜ࡋ࡚ Au24(CO)1q㸦q = 0, –1㸧ࡢᵓ㐀᭱㐺໬࣭ᇶ‽᣺ືゎᯒࢆ⾜࠸㸪Auࢡࣛࢫࢱ࣮ࡢᵓ㐀࣭྾╔ࢧ࢖ࢺ࣭⥲㟁Ⲵࡀ྾╔୍㓟໬Ⅳ⣲ࡢఙ⦰᣺ືᩘ࡟୚࠼ࡿຠᯝࢆㄪ࡭ࡓࠋᐇ ࡢ FT-IRࢫ࣌ࢡࢺࣝ࡜ࡢẚ㍑࡟㝿ࡋ࡚ࡣ, ᇶ‽᣺ືゎᯒ࡛ᚓࡽࢀࡓ᣺ືᩘ࡟୍ᚊ࡛ࢫࢣ࣮ࣜࣥࢢᅉᏊ 0.970 ࢆ஌ࡌࡓࠋ
ࢫࢣ࣮ࣜࣥࢢᅉᏊࡣᏙ❧ CO ࡟ࡘ࠸࡚ DFT ィ⟬࡛ᚓࡽࢀࡓఙ⦰᣺ືᩘࡀ㸪ࢪࢡ࣓ࣟࣟࢱࣥ୰࡛ᐇ ࡋࡓ COࡢఙ⦰᣺ືᩘ࡟୍⮴ࡍࡿࡼ࠺ᐃࡵࡓࠋ

3◊✲ᡂᯝ
Au240 ࡢᵓ㐀᭱㐺໬࡟ࡼࡗ࡚㸪┦ᑐ࢚ࢿࣝࢠ࣮ǻE ࡀ㏆᥋ࡋࡓᵓ㐀␗ᛶయ 6 ✀㸦ǻE < 0.7 eV㸧ࡢ௚㸪୙Ᏻᐃ࡞␗ᛶయ㸦ǻE = 1.64 eV㸧ࡀᚓࡽࢀࡓ㸦ᅗ 2㸧ࠋǻE ࡀ㏆᥋ࡋࡓ 6 ✀ࡢᵓ㐀␗ᛶయࡣ඲ᵓᡂཎᏊࡀ⾲㠃࡟㟢ฟࡋ

- 253 -

ࡓ㠀ᬗ㉁ᵓ㐀࡛࠶ࡿ୍᪉㸪୙Ᏻᐃ࡞ᵓ㐀␗ᛶయࡣ 2 ಶࡢෆ㒊ཎᏊࢆᣢࡘࢥࣥࣃࢡࢺ࡞ᵓ㐀࡛࠶ࡗࡓࠋࡑࡋ࡚㸪ࡇࢀࡽࡢィ⟬ᵓ㐀࠿ࡽண ࡉࢀࡿࢩ࣑࣮ࣗࣞࢩࣙࣥീࡣ࠸
ࡃࡘ࠿ࡢᐇ ࡢ TEM ീ࡜Ⰻ࠸୍⮴ࢆ♧ࡍࡇ࡜ࡀぢฟࡉࢀࡓ㸦ᅗ 3㸧ࠋࡇࡇ࡛㸪ࡇࢀࡽࡢᐇ ࡢ TEM ീࡣ༢୍ࡢ
ᵓ㐀␗ᛶయ࡟ࡼࡗ࡚ㄝ᫂ࡍࡿࡇ࡜ࡣ࡛ࡁࡎ㸪」ᩘࡢᵓ㐀␗ᛶయ࡟ᖐᒓࡉࢀࡓࠋࡇࡢࡇ࡜࠿ࡽ㸪ᚓࡽࢀࡓ Au24 ⢏Ꮚ⩌࡟ࡣ」ᩘࡢᵓ㐀␗ᛶయࡀྵࡲࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ

ᅗ 2 Au24 ࡢ᭱㐺໬ᵓ㐀࡜┦ᑐ࢚ࢿࣝࢠ࣮ࡓࠋḟ࡟㸪Au24 ༢⢏Ꮚࡢᵓ㐀ࡢࢲ࢖ࢼ࣑ࢡࢫ࡟ࡘ࠸᳨࡚ウࢆ⾜࡞ࡗࡓࠋAu24 ༢⢏Ꮚࡢ TEM ീࡢ⤒᫬ኚ໬ࢆ㏣㊧ࡋࡓ⤖ᯝ, TEM ീࡣ㠀ᖖ࡟ືⓗ࡞᣺ࡿ⯙࠸ࢆ♧ࡋ, ࡇࢀࡣ」ᩘࡢᵓ㐀␗ᛶయ࡟ࡼࡗ࡚ࡢࡳㄝ᫂ࡀྍ⬟࡛࠶ࡗࡓࠋࡇ
ࡢࡇ࡜࠿ࡽ㸪Au24:PVP ࡢ㔠ᒓࢥ࢔ࡣ TEM ほ ୰࡟␗ᛶ໬ࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡉࡽ࡟㸪Au24(CO)1q㸦q = 0, –1㸧ࡢᵓ㐀᭱㐺໬࠾ࡼࡧᇶ
‽᣺ືゎᯒ࡟ࡼࡗ࡚㔠ࢡࣛࢫࢱ࣮ࡢᵓ㐀࣭྾╔ࢧ࢖ࢺ࣭⥲㟁Ⲵࡀ྾╔ CO ࡢఙ⦰᣺ືᩘ࡟୚࠼ࡿຠᯝࢆㄪ࡭㸪ᐇ್࡜ẚ㍑ࡋࡓࠋᐇ ࡢࢫ࣌ࢡࢺ࡛ࣝࡣ 2106 cm–1 ࢆࣆ࣮ࢡࢺࢵࣉ࡜ࡋ್࡚༙඲ᖜࡀ 30 cm–1 ⛬ᗘࡢࣈ࣮ࣟࢻ࡞
྾཰ࣆ࣮ࢡࡀほ ࡉࢀࡓࠋࡇࢀ࡟ᑐࡋ࡚㸪CO ఙ⦰᣺ືᩘ
ࡢィ⟬್ࡣ୺࡟ࢡࣛࢫࢱ࣮ࡢ⥲㟁Ⲵ࡟ࡢࡳ౫Ꮡࡋ㸪ᗄఱ

ᅗ 3 (a-c) ␗࡞ࡿ Au24 ⢏Ꮚࡢ TEM ീ࡜㸪ᑐᛂࡍᵓ㐀ࡸ྾╔ࢧ࢖ࢺࡀኚ໬ࡋ࡚ࡶ࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠸ࡇ࡜

ࡿࢩ࣑࣮ࣗࣞࢩࣙࣥീ࡜ィ⟬ᵓ㐀

0ࡀࢃ࠿ࡗࡓࠋ୰ᛶ Au24(CO)1 ࡟ᑐࡋ࡚ DFT ィ⟬࠿ࡽ⟬ฟࡉࢀࡓ CO ఙ⦰᣺ືᩘࡣ 2103 cm–1 ࠿ࡽ 2118 cm–1 ࡢ⠊ᅖ࡟ศᕸࡋ࡚࠾ࡾ㸪ᐇ ್࡜ࡼ࠸୍⮴ࢆ♧ࡋࡓࠋ୍᪉㸪㈇࢖࢜ࣥ Au24(CO)1–ࡢሙྜࡣ᣺ືᩘࡀ 2073 cm–1 ௨ୗ࡜ィ⟬ࡉࢀ㸪ᐇ㦂⤖ᯝࡼࡾࡶⴭࡋ࠸ࣞࢵࢻࢩࣇࢺࡀぢࡽࢀࡓࠋᐇ㦂⤖ᯝࡀ୰ᛶࡢ㔠ࢡࣛࢫࢱ࣮࡟ࡘ࠸࡚ࡢィ⟬⤖ᯝ࡜Ⰻ࠸୍⮴ࢆ♧ࡋࡓࡢࡣ㸪ᐇ㝿ࡢ⣔࡟࠾࠸࡚ሷ⣲㓄఩Ꮚࡢ㟁Ꮚồᘬᛶ࡜ಖㆤ࣏࣐࣮ࣜࡢ㟁Ꮚ౪୚ᛶࡀ➇ྜࡋ࡚࠸ࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲࣭ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ۻ‬S. Hasegawa, S. Takano, K. Harano, T. Tsukuda, JACS Au 2021, 1, 660–668.
[2] ‫ۻ‬M. Suyama, S. Takano, T. Tsukuda, J. Phys. Chem. C 2020, 124, 23923.
[3] ‫ۻ‬K. Koyasu, K. Tsuruoka, S. Kameoka, A.-P. Tsai, T. Tsukuda, J. Phys. Chem. A 2020, 124, 7710.
[4] ‫ۻ‬S. Ito, K. Koyasu, S. Takano, T. Tsukuda, J. Phys. Chem. C 2020, 124, 19119.
[5] ‫ۻ‬K. Koyasu, R. Tomihara, T. Nagata, J. W. J. Wu, M. Nakano, K. Ohshimo, F. Misaizu, and T. Tsukuda, Phys.
Chem. Chem. Phys. 2020, 22 17842.
㸦௚ ཱྀ㢌 4 ௳㸪࣏ࢫࢱ࣮ 1 ௳㸧

- 254 - 
                   
ż

!

"



 
Þv"@A95QMh ÅÕÆ&"'kv95QM!°Ëe"!·¸Û² ¥ 
 &! +·¸"@AÞv-g+EN:9a (²¯,+¤Ã-ºRk°Ì¼ t kv95QM°Ë+-´³+,) (),yÇ³¶Ð-_ EN:9'¤Ã-W¬³ Î¾e+Ù-+-´ 
1,06



UÛ²

+ T c Ì ¼ }  ! º R k ° Ì ¼ E N 4 K I 3+$6(áKWWSVD]XPDQLPVJRMSFPVâ-ODSDFNEODVPNOIIWZ !nK0DKL ,QWHO )RUWUDQ  ,QWHO 03, -±6PB0Md± +|Æ " PSLUXQ 6HP?-d± 6/Tc!\±+ ¦_q VXSHUVODE ¨-±  iZÂ*!kv"  ^Ä­µ 6&) YGZGI ') ¨¡¨C.P=MOQM9f-l*`,$ÝuàÍ]!% &,1(% ¨-±  + 
&X  ßS#! &9' ¨ (+kv~®Ñ4KC1P K%1 !F<N Ô!e!%pµ & kv
!z{70>ÀÓÝuà»-Ì¼¤ !Ë-Õ% +X"|Ü
ALGP'4KC1P@ALGP

K%1 @&X Èß-×b³ É +J=M-± & kv!z{pµ70>!½-Æ@ALGP!2;8+ ¿¹,  2;8 pµ+! z{++ ¿¹, + "+-)

! )w!2;8! + ¿¹!­ )Ás! K%14KC1PF<N Ô'2;8  ¢s! K%14KC1PF<NÔ![*b-|¯+mÃ-Êa  + .DJHVKLPD 6 :DQJ DQG + +LELQR ³2ULJLQ RI *URZWK 'LUHFWLRQ 6HOHFWLYLW\ LQ &9' RI K%1*UDSKHQH
+HWHURVWUXFWXUH´  ,QWHUQDWLRQDO &RQIHUHQFH RQ 6ROLG 6WDWH 'HYLFHV DQG 0DWHULDOV 66'0  RQOLQH +
      jV6KHQJQDQ:DQJ§Ø©£
K%14KC1PF<N Ô! &9'

+ÚoÖ!

Òªº  r±®°yYxyÇÏ«Y3PK0PD=     

 +.DJHVKLPD6:DQJDQG++LELQR7KHRUHWLFDOVWXG\RQ&DGVRUEDWHDWJUDSKHQH&X  RUK%1&X  
LQWHUIDFHVH-6XUI6FL1DQRWHFKQROSS  - 255 -

➨୍ཎ⌮ศᏊືຊᏛ䝅䝭䝳䝺䞊䝅䝵䞁䛻䜘䜛㻴㻯㼘 Ỉ⁐ᾮ⾲㠃䛷䛾 㼆㼡㼚㼐㼑㼘㻘㻌㻱㼕㼓㼑㼚 ᵓ㐀◊✲$ELQLWLR0ROHFXODU'\QDPLFV6WXG\RI=XQGHODQG(LJHQ6WUXFWXUHVDWWKH6XUIDFHRI+&O$TXHRXV6ROXWLRQ
‫▼ۑ‬ᒣ


㐩ஓ

໭୰

୍ஓ㸪

㧗⏣

ྐᩯ㸦ᐩᒣ኱Ꮫ⌮ᕤᏛ◊✲㒊㸧◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࡣࠊ+&OỈ⁐ᾮ⾲㠃࡛ࡢ➨୍ཎ⌮ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺஦࡟ࡼࡾࠊỈ⁐ᾮ⾲㠃࡛ࡢ

=XQGHOᵓ㐀ࠊ(LJHQᵓ㐀ࡢヲ⣽ࢆ㆟ㄽࡋࠊᐇ㦂࡛ᚓࡽࢀࡿ⏺㠃㑅ᢥⓗ࡞᣺ືศගࢫ࣌ࢡࢺࣝࡢᖐᒓࢆ⾜࠺஦ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ
ᖺࠊ7RNPDNRIIࡽࡢࢢ࣮ࣝࣉࡣ6FLHQFHㄅ࡟࠾࠸࡚0ࡢ⃰ᗘࡢࣂࣝࢡ+&OỈ⁐ᾮ࡟ᑐࡍࡿ஧ḟඖ㉥እ྾཰ࢫ࣌ࢡࢺࣝ ',5VSHFWUXP ࢆሗ࿌ࡋࠊ=XQGHOᵓ㐀≉᭷ࡢఙ⦰᣺ືኚゅ᣺ື┦஫స⏝ࢆほࡋࡓࠋᖺ࡟ࡣࠊ(OVDHVVHUࡽࡢࢢ࣮ࣝࣉࡀ6FLHQFHㄅ࡟࠾࠸࡚ྠᵝࡢࣂࣝࢡ+&OỈ⁐ᾮ࡟ᑐࡍࡿ஧ḟඖ㉥እ྾཰ࢫ࣌ࢡࢺ
ࣝࢆሗ࿌ࡋࠊ=XQGHOᵓ㐀࡟≉᭷ࡢࣉࣟࢺࣥࢩࣕࢺࣝ᣺ື ⣙ FP ࡢ࣍ࢵࢺࣂࣥࢻࡀ㏻ᖖほᩘഃ࡛ࡣ࡞ࡃࠊ㧗Ἴᩘഃ࡟ほࡉࢀࡿపἼࡉࢀࡿࡇ࡜ࢆⓎぢࡋࡓࠋࡇࢀࡽࡢ◊✲࡟ࡼࡾࠊẚ㍑ⓗ㧗⃰ᗘࡢ㓟Ỉ⁐ᾮ࡛ࡣࠊࣂࣝࢡ㡿ᇦ࡟࠾࠸࡚(LJHQᵓ㐀ࡼࡾࡶࡴࡋࢁ=XQGHOᵓ㐀ࡀᨭ㓄ⓗ࡛࠶ࡿ࡜࠸࠺஦ࡀ㏆ᖺ㆟ㄽࡉࢀ࡚ࡁ࡚࠸
ࡿࠋ୍᪉ࠊ⏦ㄳ⪅ࡢඹྠ◊✲ࢢ࣮ࣝࣉࡣࠊ㏆ᖺࠊྠᵝࡢ+&OỈ⁐ᾮࡢ⏺㠃᣺ືศගࢫ࣌ࢡࢺࣝࡢほ࡟ᡂຌࡋࡓࠋᙼࡽࡣ࣊ࢸࣟࢲ࢖᳨ࣥฟ᣺ື࿴࿘Ἴศගἲࢆ⏝࠸࡚ࠊ FP࠿ࡽ FPࡢ㡿ᇦ࡟ᑐࡍࡿᗈ⠊ᅖࡢ᣺ືࢫ࣌ࢡࢺࣝࢆ᫂ࡽ࠿࡟ࡋࡓࡀࠊࡑࡢࢫ࣌ࢡࢺࣝᙧ≧ࡢゎ㔘࡟㛵ࡋ࡚ᐇ㦂ࡔࡅ࡛ࡣ୙᫂࡞Ⅼࡀ࠸ࡃࡘ࠿Ꮡ
ᅾࡍࡿࠋࡲࡎࠊL 0⛬ᗘࡢ⃰ᗘ࡛ࡣࠊ FPࡃࡽ࠸ࡢࢫ࣌ࢡࢺࣝᛂ⟅ࡀᙉࡃほࡉࢀࡓࡇ࡜࡜ࠊLL 0⛬ᗘࡢ⃰ᗘ࡛ࡣࠊ FP௨ୗࡢᛂ⟅ࡀฟ⌧ࡉࢀጞࡵࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࡀࠊࡇࢀࡽࡀ=XQGHOࡸ(LJHQᵓ㐀ࡢ࡝ࡢࡼ࠺࡞≉ᚩࢆ཯ᫎࡋ࡚࠸ࡿࡢ࠿ࡣ᫂ࡽ࠿࡛ࡣ࡞࠸ࠋᮏ◊✲ࡣࠊࡇࢀ࡜ྠᵝࡢ⣔ࡢ➨୍ཎ⌮ศᏊືຊᏛࢩ࣑
࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊ⏺㠃᣺ືࢫ࣌ࢡࢺࣝ࡜ඹ࡟ࠊ=XQGHOࡸ(LJHQᵓ㐀ࡢ⏺㠃ࡸࣂࣝࢡ࡛ࡢᏑᅾẚ࡞࡝ࢆ᫂ࡽ
࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ  ◊✲᪉ἲࠊィ⟬᪉ἲ➨୍ཎ⌮ศᏊືຊᏛࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ࡟ࡣ㸪&3.ࣉࣟࢢ࣒ࣛ
ࣃࢵࢣ࣮ࢪࢆ⏝࠸ࡓࠋୖグ┠ⓗࡢィ⟬ࢆᐇ⾜ࡍࡿୖ࡛ࡣࠊศᏊ
ືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽ⏕ᡂࡉࢀࡿࢺࣛࢪ࢙ࢡࢺ࣮ࣜ࡟ᑐ
ࡋ࡚=XQGHOᵓ㐀ࡸ(LJHQᵓ㐀ࢆ᫂☜࡟ศ㢮ࡍࡿᚲせࡀ࠶ࡿࠋࡑࡢᅗ

=XQGHO(LJHQ ᵓ㐀ࡢᐃ⩏ࡓࡵ࡟ࡣࠊ=XQGHO≧ែ࡜(LJHQ≧- 256 -

ែ࡟ᑐᛂࡍࡿศᏊᵓ㐀ࢆᐃ⩏ࡍࡿᚲせࡀ࠶ࡿ ᅗ ࠋᮏ◊✲࡛ࡣࠊ㸯ࡘࡢࣉࣟࢺࣥ࠿ࡽ࠶ࡿࡋࡁ࠸㊥㞳UFෆ࡟㓟⣲ཎᏊࡀ㸰ಶᏑᅾࡋࠊ࠿ࡘࡑࡢ㸰ಶࡢ㓟⣲ࡢ㏆᥋࡟ಶࡢࣉࣟࢺࣥࡀᏑᅾࡍࡿሙྜࡣ=XQGHOᵓ㐀࡜ᐃ⩏ࡍࡿࠋࡲࡓࠊ㸯ࡘࡢ㓟⣲ཎᏊ࠿ࡽ࠶ࡿࡋࡁ࠸㊥㞳UFෆ࡟ࣉࣟࢺࣥ
ࡀಶᏑᅾࡋࠊ࠿ࡘࡑࢀࡒࢀࡢࣉࣟࢺࣥࡢ㏆᥋࡟㓟⣲ࡀ㸯ࡘࡔࡅᏑᅾࡍࡿᵓ㐀ࢆ(LJHQᵓ㐀࡜ᐃ⩏ࡍࡿࠋࡋࡁ࠸
㊥㞳UFࢆỴࡵࡿࡓࡵ࡟㸪UFࢆኚ໬ࡉࡏࡓ࡜ࡁࡢࣂࣝࢡࡢ
᣺ື≧ែᐦᗘ 9LEUDWLRQDO'HQVLW\RI6WDWH9'26 ࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࠊࢡࣛࢫࢱ࣮◊✲࡛Ỵࡵࡽࢀࡓ=XQGHOᵓ㐀ࡶࡋࡃࡣ(LJHQᵓ㐀࡟ᑐᛂࡍࡿࢫ࣌ࢡࢺࣝ࡜࡞ࡿ್ࢆồࡵࡿࠋ௨ୗࡢ⤖ᯝ࡛ヲࡋࡃ㏙࡭ࡿࡀ㸪⌧ᅾࡲ࡛ࡢ࡜ࡇ
ࢁ㸪UF cࡀ㐺ᙜ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋࡇࡢᐃ
⩏ࡢࡶ࡜ࠊ00ࡢ+&OỈ⁐ᾮ࡟ᑐࡍࡿࢫࣛࣈࡶࡋࡃ
ࡣࣂࣝࢡࡢ➨୍ཎ⌮ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺஦࡟ࡼࡾࠊࣂࣝࢡ࠶ࡿ࠸ࡣ⏺㠃࡛ࡢ=XQGHOᵓ㐀࡜(LJHQᵓ㐀ࡢᏑᅾẚࠊ࡞ࡽࡧ࡟᣺ືࢫ࣌ࢡࢺࣝࢆィ⟬ࡍ
ࡿࠋ



◊✲ᡂᯝ

ᅗ࡟㸪0ࡢ⃰ᗘࡢࣂࣝࢡ+&OỈ⁐ᾮ࡟ᑐࡋ࡚ィ⟬ࡋ
ࡓ9'26ࢫ࣌ࢡࢺࣝࡢUF౫Ꮡᛶࡢィ⟬⤖ᯝࢆ♧ࡍࠋUFࡀ
ᑠࡉ࠸ሙྜ࡟ࡣ㸪ୖグᐃ⩏࡟ࡼࡾࣉࣟࢺࣥ㏆ഐ࡟㓟⣲ࡀࡘࡔࡅᏑᅾࡍࡿሙྜ (QJHQᵓ㐀 ࡢ☜⋡ࡢ᪉ࡀ㸪ࡑࢀࡀࡘྠ᫬࡟Ꮡᅾࡍࡿሙྜ =XQGHOᵓ㐀 ࡼࡾࡶ኱ࡁࡃ࡞
ࡿࡓࡵ㸪UF c࡛ࡣ࡯࡜ࢇ࡝ࡢపἼᩘᡂศࡣ(LJHQᵓ㐀࡜ᐃ⩏ࡉࢀࡿࠋ୍᪉㸪UFࡀ኱ࡁ࠸ሙྜ࡟ࡣ㸪ࡇࢀ࡜ࡣ㏫
ࡢࡇ࡜ࡀ⏕ࡌࡿࡓࡵ㸪UF c࡛ࡣ࡯࡜ࢇ࡝ࡀ=XQGHOᵓ㐀࡜ᐃ⩏ࡉࢀࡿࠋࡇࢀࡽ(LJHQᵓ㐀࡜=XQGHOᵓ㐀ࡢ᣺ືࣆ࣮ࢡࡣ㸪ࡑࢀࡒࢀ࠾ࡼࡑ FP㸪 FP࡜ぢ✚ࡶࡽࢀ㸪ࡑࢀࡽࡢࣆ࣮ࢡᡂศࡀẚ㍑ⓗࡼࡃศ㞳ࡉࢀࡿUFᅗ 0 +&O Ỉ⁐ᾮ࡟࠾ࡅࡿ᣺ື≧ែᐦᗘࢆc࡜ุᐃࡋࡓࠋィ⟬⤖ᯝࡣUFࡢ㑅ᢥ࡟࠶ࡿ⛬ᗘ౫Ꮡ

9'26 ࢫ࣌ࢡࢺࣝࡢ UF ౫Ꮡᛶࠋ㯮⥺ࡣỈࡢ 2+ࡍࡿࡀ㸪ᐃᛶⓗ࡞ഴྥࡣࡇࡢ್㏆ഐ࡛ኚࢃࡽ࡞࠸࡜⪃᣺ື㸪㉥⥺ࡣ =XQGHO ᵓ㐀ࡢ 2+ ᣺ື㸪㟷⥺ࡣ࠼ࡽࢀࡿࠋ

(LJHQ ᵓ㐀ࡢ 2+ ᣺ື≧ែᐦᗘࢆ⾲ࡍࠋḟ࡟㸪UF c࡟ᅛᐃࡋࡓሙྜࡢ⃰ᗘ0࡜0ࡢ+&OỈ⁐ᾮ࡟ᑐࡍࡿ9'26ࢫ࣌ࢡࢺࣝࢆᅗ㸱࡟♧ࡍࠋ0ࡢ⤖ᯝࡣ㸪ᅗࡢୖ࠿ࡽ␒┠ࡢィ⟬⤖ᯝ࡟ᑐᛂࡋ࡚࠸
ࡿࠋ⤖ᯝࢆࡳࡿ࡜㸪0ࡢ⃰ᗘ࡛ࡣ=XQGHOᡂศ࡜(LJHQᡂศࡢࣆ࣮ࢡ㧗ࡉࡣྠ⛬ᗘ࡛࠶ࡗࡓࡀ㸪0࡛ࡣ
=XQGHOᵓ㐀ࡢ᪉ࡀ(LJHQᵓ㐀ࡼࡾࡶ኱ࡁ࠸9'26ࢫ࣌ࢡࢺࣝ࡜࡞ࡗࡓࠋࡇࢀࡣ㸪0ࡢࣂࣝࢡ+&OỈ⁐ᾮ࡛ࡣ㸪

- 257 -



u

5M





u

:$7
='/
(*1









)UHTXHQF\
ᅗ

:$7
='/
(*1






10M











)UHTXHQF\00+&O Ỉ⁐ᾮ࡟࠾ࡅࡿ᣺ື≧ែᐦᗘ 9'26 ࢫ࣌ࢡࢺࣝ

(LJHQᵓ㐀ࡼࡾࡶࡴࡋࢁ=XQGHOᵓ㐀ࡢ᪉ࡀᨭ㓄ⓗ࡛࠶ࡿ஦ࢆ♧ࡋ࡚࠾ࡾ㸪ࡇࢀࡣ㐣ཤࡢࣂࣝࢡ᣺ືศගᐇ㦂ࡢ⤖ᯝࢆᨭᣢࡋ࡚࠸ࡿࠋ
Ỉ⁐ᾮ⾲㠃࡛ࡢ=XQGHO(LJHQ✀࡜&O࡜ࡢFRPSOH[ᵓ㐀࡞࡝㸪௦⾲ⓗ࡞SURWRQFRPSOH[ᵓ㐀ࢆㄪ࡭ࡓ࡜ࡇࢁ㸪ᅗ࡟♧ࡉࢀࡿࡘࡢᵓ㐀ࡀᨭ㓄ⓗ࡛࠶ࡿ஦ࡀศ࠿ࡗࡓࠋỈ⁐ᾮ⾲㠃࡟ࡣ&O࡜ࡢFRPSOH[ᵓ㐀ࢆ♧ࡍ=XQGHOᵓ㐀 ᅗࡢᕥ➃ᅗ ࡀࡳࡽࢀࡿࠋࡲࡓ㸪&O࡜(LJHQᵓ㐀࡜ࡢFRPSOH[ᵓ㐀࡜ࡋ࡚ᅗࡢᕥ࠿ࡽ␒┠ࡢࡼ࠺࡞ᵓ㐀ࡀࡳࡽࢀࡓࠋ᭱ࡶ⯆࿡῝࠸⤖ᯝࡣ㸪ᅗྑ➃ᅗ࡟♧ࡉࢀࡿࡼ࠺࡟㸪⾲㠃࡛ゎ㞳ࡋࡁࢀ࡞࠸ศᏊᛶ+&Oࡀ㧗⃰ᗘỈ⁐ᾮ࡟࡞ࡿ࡯࡝ከࡃᏑᅾࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ௒ᚋࡣ㸪ࡇࢀࡽࡢᵓ㐀ࡢᐃ㔞ゎᯒࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ

ᅗ+&O Ỉ⁐ᾮ⾲㠃࡟࠾ࡅࡿ௦⾲ⓗ࡞ &O ࡜ࡢ FRPSOH[ ᵓ㐀>ཧ⪃ᩥ⊩@@>@07KDPHU/'0DUFR.5DPDVHVKD$0DQGDODQG$7RNPDNRII6FLHQFH  >@)'DKPV%3)LQJHUKXW(7-1LEEHULQJ(3LQHVDQG7(OVDHVVHU 6FLHQFH  >@-+XWWHU0,DQQX]]L)6FKLIIPDQQDQG-9DQGH9RQGHOH:LOH\,QWHUGLVFLSOLQDU\5HYLHZV&RPSXWDWLRQDO
0ROHFXODU 6FLHQFH  - 258 -

Ⓨ⾲ࠊฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬7,VKL\DPD([LVWHQFHRI:HDNO\,QWHUDFWLQJ2+%RQGDW$LU:DWHU,QWHUIDFH
7KH-RXUQDORI&KHPLFDO3K\VLFV9RO  S SDJHV ‫ۻ‬7,ZDKDVKL7,VKL\DPD<6DNDL$0RULWD'.LPDQG<2XFKL %LOD\HULQJDW,RQLF/LTXLG6XUIDFHV$6XP)UHTXHQF\*HQHUDWLRQ9LEUDWLRQDO6SHFWURVFRS\DQG0ROHFXODU'\QDPLFV
6LPXODWLRQEDVHG6WXG\
3K\VLFDO&KHPLVWU\&KHPLFDO3K\VLFV9RO  SS
‫ۻ‬7,VKL\DPDDQG..LWDQDND $V\PPHWULF+\GURJHQ%RQGLQJ6WUXFWXUHDW:DWHU,FH,QWHUIDFH 
7KH-RXUQDORI3K\VLFDO&KHPLVWU\&9RO  SS
‫ۻ‬7,VKL\DPD67DNDJL7+LUDQR/:DQJDQG$0RULWD &RPPHQWRQ 7RZDUG8QUDYHOLQJWKH3X]]OHRI6XP)UHTXHQF\*HQHUDWLRQ6SHFWUDDW,QWHUIDFHRI$TXHRXV0HWKDQRO6ROXWLRQ(IIHFWVRI&RQFHQWUDWLRQ'HSHQGHQW+\SHUSRODUL]DELOLW\  
7KH-RXUQDORI3K\VLFDO&KHPLVWU\&9RO  SS
‫ۻ‬7,VKL\DPD(QHUJ\5HOD[DWLRQ3DWKRI([FLWHG)UHH2+9LEUDWLRQDWDQ$LU:DWHU,QWHUIDFH5HYHDOHGE\1RQHTXLOLEULXP$E,QLWLR
0ROHFXODU'\QDPLFV6LPXODWLRQ
7KH-RXUQDORI&KHPLFDO3K\VLFV9RO  S SDJHV ‫ۻ‬ඵ༑ᓥரᏹ㸪▼ᒣ㐩ஓ㸪※᫂ㄔ㸪ᗘྍኚ୰㉥እศගἲ࡜ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓ㧗ศᏊ୰ࡢỈࡢ෌⤖ᬗ໬࣓࢝ࢽࢬ࣒ࡢゎᯒศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥᏛ఍࢔ࣥࢧࣥࣈࣝ9RO1RSS  ୍⯡ㅮ₇㸸㧗ศᏊᏛ఍  ௳ࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍  ௳ࠊᣍᚅㅮ₇  ௳

- 259 -

ග㉳㟁ຊࢹࣂ࢖ࢫࡢ㟁Ⲵ⛣ື࣓࢝ࢽࢬ࣒
7KHRUHWLFDO6WXGLHVRI6WUXFWXUH$QDO\VLVLQ3KRWRYROWDLFGHYLFH
żᮧᒸ ᱻࠊᏳᩧឡᏊࠊụᒣࡍࡳࢀࠊᑑᓮᩥ㡢㸦᪥ᮏዪᏊ኱Ꮫ ⌮Ꮫ㒊㸧◊✲┠ⓗࠊෆᐜʌ ඹᙺ໬ྜ≀ࡣࠊʌ 㟁Ꮚ࡟⏤᮶ࡋࡓග྾཰ࡸⓎග≉ᛶࢆ♧ࡋࠊศᏊ㛫┦஫స⏝࡜࢟ࣕࣜ࢔Ⓨ⏕ࢆไᚚࡍࡿࡇ

࡜࡛㟁Ẽࢆὶࡍࡇ࡜ࡀྍ⬟࡛࠶ࡿࡇ࡜࠿ࡽࠊ࢚ࣞࢡࢺࣟࢽࢡࢫࡢศ㔝࡛ά⏝ࡉࢀ࡚࠸ࡿࠋ
୰࡛ࡶࠊⰾ㤶⎔ ʌ ඹᙺ㧗ศᏊࡣࠊᑟ㟁ᛶࡸⓎගᛶ࡞࡝ࡢ㟁Ẽⓗ࣭ගᏛⓗ࡟≉᭷ࡢᛶ㉁ࢆ♧ࡍࡓࡵࠊ᭷ᶵ⣔ኴ㝧㟁ụ࡞࡝᭷ᶵ༙ᑟయ㉳㟁ຊࢹࣂ࢖ࢫ࡬ࡢᛂ⏝࡟ᮇᚅࡀᣢࡓࢀ࡚࠸ࡿࠋ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢගኚ᥮ຠ⋡ࡣࢩࣜࢥࣥ⣔↓ᶵኴ㝧㟁ụ࡟ẚ࡭࡚ගኚ᥮ຠ⋡ࡣప࠸ࡀࠊ㍍㔞࠿ࡘᰂ㌾ᛶࠊᏳ౯࡛࠶ࡿ฼Ⅼ࡟ࡼࡾࡑࡢỗ⏝ᛶࡀὀ┠ࡉࢀ࡚࠸ࡿࠋ᭷ᶵග㉳㟁ຊ࡟ࡼࡿࢹࣂ࢖ࢫ࡟࠾࠸࡚ࠊࢻࢼ࣮ᒙ࡜࢔ࢡࢭࣉࢱ࣮ᒙࡢ⏺㠃࡛⏕ᡂࡍࡿ࢟ࣕࣜ࢔㟁Ꮚ࡜࣮࣍ࣝࡣບ㉳Ꮚࢆᙧᡂࡍࡿࠋ᭷ᶵⷧ⭷ኴ㝧㟁ụࡀຠ⋡ⓗ࡟㟁ὶ⏕ᡂࡍࡿࡓࡵ࡟ࡣࠊບ㉳Ꮚࡢศゎ࡜⮬⏤㟁Ꮚ࢟ࣕࣜ࢔ࡢ㟁ᴟ࡬ࡢ⛣ືࢆಁ㐍ࡍࡿ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࡀㄢ㢟࡜࡞ࡗ࡚࠸ࡿࠋᡃࠎࡣࠊࣂࣝࢡ࡬
ࢸࣟ᥋ྜᆺࡢ᭷ᶵ⣔ኴ㝧㟁ụࡢኚ᥮ຠ⋡ྥୖࡢࡓࡵࠊࢻࢼ࣮࢔ࢡࢭࣉࢱ࣮⏺㠃࡟࠾࠸࡚ࠊ⮬⏤㟁Ꮚ࢟ࣕࣜ࢔
ࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࠊࡑࡋ࡚ග࢚ࢿࣝࢠ࣮ኚ᥮࡟᭷ຠ࡟ാࡃ㉳ᅉᏊࡢゎ᫂ࢆ┠ᣦࡋ࡚ࡁࡓࠋ
௦⾲ⓗ࡞஧ḟ㟁ụࡢ୍ࡘ࡛࠶ࡿࣜࢳ࣒࢘࢖࢜ࣥ㟁ụࡣࠊ㧗㟁ᅽࠊ㧗࢚ࢿࣝࢠ࣮ࠊ㧗ຠ⋡ࡢ඘ᨺ㟁ࢧ࢖ࢡࣝࢆࡶࡘࡇ࡜࠿ࡽࠊ࢚ࢿࣝࢠ࣮㈓ⶶࢩࢫࢸ࣒࡜ࡋ࡚ᗈࡃ౑⏝ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࣜࢳ࣒࢘࢖࢜ࣥ㟁ụ࡟ࡣ /Lࡢ㈨※ࡸࢥࢫࢺ࡟㛵ࡋ࡚ࡢၥ㢟ࡀ࠶ࡿࡇ࡜࠿ࡽࠊ㈨※ࡀ㇏ᐩ࡛ࠊྠ➼ࡢ㟁ᴟ㟁఩ࢆࡶࡘࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụࡢ㛵ᚰࡀ㧗ࡲࡗ࡚࠸ࡿࠋࡑࡢ୰࡛ࡶ 1D ⣔࡟࠾࠸࡚㟁Ꮚ໬Ꮫⓗ࡞άᛶࡀⓎ⌧ࡍࡿࡇ࡜࠿ࡽࠊ㈇ᴟ࡟ࣁ࣮ࢻ࢝
࣮࣎ࣥࢆ⏝࠸ࡓࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụࡀὀ┠ࡉࢀ࡚࠸ࡿࠋ㧗ᐜ㔞ࠊ㧗ຠ⋡ࠊ㛗ᑑ࿨ࠊࡑࡋ࡚Ᏻ඲ᛶࢆഛ࠼ࡓ
1,% ࡢ㛤Ⓨ࡟ྥࡅ࡚ࠊ㟁ᴟ࡛ࡢ඘ᨺ㟁ࡢ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡇ࡜ࡣ୙ྍḞ࡛࠶ࡿࠋ
ᮏ◊✲࡛ࡣࠊ௨ୗ  Ⅼ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ
◊✲᪉ἲࠊィ⟬᪉ἲ  㠀ࣇ࣮ࣛࣞࣥ࢔ࢡࢭࣉࢱ࣮࡟ᇶ࡙ࡃࠊ17] 1DSKWKR>FFµ@ELV>@WKLDGLD]ROH ࢆྵࢇࡔ࢔ࢡࢭࣉ
ࢱ࣮㸦ᅗ 㸧ࡣࠊ L /802 ࢚ࢿࣝࢠ࣮ࣞ࣋ࣝࢆపࡃࡋࠊ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࢆῶࡽࡍࡇ࡜࡟ࡼࡗ࡚ࠊᙉ࠸
㟁Ꮚཷᐜ≉ᛶ࡜࡞ࡾࠊ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢ඲యⓗ࡞ᛶ⬟ࢆ㧗ࡵࡿࡇ࡜ࠊ LL  17] ࢆࣇࢵ⣲໬ࡋࡓ )17] ࢆ࢔ࢡࢭࣉࢱ࣮࡜ࡋ࡚⏝࠸ࡓࣂࣝࢡ࣊ࢸࣟ᥋ྜᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụࡀ㧗࠸ኚ᥮ຠ⋡ࢆᣢࡘࠋᮏ◊✲࡛ࡣࠊศᏊᵓ㐀ࠊ྾཰ࢫ࣌ࢡࢺࣝࠊ+202/802 ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࠊ㟼㟁࣏ࢸࣥࢩࣕࣝࠊ཮ᴟᏊ࣮࣓ࣔࣥࢺࠊ
ศᴟ⋡ࡢほⅬࠊ㟁Ꮚ⛣ືບ㉳࢚ࢿࣝࢠ࣮⛣ື࠿ࡽࣇࢵ⣲໬࡟ࡼࡿኚ᥮ຠ⋡࡬ࡢᙳ㡪ࢆ⌮ㄽⓗ࡟⪃ᐹࡍࡿࠋ*DXVVLDQ ࢆ⏝࠸ࡿࠋィ⟬ࣞ࣋ࣝࡣࠊZ%;'* G ࡛࠶ࡿࠋ  ᅛయ 1D105 ໬Ꮫࢩࣇࢺࢆ⏝࠸ࡓ㈇ᴟ࡟ᤄධࡉࢀࡓ 1D 㔞࡟ᑐࡋ࡚ࡢ +& సᡂ᮲௳ࡢᙳ㡪࡟ࡘ࠸࡚ᐇ㦂ⓗ࡟ሗ࿌ࡉࢀࡓࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣ +& ୰ࡢࢼࢺ࣒ࣜ࢘ࢡࣛࢫࢱ࣮ࡢᙧᡂᡭἲゎ᫂࡟ྥࡅ࡚ࠊᐦᗘỗ㛵ᩘἲࢆ⏝࠸࡚ 1D Q ࡢ 1D105 ໬Ꮫࢩࣇࢺ࡟ࡘ࠸࡚ 1D Q ࢡࣛࢫࢱ࣮ᵓ㐀౫Ꮡᛶ࡜ 1D ᭱እẆ㌶㐨࡟࠾ࡅࡿ㟁Ꮚᐦᗘ౫ᏑᛶࡢほⅬ࠿ࡽ᳨ウࡍࡿࠋ*DXVVLDQ ࢆ⏝࠸ࡿࠋィ⟬ࣞ࣋ࣝࡣࠊ%/<3* G ࡛࠶ࡿࠋ

- 260 -◊✲ᡂᯝ ࣇࢵ⣲໬㠀ࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢ࢔ࢡࢭࣉࢱ࣮ศᏊࡢග྾཰ᛶ
3&3'7%717]7HK)$ 」ྜయ㸦㠀ࣇࢵ⣲໬」ྜయ㸧࡜

3&3'7%7)17]7HK)$ 」ྜయ㸦ࣇࢵ⣲໬」ྜయ㸧ࢆẚ㍑ࡍࡿࠋ
࠸ࡎࢀ࡟࠾࠸࡚ࡶ )DFHRQ ࡢᵓ㐀ࡀ㧗࠸Ᏻᐃ໬ࢆ♧ࡍࠋࡇࢀࡽ
ࡢᵓ㐀ࡢ ((7 ࡟╔┠ࡋࡓ࡜ࡇࢁࠊࣇࢵ⣲໬」ྜయࡢ᪉ࡀࠊ((7ࡀ኱ࡁ࠸ࡇ࡜ࠊࢡ࣮ࣟࣥ┦஫స⏝ࡢᐤ୚ࡀ኱ࡁ࠸ࡇ࡜ࡀ☜ㄆᅗ  ࢔ࢡࢭࣉࢱ࣮ࡢศᏊᵓ㐀࡛ࡁࡓࠋࡇࢀࡣࠊࣇࢵ⣲໬」ྜయࡣ㠀ࣇࢵ⣲໬」ྜయ࡜ẚ࡭ࠊෆ㒊㔞Ꮚຠ⋡ࡀቑຍࡋࠊ▷⤡㟁ὶᐦᗘࡀྥୖ
ࡍࡿࡇ࡜࡛ࠊග㟁ኚ᥮ຠ⋡ࢆ㧗ࡃࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ

஧ḟ㟁ụ࡟࠾ࡅࡿࢼࢺ࣒ࣜ࢘ࢡࣛࢫࢱ࣮ࡢ㟁Ꮚ≧ែ࡜ 1D105 ࢫ࣌ࢡࢺࣝ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

1D Q Q   ࢡࣛࢫࢱ࣮ࡢᏳᐃᵓ㐀ࢆ⪃࠼ࡿࠋQ ࡛ࡣࠊ୕ゅ㠃ࢆ༢఩࡜ࡋࡓᖹ㠃ᵓ㐀ࢆᏳᐃᵓ㐀࡟ᣢࡘࡇ࡜࡟ᑐࡋࠊQ! ࡢࢡࣛࢫࢱ࣮ࡣࠊ୕ゅ㠃࠿ࡽᵓᡂࡉࢀࡿ❧యᵓ㐀ࢆᣢࡘᏳᐃᵓ㐀࡜࡞ࡗࡓࠋࡲࡓ 105ゎᯒ࡛ࡣࠊ1D105 ࢫ࣌ࢡࢺࣝࢆẚ㍑ࡍࡿ࡜ࠊࢫ࣌ࢡࢺࣝࡣ 1D1D 㛫ࡢ┦஫స⏝࡟౫Ꮡࡋࠊࢡࣛࢫࢱ࣮ࢧ
࢖ࢬࡀ኱ࡁࡃ࡞ࡿ࡟ࡘࢀࠊ1D1D 㛫┦஫స⏝ࡀ୍ᐃ್࡟₞㏆ࡍࡿࠋࡲࡓࠊ᭱እẆ V ㌶㐨࡟࠾ࡅࡿ㟁Ꮚᐦᗘศᕸࢆゎᯒࡋࡓ⤖ᯝࠊྛ㔞య࡟࠾ࡅࡿ V ㌶㐨㟁Ꮚᐦᗘࡣ 1D105 ࢫ࣌ࢡࢺࣝ࡜Ⰻ࠸┦㛵ࢆ♧ࡋࡓࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ

մụᒣ ࡍࡳࢀ㸪ኴ⏣ ᕼ㸪ᒣୗ ᫭୍㸪ᮧᒸ ᱻ㸪㠀ࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụ࡟࠾ࡅࡿ࢔ࢡࢭࣉࢱ࣮ศ
Ꮚ 17] ࡀ᭷ࡍࡿග྾཰ᛶ㸪➨  ᅇ &6- ໬Ꮫࣇ࢙ࢫࢱ㸪࢜ࣥࣛ࢖ࣥ㸪 ᖺ  ᭶մᑑᓮ ᩥ㡢㸪ᮧᒸ ᱻ㸪ᒣୗ ᫭୍㸪')7 ィ⟬ࢆ⏝࠸ࡓࢼࢺ࣒ࣜ࢘࢖࢜ࣥ㟁ụ࡟࠾ࡅࡿࢼࢺ࣒ࣜ࢘ࢡࣛࢫࢱ࣮
ࡢᏳᐃᵓ㐀࡜ 105 ゎᯒ㸪➨  ᅇ &6- ໬Ꮫࣇ࢙ࢫࢱ㸪࢜ࣥࣛ࢖ࣥ㸪 ᖺ  ᭶մᏳ㰻 ឡᏊ㸪㯮ᓮ ㆡ㸪୰す 㝯㐀㸪బ఑ ┒ஂ㸪኱ሙ ᘯ๎㸪ᮧᒸ ᱻ㸪7'')7 ィ⟬ࢆ⏝࠸ࡓ 3G&Oࡢග྾
཰㸪➨  ᅇ &6- ໬Ꮫࣇ࢙ࢫࢱ㸪࢜ࣥࣛ࢖ࣥ㸪 ᖺ  ᭶մኴ⏣ ᕼ㸪ᒣୗ ᫭୍㸪ᮧᒸ ᱻ㸪㠀 ࣇ ࣛ ࣮ ࣞ ࣥ ᆺ ᭷ ᶵ ⷧ ⭷ ኴ 㝧 㟁 ụ ࡢ ࣇ ࢵ ⣲ ⨨ ᥮ ࡟ ࠾ ࡅ ࡿ '$ 㑄⛣ ࣓ ࢝ ࢽ ࢬ ࣒ 㸪  ᖺ➨  ᅇᛂ⏝≀⌮Ꮫ఍⛅ᏘᏛ⾡ㅮ₇఍
մ6 ,NH\DPD 1 2KWD . <DPDVKLWD $ 0XUDRND 5HODWLRQ RI 3KRWRDEVRUSWLRQ DQG ([FLWDWLRQ (QHUJ\ 7UDQVIHU LQ
)OXRULQDWHG1RQ)XOOHUHQH7\SH2UJDQLF7KLQ)LOP6RODU&HOOV$36 0DUFK0HHWLQJ ࢜ࣥࣛ࢖ࣥ㸪 ᖺ ᭶մ$ 6X]DNL $ 0XUDRND . <DPDVKLWD 7KHRUHWLFDO 6WXG\ RI &RUUHODWLRQ RI 6RGLXP &OXVWHU DQG 105 $QDO\VLV LQ
6RGLXPLRQ5HFKDUJHDEOH%DWWHULHV $36 0DUFK0HHWLQJ ࢜ࣥࣛ࢖ࣥ㸪 ᖺ  ᭶
մ$$Q]DL<.XURVDNL51DNDQLVKL0 6DHNL+2KED$0XUDRND3KRWRGLVVRFLDWLRQRI3G&OLQDTXHRXV(W2+VROXWLRQXVLQJ 7'')7FDOFXODWLRQV $36 0DUFK0HHWLQJ ࢜ࣥࣛ࢖ࣥ㸪 ᖺ  ᭶- 261 -

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

մ$7+LGD\DW+%HQWHQ7.DZDQLVKL12KWD$0XUDRND01DNDPXUD³(OHFWURQ7UDQVSRUWLQ7KLQ)LOPVRI
3RO\PHU DQG 6PDOO0ROHFXOH $FFHSWRUV 9LVXDOL]HG E\ &RQGXFWLYH $WRPLF )RUFH 0LFURVFRS\´ - 3K\V &KHP &̽

- 262 -

᭷ᶵศᏊ༙ᑟయ⭷୰ࡢ✚ᒙᵓ㐀Ḟ㝗ࡢ㟁Ꮚ≀ᛶࡢ◊✲)LUVWSULQFLSOHVVWXG\RQHOHFWURQLFSURSHUWLHVRIVWDFNLQJIDXOWGHIHFWVLQRUJDQLFPROHFXODUVHPLFRQGXFWLQJILOPV‫ۑ‬୰ᒣ㝯ྐ㸪Ώ㑓㥴ử㉿⚈໏➓ᕝᣅஓ᳜⏣ኟⴥึ㮵⣧ዉ᪂஭༓្ຍ⸨⌔Ⰻ೧すᮏ⍛༓ⴥ኱Ꮫ 
◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࡢ┠ⓗࡣࠊ➨୍ཎ⌮ィ⟬ࢆ⏝࠸࡚ࠊ᭷ᶵศᏊᅛయ㸦୺࡟࣌ࣥࢱࢭࣥⷧ⭷㸧୰࡟Ⓨ⏕ࡍࡿ✚ᒙḞ㝗࠾ࡼࡧࢻ࣓࢖ࣥቃ⏺Ḟ㝗ࡢᵓ㐀࡜ఏᑟ㟁Ꮚ≀ᛶࠊ୙⣧≀ཎᏊࡢྲྀࡾ㎸ࡳ≉ᛶࢆゎ᫂ࡍࡿࡇ࡜࡛࠶ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛ࡣࠊᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃ➨୍ཎ⌮㟁Ꮚ≧ែィ⟬ࢆ⏝࠸ࠊ࣌ࣥࢱࢭࣥⷧ⭷୰ࡢ௦⾲ⓗ࡞㸦㸧✚ᒙḞ㝗࡜⢏⏺ࢆᑐ㇟࡟ࠊࡑࡢᏳᐃ࡞ᙧែ࡜ᙧᡂ࢚ࢿࣝࢠ࣮ࠊ࢟ࣕࣜ࢔࡬ࡢᩓ஘ຠᯝࠊ୙⣧≀ࡢྲྀࡾ㎸ࡳ࢚ࢿࣝࢠ࣮ࢆㄪ࡭ࠊ㟁Ꮚᵓ㐀ࡢほⅬ࠿ࡽࡑࡢ㉳※ࢆ᳨ウࡋࡓࠋᩘ್ィ⟬࡟ࡣࠊ⮬๓࡛㛤Ⓨࡋ࡚࠸ࡿ [7$33 7RN\R
$ELQLWLR3URJUDP3DFNDJH ࡜ SVSZIࠊ࠾ࡼࡧỗ⏝ࡢ 9$63FRGH ࢆ⏝࠸ࡓࠋ



◊✲ᡂᯝ
ᅗ  ࡟ࠊ࣌ࣥࢱࢭࣥ⭷୰࡟㢖⦾࡟Ⓨ⏕ࡍࡿ㸦㸧⢏⏺࿘ࡾࡢྛศᏊࡢ +202 /802 ࡢ࢚ࢿࣝࢠ࣮
఩⨨ࢆ♧ࡍࠋ⢏⏺ࡢᕥྑ࡛࢜ࣇࢭࢵࢺࡀⓎ⏕ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋ㟁Ꮚᵓ㐀ࢆゎᯒࡍࡿࡇ࡜࡛ࠊ
ࡑࡢ㉳※ࡣᕥྑࡢࢻ࣓࢖ࣥෆࡢศᏊ㓄ิ࡜ศᏊᐦ
ᗘࡢᕪ࡟࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡽ࢜ࣇࢭࢵࢺ
ࡣࠊୖᅗࡢࡼ࠺࡟ࠊṇᏍ࣭㟁Ꮚࡢ⢏⏺㏆ࡃ࡬ࡢᒁᅾࢆㄏ㉳ࡍࡿࠋࡲࡓࠊ⢏⏺࡟ࡣ +2 ➼ࡢ㍍ཎᏊࡸ
㔠ᒓ୙⣧≀ཎᏊࡀ㞟ࡲࡾࡸࡍࡃ㸦ᙧᡂ࢚ࢿࣝࢠ࣮

ᅗ  ࣌ࣥࢱࢭࣥ⢏⏺ *% ᕥྑࡢྛศᏊࡢ +202
/802 ఩⨨࡜ṇᏍ㺃㟁Ꮚ࢟ࣕࣜ࢔ࡢศᕸ㸦ୖᤄධᅗ㸧ࠋ㸻⣙㸫H9㸧ࠊ⢏⏺ࡣཎᏊ࡜࢟ࣕࣜ࢔࠸ࡎࢀࡢᤕ⋓୰ᚰ࡜ࡋ࡚ࡶാࡃࡇ࡜ࡀึࡵ࡚ゎ᫂ࡉࢀࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬6 :DWDQDEH 7 1DND\DPD ³(OHFWURQLF VWUXFWXUHV DQG LPSXULW\ DFFXPXODWLRQ DURXQG H[WHQGHG GHIHFWV LQ
SHQWDFHQHILOPVILUVWSULQFLSOHVVWXG\´,QW&RQI6ROLG6WDWH'HYLFHVDQG0DWHULDOV2QOLQH6HSW
‫ۻ‬Ώ㑔㥴ử୰ᒣ㝯ྐ ³࣌ࣥࢱࢭࣥ⭷୰ࡢᵓ㐀Ḟ㝗ࡢ㟁Ꮚ≧ែ㸸➨୍ཎ⌮ィ⟬࡟ࡼࡿ᳨ウ´ ➨  ᅇᛂ⏝≀⌮Ꮫ఍⛅ᏘᏛ⾡ㅮ₇఍ 2QOLQH  ᖺ  ᭶ࠊཬࡧ ´࣌ࣥࢱࢭࣥ⭷୰ࡢ㔠ᒓཎᏊࢡࣛࢫࢱ࣮ࡢᙧែ࡜Ᏻᐃ
ᛶ㸸➨୍ཎ⌮ィ⟬࡟ࡼࡿ᳨ウ´ ➨  ᅇᛂ⏝≀⌮Ꮫ఍᫓ᏘᏛ⾡ㅮ₇఍2QOLQH ᖺ  ᭶ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬6:DWDQDEH71DND\DPD(OHFWURQLFVWUXFWXUHVDQGLPSXULW\VHJUHJDWLRQDURXQGH[WHQGHGGHIHFWVLQSHQWDFHQH
ILOPVILUVWSULQFLSOHVVWXG\-SQ-$SSO3K\V606%%*  - 263 -

཯ᛂ⤒㊰⮬ື᥈⣴ࢆ⏝࠸ࡿゐ፹࣭Ⓨගᮦᩱࡢ⌮ㄽⓗ◊✲ 
7KHRUHWLFDOVWXG\RIFDWDO\VWVDQGOXPLQHVFHQFHPDWHULDOVXVLQJWKH
JOREDOUHDFWLRQURXWHPDSSLQJ‫⏿ۑ‬୰ ⨾✑ ✄ᇉ Ὀ୍ ྜྷᮧ ㄔ៞3XULSDW0DQHHSRUQ ධబ 㥴୍ ኱ஂಖ ಇ ᐑᕝ ᭸அ㸦៞᠕኱ ⌮ᕤ㸧 ◊✲┠ⓗᡃࠎࡣࠊゐ፹࠾ࡼࡧⓎගᮦᩱࡀാࡃ࣓࢝ࢽࢬ࣒ࢆ㟁Ꮚ≧ែࡢほⅬ࠿ࡽゎ᫂ࡍࡿࡇ࡜ࢆ┠ᣦࡋ࡚࠸ࡿࠋ
ᖺᗘࡣ୺࡟   ᭷ᶵゐ፹ࢆ⏝࠸ࡿ୙ᩧࣅࢠࢿࣜ཯ᛂࡢ࢚ࢼࣥࢳ࢜㑅ᢥไࡢゎ᫂ࠊ   ࢫࣆࣥ㌶㐨┦஫స⏝ࡢไᚚ࡟ࡼࡿගቑឤ๣ࡢศᏊタィᣦ㔪ࡢᵓ⠏ࠊ   ࣛࣥࢱࣀ࢖ࢻⓎග㘒యࡢⓎග࣭ᾘගᶵᵓࡢゎᯒࢆ⾜ࡗࡓࠋ ᭷ᶵゐ፹ࢆ⏝࠸ࡿ୙ᩧࣅࢠࢿࣜ཯ᛂࡢ࢚ࢼࣥࢳ࢜㑅ᢥไࡢゎ᫂ࢪࣄࢻࣟࣆ࣑ࣜࢪࣀࣥ '+3 ࡣᢠ⒴άᛶ࡞࡝㔜せ࡞⏕⌮άᛶࢆ᭷ࡍࡿ≀㉁࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋ'+3 ࡣ࢟ࣛࣝ୰ᚰࡢᏑᅾ࡟ࡼࡾගᏛ␗ᛶయࢆᣢࡘࡓࡵࠊ㧗࠸⏕⌮άᛶࢆ♧ࡍ␗ᛶయࡢࡳࢆ㑅ᢥⓗ࡟ྜᡂࡍࡿࡇ࡜ࡀ
ᮃࡲࢀࡿࠋࡑࡢྜᡂἲࡢ  ࡘࡀࣅࢠࢿࣜ཯ᛂ࡛࠶ࡿࠋ୕ᡂศ⦰ྜ཯ᛂ࡛࠶ࡿࣅࢠࢿࣜ཯ᛂࡣࠊ࢔ࣝࢹࣄࢻࠊ
ᒀ⣲ࠊࡑࡋ࡚șࢣࢺ࢚ࢫࢸࣝ࠿ࡽ '+3 ࢆᙧᡂࡍࡿࠋ≉࡟ࠊ➨  ⣭࢔࣑ࣥࢆ᭷ࡍࡿ࢟ࣛࣝ࡞᭷ᶵゐ፹ࢆ⏝࠸ࡿࡇ࡜࡛ࠊHH ࢆ㉸࠼ࡿ㧗࠸࢚ࢼࣥࢳ࢜㑅ᢥᛶࢆᣢࡗ࡚ '+3 ㄏᑟయࢆᚓࡿࡇ࡜࡟ᡂຌࡋ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀ
ࡽࠊࡑࡢ࣓࢝ࢽࢬ࣒ࡣᮍࡔࡼࡃࢃ࠿ࡗ࡚࠾ࡽࡎࠊ᪂つ࡞ '+3 ㄏᑟయࢆྜᡂࡍࡿ㝿ࡢゐ፹ࡢᨵኚᣦ㔪ࡣᚓࡽࢀ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣ࢚ࢼࣥࢳ࢜㑅ᢥᛶࡢ㉳※ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊඛ⾜◊✲࡛ᚊ㏿ẁ㝵࡜ணࡉࢀ࢚ࢼࣥࢳ࢜㑅ᢥᛶࡢ㉳※࡜⪃࠼ࡽࢀࡿࣆ࣑ࣜࢪࣥ⎔ᙧᡂ㐣⛬ࢆㄪᰝࡋࡓࠋ ࢫࣆࣥ㌶㐨┦஫స⏝ࡢไᚚ࡟ࡼࡿගቑឤ๣ࡢศᏊタィᣦ㔪ࡢᵓ⠏ගቑឤ๣ࡣࠊගບ㉳࡛ᚓࡓ࢚ࢿࣝࢠ࣮࡟ࡼࡗ࡚௚ࡢ≀㉁ࢆάᛶ໬ࡍࡿ㸦ග࢚ࢿࣝࢠ࣮ࢆ໬Ꮫ࢚ࢿࣝࢠ࣮࡟
ኚ᥮ࡍࡿ㸧ᶵ⬟ࢆᣢࡘ≀㉁࡛࠶ࡿࠋࡑࡢᶵ⬟ࢆ⏝࠸࡚ࠊ㏆ᖺ࡛ࡣᙉ࠸ẅ⳦స⏝ࢆ᭷ࡍࡿ୍㔜㡯㓟⣲ࢆຠ⋡ⓗ࡟⏕ᡂࡍࡿ᪉ἲࡀᶍ⣴ࡉࢀ࡚࠸ࡿࠋࡑࡢࡓࡵ࡟ࡣࠊගቑឤ๣࠿ࡽ୕㔜㡯㓟⣲࡬ࡢບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟ඛ❧ࡗ࡚ࠊගቑឤ๣ࡢ୍㔜㡯ບ㉳≧ែ࠿ࡽ୕㔜㡯ບ㉳≧ែ࡬ࡢ⣔㛫஺ᕪࡀ⣲᪩ࡃ㐍⾜ࡍࡿࠊࡘࡲࡾ኱ࡁ࡞ࢫࣆࣥ
㌶㐨┦஫స⏝ 62& ࡀാࡃᚲせࡀ࠶ࡿࠋᮏ◊✲࡛ࡣࠊ㛤Ⓨ୰ࡢ࠶ࡿࢱ࣮ࢤࢵࢺศᏊࡢ㧗ᶵ⬟໬ࢆ┠ᣦࡋࠊ࡝ࡢ
ࡼ࠺࡞⨨᥮ᇶࢆᑟධࡍࢀࡤ 62& ࡀቑ኱ࡋ⣲᪩࠸⣔㛫஺ᕪ࡟⧅ࡀࡿ࠿ࢆㄪᰝࡋࡓࠋ ࣛࣥࢱࣀ࢖ࢻⓎග㘒యࡢⓎග࣭ᾘගᶵᵓࡢゎᯒࣛࣥࢱࣀ࢖ࢻ㔠ᒓ㘒యࡣ⎔ቃ౫Ꮡᛶࡀᑡ࡞ࡃᏳᐃ࡞Ⓨගᮦᩱ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋ㓄఩Ꮚ࡟ࡼࡿග྾཰
࡟⥆ࡃࣛࣥࢱࣀ࢖ࢻࡢ II Ⓨගࢆ㧗ຠ⋡໬ࡍࡿࡓࡵ࡟ࡣࠊ㓄఩Ꮚࡢྜ⌮ⓗタィࡀᚲせ୙ྍḞ࡛࠶ࡿࠋ ࡘࡢࣅࣆࣜࢪࣝᇶࢆྵࡴ㓄఩Ꮚࢆᣢࡘࢸࣝࣅ࣒࢘ 7E 㘒య %S\7E ࡛ࡣࠊ7E ࡢ II Ⓨගࡀほࡉࢀ࡞࠸ࡇ࡜ࡀᐇ㦂ⓗ࡟☜ㄆࡉࢀࡓ୍᪉࡛ࠊࣅࣆࣜࢪࣥ࡟ࡼࡃఝࡓࣇ࢙ࢼࣥࢺࣟࣜࣥࢆ  ࡘྵࡴ㓄఩Ꮚࢆᣢࡘ 7E 㘒య 3KH7E ࡛ࡣࠊ
7E ࡢ II Ⓨග࡟ຍ࠼ࠊ㓄఩Ꮚ࠿ࡽࡢⓎගࡶ☜ㄆࡉࢀࡓࠋᮏ◊✲࡛ࡣࠊࡇࡢࢃࡎ࠿࡞㓄఩Ꮚࡢ㐪࠸ࡀࡶࡓࡽࡍ
Ⓨග࣭ᾘග㐣⛬ࡢኚ໬ࢆ⌮ゎࡍࡿࡓࡵ࡟୧㘒యࡢບ㉳≧ែ࣏ࢸࣥࢩࣕࣝ㠃ࢆィ⟬ࡋࡓࠋ ◊✲᪉ἲࠊィ⟬᪉ἲศᏊࡢ㟁Ꮚ≧ែゎᯒ࡟ࡣ㔞Ꮚ໬Ꮫィ⟬ࣉࣟࢢ࣒ࣛ *DXVVLDQ ࢆ౑⏝ࡋࠊᏳᐃᵓ㐀ࡸ㑄⛣≧ែࠊ཯ᛂ⤒㊰ࡢ᥈⣴࡟ࡣ *550 ࣉࣟࢢ࣒ࣛࢆά⏝ࡋࡓࠋࡉࡽ࡟ࠊࢸ࣮࣐  ࡛ࡣ 3\62& ࣉࣟࢢ࣒ࣛࢆ฼⏝ࡋ࡚ 62& ࢆィ⟬ࡋࡓࠋ- 264 - ◊✲ᡂᯝ ᭷ᶵゐ፹ࢆ⏝࠸ࡿ୙ᩧࣅࢠࢿࣜ཯ᛂࡢ࢚ࢼࣥࢳ࢜㑅ᢥไࡢゎ᫂ࣅࢠࢿࣜ཯ᛂࡢ࢚ࢼࣥࢳ࢜㑅ᢥᛶࢆỴᐃࡍࡿࣆ࣑ࣜࢪࣥ⎔ᙧᡂ㐣⛬ࢆゎᯒࡋࡓࠋ཯ᛂጞ≧ែ࡛ࡣ  ࡘࡢ❧య␗ᛶయࡢᏑᅾࡀ⪃࠼ࡽࢀࡓࡓࡵࠊࡑࢀࡒࢀࡢ⎔ᙧᡂ㐣⛬࡟࠾ࡅࡿ୰㛫యᵓ㐀ࡸ㛵㐃ࡍࡿ㑄⛣≧ែᵓ㐀ࢆồࡵࡓࠋࡑࡢ⤖ᯝࠊ୺࡟Ⅳ⣲❅⣲⤖ྜࡢᙧᡂ࡜  ࡘࡢࣉࣟࢺࣥ⛣ື㐣⛬ࢆ⤒࡚ẁ㝵ⓗ࡟⎔໬ࡀ㉳ࡇࡿ࡜࠸࠺ࡇ
࡜ࡀศ࠿ࡗࡓࠋࡑࡋ࡚ࠊ᭱ࡶప࠸㑄⛣≧ែࡢ࢚ࢿࣝࢠ࣮ࢆᣢࡘ཯ᛂ⤒㊰ࢆ≉ᐃࡋࠊࡑࡢ⤒㊰࠿ࡽᚓࡽࢀࡿ␗
ᛶయࡣᐇ㦂࡛ᚓࡽࢀࡓࡶࡢ࡜୍⮴ࡍࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋࡉࡽ࡟ࡑࡢ࢚ࢼࣥࢳ࢜㐣๫⋡ࡣ HH ࡜ぢ✚ࡶࡽࢀᐇ㦂஦ᐇ࡜▩┪࡞࠸⤖ᯝࢆᚓࡿࡇ࡜࡟ᡂຌࡋࡓࠋィ⟬⤖ᯝࡀᐇ㦂஦ᐇ࡜ᩚྜࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࡓࡵࠊ㑄⛣≧ែࡢᵓ㐀ゎᯒ࠿ࡽࡑࡢ㉳※ࢆㄪ࡭ࡓࠋࡑࡢ⤖ᯝࠊࣉࣟࢺࣥ⛣ືࢆᢸ࠺❅⣲ࡸ㓟⣲ࡢ࿘ࡾ࡛ዲࡲࡋ࠸ศᏊ
ෆỈ⣲⤖ྜ㙐ࢆᵓ⠏ࡋ≉ᐃࡢᇶ㉁ᵓ㐀ࢆᏳᐃ໬ࡍࡿࡇ࡜࡛㧗࠸࢚ࢼࣥࢳ࢜㑅ᢥᛶࡀ㐩ᡂࡉࢀ࡚࠸ࡿࠊ࡜࠸࠺
ࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡲࡓࠊ
ࠕ↓ᴟᛶ⁐፹࡛㧗ࡃᴟᛶ⁐፹࡛ప࠸࢚ࢼࣥࢳ࢜㑅ᢥᛶࡀ࠶ࡿࠖ࡜࠸࠺ᐇ㦂஦ᐇࡣࠊᴟᛶ⁐፹ࡀศᏊෆỈ⣲⤖ྜ㙐ࡢᵓ㐀ࢆቯࡍࡼ࠺࡟ാࡃࡓࡵ࡛࠶ࡿ࡜ㄝ࡛᫂ࡁࡓࠋ ࢫࣆࣥ㌶㐨┦஫స⏝ࡢไᚚ࡟ࡼࡿගቑឤ๣ࡢศᏊタィᣦ㔪ࡢᵓ⠏ᮏ◊✲࡛ࡣࠊ࠶ࡿࢱ࣮ࢤࢵࢺศᏊ࡟ᵝࠎ࡞⨨᥮ᇶࢆᑟධࡋ࡚ᚓࡽࢀࡿㄏᑟయ㸦ィ  ✀㢮㸧ࢆᑐ㇟࡜ࡋ࡚
タィᣦ㔪ࡢᵓ⠏ࢆ┠ᣦࡋࡓࠋࡲࡎࠊࢱ࣮ࢤࢵࢺศᏊࡢ 62& ࢆィ⟬ࡋࠊ⣙  FP㸫 ࡢ್ࢆᚓࡓࠋḟ࡟ㄏᑟయࡢ
62& ࢆィ⟬ࡋࡓ࡜ࡇࢁࠊࡑࡢ್ࡀ  FP㸫 ࢆ㉸࠼ࡿㄏᑟయࡀᩓぢࡉࢀࡓࠋ࡝ࡢࡼ࠺࡞ㄏᑟయࡀ኱ࡁ࡞ 62&ࢆᣢࡘࡢ࠿ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊ⨨᥮ᇶࡢ 62& ࡢ್ཬࡧㄏᑟయࡢ⣔㛫஺ᕪ࡟㛵ࢃࡿບ㉳≧ែ 6 ࡢᛶ㉁ࢆゎᯒࡋࡓࠋࡑࡢ⤖ᯝࠊ኱ࡁ࡞ 62& ࢆᣢࡘㄏᑟయ࡟ࡣẚ㍑ⓗ኱ࡁ࡞ 62& ࢆᣢࡘ⨨᥮ᇶࡀᑟධࡉࢀ࡚࠸ࡿࡇ࡜
࡟ຍ࠼ࠊࡑࡢㄏᑟయࡢ 6 ࡣ⨨᥮ᇶ㒊ศ࡟ᒁᅾ໬ࡋࡓ㟁Ꮚ㑄⛣࡟⏤᮶ࡍࡿບ㉳≧ែ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇ
ࡢ⤖ᯝࡣࠊ⨨᥮ᇶࡀᣢࡘ኱ࡁ࡞ 62& ࢆࡑࡢࡲࡲㄏᑟయࡢ 62& ࡜ࡋ࡚ά⏝࡛ࡁࡿྍ⬟ᛶࢆ♧ࡋ࡚࠸ࡿࠋࡉࡽ
࡟ࠊᒁᅾ㟁Ꮚ㑄⛣ࢆ㉳ࡇࡍㄏᑟయࡣᏙ❧⨨᥮ᇶࡢ +202 ࡜ /802 ࡀᏙ❧ࢱ࣮ࢤࢵࢺศᏊࡢ +202/802ࢠࣕࢵࣉ୰࡟㏆࠸఩⨨࡟Ꮡᅾࡋ࡚࠸ࡿࡇ࡜ࡶ᫂ࡽ࠿࡟ࡋࡓࠋࡼࡗ࡚ࠊࢱ࣮ࢤࢵࢺศᏊ࡜ 62& ࡢ኱ࡁ࡞⨨᥮ᇶࡢ୍㟁Ꮚ㌶㐨ࡢ฼⏝ࡔࡅ࡛ࠊ⣲᪩࠸⣔㛫஺ᕪࢆ㉳ࡇࡍගቑឤ๣ࢆ᥎ ࡛ࡁࡿྍ⬟ᛶࡀ࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ ࣛࣥࢱࣀ࢖ࢻⓎග㘒యࡢⓎග࣭ᾘගᶵᵓࡢゎᯒ%S\7E ࡢບ㉳≧ែ࣏ࢸࣥࢩࣕࣝ㠃ࢆィ⟬ࡋࡓ࡜ࡇࢁࠊ㓄఩Ꮚෆບ㉳≧ែࡢ↓㍽ᑕ⦆࿴ࢆᢸ࠺ 7 ࡜ 6 ࡢ࣏ࢸࣥࢩࣕࣝ஺ᕪⅬ ;76 ࡣ࢚ࢿࣝࢠ࣮ⓗ࡟ 7 ࡢᏳᐃᵓ㐀࡜࡯ࡰྠࡌ఩⨨㸦 NFDOPRO ௨ෆ㸧࡟Ꮡᅾࡋࡓࠋࡇ
ࢀࡣࠊ㓄఩Ꮚෆ࡛ࡢ㧗㏿࡞↓㍽ᑕ⦆࿴㐣⛬ࡢᏑᅾࢆ♧၀ࡋ࡚࠸ࡿࠋ୍᪉ࠊ3KH7E ࡛ࡣ 7 ࡢᏳᐃᵓ㐀ࡀ ;76ࡼࡾࡶ NFDOPRO ࡯࡝ప࠸఩⨨࡟࠶ࡾࠊ7E ࡢ II ບ㉳≧ែ࡬ࡢບ㉳࢚ࢿࣝࢠ࣮⛣ືࡀ┦ᑐⓗ࡟㉳ࡇࡾࡸࡍࡃ࡞
ࡗ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ3KH7E ࡟࠾࠸࡚ 7 ࡢᏳᐃᵓ㐀ࡢ࢚ࢿࣝࢠ࣮ࡀୗࡀࡗࡓཎᅉࡸ㓄఩Ꮚ࠿ࡽࡢ
Ⓨගࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࡣࠊ⌧ᅾゎᯒ୰࡛࠶ࡿࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

>@⏿୰⨾✑͆཯ᛂ⤒㊰ࡢࢹ࣮ࢱ࣮࣋ࢫ࡜ᶵᲔᏛ⩦ࢆ⏝࠸ࡓゐ፹᥎⸀ࢩࢫࢸ࣒ࡢᵓ⠏͇᪥ᮏ໬Ꮫ఍➨᫓Ꮨᖺ఍   ᖺ  ᭶࢜ࣥࣛ࢖ࣥ
>@⏿୰⨾✑͆཯ᛂ⤒㊰⮬ື᥈⣴ࢆ⏝࠸ࡿゐ፹཯ᛂࡢ⌮ㄽⓗ◊✲㸫ᶵᵓゎ࣭᫂ゐ፹タィࢆ┠ᣦࡋ࡚㸫͇᪥ᮏ໬Ꮫ఍➨᫓Ꮨᖺ఍   ᖺ  ᭶࢜ࣥࣛ࢖ࣥ
>@⏿୰⨾✑͆⌮ㄽ࣭ィ⟬໬Ꮫ࡟ࡼࡿᶵ⬟ᛶᮦᩱࡢᶵᵓゎ᫂࡜ศᏊタィ͇᪥ᮏ໬Ꮫ఍➨᫓Ꮨᖺ఍
  ᖺ  ᭶࢜ࣥࣛ࢖ࣥ
>@⏿୰⨾✑͆⮬ື཯ᛂ⤒㊰᥈⣴ࢆ⏝࠸ࡿࣁ࢖ࣈࣜࢵࢻゐ፹⣔ࡢᶵᵓゎ᫂࡜཯ᛂᛶỴᐃᅉᏊࡢᢳฟ͇ࣁ
࢖ࣈࣜࢵࢻゐ፹➨  ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘ ᖺ  ᭶࢜ࣥࣛ࢖ࣥ
>@⏿୰⨾✑͆཯ᛂ⤒㊰ࡢࢹ࣮ࢱ࣮࣋ࢫ࡜ᶵᲔᏛ⩦ࢆ⏝࠸ࡿゐ፹࣭Ⓨගᮦᩱࡢ⌮ゎ࣭ศᏊタィ͇ศᏊ◊- 265 -

ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ZRUNVKRS ᖺ  ᭶࢜ࣥࣛ࢖ࣥ
>@⏿୰⨾✑͆7KHRUHWLFDOVWXG\RQ/DQWKDQLGH/XPLQHVFHQFH0DWHULDOV͇ࢼࣀᏛ఍ྜྠ㒊఍ࢩ࣏ࣥࢪ࣒࢘ ᖺ  ᭶㔠ἑ>@⏿୰⨾✑͆཯ᛂ⤒㊰⮬ື᥈⣴ࢆ⏝࠸ࡿゐ፹཯ᛂࡢ⌮ㄽⓗ◊✲࣮ᶵᵓゎ࣭᫂ゐ፹タィࢆ┠ᣦࡋ࡚࣮͇
᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍  ᖺ⛅Ꮨᖺ఍ ᖺ  ᭶࢜ࣥࣛ࢖ࣥ
>@⏿୰⨾✑͆཯ᛂ⤒㊰ࡢࢹ࣮ࢱ࣮࣋ࢫ࡜ᶵᲔᏛ⩦ࢆ⏝࠸ࡿゐ፹࣭Ⓨගᮦᩱࡢ⌮ゎ࣭ศᏊタィ͇㏆␥໬Ꮫ༠఍ᶵ⬟ᛶⰍ⣲㒊఍࣭࢚ࣞࢡࢺࣟࢽࢡࢫ㒊఍ྜྠබ㛤ㅮ₇఍ ᖺ  ᭶࢜ࣥࣛ࢖ࣥ
>@⏿୰⨾✑͆⌮ㄽ࣭ィ⟬໬Ꮫࢆ⏝࠸ࡿࣛࣥࣀ࢖ࢻⓎගᮦᩱࡢ⌮ゎ࣭ศᏊタィ͇㘒య໬Ꮫ఍࢜ࣥࣛ࢖ࣥ◊✲఍ ᖺ  ᭶࢜ࣥࣛ࢖ࣥ

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ @>ۻ‬7 <RVKLPXUD 0 3XULSDW 9 3DUDVXN 0 +DWDQDND ³6WHUHRVHOHFWLYLW\ RI WKH %LJLQHOOL 5HDFWLRQ &DWDO\]HG E\&KLUDO3ULPDU\$PLQH$&RPSXWDWLRQDO6WXG\´+HWHURF\FOHVLQSUHVV  >@ <<DPDVKLWD $1RJXFKL 6 )XVKLPL 0 +DWDQDND 6.RED\DVKL ³&KLUDO 0HWDO 6DOWV DV /LJDQGV IRU &DWDO\WLF
$V\PPHWULF0DQQLFK5HDFWLRQVZLWK6LPSOH$PLGHV´-$P&KHP6RF


- 266 - ࢖࢜ࣥᛶᾮయ࡟࠾ࡅࡿ࢖࢜ࣥఏᑟ⋡ࠊෆ㒊⛣ືᗘࠊ࠾ࡼࡧ +DYHQ ẚࡢໟᣓⓗ◊✲㸯㸸࢖࢜ࣥ㉁㔞౫Ꮡᛶ&RPSUHKHQVLYHVWXG\RQWKHLRQLFFRQGXFWLYLW\LQWHUQDOPRELOLW\DQG
WKH+DYHQUDWLRLQLRQLFOLTXLGVLRQLFPDVVGHSHQGHQFH‫ۑ‬኱㫽 ⠊࿴ ᭹㒊 ⏤ె ಙ⏣ Ẹ⏕ ᕝ➃ ᾏ㒔 㜿㒊 ಇኴ㸦᪂₲኱Ꮫ⌮Ꮫ㒊  ྠ኱Ꮫ㝔⮬↛⛉Ꮫ◊✲⛉㸧




◊✲┠ⓗ

 ⁐⼥ሷࡸ࢖࢜ࣥᾮయࡢ࢖࢜ࣥఏᑟᛶࡣࠊ㟁ụࡢ㟁ゎ㉁࡜ࡋ࡚ࡢᐇ⏝ᛶࡶࡉࡿࡇ࡜࡞ࡀࡽࠊᾮయࡢ≀⌮໬Ꮫࡢᇶ♏ⓗ⌮ゎࡢほⅬ࠿ࡽࠊ࠸ࡲࡔከࡃࡢ◊✲ㄢ㢟ࢆṧࡋ࡚࠸ࡿࠋᚑ᮶ࡢ◊✲ࡣࠊᕧどⓗ࡞㍺㏦ಀᩘ㸦࢖࢜ࣥఏᑟ⋡㸧ࡢホ౯࡜ᚤどⓗ࡞ఏᑟᶵᵓࡢほⅬ࠿ࡽ㐍ࡵࡽࢀ࡚ࡁࡓࡀࠊ⁐⼥ሷࡸ࢖࢜ࣥᾮయ࡛ࡣࠊྛ࢖࢜ࣥ✀࡟ࡼࡿ࢖࢜ࣥఏᑟ⋡࡬ࡢᐤ୚ࢆ♧ࡍ㍺⋡ࡢᐃ⩏ࡀࠊỈ⁐ᾮ࡜ࡣ␗࡞ࡾ୍⩏ⓗ࡛ࡣ࡞࠸ࡓࡵࠊ࢖࢜ࣥఏᑟ⋡࡜ྛ࢖࢜ࣥ✀ࡢࢲ࢖ࢼ࣑ࢵࢡࢫ࡜ࡢ㛵ಀࢆ㆟ㄽࡍࡿᇶ┙ࡀ᭕᫕࡛࠶ࡿ࡜࠸࠺ㄢ㢟ࡀᣦ᦬ࡉࢀ࡚࠸ࡿࠋ୍᪉ࠊ⁐⼥ሷࡢ㟁ẼὋື࡟ࡼࡗ࡚ほࡉࢀࡿྛ࢖࢜ࣥ✀ࡢ⛣ືᗘ࡜࠸࠺ᴫᛕࡀ᪤࡟ᥦၐࡉࢀ࡚࠾ࡾࠊࡇࡢᴫᛕ࡟ᇶ࡙࠸

࡚ࠊΰྜ⣔࡟࠾ࡅࡿྠ఩య⃰⦰ࡸྛ࢖࢜ࣥ✀ࡢศ㞳ࡀᐇ⌧ࡉࢀ࡚࠸ࡿࠋ౛࠼ࡤ /L%U.%U ࡢ⁐⼥ሷࡢΰྜ≀࡟࠾࠸࡚ࠊ㝜࢖࢜ࣥࢆඹ㏻ࡢཧ↷⣔࡜ࡍࡿෆ㒊⛣ືᗘȣࡣࠊ࢖࢜ࣥఏᑟ⋡Ȫ࡜ߪൌ௘ே௏ሺ ‫ݔ‬ଵ ߤଵି ൅ ‫ݔ‬ଶ ߤଶି ሻ                                ࡢ㛵ಀ࡛⤖ࡤࢀ࡚࠸ࡿࠋࡇࡇ࡛ࠊ[ ࡜ [ ࡣࡑࢀࡒࢀ /L%U ࡜ .%U ࡢࣔࣝศ⋡ࠊȝ࡜ ȝࡣࡑࢀࡒࢀ /L࢖࢜ࣥ࡜ .࢖࢜ࣥࡢ %U࢖࢜ࣥ࡟ᑐࡍࡿෆ㒊⛣ືᗘࢆ⾲ࡍࠋࡍ࡞ࢃࡕࠊෆ㒊⛣ືᗘࡣ㍺⋡ࡑࡢࡶࡢ࡛ࡣ࡞࠸ࡀࠊ㍺⋡࡟௦ࢃࡿ≀⌮㔞࡜ࡋ࡚㆟ㄽࡢ౯್ࡀ࠶ࡿ࡜ゝ࠼ࡿࠋෆ㒊⛣ືᗘࢆṇ☜࡟ゝⴥ㸦࢖࣓࣮ࢪ㸧࡛ㄝ᫂ࡍࡿࡇ࡜ࡣ㞴ࡋ࠸ࡀࠊ⮬ᕫ஺᥮㏿ᗘ࡜ࡢ┦㛵࠿ࡽࠊྛ㝧࢖࢜ࣥࡀ㝜࢖࢜ࣥ࠿ࡽ㞳ࢀࡿ࡜ࡁࡢ⛣ືࡢࡋࡸࡍࡉ࡜࠶ࡿ⛬ᗘⰋ࠸┦㛵ࡀ࠶ࡿ࡜ࡉࢀ࡚࠸ࡿࠋ
ෆ㒊⛣ືᗘࡢᣲືࡣࠊ࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀ࡢΰྜ⣔ࢆ୰ᚰ࡟ࠊࡇࢀࡲ࡛ᐇ㦂ⓗ࡟ヲ⣽࡟ㄪ࡭ࡽࢀ࡚ࡁࡓ
ࡀࠊࡑࡢ⯆࿡ࡢ୰ᚰࡣࠊ⤌ᡂ࡟ࡼࡿෆ㒊⛣ືᗘࡢ࢖࢜ࣥ✀㛫࡛ࡢ㏫㌿⌧㇟࡜ࡉࢀ࡚࠸ࡿࠋࡇࡢ⌧㇟ࡣ➨୍Ⓨぢ⪅ࡢྡ࡟⏤᮶ࡋ࡚ &KHPOD ຠᯝ࡜ࡼࡤࢀ࡚࠸ࡿࠋࡍ࡞ࢃࡕࠊ┤ឤⓗ࡟ࡣᑠࡉࡃ࡚㍍࠸࢖࡛࢜ࣥ࠶ࡿ /L㸩ࡢ⛣ືᗘࡀ .ࡼࡾࡶ኱ࡁ࠸࡜⪃࠼ࡽࢀࡿࡀࠊᚲࡎࡋࡶࡑ࠺࡛ࡣ࡞ࡃࠊ/L%U.%U ࡸ /L&O.&O ࡞࡝ࡢΰྜ⣔࡛ࡣࠊࡴࡋࢁᗈ࠸⤌ᡂ㡿ᇦ࡟Ώࡗ࡚㏫㌿⌧㇟ࡀㄆࡵࡽࢀࡿࠋ
ᡃࠎࡣࠊࡇࢀࡽࡢၥ㢟ࡀ࢖࢜ࣥᛶࡢᇶᮏⓗ≀㉁࡛࠶ࡿ࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀࡛ほࡉࢀ࡚࠸ࡿࡇ࡜࠿ࡽࠊ

ࡇࢀࡽࡢၥ㢟ࡢ㉳※ࡣ␗࡞ࡿ㝧࢖࢜ࣥ㛫࡛ࡢࢧ࢖ࢬ࡜㉁㔞ࡢ㠀ᑐ⛠ຠᯝ࡛࠶ࡿ࡜ࡢ௬ㄝ࡟❧ࡗ࡚ࠊᮏ◊✲ࢆ㐍ࡵࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ/L,., ࡢΰྜ⣔ࢆ࣮࣋ࢫ࡜ࡋ࡚ࠊࡍ࡭࡚ࡢ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡣ㉁㔞ࠊࢧ࢖ࢬ࠾
ࡼࡧ┦஫స⏝ࡀ➼ࡋࡃࠊ➢ྕࡔࡅࡀ␗࡞ࡿ࣏ࢸࣥࢩࣕࣝ㛵ᩘ⣔ࢆ᪂ࡓ࡟ᵓ⠏ࡋࠊࡇࢀࢆཧ↷⣔㸦ᇶ‽㸧࡜ࡋࡓࠋࡇࢀ࡟ࠊ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥ㛫࡟㉁㔞ࡢᕪ␗ࢆᑟධࡋࠊ࢖࢜ࣥఏᑟ⋡࠾ࡼࡧෆ㒊⛣ືᗘࢆᵓᡂࡍࡿ࢖࢜
ࣥࡢኚ఩ࡢྛ┦㛵㡯࡟ཬࡰࡍຠᯝࢆศᏊືຊᏛἲ࡟ࡼࡾ⊂❧࡟ホ౯ࢆ㐍ࡵࡓࠋ◊✲᪉ἲࡢ㡯࡛♧ࡍࡼ࠺࡟ࠊ
ෆ㒊⛣ືᗘࡣࠊྛ࢖࢜ࣥ✀ࡢኚ఩ࡢ᫬㛫Ⓨᒎࡢ㡯㸦㸺㸼࡛♧ࡍᖹᆒ್ࡢ㡯㸧ࡢ࿴࡟ศゎ࡛ࡁࡿࡓࡵࠊࡑࢀࡽ
ଶࡢᣲືࢆヲ⣽࡟ㄪ࡭ࡿࠋ≉࡟ࠊൻοଵᇱ ଶ ൿࠊൻοᇱଶ ൿࠊ࠾ࡼࡧൻοᇱି ଶ ൿࡢ㡯ࡣࠊྛ࢖࢜ࣥࡢኚ఩ࡢ⮬ᕫ┦㛵࡜┦஫┦㛵ࡢ㡯

- 267 -

࠿ࡽ࡞ࡿࡓࡵࠊࡑࡢᣲືࡣ኱ኚ⯆࿡῝࠸ࠋࡍ࡞ࢃࡕࠊ⮬ᕫ┦㛵㡯ࡣᖹᆒ⮬஌ኚ఩ࠊࡘࡲࡾ⮬ᕫᣑᩓಀᩘ࡟ᑐ
ᛂࡍࡿࠋࡇࢀࡽࡢ┦஫┦㛵㡯࠾ࡼࡧ ൻοᇱఈ οఉᇱ ൿ ሺߙ ് ߚ ࡀࢮࣟࡢ࡜ࡁࠊ࢖࢜ࣥఏᑟ⋡ࡣࠊྛ࢖࢜ࣥࡢ⮬ᕫᣑᩓಀᩘࢆ 'Į ࡜ࡋ࡚ࡑࢀࡽࡢ࿴࡛⾲ࡍࡇ࡜ࡀ࡛ࡁࡿࠋࡍ࡞ࢃࡕ

ߪൌ

ఉ௘ మ
௏

ሺܰଵ ‫ܦ‬ଵ ൅ ܰଶ ‫ܦ‬ଶ ൅ ܰି ‫ ିܦ‬ሻሺ1 െ οሻ                         ࡟࠾࠸࡚Ǽࡀࢮࣟࡢሙྜ࡟┦ᙜࡋࠊࡇࡢ࡜ࡁୖᘧࢆ 1HUQVW(LQVWHLQ㸦1(㸧ࡢᘧ࡜ࡼࡪࠋᕼⷧỈ⁐ᾮ࡜␗࡞ࡾࠊ
⁐⼥ሷࡸ࢖࢜ࣥᾮయ࡛ࡣ୍⯡࡟ 1( ᘧࡣᡂ❧ࡏࡎࠊ౛࠼ࡤࠊ⣧⢋࡞⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀࡛ࡣࠊοൎ
0.2~0.3 ࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡘࡲࡾࠊ࢖࢜ࣥఏᑟ࡟࠾࠸࡚ࠊኚ఩ࡢ┦஫┦㛵㡯ࡣ⮬ᕫᣑᩓ࡟ࡼࡿ࢖࢜
ࣥఏᑟࢆపῶࡍࡿຠᯝࢆᣢࡘ࡜ゝ࠼ࡿࠋࡲࡓࠊሺ1 െ οሻିଵ ࡣ +DYHQ ẚ࡜ࡼࡤࢀࠊపῶࡢ኱ࡁࡉࢆẚ㍑ࡍࡿᑻᗘ࡜ࡋ࡚ࡋࡤࡋࡤ㆟ㄽࡉࢀࡿࠋ+DYHQ ẚࡢ㉳※࠾ࡼࡧᣲືࡢ⌮ゎࡣ࢖࢜ࣥᛶᾮయࡢఏᑟ⋡ࡢᮏ㉁࡟㛵ࢃࡿᇶ♏
ⓗၥ㢟࡛࠶ࡿࡀࠊࡑࡢ⌮ゎࡣ࠸ࡲࡔᐃᛶⓗ⠊␪࡟␃ࡲࡗ࡚࠸ࡿࠋࡍ࡞ࢃࡕࠊ࢖࢜ࣥఏᑟ⋡ࡸෆ㒊⛣ືᗘࢆṇ☜࡟ホ౯ࡋࠊࡑࢀࡽࢆᵓᡂࡍࡿྛ࢖࢜ࣥࡢኚ఩ࡢ┦㛵㡯ࡢᣲືࢆᐃ㔞ⓗ࡟ㄝ᫂ࡍࡿࡇ࡜ࡀࡇࡢၥ㢟ࡢゎỴ࡟ࡘ࡞ࡀࡿࠋᮏ◊✲࡛ࡣࠊ࢖࢜ࣥ㉁㔞౫Ꮡᛶࢆヲ⣽࡟᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ࢖࢜ࣥࢧ࢖ࢬ

౫Ꮡᛶ࡟ࡘ࠸࡚ࡣḟᖺᗘ࡟ྲྀࡾ⤌ࡴணᐃ࡛࠶ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲࡇࢀࡲ࡛ࠊෆ㒊⛣ືᗘࡢᣲືࢆศᏊືຊᏛィ⟬࡛෌⌧ࡍࡿヨࡳࡀ࠸ࡃࡘ࠿ሗ࿌ࡉࢀ࡚ࡁࡓࡀࠊ≉࡟ୖグࡢෆ㒊⛣ືᗘࡢ㏫㌿⌧㇟ࡀ෌⌧࡛ࡁ࡚࠸࡞࠿ࡗࡓࠋࡇࢀࡣ୺࡟⤫ィ㔞ࡢၥ㢟࡜⪃࠼ࡽࢀࡿࠋᚑ᮶ࡢ◊✲࡛ࡣࠊ⣔ࡢ᫬㛫Ⓨᒎࡀࡏ࠸ࡐ࠸ QV ࡲ࡛ࡢィ⟬࡟␃ࡲࡗ࡚࠸ࡓࡀࠊᮏ◊✲࡛ࡣศᴟ࢖࢜ࣥࣔࢹࣝࢆ⏝࠸ࡓศᏊືຊ
Ꮫィ⟬࡟ࡼࡗ࡚ࠊᐇ㦂⤖ᯝࡢ☜❧ࡋ࡚࠸ࡿ௦⾲ⓗ࡞ /L).)ࠊ/L&O.&Oࠊ/L%U.%Uࠊ/L,., ࡢྛ⁐⼥ΰྜ⣔࡟ࡘ࠸࡚ࠊQV ⛬ᗘࡲ࡛⤫ィࢆቑࡸࡋ࡚ࠊᐇ㦂್࡜ࡢ☜ᐃⓗ࡞ẚ㍑ࢆヨࡳࡓ෌⌧ࢆヨࡳࡓࠋෆ㒊⛣ືᗘࡢ࢖࢜ࣥ㉁㔞౫Ꮡᛶ࡟ࡘ࠸࡚ࡣࠊෆ㒊⛣ືᗘࢆḟࡢࡼ࠺࡟ྛ࢖࢜ࣥ✀ࡢኚ఩ࡢ᫬㛫Ⓨᒎࡢ㡯㸦㸺㸼࡛♧ࡍᖹᆒ್ࡢ㡯㸧࡟ศゎࡋࠊࡑࢀࡽࡢᣲືࢆヲ⣽࡟ㄪ࡭ࡓࠋ

ߤଵି ൌ െఉ௘ேషߤଶି ൌ െ

ఉ௘ேష



ࡇࡇ࡛

οᇱఈ ൌ

ଵ
ேഀ

଺

଺

lim

ଵ

lim

ଵ

௧
௧՜ஶ
௧
௧՜ஶ

ଶ

ଶ

ଶ

ଶ

ൣ‫ݔ‬ଵ ൻοଵᇱ ൿ ൅ ‫ݔ‬ଶ ‫ۦ‬οᇱଶ οଵᇱ ۧ െ ‫ۦ‬οଵᇱ οᇱି ۧሺ1 ൅ ‫ݔ‬ଵ ሻെ‫ݔ‬ଶ ‫ۦ‬οᇱଶ οᇱି ۧ ൅ ൻοᇱି ൿ൧ൣ‫ݔ‬ଶ ൻοᇱଶ ൿ ൅ ‫ݔ‬ଵ ‫ۦ‬οଵᇱ οᇱଶ ۧ െ ‫ۦ‬οᇱଶ οᇱି ۧሺ1 ൅ ‫ݔ‬ଶ ሻെ‫ݔ‬ଵ ‫ۦ‬οଵᇱ οᇱି ۧ ൅ ൻοᇱି ൿ൧




ഀ
ሼ ሺ‫ݐ‬ሻ െ ࢘௜ ሺ0ሻሽ ߙ ൌ 1, 2, െ                                       σே௜ୀଵ ࢘௜

࡛࠶ࡾࠊ౛࠼ࡤ /L%U.%U ࡢ⁐⼥ሷࡢΰྜ≀⣔࡟࠾࠸࡚ࡣࠊĮ ࡣ  ࡢ࡜ࡁ /L࢖࢜ࣥࠊ ࡢ࡜ࡁ .࢖࢜ࣥࠊ
㸫ࡢ࡜ࡁ %U࢖࢜ࣥ࡟ࡑࢀࡒࢀᑐᛂࡍࡿࠋ



◊✲ᡂᯝ
/L).)ࠊ/L&O.&Oࠊ/L%U.%Uࠊ/L,., ࡢྛ⁐⼥ΰྜ⣔࡟ࡘ࠸࡚ࠊQV ⛬ᗘࡲ࡛⤫ィࢆቑࡸࡋ࡚ศᏊືຊィ⟬ࢆ⾜ࡗࡓ⤖ᯝࠊࡍ࡭࡚ࡢ⣔࡛ᐇ㦂⤖ᯝ࡜༙ᐃ㔞ⓗ࡟Ⰻ࠸୍⮴ࢆぢฟࡋࠊ≉࡟ /L%U.%U ࡜ /L,., ࡢ⣔࡛ࡣෆ㒊⛣ືᗘࡢ㏫㌿⌧㇟ࢆほ ࡍࡿࡇ࡜ࡀ࡛ࡁࡓ㸦ᅗ㸰 F ཧ↷㸧ࠋ
/L,., ࡢΰྜ⣔ࢆ࣮࣋ࢫ࡜ࡋ࡚ࠊࡍ࡭࡚ࡢ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡣ㉁㔞ࠊࢧ࢖ࢬ࠾ࡼࡧ┦஫స⏝ࡀ➼ࡋࡃࠊ➢ྕࡔࡅࡀ␗࡞ࡿ࣏ࢸࣥࢩࣕࣝ㛵ᩘ⣔ࢆ᪂ࡓ࡟ᵓ⠏ࡋࠊࡇࢀࢆཧ↷⣔㸦ᇶ‽㸧࡜ࡋ࡚ࠊ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥ- 268 -

㛫࡟㉁㔞ࡢᕪ␗ࢆᑟධࡋࠊ࢖࢜ࣥఏᑟ⋡࠾ࡼࡧෆ㒊⛣ືᗘࢆᵓᡂࡍࡿ࢖࢜ࣥࡢኚ఩ࡢྛ┦㛵㡯࡟ཬࡰࡍຠᯝ
ࢆศᏊືຊᏛἲ࡟ࡼࡾ⊂❧࡟ホ౯ࡋࡓ⤖ᯝࢆᅗ㸯࡟♧ࡍࠋ

㻢



㻡







㻢
㻌㻙㻌㻙㻌
㻌㻝㻌㻝
㻌㻞㻌㻞

D

㻠
㻟
㻞
㻝
㻜



㻌㻙㻌㻙㻌
㻌㻝㻌㻝
㻌㻞㻌㻞

E

㻡

'cD'cE>P@'cD'cE>PV@



㻠
㻟
㻞
㻝
㻜

㻞㻜

㻠㻜

㻢㻜

㻤㻜

㻝㻜㻜

㻝㻞㻜

㻞㻜

㻠㻜

P$>JPRO@



㻢㻜

㻤㻜

㻝㻜㻜

㻝㻞㻜



P$>JPRO @




F

㻝㻚㻡








㻝㻚㻡

㻌㻝㻌㻙㻌
㻌㻞㻌㻙
㻌㻝㻌㻞

㻝㻚㻜

'cD'cE>PV@'cD'cE>PV@


㻜㻚㻡
㻜㻚㻜
㻙㻜㻚㻡
㻙㻝㻚㻜
㻞㻜

㻠㻜

㻢㻜

㻤㻜

㻝㻜㻜

㻝㻞㻜

P$>JPRO@



㻌㻝㻌㻙㻌
㻌㻞㻌㻙
㻌㻝㻌㻞

G

㻝㻚㻜
㻜㻚㻡
㻜㻚㻜
㻙㻜㻚㻡
㻙㻝㻚㻜
㻞㻜

㻠㻜

㻢㻜

㻤㻜

㻝㻜㻜

㻝㻞㻜



P$>JPRO @ᅗ㸯 ⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀࡜ᕼ࢞ࢫᾮయΰྜ≀ࡢཎᏊࡢᗙᶆኚ఩ࡢྛ┦㛵㡯ࡢᣲືࡢẚ㍑
ᅗ㸯ࡢᕥഃࡢୖୗࡣࠊ⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀ࡢཧ↷⣔࡟ࠊ㉁㔞ࡢᕪ␗࠶ࡿ࠸ࡣ⥲㉁㔞ࡢኚ໬ࢆᑟධࡋࡓ ⤖ ᯝ ࢆ ࡲ ࡜ ࡵ ࡓ ࡶ ࡢ ࡛ ࠊ ୖ ẁ ࡀ ෆ 㒊 ⛣ ື ᗘ ࢆ ᵓ ᡂ ࡍ ࡿ ൻοଵᇱ ଶ ൿࠊൻοᇱଶ ଶ ൿࠊ࠾ࡼࡧൻοᇱି ଶ ൿ  㡯 ࡛ ࠊ ୗ ẁ ࡀൻοᇱఈ οఉᇱ ൿ ሺߙ ് ߚ㸧ࢆ⾲ࡋ࡚࠸ࡿࠋࡇࢀ࡟ᑐࡋ࡚ྑഃࡣࠊ ✀㢮ࡢᕼ࢞ࢫཎᏊ࠿ࡽ࡞ࡿᾮయΰྜ≀࡛ࠊࢧ࢖ࢬ࡜
┦஫స⏝ࡀ➼ࡋࡃࠊ㉁㔞ࡢࡳ␗࡞ࡿ⣔࡛ࠊࡍ࡞ࢃࡕࠊᕥഃࡀࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࠊྑഃࡀ /HQQDUG-RQHV ࣏ࢸࣥࢩࣕࣝ࡟ࡼࡿ㉁㔞ຠᯝࢆẚ㍑ࡋࡓࡶࡢ࡛࠶ࡿࠋࡇࡢᅗ࠿ࡽࠊୖグࡢྛ㡯ࡢ࢖࢜ࣥ㉁㔞౫Ꮡᛶࡀࠊᐃ㔞ⓗ࡟ࡣᗘࡢ㐪࠸࡟ẚ౛㸦⦪㍈ࡢࢫࢣ࣮ࣝࡀ  ಸ␗࡞ࡿ㸧ࡍࡿࡢࡳ࡛ࠊᐃᛶⓗ࡞ᣲືࡣ㟁Ⲵࡢ᭷↓࡟㛵ಀࡋ࡞࠸ࡇ࡜ࡀࢃ࠿ࡿࠋ≉࡟ࠊෆ㒊⛣ືᗘࡢࡼ࠺࡞」㞧࡞≀⌮㔞࡟࠾࠸࡚ࠊ㉁㔞ຠᯝࡀ㟁Ⲵ࡜ GHFRXSOH ࡍࡿࡇ࡜ࡀ
ଶุ᫂ࡋࡓࡇ࡜ࡣᐃᘧ໬ࢆ㐍ࡵࡿୖ࡛᭷⏝࡞▱ぢ࡛࠶ࡿࠋࡍ࡞ࢃࡕࠊࡇࢀࡽࡢ⤖ᯝ࡟ᇶ࡙࠸࡚ࠊൻοଵᇱ ൿࠊଶൻοᇱଶ ൿࠊ࠾ࡼࡧൻοᇱି ଶ ൿ 㡯ࡢ㉁㔞౫Ꮡᛶࡀࠊ⮬ᕫᣑᩓಀᩘ࡜ྠᵝ࡟ࠊ݉୅ ି଴.ହ ሺ݉௜ Τ݉୅ ሻି଴.ଵ  ࡛⾲⌧࡛ࡁࡿࡇ࡜ࡀࢃ࠿
ࡗࡓ㸦ࡇࡇ࡛ࠊL ࡣ࢖࢜ࣥࡢ✀㢮ࠊ$ ࡣ⣔඲యࡢᖹᆒ್ࢆࡑࢀࡒࢀព࿡ࡍࡿ㸧ࠋᅗ㸰࡟ࠊෆ㒊⛣ືᗘ࡟ཬࡰࡍ
㉁㔞ຠᯝࢆ♧ࡍࠋᅗ㸰 D ࡣཧ↷⣔ࠊ E ࡣཧ↷⣔ࡢྛ࢖࢜ࣥࡢ㉁㔞ࢆ /L,., ⣔࡜ྠ୍࡟ࡋࡓ⣔ࠊ F ࡣ /L,., ࡢ⤖ᯝ࡛࠶ࡿࠋࡍ࡞ࢃࡕࠊ㉁㔞ࡢࡳ࡛ࡣෆ㒊⛣ືᗘࡢ㏫㌿⌧㇟ࡣ㉳ࡇࡽࡎࠊ࢖࢜ࣥࢧ࢖ࢬࢆ㠀ᑐ⛠࡟ࡍࡿࡇ࡜
࡟ࡼࡗ࡚ෆ㒊⛣ືᗘࡢ㏫㌿⌧㇟㸦&KHPOD ຠᯝ㸧ࡀ⏕ࡌࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
- 269 -

㻞㻜

㻞㻜
㻌F
F

㻝㻡

㻝㻜

㻡

㻜
㻜㻚㻜

㻜㻚㻞

㻜㻚㻠

㻜㻚㻢

㻜㻚㻤

㻝㻡

㻝㻜

㻡

㻜
㻜㻚㻜

㻝㻚㻜

㻜㻚㻞

㻜㻚㻠

㻜㻚㻢

㻜㻚㻤

㻝㻚㻜

[F

[F
ᅗ㸰 ⁐⼥ /L,., ΰྜ⣔ࡢෆ㒊⛣ືᗘ㻟㻡‫   @>ۻ‬ᕝ➃ᾏ㒔㸪᭹㒊⏤ె㸪▼஭Ⰻᶞ㸪኱㫽⠊࿴㸪
⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀ࡢ㍺㏦ಀᩘࡢ࢖࢜ࣥ㛫┦஫స⏝࢚ࢿࣝࢠ࣮౫Ꮡᛶ㸦ཱྀ㢌㸧㸪➨XD>P9V@Ⓨ⾲ᐇ⦼ ᅇ⁐⼥ሷ໬Ꮫウㄽ఍㸪࢜ࣥࣛ࢖ࣥ㸪 ᖺ

.
/L

F

㻟㻜





㻌F
F

E
XD>P9V@XD>P9V@

D

㻞㻡
㻞㻜
㻝㻡
㻝㻜
㻡

㻜㻚㻜

 ᭶  ᪥

㻜㻚㻞

㻜㻚㻠

㻜㻚㻢

㻜㻚㻤

㻝㻚㻜

[.

‫   @>ۻ‬᭹㒊⏤ె㸪▼஭Ⰻᶞ㸪ᒸ⏣໏㸪኱㫽⠊࿴㸪ศᏊືຊᏛἲ࡟ࡼࡿ⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀ࡢෆ㒊⛣ືᗘࡢホ౯ ,,㸦ཱྀ㢌㸧㸪➨  ᅇ⁐⼥ሷ໬Ꮫウㄽ఍㸪࢜ࣥࣛ࢖ࣥ㸪 ᖺ  ᭶  ᪥‫   @>ۻ‬㜿㒊ಇኴ㸪㏆⸨ඃከ㸪▼஭Ⰻᶞ㸪኱㫽⠊࿴㸪஧ཎᏊศᏊᾮయࡢ⇕ఏᑟ⋡㸦ཱྀ㢌㸧㸪➨  ᅇ᪥ᮏ⇕≀ᛶࢩ࣏ࣥࢪ࣒࢘㸪࢜ࣥࣛ࢖ࣥ㸪 ᖺ  ᭶  ᪥‫   @>ۻ‬ಙ⏣Ẹ⏕㸪▼஭Ⰻᶞ㸪኱㫽⠊࿴ RτϩϓΥωϩ͹ӹର‫;ٶ‬գྮ‫٭‬য়ସͲ͹ 6WRNHV(LQVWHLQ ͕Γ;
6WRNHV(LQVWHLQ'HE\H ͹‫޳ ܐؖ‬ಆ  ༻ӹԿָ‫ڂݜ‬ճऑघ͹ճΨϱϧ΢ϱεϱϛζΤϞ Ψϱϧ΢ϱ ೧  ݆  ೖ ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ < @>ۻ‬,VKLL 7 0XUDNDPL DQG 1 2KWRUL ࠕ0ROHFXODU KHWHURJHQHLW\ EHWZHHQ VROXWH DQG VROYHQW (IIHFW RQ WKHWUDQVODWLRQDOGLIIXVLRQDQGWKH6WRNHV(LQVWHLQUHODWLRQࠖLQSUHSDUDWLRQ‫@>ۻ‬12KWRUL<.RQGRDQG<,VKLL ࠕ0ROHFXODUVL]HDQGVKDSHHIIHFWV5RWDWLRQDOGLIIXVLRQDQGWKH6WRNHV(LQVWHLQ
'HE\HUHODWLRQࠖ-0RO/LT314  ‫@>ۻ‬12KWRUL<.RQGR.6KLQWDQL70XUDNDPL71REXWDDQG<,VKLL ࠕ7KH6WRNHV(LQVWHLQUHODWLRQIRUQRQVSKHULFDOPROHFXODUOLTXLGVࠖ&KHP/HWWHUV49  ‫ @>ۻ‬1 2KWRUL + 8FKL\DPD DQG< ,VKLL ࠕ7KH 6WRNHV(LQVWHLQ UHODWLRQ IRU VLPSOH IOXLGV )URP KDUGVSKHUH WR
/HQQDUG-RQHVYLD:&$SRWHQWLDOVࠖ-&KHP3K\V149  ‫<@>ۻ‬,VKLLDQG12KWRUL ࠕ0ROHFXODULQVLJKWVLQWRWKHERXQGDU\FRQGLWLRQVLQWKH6WRNHV(LQVWHLQUHODWLRQࠖ3K\V
5HY(93  - 270 -





Properties of Bowl-shaped aromatic compounds
and studies on the catalytic activity of metal clustersĝ ţ±ĮÝ řSartyoungkul SitananĬ åÕŨĐ ŀķÞ êĖÃ šÐ(ÊƑÊÑ)

1 ŃňĽļ¢×<>Â¡ì®·İ _WFxhBs -cqxtv6[^Vpxd,nYs®·İ(&!'*<>ĚƁ+ŋŜ ĳŞ,þ­İò=Ņ ſáĳŞ,·÷ĥ+79ņ ,ŘĀÄ=ď:ŘĀPj
]v,·÷µś(*9<>ĚƁhBs³Žƃ­®Ñ³ñòō+$&Ôƛļ+ş»ħłŪ
î8;&&: ;8,ÔƛļłŪ+Ɛ&Ôƛļ*?euxV,4'-¯¤*ĵŷļŶĊ
=}:(¾Ɣ' 9ůŎ®Ñļ*?euxV+7#&,İò+ĵŷļ*ŶĊ=}: :ĩ:(ðũ(;&:yĆ[^MAQ,ƊHqPTx-_sHƊ'-Ņ*ĳı*ŮËĦò=Ņ ı+Ɲ¤Ì'ź; āÁyő[^HqPTx+&-ÖĨſ',Ň6*Ē{+&5ŉġƈ®³ñ*)+ŤŮËĦòŪ8;,ĵĹ,y$(&³ñő'HqPTx,éĲĕż+È®:(ĩ;&: ſá,LvbpxTx,ƂĠ+79ƊÜHqPTx=ľÿ ¤Ì (&ú³ñő+:ĚƁÈ®51&Śö+; ůŎµś(*#&Ôƒø -Ĉ+ƊơƉ6·ƊHqPTx,

ƢƤƉƣơƉ=Ôƒ,HqPTxMAQ5Śö nYs(&ƅ/ě *ŮË³ñ, euRPŭē+÷«&:z+¬áã-ą + X ÎÂĚƁ=ý$AvUvODvƉƚĚŏ:ŕČĚƁ+:¤ÌƏĿĸ+Ɛ&ůŎŃň=Ôć¤ÌĚƁ(8î8;:ŕČĚƁ(,ĿƐ,ų=ť# ,',ŕĔ+$&Æº:

2 ŃňĆĥůŎĆĥ&,ůŎ- GAUSSIAN16 euIql=ĸ&ť#ůŎĆĥ- DFT ĥ=ĸģƐă(& B3LYP

ÄâƐă(& 6-311+G(d,p)=ĸŕČĚƁ=+Ģœ²Ì,ŐÙ®=ť# í+ 1 ĭůŎ+&C]sG
xůŎ=ť#*ůŎ+ƒ&- Grimme ,¤Ăªŧğ=ÛCounterpoise ĥ+& BSSE ŧğ=ť#3 Ńň÷Ĕ
 ;3'ø-brOsAvUvODvƉ    ņÏÀ{',ŕČ®+79  ĞVo]s=ď:ĚƁ=ƅûļ+}:(=Ū!

,ĪËęò=

ƗęòĪË

ęòĪËÏÀ{'Vo]s,ƍ(¿ 1) (Chem. Commun. 2020) č+,

- 271 -

ŵŹ

 w





 ĚƁ-©

ļ*ĚƁÈ®=+5Ɛ<8ŕČĲõ=# 33Vo]s¢ƆKPZ¤Ì,¹ŝŁ+7
9µƀ+È®:(µś': ,ŔÍĚƁ,Ěŏ+Ɛ&- Ŋœ²Ì(fvSvĶ&+ ƆƏ, &+ÂÂÂ1 ĿĸEsh\sƈœ(fvSvĶ &+ ƆƏ, &+ÂÂÂ2 Ŀĸ(Ɨß+ç¤ÌƏĿĸÉ+02) ō'Ŭĩ;:Ċń*è
ŕ·-ÏÀ&* ,(-   8*:

¿ 1. 4PID ,: CLOSE 7/ OPEN ĚƁĚƁÅż8 ¤ÌŕČƋÂ(&ƝiXvNos=ď&:(=Ņ&9ƅûļ+
Vo]sĚƁ=Ěŏ:(';.ě *¤Ì=yĞļ+Ƈ¦:(,': ż8ŕČògPZ (&,ñĸµś(*:,łŪ=+brOvƆ¤=ě +ÈĀ ¤Ì}:ŕČĚƁ+$&ĘŰ=ť# ŕĔŊœŘ,ĺ*: 2-brOsAvUvODvƉ (2PID) '-zű, OPEN ĚƁ=}+TAZ+`WFv
I ĚƁ=}:(<#(¿ 2a) ;8,ŕČ-(5+ç¤ÌƏª+79Ěŏ;&9ı

+ 4PID +:Ċń*¤ÌƏ CHN Ŀĸ,ÏÀ,Ƅ=ķ4£&:(ôÓ;'°Œ*ŊœŘ,Ƅ}:ëƙ=Ċ8+14PID , OPEN ĚƁ,°ėÌ+¸3;: 4 ņƚ,ŕČÑļ+ĳŋ* 2 ¤ÌƏƇŘ=¥9£,C]sGxůŎ=ť#(¿ 2b) 3 2PID +$&-

4PID ,²ÌƇŘ,"brOvĶz,Ŋœ²Ì,Ř=È ôļ*ĚƁ=+ůŎ=ť#,ŕ

ĔA~D , 4 ņƚ,ƇŘ+:ĿĸC]sGx,"C Â,ƇŘ+&4PID '-NFDOPRO' #,-¤ÌƏ CHN Ŀĸ,Ø}+Ä%5,(Ś8;:5,,CLOSE ĚƁ+Ú:

OPEN ĚƁ,ò=ĤÓ%:2)ĤÓļ*'-* yĆ2PID '-+3.33 kcal/mol (|ÒÓ®&
:(<#',Ƅ=79ŴŔ+ų1ůŎ+79î8; ƕÌÙãóÆ=+AIM ůŎ7/+ noncovalent interaction index-reduced density gradient (NCI-RDG) ĥ+79ƇŘ C '¤ÌƏĿĸ=µū®

4PID 7/ 2PID ¢+Ŭĩ; ¤ÌƏĿĸ-ƚ&9brOvĶz
,Ŋœ²ÌŘ,Ƅ+7:¤Ì¢Ŀĸ7/Ƈä0,ëƙ-2(>)Ŭĩ;*#3)(¿¤ÌƏ+Ŀĸ+-ƄŪ
8;

4PID  7 /2PID Ć,JxP+
¿ 2. a) 2PID ,ĚƁ b) OPEN ĚƁ,°ėÌ+¸3;:ŕČÑļ+ĳŋ* 2¤ÌƏƇŘ A~D

- 272 -

&¤ÌƏ+- 2 $,¿ 3. a) 4PIDb) 2PID +:ƇŘƩ',¤ÌƏĿĸ, ¿ signλ2 +Ä% NCI-isosurface 5&Ņ *EqxPJxs-¶Çù',signλ2 ,+Úñ&:bond critical point (BCP) ( 1 $, RCP (ring critical point) Ŭĩ;

2 $, BCP +:BCP (2BCP -;; 0.009–0.010 e/Å3, 0.029–0.031 e/Å5 (in 4PID)0.018–0.019
e/Å3, 0.029–0.0672 e/Å5 (in 2PID) ' 9(5+ç¤ÌƏæª,ÏÀŅ½;

8+Úñ:ĿĸÒÓ® (signλ2 < 0) 5-|ÒÓ® (signλ2 > 0)+Ø}
:  = Ĥ Ó %  : ` q m x T  signλ2 - ( 5 +NCI-isosurface z'ƖŖŠƫƖŠ'ŦĴ;&9;8(¿ 4)ÒÓ®+Ø}:Ŀĸ' :Ņ;¿ 4. ¿ 3 +: a) 4PIDb) 2PID ,¤ÌƏƆ,üÊ¿yĆ;;,¤Ì+:¤ÌƏ, RCP +$&-
2PID +&Ê*Ąª&:<#Ôƒ+ 2PID +&-¤ÌƏ+Ģœ²ÌƏ,ſÿÏÀ&9;|ÒÓ®+Ø} 5,(Ś8;: zű,ŕĔ- 2PID  OPEN ĚƁ=}*,-¤ÌƏ CHN Ŀĸ,Ø}*OPEN ĚƁ=(# ƒ,Ģœ²ÌƏ,³Ļ+7:5,':(=Ņ((5+4PID +&5 OEPN ĚƁ,Ěŏ+&-¤ÌƜė(Vo]s¢+´9ž
3; KPZ¤Ì(,Ŀĸ+7:ÒÓ®,Ø}Ê((=Ņ&:- 273 -

4 ĻŦÔŗ3-ÓƢƟƞyƆ★Ɵ“ƗàƘasY@vIduWH8*:¤ÌƓ·”ƠĮÝř¤ÌŃŃň ƌ®Ñ+Ä%¤Ì,ĚƁÈĀŲů(Ĝś¨ï DvqAvƎ2020 á 7 Ď.
ƣƟƞyƆƟ“brkOsÄ=Û AvUvODvƉ,ŕČĚƁ(òŻ”ƠŨđřķĮÝřĝ
ţ±ĉĐŕČÑ¼ƣáãáDvqAvƎ2020 á 11 Ď.
ƤƟƞyƆ★Ɵ“ƗàƘasY@vIduWH8*:¤ÌƓ·,Ěŏ(Ĝś”ƠĮÝřŢ~,ı§ŸīĉĐ®ÑŌ 101 ċÐáDvqAvƎ2021 á 3 Ď.

5 £įÔŗ3-ÓƢƟƞyƆƟ6HOHFWLYH 2[LGDWLYH +\GUR[\ODWLRQ RI $U\OERURQLF $FLGV E\ &ROORLGDO 1DQRJROG &DWDO\]HG LQ 6LWX*HQHUDWLRQRI+2IURP$OFRKROV8QGHU$HURELF&RQGLWLRQV9LQVHQ<8HWDNH+6DNXUDL%XOO&KHP6RF
-SQ±
ƣƟƞyƆƟ*ROG 1DQRSDUWLFOHV 6WDELOL]HG E\ 0ROHFXODU )XOOHUHQROV . .RNXER 0 . ( &DEHOOR 1 6DWR <
8HWDNH+6DNXUDL&KHP1DQR0DW±
ƤƟƞyƆƟ6\QWKHVLVDQG'LPHUL]DWLRQ3URSHUWLHVRI&XSDQG%RZOVKDSHG&\FOLF7ULODFWDPV66DUW\RXQJNXO<<DNL\DPD+6DNXUDL$VLDQ-2UJ&KHP±ƥƟƞyƆƟ3W±3G1DQRDOOR\IRUWKH8QSUHFHGHQWHG$FWLYDWLRQRI&DUERQ±)OXRULQH%RQGDW/RZ7HPSHUDWXUH51
'KLWDO.1RPXUD<6DWR6+DHVXZDQQDNLM0(KDUD+6DNXUDL%XOO&KHP6RF-SQ±Ʀ Ɵƞ y Ɔ  Ɵ $SSOLFDWLRQ RI FXSVKDSHG WULODFWDPV IRU VHOHFWLYH H[WUDFWLRQ RI YRODWLOH FRPSRXQGV E\ JDVFKURPDWRJUDSK\PDVV VSHFWURPHWU\ 6 6DUW\RXQJNXO , 7KDYHHVDQJVDNXOWKDL 0 . ( &DEHOOR & .XOVLQJ +
6DNXUDL$QDO\VW±
ƧƟƞyƆƟ6L]H&RQWUROOHG3UHSDUDWLRQRI*ROG1DQRSDUWLFOHV'HSRVLWHGRQ6XUIDFH)LEULOODWHG&HOOXORVH2EWDLQHG
E\ &LWULF $FLG 0RGLILFDWLRQ 7 &KXWLPDVDNXO < 8HWDNH - 7DQWLUXQJURWHFKDL 7 $VRK + 8\DPD + 6DNXUDL$&62PHJD±
ƨƟƞyƆƟPyridine Ring Modification of Indane-1,3-dione Dimers for Control of their Crystal Structureƪ<DNL\DPD7)XMLQDND01LVKLPXUD56HNL+6DNXUDL$VLDQ-2UJ&KHPXQGHUUHYLHZLQJ- 274 -

  
                       $&#"

*)

.

-

$&%/

ńÄÃŝČ'¯ĐĳšÝćûħţ3$+Ť
RUEfX?k2[kIkĐx &ĬĐòŅ:1ĤČĳšÝ´ĮĳšÝćûħ" 6Bl^kRU[hPţ&1%Ť%$ó %P_jGl:1 ĬĐÉĊĮêÛ·2òŅæö·'Ŏ"Ţ ÿĘ:Ś0! 6â&74ĊĮ'č
Ė%Ðý'œĕ2ªĝĖĊÎ'ĺßěĢė;&ķ97! 67."&~ĵ~t4(ºįª
7! %Ò¾à%ĳšÝĊ:1 !mùŗ" 3$+ 2RUEfX?k%$:Ð6Ü ÐÒý ĬĐÕÆţ$QQXODWLYHʌ([WHQVLRQ$3(;ŤÍ 'œĕ:ķ%!.Bl^kRULdlY &17'ŋòŅ"1 6 &1% ('¹·Ð:¼Ď6ő´#!1ÿĘ:Ś0!!5ÇěĢ½'ĆÁ~t4  Ä&rĔ"0!' &1% #%6  &1% 'Ð&Ð!}ŖrĔs"Ð2ĊÎĺß&ŕ6ěĢņ;" 6¼ŘěĢ½'ç4(Ü% &1% " 6aLikïõFDjVf
X?Sik 0&33 'Ð&äńÐ! 6   "éěĢ"(Ñ Ň&«¢GelQW<glhÕÆ#VfG>`Ļ³:Ē  $3(; Íţ0DWVXRND HW DO $QJHZ &KHP ,QW (G   ±Ť'ÍöòĺßěĢ&0&33 'ªéĖĊÎ'ďĺ:Ă060'ěĢ: *DXVVLDQ :Ē ŏ´
·ļĥ&3!ķ$3(; Í(ÈÅĖ&ĳšĐ'w }n'pāÎ%ćħûħĪ:ęÖ®×
m }n'Ü ĬĐĳšĐ:òĦ6Í" 67."'ěĢ" 0H6L3K #VfG>`Ļ³:Ē &+ <glh'öò&!(ß4&!ţ6KLEDWDHWDO-$P&KHP6RF±Ť
ĬĐ: 0 $3(; Í'öò&!(èĚ"  $&,'
éěĢ"(!'ļĥ: *DXVVLDQ  ZjEf`:Ē !ķ   ÍöòĺßěĢ& !´òŅ'äň(Ňĉ'ĿÚţ- $P &KHP 6RF   Ť&Ą')7%3:* G * G * :Ē VfG>`&ŕ!(ðŜ´:æð_NkFch (&3 &ĭ×! /$1/'=&3!ļĥ:ķ 35øĜ%@ThCl: 6&603* G * G * GS 6'' :Ē !
77ļĥ.ą³î'ļĥ( ,()3&0 :Ē    0&33 'òŅäň#@ThClļĥ(%/<3* G :105 ļĥ( GIAO B3LYP/6-311+G(2d,p):Ē !ķ%

3

$&

3.1. X?RkPik(1a)# 1,1ƍGLLRGRELSKHQ\O  : 3G 0H&1  %)  ŐĻ³$J23LY7I2+ µ¨o&O&+&+&O s"ĈØÔ6#$3(; Íł5GLEHQ]RFKU\VHQH  Ĳ²%č476#9
! 6ţ)LJXUHŤ
'Í&!Ġ ñĽ:#8)LJXUH '@ThClK=<Ef`&Ğ3%ÍÂğ:ĩ! 6#Ğ¥7%9VfG>`  Ġ#  'ŌĖ|&35¸»%<glhVfG>`sŔ :qX?RkPik'ä1wōĪÎŢ . Ş©   ,'Bh^aJhţ Ťûħİśţ  Ť ¦Ę' 3G  Ġ'ŌĖ|ţ  Ť±ĖİZjPk
aJhţ  ŤŉĖİśţ  Ť:ĩ! đÐ6Ňğ:ļĥ&35ß4&éÂğ& !  1#1Ţ āÎř¬ţ* NFDOPROŤ:1 #9}n35úŃĖBLAkÎ'Ţ <glh 3G Ġ" 7)X?RkPik%$'pāÎ% &±+ Ī:āÎî
Ė% $3(; Íķ6#Ğ¥7{Ê
74'ěĢ:.#0!ĿÚÓġ:ķv»" 6    

- 275 -

(VWLPDWHGUHDFWLQPHFKDQLVPRI3GFDWDO\]HG$3(;UHDFWLRQRISKHQDQWKUHQH  ZLWKGLLRGRELSKHQ\O 
3.2. Ð MCPP Š'òŅäň3+@ThClļĥ:ķ ó %[kIkĐÙ'1''ä¸»òŅ
GIAO ý&36ZjPk NMR 'văH\DPh(¼ă'ZjPk NMR#@ThClË47(Figure 2)  
H\DPh#Ĳ mı:Ğ. X īĪãòŅĺí"Ë47ĚĹ#'úŃ:ķ#" MCPP Š'1òŅĖċÌ:ß4&6#"]bOHbLMDÍ:Ï»*/@ThCl'ļĥ&3
5Š'ĐČ1(ĤČ´&ú-! MCPP Š°%*/@ThCl:æ6#9
TD-DFT ļĥ&3! MCPP Š'ĊÎ:ľĨ&ĺíMCPP '1 ŒþŒŞ©'¡'ēë2 MCPP ĶH\DPh:1% ĸ§%$:ŀĿ6#"¼ă' CV H\DPhļĥ#Ĳ mı:
Ğ#196WUDLQHQHUJ\FDOFXODWLRQVRI0&33E\+RPRGHVPRWLFUHDFWLRQ DQGHVWLPDWLRQVRIHDFKWUDQVLWLRQ DQGIURQWLHURUELWDOE\7'')7FDOFXODWLRQ 

3!+(

(1) üŎ Ĵu, Yuanming Li, ĆÁ ĀĚ, ç zô´, ~t mŊ y¤Đ æĳšÝ[hP'Ð#ÎŁ Þé·ģ 101 á¶Ä, A17-2pm-12, 2021 Ä 03 å 20 ÞţşŤ
(2) üŎ Ĵu, Yuanming Li, ĆÁ ĀĚ, ç zô´, ~t mŊ Synthesis and Properties of Non-alternant Aromatic Belts GTR Ä÷«¢ 2020, P-416, ¿°·, 2021 Ä 01 å 08 Þţ_HJlŤ4(

(1) </L<6HJDZD$<DJL.,WDPL&KHP5[LY '2,FKHPU[LYY-$P&KHP6RF
±'2,MDFVF   :0DWVXRND+,WR.,WDPLPDQXVFULSWLQSUHSDUDWLRQ   ìÀ£­ĿÚ 'HYHORSPHQW RI $QQXODWLYH ʌ([WHQVLRQ 5HDFWLRQV 7RZDUG 3URJUDPPHG 6\QWKHVLV RI
3RO\F\FOLF$UHQHV  Ä  å¿°·- 276 -

7KHRUHWLFDOVWXG\WRLPSURYH,U2[W\SHHOHFWURGHVIRUZDWHUR[LGDWLRQ
ż-8+$6=*HUJHO\ 7RN\R,QVWLWXWHRI7HFKQRORJ\6FKRRORI6FLHQFH  ,QWURGXFWLRQDQG*RDO
7KLV \HDU ZH ZHUH VWXGLHG WKH VLPXODWLRQ RI ODUJH R[LGH VWUXFWXUHV OLNH DQDWDVHW\SH 7L2 QDQRSDUWLFOHV DQG WKHZDWHUR[LGDWLRQUHDFWLRQRYHU7L2,U2[PL[HGR[LGHVXUIDFHV,QWKLVUHSRUWZHGLVFXVVWKHODWHU :DWHU2[LGDWLRQRU
2[\JHQ(YROXWLRQ5HDFWLRQ 2(5 LVDFRPPRQHOHFWURGHUHDFWLRQ RIPDQ\HOHFWURFDWDO\WLFV\VWHPV8QIRUWXQDWHO\LWLV
RIWHQ D ERWWOHQHFN IRU WKH SHUIRUPDQFH WRR 7KLV LV GXH WR WKHLU VOXJJLVK UHDFWLRQ UDWH DQG KLJK RYHUSRWHQWLDO IRU WKHUHDFWLRQ,ULGLXPR[LGH ,U2[ EDVHGHOHFWURGHVDUHRQHRIWKHPRVWSRSXODURQHVZKHQZDWHUR[LGDWLRQLVSHUIRUPHGLQDFLGLFPHGLD5HFHQWVWXG\IRXQGWKDW,U2[QDQRSDUWLFOHVRQWLWDQLXPVXUIDFHDQGZLWKKLJKVXUIDFHZDWHUFRQWHQWKDYHH[FHOOHQWSURSHUWLHVERWKLQDFWLYLW\DQGVWDELOLW\7KHNH\IRUWKHEHWWHUSHUIRUPDQFHZDVPRVWSUREDEO\WKHPRELOLW\RIVXUIDFHZDWHUFRQWHQW RQWKH,U2[QDQRSDUWLFOHVDFFRUGLQJWRRXUSUHOLPLQDU\FDOFXODWLRQV
7KH,U2[QDQRSDUWLFOHVLQYROYHGLQWKHFDWDO\VLVDUHQRWVWULFWO\VWRLFKLRPHWULF KHQFH,U2[ DQGDPRUSKRXV DFFRUGLQJ
WR ;UD\ GLIIUDFWLRQ 2WKHU UHSRUWV VKRZ WKDW WKH ORFDO VWUXFWXUH RI WKH QDQRSDUWLFOHV DURXQG WKH ,U LRQV VLPLODU WR WKHFU\VWDOOLQHRQH ZLWKUXWLOHW\SHODWWLFH,QVLWX;$6VKRZVWKDWWKHR[LGDWLRQVWDWHRI,U ,9 LVWKHPRVWFRPPRQVWDWH
EXW ,U 9  DOVR SUHVHQW GXULQJ WKH HOHFWURFDWDO\WLF FRQGLWLRQV 2XU JRDO ZDV WR FRPSDUH WKH JHRPHWU\ DQG HOHFWURQLF
SURSHUWLHV RI IUHH ,U2[ QDQRFOXVWHUV ZLWK WKH RQHV RQ WKH 7L2 VXSSRUW 'XH WR WKH VLPLODULW\ RI WKH 7L2 DQG ,U2UXWLOHW\SH  ODWWLFH DQG WKH SRVVLEOH VWURQJ LQWHUIDFLDO ELGLQJ WKURXJK WKH ZDWHU PROHFXOHV ZH H[SHFWHG D VLJQLILFDQW
LPSDFW +HUHZHVKRZWKHFDOFXODWLRQRQWKUHHQXFOHDU ,U2[ ,U PRGHOVRQDQDWDVHW\SH7L2 VXUIDFH
0HWKRG
7KHLQLWLDO  7L2 VXUIDFH DQG,U2[QDQRSDUWLFOHVZHUHFUHDWHGIURPWKHUHVSHFWLYHEXONVWUXFWXUHVDQGPDQXDOO\PRGLILHG SURWRQDWLRQDQGSODFHPHQWRQHDFKRWKHU 2QWKHVXUIDFHVXSHUFHOOWKH,UFOXVWHUVDUHDSSUR[LPDWHO\ 
DQG  c IURP HDFK RWKHUDORQJ WKH WZRGLUHFWLRQV )RU SUHRSWLPL]DWLRQ RI VWUXFWXUHV')7% ZLWK *)1[7%  DQGOLQHDUVFDOLQJ')7 '0RO3%(EDVLV '1 ZHUHXVHG)LQDORSWLPL]DWLRQZDV FDUULHGRXWXVLQJ&$67(3PHWKRG
3%(27)*XOWUDVRIWSVHXGRSRWHQWLDOVFXWRIIH9[[IRUD[[ VXSHUFHOO  5HVXOWV
7KHPHFKDQLVPRIWKHUHDFWLRQZLWKWKH FDOFXODWHG IUHHHQHUJ\ IRU WKHIUHH
,U FOXVWHUV DUH VKRZQ LQ )LJXUH &DOFXODWLRQVVKRZHG

WKDW

WKH

FRQFHUWHG PRYHPHQW RI + LQ WKHQHLJKERUKRRG RI WKH DFWLYH VLWH FDQORZHU WKH RYHUSRWHQWLDO E\ 9
RQIUHH,U2[QDQRFOXVWHUV)LJXUH 7KHVXPPDU\RIZDWHUR[LGDWLRQRQ,U2[VXUIDFHV DVWKHZDWHU
R[LGL]HV LQ IRXU VWHSV RQ DQ DFWLYH FHQWHU OHIW  WKH SURWRQDWLRQ RI WKHQHLJKERULQJ ,U VLWHV FDQ FKDQJH 6LQFH GLIIHUHQW SURWRQDWLRQ VWDWHV + + KDV GLIIHUHQW VWDELOL]DWLRQ HIIHFW RQ WKH DFWLYH VLWH FKDUJHV WKH IUHH
HQHUJ\DVVRFLDWHGWRWKH FDWDO\WLFVWHSVDUHGLIIHUHQW ULJKW       - 277 -

7RVWXG\WKHHQHUJHWLFV RIVXFKSURWRQDWLRQ VXSSRUWHGQDQRFOXVWHUV ZH KDYH VHDUFKHG IRU VWDEOH SRVLWLRQV IRUWKH VXSSRUWHG FOXVWHU 8QIRUWXQDWHO\ ZH KDYH IRXQG D
ODUJH

QXPEHU

RI

VXFK

SRVLWLRQVGXULQJWKH

SUHRSWLPL]DWLRQVKRZLQJUHSUHVHQWDWLYH RQHVLQ )LJXUH
 7KHUHODWLYHHQHUJ\RIWKHVHVWUXFWXUHV aN-PRObN-PROdN-PRO FRPSDUHGWRc DUH FORVHDQG
KDUGWRSLQSRLQWDVLQJOHVWUXFWXUH8SRQ GHHSHUDQDO\VLVWKH IOH[LELOLW\ RI ZDWHU PROHFXOHV UHVSRQVLEOH IRU WKHVWURQJ LQWHUDFWLRQ EHWZHHQ WKH R[LGH VXUIDFHV DOORZV D
JUHDW YDULDELOLW\ RI GLIIHUHQW RULHQWDWLRQV ZLWKLQ D
UHODWLYHO\VPDOOHQHUJ\UDQJH :HKDYHWHVWHGDIDVWDOWHUQDWLYHPHWKRGWRSUHVHOHFWUHDVRQDEOH VWUXFWXUHV ')7% [7%  LV D WLJKW ELQGLQJPHWKRGV ZLWK RYHUDOO JRRG WUDQVIHUDELOLW\ IRU GLIIHUHQW)LJXUH)RXUGLIIHUHQWVWDEOHSRVLWLRQVRI,URQD
DQDWDVHW\SHVXUIDFH )RUWKHFOXVWHU,UEOXH2UHG+
ZKLWHDQDWDVHODWWLFHLVUHSUHVHQWHGE\JUD\UHGOLQHV  

PDWHULDO FDWHJRULHV 7KHVHWHVWVVKRZHGKRZHYHUDODUJH
YDULDQFH LQ ,U,U GLVWDQFHV DIWHU RSWLPL]DWLRQ IRU ERWK IUHH FOXVWHUV DQG VXSSRUWHG RQHV UHVXOWLQJ LQ ODUJHO\ GLVWRUWHGVWUXFWXUHV IDU IURP RSWLPDO JHRPHWULHV 2QH RI WKH XQVROYHG FKDOOHQJHV RI WKLV UHVHDUFK LV ILQGLQJ IDVW DQG UHOLDEOH
SUHVFUHHQLQJPHWKRGVIRUVXUIDFHVWUXFWXUHV)RU WKH HVWLPDWLRQ RI WKH RYHUSRWHQWLDO XVLQJ FRPSXWDWLRQDO +HOHFWURGH PRGHO WKH HQHUJ\ RI ZDWHU R[LGDWLRQ
LQWHUPHGLDWHV ZDV FDOFXODWHG RQ WKH ORZHVW HQHUJ\ VXUIDFH VWUXFWXUHV )LJXUH  F ZLWK WKH H[FHSWLRQV RI WKH 22+
LQWHUPHGLDWHVZKLFKVKRZHGVHYHUHFRQYHUJHLVVXHV7KHSRVLWLRQRISURWRQDWLRQKDVODUJHULQIOXHQFHRQWKHHQHUJ\RI
WKHVH LQWHUPHGLDWHV FRPSDUHG WR WKH IUHH FOXVWHU 7KH UHDVRQ RI WKLV HQKDQFHG HIIHFW LV WKDW WKH SURWRQDWLRQ DOVRLQIOXHQFHVWKHK\GURJHQERQGVW\LQJ WKHFOXVWHUWRWKHVXSSRUWLQJVXUIDFHWKHUHIRUHWKHELQGLQJHQHUJ\LVSHUWXUEDWHGDVZHOO DV WKH VKDSH RI WKH ZKROH FOXVWHU FKDQJHV ZKHQ D SURWRQ LQFOXGHG WR WKDW QHWZRUN LV PLJUDWLQJ )RU DQ DFWXDOHVWLPDWLRQ RIWKHRYHUSRWHQWLDOKRZHYHUZH DUHPLVVLQJWKHIUHHHQHUJ\RI22+LQWHUPHGLDWHVDQGDEHWWHUFRPSDULVRQRIGLIIHUHQWFOXVWHURULHQWDWLRQVRQWKHVXUIDFH6LQFHWKHHQHUJ\GLIIHUHQFHEHWZHHQGLIIHUHQWRULHQWDWLRQV DUHVPDOODQG
VLQFHLWLVQRWREYLRXVWKDWWKHHOHFWURFKHPLFDOO\PRVWDFWLYHVWUXFWXUHDQGWKHPRVWVWDEOHVWUXFWXUHZLOOEHWKHVDPH D
EURDGHULQVSHFWLRQRIFOXVWHUVLVQHFHVVDU\  
7DONV&DOFXODWLRQVUHODWHGWR7L2 VXUIDFHVWUXFWXUH7L2 QDQRSDUWLFOHVFDOFXODWHGGXULQJWKLVWHUPZHUHSUHVHQWHG DW'3*
PHHWLQJ RQOLQH SRVWHU '3* 6XUIDFH 6FLHQFH   ³6HOHFWLYH HOHFWURFKHPLFDO UHGXFWLRQ R[DOLF DFLG RQ DQDWDVH
VXUIDFHV´DQGLQDVFKHGXOHGWDONRQ(&6 (&6WK PHHWLQJ2UODQGR)ORULGD  
3XEOLFDWLRQ
1RQH

- 278 -



Development of Organometallic Molecular Wireswith Thioether Anchor Groups5 @E-%/!" :"(>'9;DF1 9;87Ğ~*ƛÓÁż%#Ó=ƛÓƋ¿*ęòūŕ%#ęŒ9ÓÁżĥŁ=ƙ3# 9$
4ƛÓðÈ= 9ÓtBmw(ÓÞř)5ÓPBUT+Č4ÇĒŀ"Ǝū'ÓŕÓ$ 9ó
+:1$(đŌ@uHw%#@RTpY=Ď9ĎĝƏàÓtBmwƤ ¯ÓƛġÞã=ń
%=ć7%#(Y. Tanaka et al. Chem. Commun., 2016, 52, 5796, J. Am. Chem. Soc. 2018, 140, 10040.)ƤÞã=ńƛė%*Ďŗ·éò(+đŌ(Ħï¬Ç%'9ƏƑ=Ƣ9íū 8:ÓtBmw*|Ö×ï5ƍ¬¤ĭ(69Šƚ'&=$ĒŃň$+ƍ¬Ɗ(Ö×'@uHw%#TGEwVq=ĸ ĎĝƏà¯ÓtBmw*Ɠľ=ű22 9;+0A<+0Ó 6,ÓOluJNnukWq*ęƆČƉ¬+ Gaussian 09 (rev D01) 6, Gaussian 16 (rev C01)=ĸ B3LYP/LanL2DZ,6-31G(d)*ŮŐrbq=ĸ ÞŮŐ+ÌĹ7Ɠľ hybrid DFT-NEGF asKoi=ĸ ƥT. Tada et al. J. Chem. Phys. 2004, 121, 8050–8057.Ʀ
ÓOluJNnu*kWq%#yŭƐÅ*ƏJoPSwƥAu35Ʀ=ÓtBmw*Ō(ƌŜęƆ*ęƆČƉ¬=ŧ!

3 9;'.
đŌ(TGEwVq@uHwÇ=Ď9ÓtBmw 5 KH[$U =·ò*¯ÓƛġÞã
= 670 `rBJOluJNnuĤ(68Ůĩ*ŗĕ =ƗŤÑ'Óý·éò:Þ
ã=ģ×xĄ +Óý·(ĺĔ9Þ^wJŬ7:'!*Ķĺ%#Ŋƀ2
9%$Əƛė(TGEwVqƋƁý$'!3$ 9%Ş 7:9Þã+ !!!
 *ƞ%'!1




 %

+Ďŗ·ïđ

Ō=ú"ÓtBmw%

Ph2P

PPh2
Ru
n
Ph2P PPh

Au
Au
Au

Au
Au
Au

Au
Au
Au
n

S
R

2

¸Ě*Óƒ$¸ņã*Ph2P

高い伝導度・末端活性化が必要

PPh2
Ru
n
Ph2P PPh

R
n

S

2

Au
Au
Au

高い伝導度・末端活性化不要Þã=ń%4ć7
%'!*Ƥ

Þï%â*Ķĺ=ć7
%.
')71(*) ŮŐ(69ƄƇPcJXq*ŬŇ48=ŧ!

Ph2P

S

R

PPh2
Ru
Ph2P PPh

Ph2P

R
S

S

R

2

PPh2
Ru
Ph2P PPh

R
S

2

1R

(MeO)3P

P(OMe)3 n-hex
RuSS
n-hex (MeO)3P P(OMe)
3

2R

3hex
R=

R=

R = hex

t-Bu

R = ArÃ 1. ÓOluJNnu*ęƆ%TGEwVqđŌ=ú"ĎĝƏàÓt

Bmw 5 KH[$U- 279 -

(a)1hex 3hex2Ar

2hex(b) Au35-1hex-Au35

Au35-2hex-Au35

Au35-2Ar-Au35

Au35-3hex-Au35

HOMO transmission peaks

18

Transmission / a.u.

6
4
2

0.18
6
4
2

0.018
6
4

-1.0

0.0

1.0

E-E
E
–E
/ eV
F F/ eVÃƩƧƥaƦƄƇPcJXq%ƥbƦÓOluJNnukWq%ÞŽƈƄƇPcJXq%ÓOluJNnu*ÞŽƈ=ÃƩ(ńƄƇPcJXq7ŬŇ47:9Þã+  !! ! %'8đŌ*ŜāÇ*º=ƗĘ)Øƣ%xŢ_Dqhī(Ɓ ÞŽƈ+ HOMO $ 8HOMO ÞŖż%'!# 9%<8ƥÃ 2bƦƛÓŹÚ'qVZCiƑ% S Žƈ*ç ŽƈłĸƤÞï*ūÂ$ 9%<!ţ½ħ %( HOMO Þ^wJ*Ŝ+  !! ! %'8Þã*º%+Ľ'9%<!   (ğ.#Ƥ Þ
ã=ńĶĺ(" #ŞÛ93(  *dP_AuƌÓ*_DZqÇ=Ģŕ(Ŝā (" #ƄƇPcJXq=ŮŐ%; %/0¸E[qIw*Þ^wJ=ń*%7ƌÓ*Ŋŀ'Ƥƛė%*łĸ(êƜ=²0:Þã-êƜ9%ć7%'!

4

6?$=

#Ƒ¬Õťõ*ōƫÁCD`ªçƥGuoBuƦ2020 á 11 č 30 ĆĹũ ĎĝƏàÓOluJNnu*ŰŮ%¯ÓƛġÞĳïƥ÷ëŷĬƦ
Ä´ƟľŨƪfPSwľŨƨ5

3$=



$<DVKLUR 





#
 77DGD6)XMLL71LVKLQR0$NLWD &KHP(XU- LQSUHVV <.DWR.6XJLPRWR5.DZDQR77DGD6)XMLL0.LJXFKL0$NLWD &KHP

6FL 


.0LVKLED  0$NLWD &KHP(XU- 

02VDZD 66RPD0+RVKLQR 







1.LVKLGD.0DWVXPRWR 0$NLWD'DOWRQ7UDQV

 .2KPXUD6)XMLL77DGD0.LJXFKL0$NLWD ,QRUJ&KHP
0$NLWD+6DNXUDL0<RVKL]DZD -$P&KHP6RF



+'REDVKL/&DWWL 8.

<0DWVXVKLWD52FKL 0$NLWD0<RVKL]DZD $QJHZ&KHP,QW(G
7.RLNH 0$NLWD  2UJ&KHP)URQW

- 280 -













Theoretical Studies on Structures and Reactivities ofMetal Complexes with Multifunctional Ligands
 

# 

 #!

"

1 #¦Ã·*"~he mÕi %+¥*- ÉÏz¿r.¥,½Åph.Ó¨ _ #Y§ aÖÐ7@S>5ULKV4V!°XÊ­Ïz¿r.¥,³³µi«v¸ogh.Ó¨Ïz`³ ©h.¼d %NRD=V¿r.¥,3SI?Sgi(85UEUAVuwgi *!¿r©3
SGV¨¤.Ó,-*!h"-'Ì]s ),Ïz®!he Ò,¬¯"ÎsgtÀ± ),½q¸Ì]s.'ÏzÑ^!Ç )$h!¾
- o²yih!Ó¨.ª©,[¦Ã·* ÆÓ¨½ih!¾
- oh!´.Z ¬¯. {}"[ 0R91L¿r ),CS2U/T
WV!2S>]Ë ©³³µiH1³gh.Ó¨')7 À± ),h¬¯.»Ù¶ÜÛÞÚ%bj¬¯Íg©¹³n£gh ),ßl£Ç )$Ä!¡.'P?W
5FR:Vi!h.¾Ù¶ÝÚ

2 #

À±" Gaussian 16 EU6QL.¥À± B3LYP(-D3)%" M06 .¥Á. o|Ô " SVP o|'"Ê­Ïz`³ fcJ<V8OS.k& SDD o|'" LANL2DZ o|!\!`³  6-31G(d)%"- ,o|Ô.¥3 
[1] 0R91L¿r ),CS2U/TWV!2S>]Ë ©³³µiH1³ghÙ¶ÜÛÞÚ¦Ã·*"Æ º ÂÀ;WBR9VÌ]s.¥,0R91L¿r ),CS2U/TW
V!³³µiH1³gh Ø2S>]Ë © È»,.¼dx× )$ ')7 À± )+;WBR9VÌ]s UWS2W@W85UM;Sg0R91LÑ^ )$H1³g-Ì]s.'0R91LÑ^ 2S>]Ë ¨¢ Ô,®,  -

[2] ¹³n£gh ),FR:VihÙ¶ÝÚ
3’,6’-Bis(naphthylphenyl)-o-terphenylÖ^.Ü sÍgQ93S32V )$EU>Vg/T?1L32V.®Üª!³!³µi¤h.Á!µ*!® *' !¹³n£gh!"CSC?So!BUÇ.,

- 281 -

gh È»(.¼d

 n!¹³n£gh )+Ý!ßl£Ç -,.

4 #>@ 2.XOHVKRYD6$VDNR/,OLHV$&6&DWDO>@ =4LX6$VDNR<+X&:-X7/LX/5RQGLQ'6FKROOPH\HU-6/DXUHW.0OOHQ$1DULWD-$P
&KHP6RF
>@6$VDNR7.RED\DVKL6,VKLKDUD.7DNDL$VLDQ-2UJ&KHP
>@/,OLHV%XOO&KHP6RF-SQ
>@ 2.XOHVKRYD6$VDNR/,OLHV gt°   {Û2021 { 3 "
>@ 6$VDNR%5DPDGRVV/,OLHV gt°   {Û2021 { 3 "  >@/ ,OLHV ,QWHUQDWLRQDO 6\PSRVLXP RQ $GYDQFHG 6FLHQFH DQG 7HFKQRORJ\ 1DWLRQDO &KXQJ +VLQJ 8QLYHUVLW\
7DLZDQ {  - 282 -

ィ⟬ศᏊศගᏛ䠖㻌 ศᏊ䛾ᵓ㐀䛚䜘䜃཯ᛂ䛻㛵䛩䜛ィ⟬໬Ꮫ㻌
Computational Molecular Spectroscopy: Computational Chemistryon the Structure and Reaction of Molecules‫ۑ‬ᖹ㔝ᜏኵ㸦࠾Ⲕ኱⌮㸧ࠊ㛗ᔱ㞼ර㸦ᶓᕷ኱㸧ࠊ௒ᇛ ᑦᚿ㸦᪥ᮏዪᏊ኱⌮㸧 ◊✲┠ⓗࠊෆᐜ๓ᖺᗘ䛾ㄢ㢟䛻ᘬ䛝⥆䛝䚸䛂ィ⟬ศᏊศගᏛ䛃䛾どⅬ䛻❧䛳䛶䚸ḟ䛾  Ⅼ䛻㛵䛩䜛◊✲䜢⾜䛳䛯䚹䠍䠅┤⥺  ཎᏊศᏊ䠄䝫䝔䞁䝅䝱䝹䜶䝛䝹䜼䞊᭤㠃䛜┤⥺ᵓ㐀䛷ᴟᑠ䛻䛺䛳䛶䛔䜛  ཎᏊศᏊ䠅䛾᣺ື࣭ᅇ㌿ᖹᆒᵓ㐀ࡣ┤⥺ᙧ࡛࠶ࡿ࡜ࡍࡿศගᏛࡢᚑ᮶ࡢࣃࣛࢲ࢖࣒࡟ᢠࡋ࡚ࠊほࡍࢀࡤࠕ᭤ࡀࡗ࡚ぢ࠼ࡿࠖ࡜࠸࠺ᡃࠎࡢ୺ᙇࢆ☜❧䛩䜛䛯䜑䛾ドᣐᅛ䜑䛾ィ⟬䜢⾜䛖䚹䠎䠅䛭䛾ᛂ⏝䛸䛧䛶䚸䝧䞁䝊䞁䛺䛹䛾ⰾ㤶᪘Ⅳ໬Ỉ⣲䛻ぢ䛔䛰䛥䜜䛯䚸୍ぢ␗ᖖ䛺㛵ಀ䚸༶䛱 &௅+ ⤖ྜ㛗䛸 &௅' ⤖ྜ㛗䛜䜋䜌➼䛧䛟䛺䜛஦ᐇ䜢ゎ᫂䛩䜛䚹䠏䠅୍⯡䛻 2 䛻䜘䜛㓟໬཯ᛂ䛷ᇶ㉁䛛䜙䛾 㟁Ꮚ⛣⾜䛜㉳䛣䜛䛸䚸 㔜㡯㓟⣲䛸䛾཯ᛂ䛷䜒䚸 㔜㡯㓟⣲䛸䛾཯ᛂ䛷䜒ྠ䛨⏕ᡂ≀䛜ᚓ䜙䜜䜛⌮⏤䜢᫂䜙䛛䛻䛩䜛䚹 ◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ศᏊศගᏛ䛷䛿䚸䠄ᐇ㦂䠅ศᏊศගᏛ䛸㐪䛳䛶䚸᭱ึ䛻㻌 DE LQLWLR ศᏊ㌶㐨ἲィ⟬䛻䜘䛳䛶㻌 3RWHQWLDO(QHUJ\ 6XUIDFH 3(6 䜢Ỵ䜑䜛䚹䛭䛧䛶䚸䛭䛾㻌3(6䜢⏝䛔䛶䚸᣺ື䞉ᅇ㌿䛾㻌6FKU|GLQJHU᪉⛬ᘧ䜢ゎ䛝䚸ồ䜑䛯Ἴື㛵ᩘ䛾ᮇᚅ್䛸䛧䛶䇾᣺ື䞉ᅇ㌿䜢⪃៖䛧䛯䇿ᖹᆒᵓ㐀 ⤖ྜ㛗䚸⤖ྜゅ 䛾⟬ฟ䜢⾜䛖䚹3(6 䛾ィ⟬䛻䛿
02/352䜢౑䛔䚸᣺ື䞉ᅇ㌿䛾㻌6FKU|GLQJHU᪉⛬ᘧ䛿㻌ḟ䛾ᦤືㄽ䚸䜎䛯䛿㻌'LVFUHHW 9DULDEOH 5HSUHVHQWDWLRQἲ䠄'95䠅䛷ゎ䛔䛯䚹ึ䜑䛛䜙㻌 3(6 䛜ศ䛛䛳䛶䛔䜛䛸䛔䛖䛣䛸䛿䚸ィ⟬ศᏊศගᏛ䛾᭱኱䛾ᙉ䜏䛷䛒䜚䚸௨ୗ䛻
㏙䜉䜛ศᏊศගᏛ䛾ᙅⅬ䚸ḞⅬ䜢᫝ṇ䛩䜛䛣䛸䛜ฟ᮶䜛䚹ศᏊศගᏛ䛾෌ᵓ⠏䛷䛒䜛䚹ᖹ㔝䚸㛗ᔱ䚸㤿ሙ䜾䝹㻌䞊䝥䛾ᡭ䛻వ䜛ၥ㢟䛷䛿䛒䜛䛜䚸䝏䝱䝺䞁䝆䛻್䛩䜛㔜せㄢ㢟䛷䛒䜛䛸ᛮ䛳䛶䜔䛳䛶䛔䜛䚹ศᏊศගᏛࡣࠊ ᱆ࡢ࣮ࣞࢨ࣮⢭ᗘ࡟ᇶ࡙ࡃᴟࡵ࡚⢭⦓࡞ᐇ㦂ᡭẁ࡛࠶ࡿࡇ࡜ࡣㄽࢆᚅࡓ࡞࠸ࠋࡋ࠿ࡋࠊ
ᖹ㔝ࢢ࣮ࣝࣉ࡟ࡼࡿDELQLWLRィ⟬࡛ࠊศගᏛ⢭ᗘ㸦FP ࣞ࣋ࣝ㸧ࡢ3(6ࡀồࡲࡿࡼ࠺࡟࡞ࡿ࡜ࠊᖺ௨ୖࡢ
Ṕྐࡢ࡞࠿࡛ඛ㐩ࡀẼ࡟ࡋ࡚ࡇ࡞࠿ࡗࡓ኱஦࡞Ḟ㝗ࡀ⾲㠃໬ࡋ࡚ࡁࡓࠋ༶ࡕࠊ䠍䠅+DPLOWRQLDQ࡟ᇶ࡙ࡃᴟࡵ࡚
⢭⦓࡞ศගᏛ⌮ㄽ࡟ࡣࠊࡑࢀࢆほ㸦ᐇ㦂㸧ࡍࡿ࡜࡝࠺࡞ࡿ࠿ࠊ࡜࠸࠺どⅬࡀ඲ࡃḞࡅ࡚࠸ࡓࠋ䠎䠅೧࠸ඛ㐩ࡢゝ࠺ࡇ࡜࡟LPSULQWࡉࢀࡓศගᏛ⪅ࡣࠊ┤⥺ศᏊ㸦ᐃ⩏㸸3(6ࡀ┤⥺ᵓ㐀࡛ᴟᑠ࡟࡞ࡗ࡚࠸ࡿศᏊ㸧ࡢ᣺ືᅇ㌿ᖹᆒᵓ㐀ࡣ┤⥺ᙧ࡛࠶ࡿ࡜ಙࡌ㎸ࢇ࡛ấࡶ␲࠾࠺࡜ࡋ࡞࠸ࠋ䠏䠅ศගᐇ㦂࡛ᚓࡽࢀࡿᅇ㌿ᐃᩘࡣྛ័ᛶ୺
㍈࡬ࡢࠕᢞᙳᵓ㐀ࠖ࡟㛵ࡍࡿ್࡛࠶ࡿࡇ࡜ࢆᛀࢀ࡚ࠊᐇ㝿࡟᣺ືᅇ㌿ࡋ࡚࠸ࡿศᏊࡢᵓ㐀ࢆ㆟ㄽࡋ࡚ࡁࡓࠋ䠐䠅ᐇ㦂࠿ࡽ3(6ࢆồࡵࡿࡢࡣ⮳㞴ࡢᢏ࡛ࠊᖺవࡢศගᏛࡢṔྐࡢ࡞࠿࡛ࠊࡑࢀࢆࡸࡾ㐙ࡆࡓࡢࡣࠊ+&1࡟㛵ࡍࡿ ௳ࡢࡳ㸦&DUWHU ࡽ㸧࡛࠶ࡿࡇ࡜࠿ࡽศ࠿ࡿࡼ࠺࡟ࠊศගᏛ⪅࡟࡜ࡗ࡚↓⦕ࡢᏑᅾ࡛࠶ࡿἼື㛵ᩘࡢࠕᮇᚅ್㸦ᅛ᭷≧ែࢆほࡍࡿ࡜࡝࠺࡞ࡿ࠿ࢆ⌮ㄽⓗ࡟ணࡍࡿ್㸸㔞ᏊຊᏛࡢබ⌮ࡢࡦ࡜ࡘ㸧ࠖࡢᴫᛕࢆࠊ

ศගᏛ⪅ࡣ⌮ゎࡋ࡚࠸࡞࠸ࠊ࡞࡝࡞࡝࡛࠶ࡿࠋ
ᡃࠎࡣࠊ ᖺ࡟┤⥺ศᏊ1L&1 ࡢ᣺ືᅇ㌿ᖹᆒࡢ⤖ྜゅࡢᮇᚅ್ࡀ࡛࠶ࡿࡇ࡜ࢆぢ࠸ࡔࡋ࡚௨᮶ࠊ
┤⥺ศᏊࡢ᣺ືᅇ㌿ᖹᆒᵓ㐀ࡣࠕ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿࠖ࡜୺ᙇࡋ࡚ࡁࡓࠋࡈࡃ᭱㏆࡟⮳ࡿࡲ࡛ࠊᅄ㠃ᴆḷ࡛࠶ࡗࡓࡀࠊศᏊ◊ࡢィ⟬⛉Ꮫࢭࣥࢱ࣮࡛ィ⟬ࡋࡓ㉸㧗⢭ᗘ࡞3(6࡟ᇶ࡙ࡃ㆟ㄽࢆᒎ㛤ࡋ࡚࠸ࡿ࠺ࡕ࡟ࠊᡃࠎ
ࡢ୺ᙇ࡟㈶ྠࡍࡿศගᏛ⪅ࡀ⌧ࢀ࡚ࡁࡓࠋࡲࡉ࡟(SXUVLPXRYH࡛࠶ࡿࠋ ◊✲ᡂᯝ㸸ィ⟬ศᏊศගᏛ࠿ࡽࡢ࢔ࣉ࣮ࣟࢳ࡜ࡑࡢᡂᯝ
 ᪂ࣃࣛࢲ࢖࣒㸹 ┤⥺ศᏊࡢ᣺ືᅇ㌿ᖹᆒᵓ㐀ࡣࠕ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿࠖ
㔞ᏊຊᏛ䛷䛿䚸䛂⮬↛⏺䠄䝅䝳䝺䞊䝕䜱䞁䜺䞊᪉⛬ᘧ䛾ୡ⏺䠅䛃䛸䛂ᡃ䚻䛃䛿⊂❧䛺஧䛴䛾ୡ⏺䛸⪃䛘䛶䛔䜛䛾䛷䚸⮬↛⏺䛷㉳䛣䛳䛶䛔䜛䛣䛸䜢▱䜚䛯䛡䜜䜀ほ䛧䛺䛡䜜䜀䛺䜙䛪䚸ほ- 283 -

䛧䛶ᚓ䜙䜜䜛䜒䛾䛸⮬↛⏺䛷㉳䛣䛳䛶䛔䜛䛣䛸䛸䛿ᚲ䛪䛧䜒୍⮴䛧䛺䛔䚹㔞Ꮚ⛉Ꮫ⪅䛾ᖖ㆑䛷䛒䜛䛜䚸ᚑ᮶䛾ศගᏛ䛷䛿䛣䛖䛧䛯どⅬ䛜Ḟ䛡䛶䛔䛯䚹┤⥺ศᏊ䛿䛭䛾䝫䝔䞁䝅䝱䝹䜶䝛䝹䜼䞊᭤㠃䠄3(6䠅䛜┤⥺ᵓ㐀䛷ᴟᑠ䛻䛺䛳䛶䛔䜛ศᏊ䛷䛒䜚䚸䛭䛾ኚゅ᣺ື䛿 㔜⦰㏥䛧䛶䛔䛶᣺ື⮬⏤ᗘ䛿 1 ±  䛷䛒䜛䚹3(6 䛜┤⥺ᵓ㐀䛷ᴟᑠ䛺䛾䛷䚸Ἴື㛵ᩘ䛾᣺ᖜ䛿┤⥺ᙧ䛷᭱኱䛷䛒䜚䚸Ꮡᅾ☜⋡䠄䛭䛾  ஌䠅䜒┤⥺ᵓ㐀䛷᭱኱䛻䛺䜛䚹䛴䜎䜚䚸┤⥺ᵓ㐀䜢୰ᚰ䛻䛧䛶ኚゅ᣺ື䛧䛶䛔䛶䚸᣺ືᖹᆒᵓ㐀䛿┤⥺ᙧ䛷䛒䜛䠄⮬↛⏺䚸䛴䜎䜚䝅䝳䝺䞊䝕䜱䞁䜺䞊᪉⛬ᘧ䛾ୡ⏺䛷䛾ヰ䠅䚹䛧䛛䛧䚸䛣䜜䜢ほ 䛩䜛䛸ศᏊ㍈䠄D ୺㍈䠅䛾࿘䜚䛾ᅇ㌿䛸ኚゅ᣺ື䜢ษ䜚㞳䛧䛶ほฟ᮶䛺䛔䛯䜑䚸ほ 䛷▱䜚䛖䜛ᖹᆒᵓ㐀䛿䛂᭤䛜䛳䛶ぢ䛘䜛䛃䛣䛸䛻䛺䜛䚹䛩䛺䜟䛱䚸┤⥺ᵓ㐀䛛䜙䛾䝈䝺䛾ゅᗘ䜢ߩҧ 䠄䛴䜎䜚⤖ྜゅ䛾⿵ゅ䠅䚸D ୺㍈䛾࿘䜚䛾ᅇ㌿ゅ䜢F䛸䛩䜛䛸䚸 㔜⦰㏥䛧䛶
䛔䜛ኚゅ᣺ື䛾Ἴື㛵ᩘ  䛿䚸߮௩,௟ (ߩҧ , F) = ܰ exp(݈݅F)I௩,௟ (ߩҧ ), (0 d F < 2ߨ, 0 d ߩҧ < ߨ, 1 䛿つ᱁໬ᐃᩘ䠅䛺䛾䛷䚸ߩҧ 䛾ᮇᚅ್䠄䛴䜎䜚䚸ほ䛧䛶ᚓ䜙䜜䜛䛿䛪䛾ᖹᆒ್䠅¢ߩҧ ² 䛿䚸¢ߩҧ ² = ¢߮௩,௟ (ߩҧ , F)|ߩҧ |߮௩,௟ (ߩҧ , F)²

⾲   ┤⥺  ཎᏊศᏊ䛾 ‫ߩۃ‬ҧ ‫ۄ‬0‫ߩۃ‬ҧ ‫ۄ‬0 GHJUHHV గ= 2ߨܰ න I௩,௟ (ߩҧ ) ߩҧ ݀ߩҧ
ଶ

ଶ

ଶ

> 0

଴

䛸䛺䜛䚹䛴䜎䜚䚸¢ߩҧ ² 䛜 QRQ]HUR 䛺䛾䛷䛂᭤䛜䛳䛶ぢ䛘䜛䛃䛣䛸䛻䛺䜛



䚹ᐇ

㦂䛷ᚓ䜙䜜䜛┤⥺ศᏊ䛾ᖹᆒᵓ㐀䛿┤⥺䛷䛒䜛䛸䛩䜛ᚑ᮶䛾䝟䝷䝎䜲䝮䛿㛫㐪䛳䛶䛔䛯ヂ䛷䚸䛂᭤䛜䛳䛶ぢ䛘䛶䛔䜛䛃䛸䛔䛖᪂䛧䛔䝟䝷䝎䜲䝮䜈ኚ᭦䛩䜉䛝䛺䛾䛷䛒䜛䚹௨ୗ䚸⤖ྜ㛗䜢 U ;௅< 䛺䛹䛸᭩䛝䚸䝊䝻Ⅼ᣺ື≧ែ䜢ῧᏐ䇾䇿䛷⾲䛩䚹ศᏊ  ᮇ ᚅ ್ % 䛾 ෌ ゎ 㔘6&2° 
6 )H&2     

3 1&6      

3 %U&1    ) &R&1      
6 0J1&  ' 1L&1     ' )H&1     
6 +&2       
 
6 '&2    

 
6 +&1       
 
6 '&1       
'  )H1&    6  &V2+     
6 &  ഥ ²0 
 ┤⥺ศᏊࡢ᣺ືᖹᆒᵓ㐀㸸¢࣋⾲  䛻䚸ኚゅ᣺ື䛾Ἴື㛵ᩘ߮௩,௟ (ߩҧ , F)䜢⏝䛔䛶ồ䜑䛯ᮇᚅ್䛸䚸ᐇ㦂䛷ồ䜑䛯ᅇ㌿ᐃᩘ %HII 䛛䜙ߩҧ 䜢  ᗘ䛻ᅛᐃ䛧䛺䛔䛷ồ䜑䛯ሙྜ䛾¢ߩҧ ² 䜢♧䛩  䚹୧⪅䛿Ⰻ䛟୍⮴䛧䛶䛚䜚䚸┤⥺ศᏊ䛿᭤䛜䛳䛶ぢ䛘䛶䛔䜛䛣䛸䛜❧ド䛥䜜䛯䛣䛸䛻䛺䜛䚹ᚑࡗ࡚ࠊᐇ㦂ⓗ࡟ࡶࠊ⌮ㄽⓗ࡟ࡶࠊߩҧ଴ ! ࡣṇࡋ࠸ࡢ࡛࠶ࡿࠋ 㟁Ꮚ⥺ᅇᢡ࠿ࡽࡢ᳨ド  㟁Ꮚ⥺ᅇᢡ䛿 ; ⥺ᅇᢡ䛸ྠᵝ䛻䚸ཎᏊ᰾㛫䛾㊥㞳䛜ᚓ䜙䜜䜛䚹
௒㎾䛾䜘䛖䛻䚸᣺ືᖹᆒᵓ㐀䛿䛂┤⥺䛃䛷䛒䜛䛸⪃䛘䜛䛸䚸ᵓᡂ䛩䜛ཎᏊ㛫㊥㞳䛾࿴䛿ᮎ➃㛫㊥㞳䜘䜚▷䛟䛺䛳䛶䛧䜎䛖䠄VKULQNDJH HIIHFW䚸ᅗ D 䠅䚹䛧䛛䛧䚸䛂᭤䛜䛳䛶ぢ䛘䛶䛔䜛䛃䛣䛸䜢チ䛫䜀 ᅗ  E 䚸 ゅᙧ䛷䛾  ㎶䛿௚䛾  ㎶䛾࿴䜘䜚▷䛟䛺䜛䛾䛷䛒䜛䚹VKULQNDJHHIIHFW 䛿䚸᣺ືᖹᆒᵓ㐀䛜┤⥺ᙧ䛰䛸䛩䜛⪃䛘䠄ᪧ䝟䝷䝎䜲䝮䠅䛻⏤᮶䛩䜛䛂⹫ᵓ䛃䛷䛒䜛䛣䛸䛜♧䛥䜜䛯䚹ᅗ䠍 +&1 䛻䛚䛡䜛⤖ྜ㛗䛾㛵ಀ ▷ࡍࡂࡿ &Ł1 ⤖ྜ㊥㞳㸦ᐇ㦂್㸧㻦┤⥺ศᏊ FeNCࠊCoCNࠊNiCN
ᅇ㌿ᐃᩘࡢᐇ㦂್࡟཯ᫎࡉࢀࡿࡢࡣࠊ᣺ືᅇ㌿ᖹᆒࡢ⾲  &1 ⤖ྜ㊥㞳䛾ᐇ㦂್䛸⌮ㄽ್䛾ẚ㍑⤖ྜ㛗 U ࡛ࡣ࡞ࡃ࡚ࠊࡑࡢ୺㍈࡬ࡢࠕᢞᙳ㛗࡛ࠖ࠶ࡿࠋ   )H1&   &R&1      1L&1᣺ືᖹᆒᵓ㐀ࡀࠕ᭤ࡀࡗ࡚ぢ࠼ࡿࠖࡢ࡛࠶ࢀࡤࠊ୺㍈࡬ࡢᢞᙳ㛗ࡣ᣺ືᅇ㌿ᖹᆒࡢ⤖ྜ㛗 U ࡼࡾ▷ࡃ࡞ࡿࠋᐇ㦂࡛ሗ࿌ࡉࢀ࡚࠸ࡿ )H1&ࠊ&R&1ࠊ1L&1 ࡢ▷ࡍࡂࡿ &Ł1 ⤖ྜ㛗ࡣࠊᐇࡣࠕ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿࠖᖹᆒ⤖ྜ㛗ࡢ D ୺㍈

- 284 -

2EV U c          

&DOF UH c    

U c            ¢ߩҧ ² GHJ     
࡬ࡢᢞᙳ㛗࡛࠶ࡿ࡜ࡍࡿ࡜ࠊࡍ࡭࡚ࡢᐇ㦂್ࡀ⌮ゎ࡛ࡁࡿࠋᐇ㝿࡟ᮏᖺᗘࡢ෌ィ⟬࡛ࠊ1L&1 ࡟ᑐࡍࡿᐇ㦂್  c ࡣࠊᐇࡣ U ࡛ࡣ࡞ࡃ࡚ࠊU c ࡢ D ୺㍈࡬ࡢᢞᙳ㛗 USURM &Ł1 ࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ
 ኱᣺ᖜኚゅ᣺ືࢆ⾜࠺┤⥺ศᏊ࡟࠾ࡅࡿ␗ᖖ㸽࡞㛵ಀ㸸 r0 < re 5)୍⯡࡟ࠊ&௅+ ࡸ 2௅+ ⤖ྜࡢ᣺ືᖹᆒ⤖ྜ㊥㞳 U ࡣࠊ᣺ື࣏ࢸࣥࢩࣕࣝࡢ㠀ㄪ࿴ᛶࡢࡓࡵ࡟ࠊᖹ⾮⤖ྜ㊥㞳 UH ࡼࡾ㛗ࡃ࡞ࡿ㸦U!UH㸧ࠋࡇࡢᖖ㆑࡟཯ࡋ࡚ࠊ኱᣺ᖜኚゅ᣺ືࢆ⾜࠺┤⥺ศᏊ࡛ࡣࠊᐇ㦂࡛ᚓࡽࢀࡿ HIIHFWLYH
࡞ᅇ㌿ᐃᩘ࠿ࡽᑟ࠿ࢀࡿࢮࣟⅬ᣺ື≧ែ࡛ࡢ᣺ືᖹᆒ⤖ྜ㛗 UHII ࡣࠊࡑࢀࡒࢀࡢᖹ⾮⤖ྜ㛗 UH ࡼࡾ▷ࡃ࡞ࡿࡇ࡜ࡀ࠶ࡿࠋࡇࡢ୍ぢወጁ࡞ࠊᖖ㆑࡟཯ࡍࡿ⌧㇟ࡣࠊᐇࡣࠊᅇ㌿ᐃᩘࡢᐇ㦂್࠿ࡽᚓࡽࢀࡿ⤖ྜ㛗ࡣࠊD ୺㍈࡬ࡢᢞᙳ㛗 USURM ࡞ࡢ࡛ࠊᢞᙳゅࡀ኱ࡁࡃ࡞ࡿ࡜ࡑࡢᢞᙳ㛗ࡣ▷ࡃ࡞ࡗ࡚ USURM  UH࡜࡞ࡿࡇ࡜ࡀ࠶ࡿᚓࡿ
ࡇ࡜ࠊ࠾ࡼࡧࠊࡑࡢሙྜ࡛ࡶࠊᩥᏐ㏻ࡾࡢࢮࣟⅬ᣺ື⤖ྜ㛗 U ࡟㛵ࡋ࡚ࡣࠊᚑ᮶ࡢᖖ㆑㏻ࡾ U!UH ࡀᡂࡾ❧ࡘࡇ࡜ࢆ♧ࡍࡇ࡜ࡀฟ᮶ࡓࠋ
 ᐇ㦂࡛ⰾ㤶⎔࡟ࡘ࠸ࡓ &+ ⤖ྜ㛗࡜ &' ⤖ྜ㛗ࡀྠࡌ㛗ࡉ࡟࡞ࡿ⌮⏤ ㏻ᖖࠊ᣺ື࣏ࢸࣥࢩࣕࣝࡢ㠀ㄪ࿴ᛶࡢࡓࡵ࡟ࠊ&௅+ ࡢ⤖ྜ㛗 U &௅+ ࡣࠊ&௅' ࡢ⤖ྜ㛗 U &௅' ࡼࡾ㛗ࡃ࡞ࡿࠋࡇࢀ࡟཯ࡋ࡚ࠊ࣋ࣥࢮࣥࡢᅇ㌿ᐃᩘ࠿ࡽồࡵࡓᐇ㦂್   ࡛ࡣ UHII &௅+  # UHII &௅' ࡛࠶ࡗࡓࠋ࣋ࣥࢮࣥࡢ  ḟඖࡢ 3(6 ࢆ DE LQLWLR ศᏊ㌶㐨ἲ࡛ồࡵࡿࡇ࡜ࡣ୙ྍ⬟࡞ࡢ࡛ࠊ࣋ࣥࢮࣥࢆ௬᝿ⓗ࡞┤⥺  ཎᏊศᏊ>&+@௅>&@௅>+@ 䛸ぢ❧࡚࡚ࠊ&௅+ ⤖ྜ࡟㛵ࡍࡿࠊఙ⦰᣺ື䠄LVWU䠅ࠊ㠃እኚゅ᣺ື䠄LA䠅࠾ࡼࡧ㠃ෆኚゅ᣺ື䠄L‫ۅ‬䠅ࢆ⪃࠼ࡿࡇ࡜࡟ࡋࡓࠋ
LVWU ࡛ࡣఙ⦰᣺ືࡢ࣏ࢸࣥࢩࣕࣝࡢ㠀ㄪ࿴ᛶࡢࡓࡵ࡟ࠊ
ᖖ㆑㏻ࡾ &௅+ ⤖ྜࡢ᪉ࡀ &௅' ⤖ྜࡼࡾ㛗ࡃ࡞ࡿࡀࠊ
LA࡜ L‫ࡣ࡛ۅ‬䚸&௅+ ⤖ྜࡢᖹᆒኚ఩ゅᗘࡢ᪉ࡀ &௅' ⤖ྜࡢࡑࢀࡼࡾ኱ࡁ࠸ࡢ࡛ࠊD ㍈࡬ࡢᢞᙳ㛗ࡣ㏫࡟▷ࡃ࡞ࡿࠋ୧⪅ࡀ࡯ࡰ࢟ࣕࣥࢭࣝࡋ࡚ࠊ୧⪅ࡢᕪࡣc ࡜࡞ࡾࠊUHII &௅+ #UHII &௅'  ࡜࡞ࡿ⌮⏤ࢆ᫂ࡽ࠿࡟ࡋࡓ  ࠋ
࣋ࣥࢮࣥࡣࠊ㦵᱁Ⅳ⣲ࡢ VS ΰᡂࡢࡓࡵᖹ㠃ศᏊࡢ඾ᆺ࡜ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡇࡢィ⟬࡟ࡼࡿ࡜ &௅+ ⤖ྜࡢ & ⎔㠃࡬ࡢᖹᆒᢞᙳゅࡀ⣙  ᗘ࡞ࡢ࡛ࠊ࣋ࣥࢮࣥࡢ᣺ືᖹᆒᵓ㐀࡜ࡋ࡚ࡣࠊ+ ࡀ & ⎔㠃ࡢୖࠊࡲࡓࡣୗ
࡟఩⨨ࡍࡿ SODQDU EXW QRQIODW ࡞ᵓ㐀࡟ᡂࡗ࡚࠸ࡿࡇ࡜࡟࡞ࡿࠋᐃㄝ࡟཯ࡍࡿ⤖ㄽ࡛ࡣ࠶ࡿࡀࠊ័ᛶ⬟⋡Ḟᦆࡢ್࡜㟁Ꮚ⥺ᅇᢡࡢࢹ࣮ࢱ࠿ࡽࠊSODQDUEXWQRQIODW ࡞ᵓ㐀ࡢṇࡋࡉࢆド᫂ࡍࡿࡇ࡜ࡀฟ᮶ࡓ  ࠋㄽᩥᑂᰝࡢẁ㝵࡛ࣞࣇ࢙࣮ࣜ࡜኱ㄽத࡟࡞ࡗࡓࡀࠊᐇ㦂࡛ࡶ⌮ㄽィ⟬࡛ࡶࡑࢀࡀṇࡋ࠸ࡇ࡜ࢆㄝ᫂ࡋ࡚ࠊ⣡ᚓࡋ࡚㡬࠸ࡓࠋ ኱᣺ᖜኚゅ᣺ືࡢィ⟬ศᏊศගᏛ
ᡃࠎࡣࠊDE LQLWLR ศᏊ㌶㐨ἲ࡟ᕤኵࢆจࡽࡋ࡚ %DXVFKOLFKHU ᫬௦࡟㍑࡭࡚ 䡚 ᱆ࡶィ⟬⢭ᗘࢆୖࡆࠊ⢭⦓࡞ᐇ㦂ศගᏛ࡟ࡶຎࡽࡠ༑ศ࡞⢭ᗘ㸦ศගᏛ⢭ᗘ㸸ㄗᕪFP㻌 䝺䝧䝹䠅ࢆ㄂ࡿ DE LQLWLR ศᏊ㌶㐨ἲィ⟬ࢆ⾜࠺ࡇ࡜ࢆྍ⬟࡟ࡋࡓࠋࡇ࠺ࡋ࡚ồࡵࡓ 3(6 ࡟ᇶ࡙࠸࡚ࠊ᣺ືᅇ㌿ࡢ 6FKU|GLQJHU ᪉⛬ᘧࢆゎࡁࠊࡑࡢἼື㛵ᩘࡢᮇᚅ್࡜ࡋ࡚ U ᵓ㐀㸦᣺ືᅇ㌿ࢆྵࢇࡔᖹᆒ⤖ྜ㛗ࡸ⤖ྜゅ㸧ࢆ⟬ฟࡍࡿࡇ࡜࡟ᡂຌࡋࠊᐇ㦂ศᏊศගᏛ࡛
ࡣᚓࡽࢀ࡞࠸ᵝࠎ࡞▱ぢࢆᥦ౪ࡋ࡚ࡁࡓࠋᪧࣃࣛࢲ࢖࣒ࢆそࡋ࡚ࠊ┤⥺ศᏊࡢ᣺ືᅇ㌿ᖹᆒᵓ㐀ࡣࠕ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿࠖ࡜࠸࠺᪂ࡋ࠸ࣃࣛࢲ࢖࣒ࢆᡴࡕ❧࡚ࡿ࡭ࡃᣮᡓࡣ⥆࠸࡚࠸ࡿࠋ
 ཯ᛂ࡟࠾ࡅࡿືⓗ㐣⛬ࡢゎᯒ 㔜㡯㓟⣲࡟ࡼࡿ㓟໬཯ᛂ✵Ẽ୰ࡢ㓟⣲ศᏊࡣࠊ 㔜㡯 2 ࡛࠶ࡿࡀࠊ
࢔ࢫࢥࣝࣅࣥ㓟࢔ࢽ࢜ࣥ ࣅࢱ࣑ࣥ & ࡢ࢔ࢽ࢜ࣥ ࡜ࡢ཯ᛂ࡛ࡣࠊ 㔜㡯 2 ࡛ࡶࠊ 㔜㡯 2 ࡛ࡶྠࡌ⏕ᡂ≀ࡀᚓࡽࢀࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋࡲࡓࠊ6F2 ࡢ཯ᛂࡢゎᯒ࠿ࡽࠊ 㔜㡯 2 ࡜ࡢ཯ᛂ࡛ࡶࠊ཯ᛂࡢ㏵୰࡛ 6F ࠿ࡽ 2 ࡬ࡢ  㟁Ꮚ⛣⾜ࡀ㉳ࡁࡿࡓࡵࠊ⤖ᯝ࡜ࡋ࡚ࠊ 㔜㡯 2 ࡜ࡢ཯ᛂ࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗ࡚ࡁࡓࠋ୍⯡໬ࡍࢀࡤࠊ㟁Ꮚ౪୚ᛶࡢ㧗࠸ศᏊ࡜ 2 ࡜ࡢ཯ᛂ࡛ࡣࠊ཯ᛂࡢ㏵୰࡛㟁Ⲵ⛣ືࡀ㉳ࡇࡿࡓࡵ࡟ࠊ 㔜㡯 2 ࡛ࡶࠊ 㔜㡯 2 ࡛ࡶ 2 㒊ศࡢ୙ᑐࢫࣆࣥࡀ  ಶᾘ࠼࡚  㔜㡯 2 ࡜ࡋ࡚཯ᛂࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗ࡚ࡁࡓࠋከ㓄⨨ࡢ 0&6&) ィ⟬࡞ࡢ࡛཰᮰ࡋ࡟ࡃ࠸ࡀࠊ࡯ࡰ ࡢィ⟬ࢆ⤊- 285 -

࠼ࡿࡇ࡜ࡀ࡛ࡁࡓࠋィ⟬ࡣḟᖺᗘ࡟ᘬࡁ⥆࠸࡚⾜࠺ࠋ Ⓨ⾲ᐇ⦼ㄽᩥ࠾ࡼࡧᏛ఍Ⓨ⾲>ㄽᩥ@ ‫ ۻ‬0RUHHYLGHQFHIRUEHQWURYLEUDWLRQDOO\DYHUDJHGVWUXFWXUHVRIOLQHDUWULDWRPLFPROHFXOHV7KHQRQ]HUED[LV
FRPSRQHQWRIWKHGLSROHPRPHQWDQGWKHUJVWUXFWXUHLQHOHFWURQGLIIUDFWLRQ7VXQHR+LUDQR8PSHL1DJDVKLPD
0DVDDNL%DED-0RO6SHFWURVF369   ‫ ۻ‬7KHZHOOHVWDEOLVKHGUHODWLRQU!UHKROGVDOZD\V"7VXQHR+LUDQR8PSHL1DJDVKLPD0DVDDNL%DED-0RO
6WUXFW1227  3) ‫ ۻ‬Ro-vibrationally averaged molecular structure of benzene: Why almost the same bond lengths
are observed for the C̾H and C̾D bonds?, 7VXQHR+LUDQR8PSHL1DJDVKLPD0DVDDNL%DED-0RO6WUXFWLQSUHVV   ‫ ۻ‬5RYLEUDWLRQDOO\DYHUDJHGVWUXFWXUHWREHREVHUYHGIRUDOLQHDUPROHFXOH  7KHFDVHVRI+&2+&1DQG&
7VXQHR+LUDQR8PSHL1DJDVKLPD3HU-HQVHQ  -0ROHFXODU6SHFWURVF ᢞ✏‽ഛ୰.
5) ‫ ۻ‬9LEUDWLRQDOO\DYHUDJHGVWUXFWXUHDQGIUHTXHQFLHVRI ;H+;H $FRPSXWDWLRQDOPROHFXODUVSHFWURVFRS\VWXG\
7VXQHR+LUDQR8PSHL1DJDVKLPD0DVDDNL%DED  -0ROHFXODU6SHFWURVF ᢞ✏‽ഛ୰.
>Ꮫ఍Ⓨ⾲@ ‫ ۻ‬ᖹ㔝ࠊ㛗ᔱࠊ㤿ሙࠊࠕ࣋ࣥࢮࣥཬࡧࡑࡢ㔜Ỉ⣲໬≀ࡢ᣺ືᖹᆒᵓ㐀㸸 &௅+ ࡜ &௅' ࡢ⤖ྜ㛗ࡣ࡯ࡰ➼ࡋ࠸ࠋ, ᐇ㦂ⓗ᳨ド࡜ㄝ᫂ࠖ ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍⛅Ꮨᖺ఍ࠊ2   㮵ඣᓥ ‫ ۻ‬ᖹ㔝ࠊ㛗ᔱࠊ㤿ሙࠊࠕ࣋ࣥࢮࣥཬࡧࡑࡢ㔜Ỉ⣲໬≀ࡢ᣺ືᖹᆒᵓ㐀㸸 &௅+ ࡜ &௅' ࡢ⤖ྜ㛗ࡣ࡯ࡰ➼
ࡋ࠸ࠋ,, ィ⟬ศᏊศගᏛ࡟ࡼࡿ⪃ᐹࠖ ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍⛅Ꮨᖺ఍ࠊ2   㮵ඣᓥ ‫ ۻ‬5RYLEUDWLRQDOO\DYHUDJHGVWUXFWXUHRIEHQ]HQH$FRPSXWDWLRQDOPROHFXODUVSHFWURVFRS\VWXG\0DVDDNL%DED
8PSHL1DJDVKLPD7VXQHR+LUDQRWK$VLDQ:RUNVKRSIRU0ROHFXODU6SHFWURVFRS\%   ‫ ۻ‬9LEUDWLRQDOO\ DYHUDJHG VWUXFWXUH DQG IUHTXHQFLHV RI ;H+;H 㸸 $ FRPSXWDWLRQDO PROHFXODU VSHFWURVFRS\VWXG\0DVDDNL%DED8PSHL1DJDVKLPD7VXQHR+LUDQRWK$VLDQ:RUNVKRSIRU0ROHFXODU6SHFWURVFRS\$  ‫ ۻ‬ᖹ㔝ࠊ㛗ᔱࠊ㤿ሙࠊࠕィ⟬ศᏊศගᏛ㸸ࣃࣛࢲ࢖࣒ࢩࣇࢺ࡬ࡢᣮᡓࠖ ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍᫓Ꮨᖺ
఍ࠊ2   ᮾி㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋཧ⪃ᩥ⊩>@ ,%RKiþHN'3DSRXãHNâ3LFN9âSLUNR&KHP3K\V/HWW42  
>@ 7+LUDQRDQG81DJDVKLPD-0RO6SHFWURVF314  >@ 7VXQHR+LUDQR8PSHL1DJDVKLPDDQG3HU-HQVHQ-0RO6SHFWURVF343  >@ 7VXQHR+LUDQR8PSHL1DJDVKLPD0DVDDNL%DED-RI0RO6SHFWURVF369  >@ 7VXQHR+LUDQR8PSHL1DJDVKLPD0DVDDNL%DED-0RO6WUXFW1227,  >@ 7VXQHR+LUDQR8PSHL1DJDVKLPD0DVDDNL%DED-0RO6WUXFWLQSULQW  >@ 6DFKL .XQLVKLJH 7RVKLKDUX .DWRUL 0DVDDNL %DED 0DVDND]X 1DNDMLPD <DVXNL (QGR - &KHP 3K\V 143  - 286 -

࣯ྖ෾ੵ๑ͶΓΖਫ਼ର෾ࢢ͹‫ـ‬૮෾մգఖͶ‫ͤؖ‬Ζ‫ڂݜ‬
0DVV6SHFWURPHWULF&KDUDFWHUL]DWLRQRI*DV3KDVH'LVVRFLDWLRQ
3URFHVVRI%LRPROHFXOHVὸᕝ ኱ᶞ㸦⏘ᴗᢏ⾡⥲ྜ◊✲ᡤ㸧◊✲┠ⓗࠊෆᐜ
࢚ࣞࢡࢺࣟࢫࣉ࣮ࣞ࢖࢜ࣥ໬㉁㔞ศᯒἲࡢ㛤Ⓨ࡟ࡼࡾࠊከ✀ከᵝ࡞⏕యศᏊࢆ㉁㔞ศᯒ࡛ศᯒࡍ

ࡿࡇ࡜ࡀྍ⬟࡜࡞ࡾࠊ⏕యศᏊࡢ⥙⨶ⓗゎᯒࢆᇶ┙࡜ࡍࡿ࢔ࣉࣜࢣ࣮ࢩࣙࣥࡀᛴ㏿࡟ᗈࡲࡗ࡚࠸ࡿࠋ
ࡇࢀࡽࡢ࢔ࣉࣜࢣ࣮ࢩࣙࣥࡣ⏕యศᏊࢆศゎࡉࡏࡎ࡟㉁㔞ศᯒィ᳨࡛ฟࡍࡿࡇ࡜ࢆ๓ᥦ࡜ࡋ࡚ࠊศ
ᯒᡭἲࡀᵓ⠏ࡉࢀ࡚࠸ࡿࡀࠊ≉࡟௦ㅰ≀࡞࡝⏕యෆࡢపศᏊ໬ྜ≀ࡢศᯒ࡟࠾࠸࡚ࠊศゎ⏕ᡂ≀ࡀ⏕ࡌࡿࡇ࡜ࡶሗ࿌ࡉࢀ࡚࠸ࡿࠋ㔜せ࡞౛࡜ࡋ࡚ࠊ⏕యࡢࢩࢢࢼࣝఏ㐩࡟㛵㐃ࡍࡿࣇ࢙ࢿࢳࣝ࢔࣑ࣥ
㢮ࠊࢺࣜࣉࢱ࣑ࣥ㢮ࡸࠊ࢚ࢿࣝࢠ࣮௦ㅰ࡟㛵㐃ࡍࡿ $73 ࡞࡝࡟ࡘ࠸࡚㉁㔞ศᯒἲ࡟ࡼࡿศᯒࡢ㝿࡟ศゎ཯ᛂࡀㄏ㉳ࡉࢀࠊࣇࣛࢢ࣓ࣥࢺ࢖࢜ࣥ࡜ࡋ᳨࡚ฟࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊࡇ
ࡢ㉁㔞ศᯒἲ࡟࠾ࡅࡿ⏕యศᏊࡢศᯒࡢ㝿࡟㉳ࡇࡿ௦ㅰ≀ࡢゎ㞳ࡢຠ⋡ࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ண ࡋࠊࡼࡾຠ⋡ⓗ࡟㉁㔞ศᯒἲࢆ⏝࠸ࡿࡓࡵࡢᇶ┙ᢏ⾡ࢆᵓ⠏ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ



ィ⟬᪉ἲ
⌮ㄽィ⟬ࡣ *DXVVLDQ  ࣉࣟࢢ࣒ࣛ࡟ࡼࡿᐦᗘỗ㛵ᩘἲ࡟ࡼࡾ⾜ࡗࡓࠋࡑࢀࡒࢀࡢ⏕యศᏊ࡟ࡘ࠸࡚ࠊ

%/<3* GS %/<3' %- * GS Ȧ%;'* GS ࠊ0;'* GS ࢆ⏝࠸ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ඲࡚ࡢ᭱㐺໬ᵓ㐀࡟ࡘ࠸࡚᣺ືゎᯒࢆ⾜࠸ࠊᏳᐃᵓ㐀࠾ࡼࡧ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡉࡽ࡟㑄⛣≧ែࢆጞⅬ࡜ࡍࡿ ,5& ࢆ⏝࠸཯ᛂゎᯒࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ㑄⛣≧ែࠊጞ≧ែࠊ࠾ࡼࡧ⤊≧ែࡼࡾࠊ55.0 ⌮ㄽࢆ⏝࠸࡚཯ᛂ㏿ᗘᐃᩘࢆ⟬ฟࡋࡓࠋ



◊✲ᡂᯝ
㉁㔞ศᯒࡢ㝿࡟ศゎࢆཷࡅࡎ࡟⏕ࡁṧࡿ⏕యศᏊࡢ๭ྜࢆ 6XUYLYDO<LHOG㸦6<㸧࡜ࡋ࡚ᐃ⩏ࡍࡿࠋࡇࡇ࡛ࠊ

6< ࡢィ⟬್㸦6<FDOF㸧ࡣࠊ⏕యศᏊࡢෆ㒊࢚ࢿࣝࢠ࣮3 (  ศゎ㏿ᗘᐃᩘ N ( ࠊ᫬ᐃᩘȫ࡟ࡼࡗ࡚ࠊᘧ㸦㸯㸧࡟ࡼࡾᘧ㸦㸧࡟ࡼࡾồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
ஶࡿࢅࢉࢇ࢒ࢉ = ‫׬‬૙ ࡼ(ࡱ) ࢋି࢑(ࡱ)࣎ ࢊࡱ     ࡇࡇ࡛ࠊ⏕యศᏊࡢෆ㒊࢚ࢿࣝࢠ࣮3 ( ࡣࠊ(GZLQ'H3DXZ ࡽࡀᥦ᱌ࡋࡓ

ᗘィ࢖࢜ࣥࠕ࣋ࣥࢪࣝࣆࣜࢪࢽ

࣒࢘ࠖࢆ⏝࠸ࡓ࢖࢜ࣥࡢෆ㒊࢚ࢿࣝࢠ࣮ホ౯ἲ࡟ࡼࡗ࡚ࠊ୰ኸ್ N-PRO±ࠊ್༙ᖜ N-PRO± ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ᫬ᐃᩘȫࡣ᪤ሗ࡟ᇶ࡙ࡁ ± V ࡜௬ᐃࡋࡓࠋ ཯ᛂ㏿ᗘᐃᩘ N ( ࡣࠊᐦᗘỗ㛵ᩘ⌮ㄽ࡜
55.0 ⌮ㄽࢆ⏝࠸࡚ồࡵࡓࠋᚓࡽࢀࡓ 6<FDFO ࢆࠊᘧ㸦㸧࡛ồࡵࡓ 6< ࡢᐇ㦂್㸦6<H[S㸧࡜ẚ㍑ࡋࡓࠋࡇࡇ࡛ࠊ
⏕యศᏊࢆศᯒࡋࡓ㝿࡟ᚓࡽࢀࡓ࣐ࢫࢫ࣌ࢡࢺࣝ࡟⌧ࢀࡓศゎࢆཷࡅ࡞࠿ࡗࡓ⏕యศᏊࡢࢩࢢࢼࣝࢆࡵࡹశ ࠊศゎࢆཷࡅ࡚ࣇࣛࢢ࣓ࣥࢺ࢖࢜ࣥ࡜ࡋ᳨࡚ฟࡉࢀࡓࢩࢢࢼࣝࢆ࡛ࡵࡲశ ࡜ࡋࡓࠋ- 287 -

ࡿࢅࢋ࢞࢖ = ࡵࡵࡹశࡹశ ାࡵࡲశ

ᘧ㸦㸧࡛ᚓࡽࢀࡓ 6<FDOF ࢆᶓ㍈࡟ࠊᘧ㸦㸧࡛ᚓࡽࢀࡓ 6<H[S ࢆ⦪㍈࡟ࣉࣟࢵࢺࡋࡓᅗࢆ )LJXUH  ࡟♧ࡍࠋ
)LJXUH DG ࡣ ࡑ ࢀ ࡒ ࢀ ࠊ %/<3* GS  %/<3' %- * GS  0;'* GS ࠊ
Ȧ%;'* GS ࡟ࡼࡗ࡚ồࡵࡓ཯ᛂ㏿ᗘᐃᩘ N ( ࢆ⏝࠸࡚ 6<FDOF ࢆ⟬ฟࡋࡓ⤖ᯝ࡛࠶ࡿࠋ)LJXUH D ࡣ
%/<3* GS ࢆ⏝࠸࡚ 6<FDOF ࢆồࡵࡓ⤖ᯝ࡛࠶ࡿࡀࠊ6<H[S ࡜ࡢ୍⮴ᗘࡣపࡃࠊศゎ཯ᛂࢆṇ☜࡟ホ౯࡛ࡁ࡚࠸࡞࠸ࠋࡇࢀࡣ %/<3* GS ࡀศゎ཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆ㐣ᑠホ౯ࡍࡿഴྥ࡟࠶ࡿࡓࡵ
࡛࠶ࡿࠋ%/<3 ࡟ࣟࣥࢻࣥศᩓຊࢆຍ࠼ࡿࡇ࡜࡛ࠊ6<FDOF ࡜ 6<H[S ࡢ୍⮴ᗘࡢᨵၿࡀㄆࡵࡽࢀࡿ㸦)LJXUHE㸧ࠋ୍᪉ࠊ)LJXUHFG ࡟♧ࡋࡓࡼ࠺࡟ࠊȦ%;'* GS ࠊ0;'* GS ࡟ࡼࡾᚓࡽࢀࡓ 6<FDOF
ࡣࠊ6<H[S ࡜ࡼࡃ୍⮴ࡍࡿࠋȦ%;'* GS ࠊ0;'* GS ࢆ⏝࠸ࡿࡇ࡜࡛ࠊ㉁㔞ศᯒἲ࡟࠾ࡅࡿ⏕యศᏊࡢẼ┦ศゎ཯ᛂ࡟࡟ࡘ࠸࡚ṇ☜࡞᝟ሗࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

ࠊᘧ㸦㸰㸧࡟ࡼࡾồࡵࡓ
Figure 16<FDOF ࡜ 6<H[S ࡢ㛵ಀࠋ6<FDOF ࡜ 6<H[S ࡣࡑࢀࡒࢀᘧ㸦㸯㸧

4Ⓨ⾲ࠊฟ∧ᐇ⦼

‫ۻ‬1.. D. Asakawa, J. Am. Soc. Mass Spectrom. 31, 1918-1926 (2020)‫ۻ‬2.. D. Asakawa, H. Mizuno, E. Sugiyama, K. Todoroki, Anal. Chem. 92, 12033-12039 (2020)‫ۻ‬3.. D. Asakawa, H. Takahashi, S. Iwamoto, K. Tanaka, Anal. Chem. 92, 15773-15780 (2020)‫ۻ‬4.. D. Asakawa, H. Mizuno, E. Sugiyama, K. Todoroki, Analyst, 146, 2292-2300 (2021)‫ۻ‬5.. D. Asakawa, J. Mass Spectrom. 55, e4530, (2021)- 288 -











The improvement of solvation model by machine learning and theapplication to the acid dissociation constantvN }i, uÝ ia, tÎ `, N OÞ­iÒß
1¦ª£¢Vq

Zm\|!½
Å&À¾¬+¹Ó¾®Zm ')LFW!¡ Ê,)Hh!Z m

°Ê¹)!

rp¡¢ja@7C"¯yF128×[Y §«*Pº¢ja@7C!H

Conductor-like Polarizable Continuum Model (C-PCM)  ld)*"j_ÂÕ+%É³RK ÆYk+Ì´jÆÏ!ÖÕ¢¤MS¡+¿Ç)!"ja.:C/G®X!Ü X

%!(jÙe"ÂÕQg!;A?G5+$

±²^!'ËYÈÏ!¤MS¡+¿Ç



¸Õ°

)Ãw

i xy"ja@7CU!-=DG6C-PCM µ~*ËYÈ!

¾®Ãw J )zØ+¼©%(@7C#\)+xy!¦ª"¸Õ°!/<3.:C/G!
¾®Ãw
o!®X

2

_

Æ!ËYÈ ¥£Ãw!»c!o ]¶ÁHÍ½Ô"=D8E!/<2.:C/G!bÚ+½){» (xyQÑ#!ÄÚ¦ª¾®Æ!YkÈ¾®Ãw!Ï!ÐT+s$YkÈ+>08Cº)¦ª" OH f

! CHO f!n¶f!YÛ 44 ¨!ËYÈ+! -4898BC

I)·Sº +¡)ÍZÕ!pV )Z^ 122 ¨ rja9!Õ¸ 0  +1 !/<3.:C/G+ UB3LYP/6-31+G(d, p) $ C-PCM '(¾®

ÍZ.:C/G!¾® ΔG pV ΔG +>$Ãw δ = ΔG ΔG +Ç!Ykº



calc

expt

expt

calc

E0)/

!¾®" Gaussian16 +¡p¹

3

¦ª3;

8

44 ¨!Ro!";+Á)$xy ¡j 05GCj!ja.:C/

G!7G548!²;+* 1B

*X: pV¾®!=P. *K!WE , , HH)7!%!)(a) 5(/G(b) ·SºÃw+¼©%(*+J1!ja.:C/G- 289 -

!ja.:CRMSE "J 05GCj** 2.0, 2.8 kcal/mol (Jkcal/mol !²;

·S E G=BE8"[YL2¶+% K

¾®2G+¡ÍZÕ Q¡²;+* 2* 2: ÍZÕ (kcal/mol'(** 0.84, 0.82
)*_

B

4®)!¾®pV!=P(a)J , (b)·S E G=BE8 ')Ã

w!J1L δ pÓ! δ !w"ΔG !J1Ãw r|)$IJ )K )%calc )* 2

δ +IN

ΔG !J!¾®pV!6.*+B¾®Ãw" RMSE ox

5.7 kcal/mol i J!{»2 5$§M*·Sº+¡ΔG !¾®Ãw δ +)/Y:

²;RMSE  3.5(4) kcal/mol (Ãw+ 4 !?-)
1Ãw i #cΔG

ox

$µ

$1* +N + %(*){»2

AºpF"Lo1.

T

 ΔG !7 =Jsolv

 zØ+$ HOMOLUMO +µ~ Ykº " *))¡Ykº "ËYÈ

4oxUf; N O, “ÍZSÕ®X

HOMOLUMOÐ )& +µ~

B'*)Ãw!<mG+¡»c½:”, D 15 )YkCm

LO

5

X@pF"Lo1.

K. Tosaka, Y. Osaki, Y. Shigeta, and T. Matsui, “$ 6HPLHPSLULFDO ,PSURYHPHQW RI 6ROYHQW 0RGHO E\ 0DFKLQH/HDUQLQJ0HWKRG”, to be submitted.

2.

Y. Osaki, T. Fujita, K. Terayama, M. Sumita, K. Morihashi, and T. Matsui, “A simple method for parameter
determination on the range separation for long-range corrected DFT”, to be submitted.

3.

T. Matsui, Y. Tanaka, T. Otsuka, M. Sumita, H. Izawa, and K. Morihashi, “A theoretical study on molecular clusterof citric acid”, to be submitted.

- 290 -







Statistical mechanics analysis for biomolecular functions #""$

1 
¬ËÊÝ! _ ½Æhx§Ì/ZÕwjxÆ¸ *#ewihx:KNTW:PU»'m./Ö­£ Z jxV¨¤Ò² ,£/Â¥£Ðg §Ì®§Å/(°µÉÎ,>UG9ÍÐtj [¡ Ö­£ve/À´e²§Ì Ö­/¯®°µ/Â2 !
&£ÉÎ,>UG9ÍÐtj [¡ Ö­Ï%,ew:KNTW:PU 3D-

RISM §Ì *#¾·§Ì »'m. Ö­/Âew:KNTW:PU¾·§Ì/»'m.>UG9Í Ð[¡/Â ªVÞ\Ôuxß*-,!Linear response path following(LRPF)p"-, !R6UC^¿!1UJABY,(¥y R6UC¼m*,Ðtj!ÇÏ) £ n&-,14U)|ew ÉÎ,Ðtj$ Ó©!ÚÊÝ!-+R6UC ^¿V/ 3D-RISM §Ì/©¸d,¶Xk§®Ðtj[¡/z¦ ,À ÑÆ¸(LRPF/3D-RISM ) Ö­/Â
&£ve/À´e²§Ì Ö­!-&Ö­  sp-3D-RISM §Ì/£ bÛw±iØ.,Ü~Ã£vqÁ«FS8W£i®{Ø*,£vq?1DKA9<§Ì Ö­/Â3 
&LRPF/3D-RISM Ï%,! /OH7@U }¹tÒ²Ó©¼5 

LRPF/3D-RISM BQ;29BRW  4  300ns:KNTW:PU×btÒ²fÙ/& :KNTWBX¢® MD :KNTW:PU!1s:KNTW:PU×bÐtj Ä+- LRPF/3D-RISM  +-BQ;29BRW!aÂ°µ
so-,OH7@U }¹ÉÎt fÒ²Þ:WB `a®0UI3WSC,ß/c¦-+ ¼!]r &&£v³* Î-,>UG9Í Ðtj M5E=L/Èº§Å,l9/1 ,*sp-3D-RISM §Ì*,Ûwe/%£vZ Û:±i Ü~ÃÁ« FS8WJI1SØ,°µÏ%,Ü~ÃÁ« FS8W§Ì/3   S3Ó©¼ Å)*£v Ûwe Á« FS8WJI1S/ 2  /,tj, . 1 ¯!£Í£v 0© c2*,£vqÐ cD2 ¯!Û:±Â" Ûwe7q,8!~Ã.$ yj/?Ü~Ã.$ 0 ®yj/+"8!eÛ:- 291 -

*,Ü~Ã.$ £vq/?Ü~Ã.$ yj/+]r  S3!¶ 2
1

Y*uY ¶ ¼-& ew:KNTW:PU°µso-,*£v c

6 FS8W ,|, '+ &Ûweew£v ,£vqÐ

sp-3D-RISM §Ì Ö­Â!G&5WFS(4>/©G+Z ;®£Í £vq?1DK9<Ø,Æ¸/Â£Å?
1DK9< ×5Ò£Í=#s

1B{eÛ:{ Ò-® 3 *e!Ø,Èº+-C± FS8W 7q! 1W?SG@WC!¶X£vq:2Sb cD

GBWC!E<FA&-- ,À+-,
]"!-+ §Ì/ÕwjxÆ¸»'m.,*R0R< A93$©,[y
,

4 





5

1. "A computational method to simulate global conformational changes of proteins induced by cosolvent",
Shoichi Tanimoto, Koichi Tamura, Shigehiko Hayashi, Norio Yoshida, Haruyuki Nakano, J. Comput.
Chem., (2021) 42, 552-563
2.  "Solvation dynamics in electronically polarizable solvents: Theoretical treatment using solventpolarizable three-dimensional reference interaction-site model theory combined with time-dependent
density functional theory", Tsuyoshi Yamaguchi, Norio Yoshida, J. Chem. Phys., (2021) 154, 044504
3. "Nonequilibrium free-energy profile of charge-transfer reaction in polarizable solvent studied using
solvent-polarizable three-dimensional reference interaction-site model theory", Tsuyoshi Yamaguchi,
Norio Yoshida, J. Chem. Phys., (2020) 153, 034502 (doi.org/10.1063/5.0013083)
4. "Residue-Specific Binding Mechanisms of Thioflavin T to a Surface of Flat β-Sheets within a Peptide
Self-Assembly Mimic", Sae Namioka, Norio Yoshida, Hiroyuki Konno, and Koki Makabe, Biochemistry,(2020) 59, 2782-2787 (doi.org/10.1021/acs.biochem.0c00280)- 292 - π 



Design and synthesis of novel π-electronic ions which form functional
assemblies
9
9

F/92!4-M6(4#9-0NCJ)"DQ.)9=*5O39,L'

GRAP8?S
1 >@<;
 ]?BHTÝ



p

l¥

0ÏÙ{¼5«)$¡±

Òk#G@7S3Ù{¼%$Ð.Ù{¨#b|**"Øur
Øur

#b|¦$®©

^§$®©

32 #Ù{¼

y

2

tÁ1e$#¶Øu^%q¯"s

32$<PUK%**"Ç  Ù{¼$u5}©&6I9S¹Ù{¼ÞQCKDUß2AJROPA=HSM8½Ó^%Òk"6I9S Q
CKDU±6I9S[u^5 2NIFH l«20­\¯"ÙÃ5d  Ù{¼ +"Øu^$tÁ2"4QCKDUT6I9ST:E9S$  µ$¾+

u4#/1z"Ù{¼79SL6$  }©79SÕ²Y_«5Ü`**"Øu^$» tÁ235(* ¤¢X$79SL6¿Îj{>P¢XÕ²"!$ #Ö$Ù{Tf¦.Øu^ s^§"!$®©5Æi $  %¸
À  3& 11ÉÈ! 1$Øu^5»2$%~%" ³·ËÛ%6I9S
¹Ù{¼5%, **"Ç  Ù{¼$u5Ä Ù{Tf¦"!5Êc20#79SÕ²Y_«5%, 2j{Õ²Y_«5l«j{Øu^$Âw"»5,

2 >@&1KB&1
 VÑ$³·# 2Èº$}#% *DXVVLDQ/' *$0(66 5l«3 >@$+
 µ$Ù{¼$Ð.Ù{Tf¦#Ö2ªÌÈº }×$u.¦Êc 003GUD5
x° ³·5Ô>±@ ZW#ËÛ#}³·HJF;$Va52¨.Ù{¨5m£Ù{¼ -NIU;"Ù{¨5l«Á$oÅ Ï¡±3 2 #£Ù{¼%$Ð#ÍvgÚ hÚ¬"2Ù{¨5´0Òk"Ù{¼ $[u#/2Çnl$Ð$  32£Ù{¼tF$NIFH#Ù{`7"JRUPQ5!-0#I½¿uU /'6;CKDU5¾+fÇÙ{¼Þ)LJDß$u Çnl$Ð# 2Ù{¦ /'Á$Z@5Ä6I9S¹Ù{¼$&Ü^
2AJROPA=HSIQSA6S5mCWUu2 Ù{¼$?6#s<Ú¨  .Q5-AJROPS A6 JSÞß5uÞ)LJEß')7 Èº 0J,rÙS P%  %Ù{`7"hÚ Ù{a"gÚ5-- 293 -´/3Þ)LJFßV?&$"¿r#( j{$ & $-0#  j{$ 
1±+āāā1 I½¿u#/Q¨#lV ā& 5 Þ)LJG ßā&¿$ncÞF cß?+#l$2

 5@0 #Þ)LJG WßF S<Ð$ +LUVKIHOG
XÚZD 0 $$JRUPQ% & $  .Q
±BDF S<5 F c?+#q=2 ā& Õ$JRUP

& $  .Qkj$ &±+²Y_« ´/3ā& $NIFH$Õ#%0j{Õ'$#]%<SHj{bj Þ)02ß5« P U
jZZDÞ('$ß#/^T5G[}×#JRUPQ& $Õ#q¯"j>'$6 2

j


0#
"¿)$fP8#/Q¨#lV 0 & )$ÝhÙ{S) iM,*jfN4#/YN
3*F c?+#K & $Çnl$# 2ÙÃeg ´/30f_ÍÙ)$« >@32  

4  D  =* %-
,);&2$ E    ?   @  F     < ;       5 1
?%/<3/DQ/'=@ G  ā& "3(+:?>4
.# ;&7'    ;&9 &  68;&0! /@:IE

WHRL< 5B} 9E LV &R2fÂ;[uÁ52s<Ú1Ù{¼$Çnl$r050
)RUXP  762<RNRKDPD    AÞ³·ËÛ#ÖÑ23[®X  Þ9S7SÔ ß$  5\dß



H%7

>@6RQJ6*XR1/L;/L*+DNHWD<7HO\FKNR06X-/\X34LX=)DQJ+3HQJ;/L-:X;/L<6X&.RK0-:X-0DHGD+=KDQJ&/X--$P&KHP6RF ± >@0DHGD+ &KHP  ±
>@+DNHWD<.DPDGD.0DHGD+ &KHP3OXV&KHP  ± 
>@6FKPLGW$+HLQULFK%.LUVFKHU*&KDXPRQW$+HQU\0.\ULWVDNDV1+DNHWD<0DHGD+0RELDQ
3,QRUJ&KHP ± 
>@+DNHWD<0L\DVXH0.RED\DVKL<6DWR56KLJHWD<<DVXGD17DPDL10DHGD+ -$P&KHP
6RF ± 
>@1DNDPXUD.6XJLXUD6$UDRND)$\D67DNDQLVKL<:DWDQDEH*6DWR56KLJHWD<0DHGD+ 2UJ/HWW ± 
>@.XQR$0DHGD+ 0ROHFXOHV  
>@+DNHWD<0DHGD+ 0ROHFXOHV  >@*RWRK+1DNDWVXND67DQDND+<DVXGD1+DNHWD<0DHGD++DWDNH\DPD7 $QJHZ&KHP,QW(G± >@<DPDNDGR5.LWDPXUD,+DUD01DJDQR66HNL70DHGD+ &KHP&RPPXQ ± >@.LQRVKLWD7+DNHWD<0DHGD+)XNXKDUD* &KHP6FL ± 
>@)XPRWR1+DNHWD<7DQDND+<DVXGD10DHGD+ 2UJ/HWW ± >@ :op<T&R2f %O¹Ýj{$Ô®)+&0& &KLQSUHVV 
>@.XQR$+LUDWD*7DQDND+.RED\DVKL<<DVXGD10DHGD+&KHP(XU- LQSUHVV- 294 -





In silico design of synthetic oligoamides binding to proteins
+( 2@7 0V Y FV M3S #. &!QP- <6O7U 1K,'ZJ XT H=3R ?
9 <E[) WD>BA\

1 >B;:¢¡ °/ ,Zp/½»&Y !SÐÇcrZÍ ,Ì¶£¦ÀÖ,ÄxV-:HB5Ã¬i/ ,ZpDC<? _²£¦¢ Ò', *DC<?!ª¯±ÅÈ R'ª¯X :HB5Ã¬i,( /· ,ÓÀÖ 
!±ÅÈ Ú 1 ­DC<?k"-,Ow4G71E?/£¦+ª¯X:HB5Ã
°/^,Zp _Yf+«0, -%uÑª¯Xql, 0'0 k"-,:
HB5Ã °/^, 1 ­DC<?/_Y, a,>@>@ xy! -* :HB5Ã¬i¢ -*

1 ­DC<?Ð Þ £¦/u%ÝN ­DC<?  )ßWÆ/st}, /Zpb`r»¨)+¾UÞ¢ -*1 ­DC<?  ):HB5Ã 0'0´Ô/¿Â,/¾U

,'µiS Zpb`r»¨/³%1 ­DC<? u,ßWÆ o/ |,'
ß¢ £¦MÏÙ/ ȕ 1EAË | 1 ­DC<? ßWÆÎpcr»¨),¾U/³

2 >B%/NC%/
2.1. :HB5Ã¬i, N ­DC<? ßWÆ £¦ uØ¡ 0'0 ¬i,  . , N ­DC<? 2 ¥Zpb`r»¨/³st§SÊz/* ,( b¡b¾UZpb`r»¨/³!h 1 ­DC<?v,`n/ &*HQ)) T>@*URPDFV /]»¨/u³%
\Êz! -% £¦ ×Pci ¬Æ)#Îpcr»¨ ¬/e®t»¨!-=J:!MÏst}-,1 ­DC<?  QV /  UXQ ³*->F835>G

506'INÔ¹ ¸ *º,(5F9:GH6/³ )Êz/Á$

*MDM2 ¬i, N ­DC<?/ 10 ¥×½» -*K¼Þ¥

N ­DC<?(N ­DC<?j Zpb`r»¨/³»¨! 500 ns / 1 run  u-)N ­m ¤-,Q­) N ­DC<? MÏ ;2@E59  )~Õ
/g , /¾U

2.2. N ­DC<? :HB5Ã¬i{ ¾U- 295 -

 2.1 ©\¾U 0'0 ¬i, 1 ­DC<?Þ¥ -*  ):HB5Ã
´Ô/¿Â, /¾U,'0'0  µiS Zpb`r»¨/³% ©uDC<?dS »¨¬ 5F9:GH6/³S0'0¬ÆÛ3'% <&5Ü Ìi.

 *\Êz/t t 1 ­DC<? \Êz/K¼ 0'0¬Æ

K É[Q­­ Zpb`r»¨/³»¨!  ©j³*->F835>G
L *!M 1 ­DC<? Æ ;2@E59 =/f%1 ­DC<?
506'm. ]>c/C!>%1 ­DC<? 1E?K¤-, ­yp@Y,

:HB5Ã;%,/ ¾ U  ,  '   VROYHQWDFFHVVLEOHVXUIDFHDUHDÛ6$6$Ü ]>c(C!>

2.3. β 1EAË/MÏ( N ­DC<? ßWÆ£¦ 1EAËÙ *, N ­DC<?AJ st§SÊz ­m Æ))~Õ/g ,/uº,'Îpcr»¨),¾U/³»¨!Gaussian 16 /zL%/<3* /fÐXmMÐXu1EAË  NÔ¹ !ZpÆK9t-,)t! 0°(! 180° - /,)t -* )t K ¹y/ 15°>c *Êz/-*  J/»¨
F<H?FHC!>  J:}8/T
4G7J st§SÊz(Gaussian 16 /zL%/<3* /fÐXmMÐXÎpcr»¨/³*

4G7J pjL st/¾U,'1>>G L Zpb`r»¨/³h 1 ­DC<?v,`n! &*HQ)) T>@*URPDFV /]»¨/u³

3 >B"*
3.1. :HB5Ã¬i, N ­DC<? ßWÆ £¦ MDM2 ¬i,Þ¥×N ­DC<?»¨/³ >F835>G NÔ¹ C!

> *(2j »¨/³= cij MÏNÔ¹/st},  . +N ­DC<? ­m Æ)*%  #ßWÆ/st},  ¤5-RMSD . C!> *!»¨ Ln^Æ/,ni ,  ¤5-
5F9:GH6/³KQ 5F9:J '´Æ/Ìi.,% +#} M¶,  W'¤- ½» 10 ¥× ci(j»¨/³ ­m Q­)*MÏ% ,-,  ¤5--* ¬ *N ­DC<? 4G7 N < 1FH/MÏÙ,Zp ­m/K
st Q­¤,nV-,  )+N¤-
3.2. N ­DC<? :HB5Ã¬i{ ¾U Þ¥×N ­DC<?Û1, 2Ü/ MDM2K¬itRZpb`r»¨/³Û Ü
:H- 296 -

B5Ã ¬itR!N ­DC<? Æ *!dS  )+(S*- RMSD .!F.%Zpb`r»¨ ]LN ­DC<? 1E?K h­m  y:H
B5Ã;%,/p@Y, /¾U,'SASA
ßdm¢ ß xeB°m! MDM2]>c/º Ýo;%,}0p@Y vÞdm¢ B°m!p@Y,  ¤5-º ¬ *Ýßdm¢

N ­m :HB5Ã¤- MDM2  ¬i? D$,  ¤5-' -* ­m Æ/Éc, MDM2 )+N¬i, N­DC<?/_Y ,3° ¤5-%Þdm¢!:HB5Ã

¬i`

~Õ/$ N ­DC<? />c, ] ,3° ¤5-')+pÚ­m/E/, ±ÅÈ 4K/³,3° ®*-)®mÉc N ­DC<?!uÑi<ª¯/uØ/³ *+½»DC<?! MDM2 /ª¯XC ,  ¤- -* ¬!Zpb`r»¨ ¬
:HB5ÃGH? ½»`{·/$, /¤,
3.1  3.2
%!%t

¬ "!ChemRxiv 0+r

YTL,ÛYru[1] eqÜMDM2  µiStR , N ­DC<? Zpb`r»¨500 @A~ »¨/ 5 7³
i» 2.5 25!~ >F835>G 5F9:GH6/³5F9:GH6O KQÆ/Ìi.ÛaÜN ­DC<? 1
DC<? 23.3.

crÆÛKÜ5F9:GH6¬Û#ÜÛbÜN ­

crÆÛKÜ5F9:GH6¬Û#Ü

β 1EAË/MÏ( N ­DC<? ßWÆ£¦

1EAË/MÏ( N ­DC<? "¥ -% £¦AJÞ st§SÊz ql,  ¤5- Æ) )~Õ/g ,st§SÊz  JK N ­m/Îpcr»¨)+Á$ N ­m ÎÚ,- JK ? +"Z §SÊz VQst,  ¤5-1S¡!
2< m)+(JÚ N ­m/E/ni JK ? 

- 297 - Îpcr»¨)* AJ st§SÊz/i., 4G7
J st§SÊz/%QuÑ

4G7J/id¬ X Æº)uØ¡Æt/³ Îpcr»¨%Q4G7J st§SÊz)",¬ *- *Êz^-AJ/, Îpcr»¨%m3°ßWÆ/},4G7J/_Y ,  W'¤- **-¬Æ/\Êz298 K Zpb`r»¨),st ¾U/³
¬Zpb`r»¨ ]L

4G7J!zy +#}/,Uly/K 348

K (j Zpb`r»¨/³ 298 K

nijzy +#} ,U-*ly/K 398 K ,Zpb`r»¨ LZp >},p ¸m- -* ¬
*

4G7J

+stst ßWÆ/,U,  ¤5-

4 8LG
[1] b kL, “%m3°§SÆ/},Ow4G71E?  SZpVTG”, [cr* 101 \Ax*, 2021 x 3 _ 22 [
[2] cIzv, }wg6, w?|, hiL, bkL, Ha-&, “N ­DC<?/n, MDM2
GH? ½»”, [cr* 101 \Ax*, 2021 x 3 _ 19 [
[3] Jumpei Morimoto, “Oligo(N-substituted alanine) as a peptoid with a defined shape in water”, Online Peptoid
Symposia, 2021 x 2 _ 25 [
[4] bkL, “ª¯X:HB5Ã°/VT,' LZp½»”, GTR Chemistry Workshop 2020, 2020x 12 _ 7 [[5] bkL}wg6Ha-&, eLst §SÊz/},Ow4G71E?  :HB
5ÃGH?½»

5

P,  69 7ÚZp*, 2020 x 9 _ 18 [4G
[1] Fukuda, M. Yokomine, D. Kuroda, K. Tsumoto, J. Morimoto, S. Sando, “Peptoid-Based Reprogrammable Template
for Cell-Permeable Inhibitors of Protein–Protein Interactions”, ChemRxiv., DOI: 10.26434/chemrxiv.14528625, 2021.
[2] J. Morimoto, S. Sando, J. Synth. Org. Chem., Jpn. 2020, 78, 1076-84.

I$5>@-0RULPRWRHWDO-$P&KHP6RF±
>@<)XNXGDHWDO&KHP5[LY'2,FKHPU[LY
>@.9DQRPPHVODHJKHHWDO-&RPSXW&KHP±

- 298 -

᰾ኚ᥮⁐⼥ሷࢱ࣮ࢤࢵࢺ㛤Ⓨ࡟ྥࡅࡓ ')7 ศᏊືຊᏛィ⟬࡟ࡼࡿ⇕ຊᏛ㔞ホ౯(YDOXDWLRQRIWKHUPRG\QDPLFGDWDXVLQJ')7PROHFXODUG\QDPLFVWRGHYHORSPROWHQVDOWWDUJHWVIRUQXFOHDUWUDQVPXWDWLRQ‫ۑ‬᏷ᡞ ༤⣖㸦ᮾ໭኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧1◊✲┠ⓗཎᏊຊⓎ㟁ᡤࡼࡾ⏕ࡌࡿ㧗ࣞ࣋ࣝᗫᲠ≀ࡢฎ⌮ฎศ᪉ἲࢆ᪩ᮇ࡟☜❧ࡍࡿࡇ࡜ࡣཎᏊຊ࢚ࢿࣝࢠ࣮฼⏝࡟࠾ࡅࡿ᭱㔜せㄢ㢟ࡢ୍ࡘ࡛࠶ࡿࠋ㧗ࣞ࣋ࣝᗫᲠ≀࡟ࡣ࣐࢖ࢼ࣮࢔ࢡࢳࣀ࢖ࢻࡸ㛗ᑑ࿨᰾ศ⿣⏕ᡂ≀ࡀྵࡲࢀ࡚࠾ࡾࠊࡇࢀࡽࡣ㉸㛗ᮇࡢ༙ῶᮇ࠿ࡘ㧗࠸ᨺᑕᛶẘᛶࢆ᭷ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊ㧗ࣞ࣋ࣝᗫᲠ≀ࢆᆅᒙ୰࡟ฎ
ศࡍࡿ࡟ࡋ࡚ࡶࠊ࠶ࡿ࠸ࡣูࡢฎ⌮᪉ἲࢆ᥇⏝ࡍࡿ࡟ࡋ࡚ࡶࠊ㉸㛗ᮇࡢᏳ඲☜ಖࢆ⪃࠼࡞ࡃ࡚ࡣ࡞ࡽ࡞࠸ࠋ
ࡇࢀࢆཷࡅ࡚ࠊ㧗ࣞ࣋ࣝᗫᲠ≀᰾✀࡟ᑐࡋ୰ᛶᏊࢆ↷ᑕࡍࡿࡇ࡜࡛ࠊ▷༙ῶᮇࡲࡓࡣᏳᐃ᰾✀࡬᰾ኚ᥮ࡍࡿ
ࡇ࡜ࡀᥦ᱌ࡉࢀ࡚࠸ࡿ[1]ࠋࡇࢀࡲ࡛ࡢ◊✲࡛ࡣ㧗ࣞ࣋ࣝᗫᲠ≀ࢆྵࡴ୰ᛶᏊ⿕↷ᑕయ㸦ࢱ࣮ࢤࢵࢺ㸧ࡣᖖ࡟ᅛయ࡜᝿ᐃࡉࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊࢱ࣮ࢤࢵࢺࢆᾮయ࡜ࡍࡿࡇ࡜ࡀ࡛ࡁࢀࡤࠊࡑࢀࢆ᰾ኚ᥮ࢩࢫࢸ࣒ࡢෆእ࡟
ὶືࡉࡏࡿࡇ࡜࡛ࠊࢱ࣮ࢤࢵࢺࡢᐃᮇⓗ஺᥮ࡀ୙せ࡟࡞ࡿࠊ㐠㌿୰࡟ᡂศࢆㄪᩚࡍࡿࡇ࡜ࡀྍ⬟࡟࡞ࡿ࡞࡝ࠊ
ከࡃࡢᕤᏛⓗ฼Ⅼࡀ⏕ࡌࡿ࡜⪃࠼ࡽࢀࡿࠋ
ࡇࡢࡼ࠺࡞᝿ᐃࡢୗࠊ⁐⼥ሷ࡟ࡇࢀࡽ㧗ࣞ࣋ࣝᗫᲠ≀ࢆῧຍࡋࡓ᪂ࡓ࡞᰾ኚ᥮ࢱ࣮ࢤࢵࢺࢆᥦ᱌ࡍࡿࠋཎ
Ꮚຊࢩࢫࢸ࣒࡟࠾ࡅࡿ⁐⼥ሷ࡜ࡋ࡚ࠊࣇࢵ໬ࣜࢳ࣒࢘ (LiF) ࡜ࣇࢵ໬࣒࣋ࣜࣜ࢘ (BeF2) ࡢΰྜ⁐⼥ሷࡀ⏝࠸ࡽࢀ࡚ࡁࡓᐇ⦼ࡀ࠶ࡾࠊ⁐፹࡜ࡋ࡚ࡢ➨୍ೃ⿵࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊỈ㓟໬≀ሷࡶྠᵝ࡟ೃ⿵࡜⪃࠼࡚࠸ࡿࠋỈ㓟໬≀࢖࢜ࣥࡣࣇࢵ໬≀࢖࢜ࣥ࡜ྠᵝ࡟୰ᛶᏊ྾཰᩿㠃✚ࡀᑠࡉࡃࠊ࠿ࡘ୰ᛶᏊࢆῶ㏿ࡉࡏࡿࡇ࡜࠿
ࡽࠊᗫᲠ≀᰾✀ࡢ୰ᛶᏊ྾཰཯ᛂࢆಁ㐍࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࣇࢵ໬≀ሷ࡟ẚࡋ࡚Ỉ㓟໬≀ሷࡢ⼥Ⅼ
ࡣẚ㍑ⓗప࠸ࡇ࡜࠿ࡽࠊప

࡛ὶື࡛ࡁࡿ࡞࡝ࡢ฼Ⅼࡀ⪃࠼ࡽࢀࡿࠋ୍᪉࡛ࠊ㧗ࣞ࣋ࣝᗫᲠ≀୰ࡢ≉ᐃඖ⣲࡜ࡇࢀࡽ⁐⼥ሷ⁐፹ೃ⿵࡟ࡼࡿΰྜ⣔ࢆᢅࡗࡓ◊✲౛ࡣ࡯࡜ࢇ࡝ሗ࿌ࡉࢀ࡚࠸࡞࠸ࠋᙜヱࢥࣥࢭࣉࢺᡂ❧ᛶࢆ᳨ウࡍࡿࡓࡵ࡟ࠊࡲࡎ㧗ࣞ࣋ࣝᗫᲠ≀ඖ⣲ࡀ⁐⼥ሷ⁐፹୰࡛Ᏻᐃࡋ࡚Ꮡᅾࡍࡿࡼ࠺࡞໬Ꮫᙧែࢆぢฟࡍᚲせࡀ࠶ࡿࠋ௨ୖࡢ⫼ᬒ࠿ࡽࠊᮏ◊✲࡛ࡣᾮయ᰾ኚ᥮ࢱ࣮ࢤࢵࢺࡢ㛤Ⓨ࡟ྥࡅ࡚ࠊ㧗ࣞ࣋ࣝᗫᲠ≀ඖ⣲࡜⁐⼥ሷ⁐፹ࡢ㛫࡛Ⓨ⏕ࡍࡿ࡜⪃࠼ࡽࢀࡿ㟁Ꮚ⛣ື཯ᛂࢆศᯒࡋࠊᏳᐃࡋ࡚Ꮡᅾࡍࡿ⁐⼥ሷࢱ࣮ࢤࢵࢺࢆぢฟࡍࡓࡵࡢᩘ್ゎᯒホ౯ࢆᐇ᪋ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲᮏㄢ㢟ࡢᐇ᪋࡟ᙜࡓࡾࠊᮏᖺᗘࡣࢺࣛ࢖࢔ࣝ࡭࣮ࢫ࡜఩⨨࡙ࡅࠊୖ㏙ࡋࡓ◊✲┠ⓗࢆ㐩ᡂࡍࡿࡓࡵࡢ㐺ษ࡞ホ౯ᡭἲࡢ᳨ウࢆ㐍ࡵࡓࠋ⇕ຊᏛ✚ศἲࡸ⢏Ꮚᤄධἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࡸࠊㄪ࿴⁐፹ࣔࢹࣝࢆ
⏝࠸ࡓ㔞Ꮚ⛉Ꮫィ⟬࡟ࡼࡿจ⦰⣔ࡢ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬➼ࡢ㐺⏝ࢆ᳨ウࡋࡓࡶࡢࡢࠊ࠸ࡎࢀࡶ⭾኱࡞ィ⟬᫬㛫࡟ࡼࡿᐇ㉁ᛶࡢஈࡋࡉࡸࠊᮏ◊✲ᑐ㇟ࡢ⣔࡬ࡢ㐺⏝ࡀ࠺ࡲࡃ࠸࠿ࡎᙜヱᡭἲࢆ⏝࠸ࡓホ౯ࢆ᩿ᛕࡋ࡚࠸ࡿࠋ
௒ᅇ㐺⏝࡛ࡁࡿ࡜ᛮࢃࢀࡓࡶࡢࡀࠊ㟁Ⲵࢆᣊ᮰ࡋࡓᐦᗘỗ㛵ᩘἲ࡟ࡼࡿศᏊືຊᏛィ⟬࡟ࡼࡾࠊ࢚ࢿࣝࢠ

- 299 -

࣮ࢠࣕࢵࣉࢆࢧࣥࣉࣜࣥࢢࡋࠊ෌㓄ྥ࢚ࢿࣝࢠ࣮ࢆồࡵࡿᡭἲ࡛࠶ࡿ[2]ࠋᙜヱᡭἲࡣ୍⯡ⓗ࡞⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡜␗࡞ࡾࠊ≀⌮ⓗ࡟ព࿡ࡢ࡞࠸୰㛫≧ែ࡟࠾ࡅࡿ⣔࡛ࡢศᏊືຊᏛィ⟬ࡀ୙せ࡛࠶ࡿ࡞࡝ࠊィ⟬ࢥࢫࢺࢆᴟࡵ࡚ᢚ࠼ࡽࢀࡿࡇ࡜ࠊ࠿ࡘィ⟬ᡭἲࡀᐇ⿦ࡉࢀࡓࣉࣟࢢ࣒ࣛࡀᏑᅾࡍࡿࡇ࡜࠿ࡽࠊᮏ◊✲࡬ࡢᡭἲ㐺⏝ࢆヨࡳࡿࡇ࡜࡜ࡋࡓࠋ⌧᫬Ⅼ࡛ࡣᮏ◊✲ᑐ㇟⣔࡬ࡢ㐺⏝ࡲ࡛ࡣ㐩ᡂ࡛ࡁ࡚࠸࡞࠸ࡀࠊᙜヱᡭἲ࡟ࡘ࠸࡚ሗ
࿌ࡋ࡚࠸ࡿㄽᩥ[2]ࡢ෌⌧ィ⟬ࢆᐇ᪋ࡍࡿࡇ࡜࡛ࠊᡭἲࡢ㐺⏝ྍ⬟ᛶࢆ᳨ウࡋ࡚࠸ࡿࠋ
ࡇࡇ࡛ࠊ㟁Ⲵࢆᣊ᮰ࡋࡓᐦᗘỗ㛵ᩘἲ (Constrained Density Functional Theory: CDFT) ࡟ࡼࡿศᏊືຊᏛィ⟬࡟ࡘ࠸࡚ࠊ⡆༢࡟ㄝ᫂ࡍࡿࠋCDFT ࡛ࡣ㏻ᖖࡢ࢚ࢿࣝࢠ࣮ỗ㛵ᩘ E ࡟㟁Ⲵᣊ᮰ࡢ㡯ࢆ㊊ࡋ࡚ࠊᘧ(1)ࡢ㏻ࡾ᪂
ࡓ࡞࢚ࢿࣝࢠ࣮ỗ㛵ᩘ W ࢆᐃ⩏ࡍࡿࠋܹሾߩǡ ܸሿ ൌ ‫ܧ‬ሾߩሿ ൅ ܸ ൬න ‫ݓ‬ሺ‫ܚ‬ሻ ߩሺ‫ܚ‬ሻ‫ ܚ‬െ ܰ஼ ൰ሺͳሻ
ࡇࡇ࡛ࠊV ࡣࣛࢢࣛࣥࢪࣗᮍᐃ஌ᩘࠊNC ࡣ㟁Ⲵࡢᣊ᮰್ࠊw ࡣ㔜ࡳ㛵ᩘ࡛࠶ࡿࠋᘧ(1)ࢆ⏝࠸ࡿ࡜ࠊ࠶ࡿ 2 ࡘࡢᣊ᮰≧ែ A ࡜ B ࡟࠾ࡅࡿ࢚ࢿࣝࢠ࣮ࡢᕪ ΔEAB ࡜ࡢ㛫࡟ḟࡢ㛵ಀࡀᚓࡽࢀࡿࡇ࡜࡜࡞ࡿࠋ
஻ο‫ܧ‬஺஻ ൌ െ න ܸሺܰ஼ ሻܰ஼ ሺʹሻ஺Marcus ⌮ㄽ[3]࡟ࡼࡾࠊ㟁Ꮚ⛣ື࡟࠾ࡅࡿ⮬⏤࢚ࢿࣝࢠ࣮ࡣ཯ᛂ࢚ࢿࣝࢠ࣮࡜෌㓄ྥ࢚ࢿࣝࢠ࣮࡟ࡼࡗ࡚ồࡵࡽࢀࡿࠋ௒ᅇࡢ⣔࡛ࡣ⮬ᕫ㟁Ꮚ⛣ື཯ᛂࡢࡓࡵ཯ᛂ࢚ࢿࣝࢠ࣮ࡣ 0 ࡜࡞ࡾࠊ෌㓄ྥ࢚ࢿࣝࢠ࣮ࡢࡳ࡟ࡼࡗ࡚
⮬⏤࢚ࢿࣝࢠ࣮ࡀỴᐃࡉࢀࡿࠋWarshel ࡟ࡼࢀࡤࠊ෌㓄ྥ࢚ࢿࣝࢠ࣮ࢆᐃ⩏ࡍࡿ㠀᩿⇕㐣⛬࡛ࡢ⮬⏤࢚ࢿࣝࢠ࣮᭤⥺ࡣࠊ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉ ΔE ࡟ࡼࡾᚓࡽࢀࡿࠋࡇࡢ⮬⏤࢚ࢿࣝࢠ࣮᭤⥺ࡀ཮᭤⥺≧࡛࠶ࢀࡤࠊ෌㓄ྥ࢚ࢿࣝࢠ࣮࡜࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉ࡜➼ࡋࡃ࡞ࡿࠋ⮬⏤࢚ࢿࣝࢠ࣮࡜࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࡢ㛫࡟⥺ᙧ㛵ಀࡀ࠶ࡿࡇ࡜࠿ࡽࠊḟࡢᘧࡀᚓࡽࢀࡿࠋ
‫ܨ‬஺ ሺο‫ܧ‬ሻ െ ‫ܨ‬஻ ሺο‫ܧ‬ሻ ൌ ο‫ܧ‬ሺ͵ሻࡋࡓࡀࡗ࡚ࠊ2 ࡘࡢ≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮ᕪࡀࠊྛ≧ែ࡛ࡢ࢚ࢿࣝࢠ࣮ࢆィ⟬ࡍࡿࡔࡅ࡛ࠊ୰㛫≧ែࡢ᝟ሗ࡞
ࡋ࡟ᚓࡽࢀࡿࡇ࡜࡜࡞ࡿࠋ
ᮏ◊✲࡟࠾ࡅࡿ㟁Ⲵࢆᣊ᮰ࡋࡓᐦᗘỗ㛵ᩘィ⟬࡟ࡼࡿศᏊືຊᏛィ⟬ (CDFT-MD) ࡣࠊCPMD ࣉࣟࢢ࣒ࣛ
[4]ࢆ⏝࠸࡚࠾ࡾࠊᨃ࣏ࢸࣥࢩࣕࣝ㸩ᖹ㠃Ἴᇶᗏ࡟ࡼࡿᐦᗘỗ㛵ᩘィ⟬࡛࠶ࡿࠋGoedecker–Teter–Hutter ᨃ࣏ࢸࣥࢩࣕࣝࢆ౑⏝ࡋ[5]ࠊBLYP ஺᥮┦㛵ỗ㛵ᩘ࡜ࡋࡓ[4]ࠋヲ⣽࡞ィ⟬᮲௳࡟ࡘ࠸࡚ࡣࠊ3. ◊✲ᡂᯝࡢྛ⠇࡟࠾࠸࡚ㄝ᫂ࡍࡿࠋ

3◊✲ᡂᯝ

3.1 㟁Ⲵࢆᣊ᮰ࡋࡓᐦᗘỗ㛵ᩘἲࡢࢸࢫࢺィ⟬
CPMD ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ CDFT ἲࡢ౑⏝࡟ᙜࡾࠊඛ⾜◊✲[2]࡟ࡼࡿホ౯ࡢ෌⌧ィ⟬ࢆ⾜࠺ࡇ࡜࡛ࠊࡑࡢ౑
⏝᪉ἲࢆࢸࢫࢺࡋࡓࠋィ⟬ᑐ㇟⣔ࡣ(CO)−ࡢᏙ❧ศᏊ࡛࠶ࡿࠋ㓟⣲ཎᏊࢆ㟁Ꮚ౪୚యࠊⅣ⣲ཎᏊࢆ㟁Ꮚཷᐜయ࡜ࡋࠊཎᏊ㛫㊥㞳ࢆ 2 Å ࡜ࡋࡓࠋᘧ(1) ࡟࠾ࡅࡿ NC ࢆ−1 ࠿ࡽ 1 ࡬ẁ㝵ⓗ࡟ኚ໬ࡉࡏࡿࡇ࡜࡛ࠊ㐣๫㟁Ꮚࢆ㓟⣲࠿ࡽⅣ⣲࡬࡜⛣ືࡉࡏࠊࡑࢀࡒࢀ࡟࠾ࡅࡿ඲࢚ࢿࣝࢠ࣮ࢆホ౯ࡋࡓࠋ࢚ࢿࣝࢠ࣮࢝ࢵࢺ࢜ࣇࢆ 100 RyࠊἼື㛵ᩘࡢ཰᮰ุᐃࢆ 10−6 ࡜ࡋࡓࠋᅗ 1 ࡟㟁Ⲵᕪ NC ࢆኚ໬ࡉࡏࡓ࡜ࡁࡢࣛࢢࣛࣥࢪࣗ஌ᩘ࡜࢚ࢿࣝࢠ࣮ࡢ⤖ᯝࢆ♧ࡍࠋNC = −1 ࡀ C–O−࡟┦ᙜࡋࠊNC = 1 ࡀ C−–O ࡟┦ᙜࡋ࡚࠸ࡿࠋࢢࣛࣇ࡟ࡣࡑࢀࡒࢀ௒ᅇࡢ⤖ᯝ࡜ඛ⾜◊✲[2]࡟࠾ࡅࡿሗ࿌್ࢆᥖ㍕ࡋ࡚࠸ࡿࠋࣛࢢࣛࣥࢪࣗᮍᐃ஌ᩘࡢ⤖ᯝࡣඛ⾜◊✲ࡢࡶࡢ࡜࡯ࡰ୍⮴ࡋ࡚࠾ࡾࠊ࢚ࢿࣝࢠ࣮࡟ࡘ࠸࡚ࡣⱝᖸ

- 300 -ࡢᕪࡣぢࡽࢀࡿࡶࡢࡢࠊNC ࡟ᑐࡍࡿഴྥࡣ࡯ࡰྠࡌࡶࡢࡀᚓࡽࢀ࡚࠸ࡿࠋࡲࡓࠊᘧ(2)ࡼࡾࠊ௨ୗࡀᡂ❧ࡍࡿࡣࡎ࡛࠶ࡿࠋ
ଵο‫ܧ‬஺஻ ൌ ‫ܧ‬ሾି ሿ െ ‫ܧ‬ሾି ሿ ൌ െ න ܸܰ஼

ሺͶሻ

ିଵ
ଵ

ᅗ 1 (a)ࡼࡾࠊെ ‫ି׬‬ଵ ܸ݀ܰ஼ ൌ ͻǤʹ͵  ࠊ୍᪉࡛ᅗ 1 (b)ࡼࡾ‫ܧ‬ሾି ሿ െ ‫ܧ‬ሾି ሿ ൌ ͳͲǤͶ  ࡜࡞ࡾࠊ୧⪅ࡢ㛫࡛ 13%⛬ᗘࡢᕪࡀぢࡽࢀࡓࠋඛ⾜◊✲[2]࡛ࡣ 0.5%⛬࡜ࡼࡃ୍⮴ࡋ࡚࠸ࡓࡇ࡜࠿ࡽࠊᮏ◊✲࡟࠾ࡅࡿᕪࡣ㠀ᖖ࡟኱ࡁ࠸ࡇ࡜ࡀศ࠿ࡿࠋᜍࡽࡃ DFT ィ⟬ࡢ࢚ࢿࣝࢠ࣮཰᮰ุᐃ್ࡀ኱ࡁ࠸ࡇ࡜࡞࡝ࡀ⌮⏤࡜⪃࠼ࡽࢀࡿࡶࡢࡢࠊᮏ
ࢸࢫࢺ࡟ࡼࡗ࡚㟁Ⲵࢆᣊ᮰ࡋࡓ⣔࡟࠾ࡅࡿィ⟬ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ࡜ࡍࡿࠋ

ᅗ 1. 㟁Ⲵᕪ NC ࢆኚ໬ࡉࡏࡓ࡜ࡁࡢ (a) ࣛࢢࣛࣥࢪࣗᮍᐃ஌ᩘࠊ(b) ࢚ࢿࣝࢠ࣮

3.2 Ỉ⁐ᾮ୰࡟࠾ࡅࡿ Ru2+–Ru3+ࡢ㟁Ꮚ⛣ື཯ᛂḟ࡟ࠊỈ⁐ᾮ୰࡟࠾ࡅࡿ Ru2+࠾ࡼࡧ Ru3+ࡢ⮬ᕫ㟁Ꮚ⛣ື཯ᛂ࡟࠾ࡅࡿ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࢆホ౯ࡍࡿࠋィ⟬ࢭࣝࡣ࿘ᮇቃ⏺᮲௳ࢆ୚࠼ࡓࠊ14.50×11.35×11.35 Å3 ࡜ࡋࠊ2 ࡘࡢ Ru ࢖࢜ࣥ࡜ 63 ಶࡢỈศᏊࢆ㓄⨨ࡋࡓࠋ
2 ࡘࡢ Ru ࢖࢜ࣥࡢ㊥㞳ࡣ RATTLE ࢔ࣝࢦࣜࢬ࣒࡛ 5.5 Å ࡟ᅛᐃࡋ࡚࠸ࡿࠋ⣔ࡣ NVT ࢔ࣥࢧࣥࣈࣝ࡟࠾࠸࡚
ィ⟬ࡋ࡚࠸ࡿࠋ ᗘࡣ Nosé–Hoover ⇕ᾎ࡟ࡼࡾ 300 K ࡜ࡋࠊchain length ࢆ 4ࠊfrequency ࢆ 1000 cm−1 ࡜ࡋࡓࠋDFT ィ⟬࡟࠾ࡅࡿ཰᮰ุᐃࡣ 10−4 ࡜ࡋࡓࠋ㟁Ⲵᣊ᮰࡟࠾ࡅࡿ NC = −1 ࡢሙྜࡀ཯ᛂ≀ A (Ru2+ + Ru3+) ࡟┦ᙜࡋࠊ⏕ᡂ≀ B (Ru3+ + Ru2+) ࡟ࡘ࠸࡚ࡣ NC = 1 ࡜タᐃࡋ࡚࠸ࡿࠋ㟁Ⲵࡢ཰᮰ุᐃࡣ 5×10−4 ࡜ࡋࡓࠋMD ィ⟬ࡣ᫬㛫ࢫࢸࢵࣉࢆ 40 a.u.࡜ࡋࠊ⥲ࢫࢸࢵࣉᩘࢆ 2,500 ࡜ࡋࡓࠋࡇࢀࡽィ⟬᮲௳ࡢࡍ࡭࡚ࡣඛ⾜◊✲[2]࡟グ㍕ࡉ
ࢀ࡚࠸ࡿࠋඛ⾜◊✲୰࡛ࡣ DFT ࡢ཰᮰ุᐃࢆ 2×10−5 ࡜ࡋ࡚࠸ࡿࡀࠊᮏ◊✲࡛ࡣィ⟬᫬㛫ࡢ▷⦰ࡢࡓࡵ 10−4 ࡜ࡋ࡚࠾ࡾࠊࡲࡓࠊMD ࢧࣥࣉࣜࣥࢢ᫬㛫ࡶඛ⾜◊✲࡛ࡣ 5.5 ps ࡲ࡛ᐇ᪋ࡋ࡚࠸ࡿ࡜ࡇࢁࠊᮏ◊✲࡛ࡣ㒔ྜ࡟ࡼ
ࡾ 2.5 ps ࡜ࡋ࡚࠸ࡿࠋ
ᅗ 2 ࡟ NC = −1 ࠾ࡼࡧ NC = 1 ࡢྛ≧ែ࡟࠾ࡅࡿ࢚ࢿࣝࢠ࣮ࢆ♧ࡍࠋィ⟬㛤ጞ࠿ࡽ࢚ࢿࣝࢠ್࣮ࡣῶᑡࡋ࡚
࠸ࡁࠊ୧᮲௳࡟࠾࠸࡚ 1.5 ps ㎶ࡾ࠿ࡽᏳᐃࡋ࡚࠸ࡿࡼ࠺࡟ぢࡽࢀࡿࠋࡼࡗ࡚ࠊ1.5 ps ࠿ࡽ࠾࠾ࡼࡑ 2.5 ps ࡲ࡛ࡢ⠊ᅖ࡛ࠊ୧≧ែࡢ࢚ࢿࣝࢠ࣮ࡢᕪࢆྲྀࡗࡓ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉ ΔE ࢆồࡵࠊᅗ 3 ࡟♧ࡍࠋࡇࡢ⤖ᯝ࠿ࡽ ΔE
ࡢᖹᆒࢆྲྀࡿ࡜ࠊ‫ۃ‬ο‫ ۄܧ‬ൌ1.49 eV ࡛࠶ࡗࡓࠋඛ⾜◊✲࡛ࡢሗ࿌್ࡣ 1.53 eV ࡛࠶ࡾࠊ௒ᅇࡢ෌⌧ィ⟬ࡣᴫࡡ㏆࠸್ࢆ♧ࡋ࡚࠸ࡿࡶࡢ࡜ᛮࢃࢀࡿࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫ࡸ DFT ࡢ཰᮰ุᐃࡀ୙༑ศ࡛࠶ࡿ࡜ᛮࢃࢀࡿࡀࠊ
ඛ⾜◊✲࡟࠾ࡅࡿホ౯ࢆᴫࡡ෌⌧࡛ࡁࡓࡶࡢ࡜ᛮࢃࢀࡿࠋ
ḟᖺᗘ௨㝆࡟࠾࠸࡚ࡣࠊᮏᡭἲࢆ⁐⼥ሷ⁐፹࡬࡜ᣑᙇࡋࠊ㟁Ꮚ⛣ືࡢ⮬⏤࢚ࢿࣝࢠ࣮ホ౯ࢆヨࡳࡿࠋ- 301 -

ᅗ 2. ྛ㟁Ⲵᣊ᮰᮲௳ (NC = −1, 1) ࡟࠾ࡅࡿࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫࡟ᑐࡍࡿ࢚ࢿࣝࢠ࣮

ᅗ 3. ࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫࡟ᑐࡍࡿ୧≧ែࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ࡞ࡋࠋཧ⪃ᩥ⊩>@ 06WHLQEHUJ*:RW]DN%0DQRZLW]%1/%URRNKDYHQ1DWLRQDO /DERUDWRU\  
>@ +2EHUKRIHUDQG-%OXPEHUJHU-&KHP3K\V  >@5$0DUFXV-3KV\&KHP  
>@&30'9HUVLRQWKH&30'FRQVRUWLXPKWWSZZZFSPGRUJ
>@6*RHGHFNHU07HWHUDQG-+XWWHU3K\V5HY%  

- 302 -

"




#

!



Conformation of host-guest systems investigated by cold, gas-phase
spectroscopy and analysis of vibronic structures00!0%

.-

,/



 &'$#

3E/I0J9F!>8:[l"Þ£p!58:-Ì¨ ` *¸-&"!58:Ì|` È!Ó!ÔV-(*% Þ+(!>8:58:ae¢!R«[W-ºR«QM¾>8:58:ae¢!µi8=3:F"Þ` *58: ')jÖÈ-­!ÖÈ-¿+#Þ>8:58:ae¢!°SÍw-pÞ58:Ì|!ÔV-ÄÂ* d¸*¬®"ÞqÚ '{(+>8:58:ae¢!µi8=3:FN!ÖÈ-ÞÏlanÀ² g  )UDQFN&RQGRQÜ)&Ý¿-¦ srÞ!°SÍw-p*-ª¨* &'+(CONFLEX Íw´<H4EA-¦ [l]h ')>8:58:ae¢!Íw¯Ó-´Þ»!opÈ-{!opÈ-\ÈÞÏlanÀ² ')Ölgu¤~ '$Öl^Å¤~ÈËa_¿-ºÏlanÀ²" Turbomole <H4EA-¦ ÏlanÀ²'){(+Ölgu¤~ '$Öl^Å¤~!__Ô-¦ ÞPGOPHER <H4EA ') FC 7
@CGJ7DI-º &'
R«[W')»!Íw§|S

mf

*

(



*Þbenzo-15-crown-5(B15C5) ÞK+ÞRb+ÞCs+!Óy+*Ð.1I[K+(B15C5)ÞRb+(B15C5)ÞCs+(B15C5)]  Þ[l]h ')Íw´-º{(+È  ÞÏlanÀ² ')Ölgu¤~ÈËa-º Þ»!opÈ-{!opÈ-\ÈÞ±KÖl^Å¤~!ÈËa-º ÞX!\È  opÈ-{* ÞÈËa+Íw§|S&!À² "×t Ò Ó-¼!"Þ3E/I0J9F* B15C5

×t ÇÈ-&ÞR_!g _ jmf*% Þ ?9I7BF0;F2JØL!ÈËa-x (+*%*· (+*{(+È   FC 7@CGJ7DI-º ÞP!,R
«[W!qÚ¶-¹k Y¥*À²¶"{(+  ÇÈ-&>8:[l ÔÉ FC 7@CGJ7DI"ÞÖl^Å¤~!Û³vÀ² Ñ* ( Pz"Þ')³v Û »!§|S Ë¦d¸Üd¸Õ)R68:!ÝÖl^Å¤~!À²  
Á-Ê%*Op*

- 303 -

 "*)
RZb+«[l!µid½[Wß©Î089FÆclUae¢ÜTÙÃ¡Ý
Þ}Þ
6"S?[lGn @ JÜ2020.12.18, 1IE.IÝ
Surface-enhanced infrared absorption spectroscopy of lanthanide complexes with N-donor or O-donor ligands on
Au surfaceÜWÝÞShogo Meiji, Sakiko Hirata, Seita Tamekuni, Satoru Muramatsu, Takehiro Hirao, Takeharu
Haino, Tosiki Sakata, Ken-ichi Saitow, Yoshiya InokuchiÞThe 17th Nano Bio Info Chemistry SymposiumÜ2020.12.9-11,
1IE.IÝ
Experimental and theoretical study on the nonradiative decay process of cinnamates aimed for the development ofeffective sunscreen reagentsÜWÝÞShin-nosuke Kinoshita, Yu Harabuchi, Yoshiya Inokuchi, Satoshi Maeda,
Masahiro Ehara, Kaoru Yamazaki, Takayuki EbataÞThe 17th Nano Bio Info Chemistry SymposiumÜ2020.12.9-11, 1
IE.IÝ
ÆVP :GJJ[WÏlanÀ² '*©ÎM&S!Öl¤~ trans  cis W§|aK/g!¬®ÜWÝÞ5MEÞ ÞDB)NÞ:c8Þ'(XÞc=FÞA?Þ:*$Þ[lGn1IE.IÁÂ(2020.9.14-17, 1IE.I)
><N @*Wan-NÓS!«[WÜWÝÞE, }, on,  Þ[lGn1IE.IÁÂ(2020.9.14-17, 1IE.I)Structural characterization of hypervalent penta-coordinated carbon compounds by photodissociation spectroscopy
and ion mobility mass spectrometryÞ}Þ"M.7QÞ5AgÞYuan ShiÞLY;0Þ'TÞ Þ± 68 !OÏ[JeÁÂ(2020.5, ¼2UCº!)R.1IH_vOÏ[-¦FRr.1I-

I

3E/I0J9F`

ÐS!È¬®
ÞAN#Þ9+4IÞ}Þ Þ"M.7QÞLY;0Þ1an± 100 3%,(2020.3,¼2UCº!)Penta-coordinated hypervalent carbon compounds in the gas-phase: photodissociation spectroscopy and ion mobility
spectrometryÞ}Þ"M.7QÞ5AgÞYuan ShiÞLY;0Þ'TÞ Þ1an±
100 3%,(2020.3, ¼2UCº!) )

&RQIRUPDWLRQ RI . &URZQ (WKHU  &RPSOH[HV 5HYHDOHG E\ ,RQ 0RELOLW\0DVV 6SHFWURPHWU\ DQG 8OWUDYLROHW
6SHFWURVFRS\6RWD7DLQDND7RPR\XNL8MLKLUD0D\XNR.XER0RWRNL.LGD'DLVXNH6KLPR\DPD6DWRUX0XUDPDWVX
0DQDEX $EH 7DNHKDUX +DLQR 7DND\XNL (EDWD )XPLQRUL 0LVDL]X .HLMLUR 2KVKLPR  <RVKL\D ,QRNXFKL  - 3K\V&KHP$±   
(OHFWURQLF 6WDWHV DQG 1RQUDGLDWLYH 'HFD\ RI &ROG *DV3KDVH &LQQDPLF $FLG 'HULYDWLYHV 6WXGLHG E\ /DVHU
6SHFWURVFRS\ ZLWK /DVHU $EODWLRQ 7HFKQLTXH <XML ,LGD 6KLQQRVXNH .LQRVKLWD 6HL\D .HQMR 6DWRUX 0XUDPDWVX<RVKL\D,QRNXFKL &KDR\XDQ=KXDQG7DND\XNL(EDWD -3K\V&KHP$  
,QGXFHG )LW RI &URZQ &DYLW\ WR $PPRQLXP ,RQ *XHVWV DQG 3KRWRLQGXFHG ,QWUDFDYLW\ 5HDFWLRQV &ROG *DV3KDVH
6SHFWURVFRS\ RI 'LEHQ]R&URZQ &RPSOH[HV ZLWK 1+ &+1+ DQG &+&+1+ 0D\XNR .XER 0RWRNL
.LGD6DWRUX0XUDPDWVXDQG<RVKL\D,QRNXFKL -3K\V&KHP$  
(OHFWURQLF 6WDWH DQG 3KRWRSK\VLFV RI (WK\OKH[\O0HWKR[\FLQQDPDWH DV 89% 6XQVFUHHQ XQGHU -HW&RROHG
&RQGLWLRQ60XUDPDWVX 61DND\DPD6.LQRVKLWD<2QLWVXND+.RKJXFKL<,QRNXFKL&=KXDQG7(EDWD -3K\V&KHP$   

- 304 -

ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ㕲㘒య࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Studies on Iron Complexes Bearing a Pincer Ligand‫⚄ۑ‬㇂ ᫀᏹ㸦໭㔛኱Ꮫ ⌮Ꮫ㒊໬Ꮫ⛉㸧1◊✲┠ⓗ⏦ㄳ⪅ࡣࡇࢀࡲ࡛࡟᭷ᶵ໬ྜ≀ࡢゐ፹ⓗኚ᥮཯ᛂ࡟άᛶࢆ♧ࡍ㑄⛣㔠ᒓ㘒య㸦᭷ᶵྜᡂ⏝ᆒ୍⣔ゐ፹㸧࡟㛵ࡍࡿ◊✲࡟ྲྀࡾ⤌ࢇ࡛ࡁࡓࠋ᫖ᖺᗘࡲ࡛ࡢ฼⏝⏦ㄳ࡛ࡣࠊᐇ㦂ⓗᡭἲ࡛ࡣྜᡂࠊ༢㞳ࡢᅔ㞴࡞཯ᛂ୰㛫యࡢ᥎ᐃࡸࠊ᪂つᛶࡢ㧗࠸≉␗࡞㘒యᵓ㐀㸦Ni, Pd, Fe㸧࡟㛵ࡋ࡚ Gaussian ࢆ⏝࠸ࡓ DFT ィ⟬࡟ࡼࡿゎᯒࢆ㐍ࡵ࡚ࡁࡓࠋᮏᖺᗘࡣᙜ◊✲ࢢ࣮ࣝࣉ࡛㛤Ⓨࡋࡓ㕲㘒యゐ፹࡟ࡼࡿࣄࢻࣟࢩࣜࣝ໬཯ᛂ࠾ࡼࡧ C-H ⤖ྜ࣍࢘⣲໬཯ᛂ࡟ࡘ࠸࡚ࠊᐇ㦂ⓗᡭἲ࡟ࡼࡾỴᐃࠊ᥎ᐃࡋ࡚ࡁࡓゐ፹๓㥑యࡢᵓ㐀ࡸ᥎ᐃࡉࢀࡿ཯ᛂάᛶ✀ࡢ▱ぢࢆࡶ࡜
࡟ࠊGaussian ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓ DFT ィ⟬࡟ࡼࡿ཯ᛂ⤒㊰ࡢ᥈⣴ࢆ⾜ࡗࡓࠋࡲࡓࠊࣄࢻࣟࢩࣜࣝ໬཯ᛂ࡟
ࡘ࠸࡚ࡣゐ፹๓㥑యࡢᵓ㐀࡜⏕ᡂ≀㑅ᢥᛶࡸᇶ㉁ኚ᥮⋡࡞࡝ࡢ཯ᛂ⤖ᯝ࡜ࡢ┦㛵㛵ಀ࡟ࡘ࠸࡚ㄪᰝࢆ⾜࠸ࠊᵓ㐀άᛶ┦㛵࡟ࡘ࠸࡚ゎᯒࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ༢⤖ᬗ X ⥺⤖ᬗᵓ㐀ゎᯒ࡞ࡽࡧ࡟ Evans ἲࢆ⏝࠸ࡓ☢໬⋡ᐃ࡟ࡼࡾᚓࡽࢀࡓᐇ㦂⤖ᯝ࠿ࡽྛ✀㑄⛣㔠ᒓ㘒యࡢึᮇᵓ㐀࠾ࡼࡧࢫࣆࣥከ㔜ᗘࢆタᐃࡋࠊDFT ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋィ⟬ࡢጇᙜᛶ࡟ࡘ࠸
࡚ࡣィ⟬⤖ᯝ࡜ᐇ㦂⤖ᯝࢆẚ㍑ࡍࡿࡇ࡜࡛ホ౯ࡋࡓࠋDFT ィ⟬࡟ࡣ Gaussian ࣉࣟࢢ࣒ࣛ 09 ࠾ࡼࡧ 16 ࢆ⏝࠸ࠊᵓ㐀᭱㐺໬ࡢỗ㛵ᩘ࡟ࡣ B3LYP, B3PW91, M06, M06Lࠊ୍Ⅼィ⟬࡟ࡣ B3LYP, B3PW91, M06, M06L,
mPW1PW91, PBE, TPSS, PBE0 ࢆ⏝࠸ࠊ୍㒊࡟ࡣศᩓຊ⿵ṇ㸦D3, D3BJ㸧ࢆ㐺⏝ࡋࡓࠋᇶᗏ㛵ᩘ࡟ࡣ㑄⛣㔠ᒓཎᏊ࡟ LanL2DZ ࡶࡋࡃࡣ SDDࠊࡑࡢ௚ࡢཎᏊ࡟ࡣ def2-SV(P), def2-TZVP, 6-311G(d,p) ࢆ⏝࠸࡚ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋάᛶ✀ࡢ⏕ᡂ㐣⛬ࠊ཯ᛂᶵᵓゎᯒ࡛ࡣࠊ᥎ᐃࡉࢀࡿ཯ᛂ⤒㊰࡟㛵ࡋ࡚ MEP ἲ࡟ࡼࡿ㑄⛣ᵓ㐀᥈⣴⾜ࡗࡓࠋࡑࡢᚋࠊMEP ἲ࡟ࡼࡾᚓࡽࢀࡓ⤖ᯝࢆཧ⪃࡟ึᮇᵓ㐀ࢆタᐃࡋࠊTS ィ⟬ࢆ⾜ࡗࡓࠋࡲࡓࠊTS ィ⟬࡟ࡼࡾᚓࡽࢀࡓᵓ㐀࡟ࡘ࠸࡚ࠊ᣺ືゎᯒࠊIRC ィ⟬࡟ࡼࡾྛ཯ᛂᶵᵓ⤒㊰ࢆ᥈⣴ࡋࡓࠋ

3

◊✲ᡂᯝ

3-1 C-H ࣍࢘⣲໬཯ᛂ࡟㛵ࡍࡿάᛶ✀᥎ᐃᐇ㦂࡟ࡼࡾ᥎ᐃࡋࡓゐ፹άᛶ✀࡛࠶ࡿࢪ࣎ࣜࣝ㘒య࡟ࡘ࠸࡚ M06/def2-SV(P) ࡛ࣞ࣋ࣝᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊS = 1 ࡢ㘒యࡀ᭱Ᏻᐃ࡞ᵓ㐀࡜ࡋ࡚ᚓࡽࢀࡓࠋࡇࡢ⤖ᯝࡣ༢㞳ࡋࡓࢪ࣎ࣜࣝ㘒యࡢ Evans ἲ࡟ࡼࡿ☢໬⋡ᐃࡢ⤖ᯝ㸦Peff = 3.0 PB㸧࡜ࡶ୍⮴ࡍࡿࠋࢪ࣎ࣜࣝ㘒యࢆ㘽୰㛫య࡜ࡍࡿ཯ᛂᶵᵓࡢゎᯒ࡟ࡘ࠸࡚ࡶ

ィ⟬ࢆ⾜࠸ࠊC-H ⤖ྜάᛶ໬㐣⛬ࡀᚊ㏿ẁ㝵࡛࠶ࡿࡇ࡜ࠊࡲࡓࠊ๓㏙ࡢ㐣⛬ࡀࢫࣆࣥከ㔜ᗘࡢኚ໬ࢆక࠺ࢫ
ࣆࣥ⚗ไ཯ᛂ࡛࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸦'G = 19.9 kcal/mol, S = 1 to S = 0, (U)PBE-D3/def2-tzvp//(U)M06/def2-SV(P) for all atoms㸧ࠋࡇࢀࡽࡢᡂᯝ࡟ࡘ࠸࡚ࡣᏛ఍➼࡛Ⓨ⾲ࢆ⾜ࡗࡓࠋࡲࡓࠊㄽᩥᢞ✏ࡢ‽ഛࢆ㐍ࡵ࡚࠸ࡿࠋ

3-2 ࢔ࣝࢣࣥࡢࣄࢻࣟࢩࣜࣝ໬཯ᛂ࡟㛵ࡍࡿ཯ᛂᶵᵓ᥎ᐃ࡜ᵓ㐀άᛶ┦㛵ࡢㄪᰝ❧యⓗᙳ㡪ࡢ␗࡞ࡿ 6 ✀ࡢ PNN ᆺࣆࣥࢧ࣮㓄఩Ꮚ࠾ࡼࡧࡇࢀࡽ㓄఩Ꮚࢆ᭷ࡍࡿ㕲㘒యࢆྜᡂࡋࠊ༢⤖ᬗ X- 305 -

⥺ᵓ㐀ゎᯒ࡜ Evans ἲ࡟ࡼࡿ☢໬⋡ᐃࡢ⤖ᯝࢆཧ⪃࡟ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ
UM06/def2-tzvp ࡛ࣞ࣋ࣝᚓࡽࢀࡓᵓ㐀ࡣ⤖ᬗᵓ㐀࡜Ⰻ࠸୍⮴ࢆ♧ࡋࡓࠋࡇࢀࡽࡢᵓ㐀࡟ ᑐ ࡋ ࠊ SambVca 2.1 ࡟ ࡼ ࡿ ❧ య ᅉ Ꮚ(%VBUR) ࡢศᯒࢆ඲⌫ࠊ㓄Ꮚ㦵᱁ഃࡢ༙⌫࠾ࡼࡧ཯ᛂሙഃࡢ༙⌫࡟ࡘ࠸࡚ࡑࢀࡒࢀ⟬ฟࡋࡓࠋ࡞࠾ࠊ❧యᅉᏊࡣ㕲ࢆ୰ᚰ࡜ࡍࡿ
༙ᚄ 2.0 ύ࠿ࡽ 9.0ύࡲ࡛ 0.5 ύࡎࡘ⟬ฟࡋࠊ㊥㞳࡟ࡼࡿ❧యᅉᏊࡢ౫Ꮡᛶ࡟ࡘ࠸࡚

ᅗ 1㸬Optimized structure of A with S = 1 spin state. Butene andtriethylsilane were used to simplify the calculation.

ࡶㄪᰝࢆ⾜ࡗࡓࠋࡲࡓࠊ㟁Ꮚࣃ࣓࣮ࣛࢱ࡜ࡋ࡚㕲ୖࡢ Natural Charge ࡟ࡘ࠸࡚ࡶィ⟬ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ 6✀ࡢ㘒య࡟ᑐࡋࠊ
ࣄࢻࣟࢩࣜࣝ໬཯ᛂࢆ 2 ✀㢮ࡢ཯ᛂᇶ㉁࡟ࡘ࠸࡚⾜࠺ࡇ࡜࡛ィ 12 ✀ࡢゐ፹཯ᛂ⤖ᯝࢆᚓࡓࠋ
୍㐃ࡢ཯ᛂ⤖ᯝ࡜❧యᅉᏊࠊ㟁ᏊᅉᏊ࡜ࡢ┦㛵㛵ಀࢆㄪᰝࡋࡓ࡜ࡇࢁࠊ⏕ᡂ≀ࡢ㑅ᢥᛶࡀ 4.5 ύ࡟࠾ࡅࡿ཯
ᛂሙഃࡢ❧యᅉᏊ࡜Ⰻ࠸┦㛵ࢆ♧ࡍࡇ࡜ࢆぢฟࡋࡓࠋࡲࡓࠊ཯ᛂኚ᥮⋡ࡣࡼࡾ㐲࠸ 6.0 ύ௨ୖࡢ❧యᅉᏊ࡜㈇ࡢ┦㛵㛵ಀࢆ♧ࡋࡓࠋᮏゐ፹⣔ࡣࣄࢻࣟࢩࣜࣝ໬⏕ᡂ≀࡟ຍ࠼࡚⬺Ỉ⣲ࢩࣜࣝ໬≀ࡀ๪⏕ᡂ≀࡜ࡋ࡚ᚓࡽ
ࢀࡿࡇ࡜࠿ࡽࠊmodified Chalk-Harrod ᶵᵓ࡟ࡼࡾ཯ᛂࡀ㐍⾜ࡋ࡚࠸ࡿࡶࡢ࡜᥎ᐃࡋࠊ๪⏕ᡂ≀Ⓨ⏕ࡢ㘽࡜࡞ࡿ໬Ꮫ✀ A ࡟ࡘ࠸࡚ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓ㸦ᅗ 1㸧ࠋィ⟬࡟ࡼࡾᚓࡽࢀࡓᵓ㐀࠿ࡽࠊ࣍ࢫࣇ࢕ࣥୖࡢ⨨᥮ᇶ࡜ࢩࣜࣝᇶ㸦Fe-Si ⤖ྜ㊥㞳ࡣ 4.547ύ㸧ࡢ❧య཯Ⓨࡀ⏕ᡂ≀ࡢ㑅ᢥᛶ࡟ᙳ㡪ࡋ࡚࠸ࡿࡶࡢ࡜⪃ᐹࡋࡓࠋࡇࢀࡽ
ࡢᡂᯝ࡟ࡘ࠸࡚ࡶᏛ఍ࠊㄽᩥ➼ࢆ㏻ࡌ࡚Ⓨ⾲ࢆ⾜ࡗࡓࠋ༢ᗙࠊ஧ᗙ㓄఩Ꮚࡢᵓ㐀ࣃ࣓࣮ࣛࢱ㸦❧యᅉᏊ㸧࡟ࡘ࠸࡚ࡣࠊ࣍ࢫࣇ࢕ࣥ໬ྜ≀࡟ࡘ࠸࡚ࡑࢀࡒࢀ Tolmanࡢ෇㗹ゅ(cone angle)ࠊ㓄఩ᣳゅ(bite angle)࡞࡝ࡀᣦᶆ࡜ࡋ࡚ᗈࡃ⏝࠸ࡽࢀ࡚࠸ࡿࡶࡢࡢࠊ୕ᗙ㓄఩Ꮚ࡛࠶ࡿࣆ
ࣥࢧ࣮ᆺ㓄఩Ꮚ࡟ࡘ࠸࡚ࡣ⣔⤫ⓗ࡞ㄪᰝࡣ࡯࡜ࢇ࡝⾜ࢃࢀ࡚࠸࡞࠸ࠋ௒ᅇࠊ⣔⤫ⓗ࡞❧యᅉᏊࡢㄪᰝࢆ⾜࠺ࡇ࡜࡛༙⌫ࠊ㊥㞳౫Ꮡゎᯒࡀࣆࣥࢧ࣮ᆺ㘒యࡢ❧యᅉᏊゎᯒ࡟࠾࠸࡚᭷ຠ࡞ᣦᶆ࡛࠶ࡿࡇ࡜ࢆ♧ࡋࡓ㸦ᅗ 2㸧ࠋ

ᅗ 2㸬ࣆࣥࢧ࣮㘒యࡢ༙⌫ࠊ㊥㞳౫Ꮡ❧యᅉᏊゎᯒ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬4-1. ‫‮‬ᑼᾈኴࠊ⚄㇂ᫀᏹࠊᘪ๐⚽㝯ࠊ➨ 10 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ
‫ۻ‬4-2. ⚄㇂ᫀᏹࠊC’s Meeting 2020㸦࢜ࣥࣛ࢖ࣥ㛤ദ㸧‫ۻ‬4-3. ⚄㇂ᫀᏹࠊ2020 ᖺᗘ➨ 10 ᅇ⌮Ꮫ㒊ࢭ࣑ࢼ࣮㸦໭㔛኱Ꮫ㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
 ‫ ۻ‬.DPLWDQL0.RXWD<<XJH+2UJDQRPHWDOOLFV2020

- 306 -

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿගྜᡂỈศゎ཯ᛂࡢศᏊᶵᵓࡢゎ᫂
4XDQWXPFKHPLFDOFDOFXODWLRQVWXG\RQWKHPROHFXODUPHFKDQLVPRISKRWRV\QWKHWLFZDWHUR[LGDWLRQ‫ۑ‬㔝ཱྀ ᕦࠊຍ⸨ ♸ᶞࠊᑠᯘ ᬛᖾ㸦ྡྂᒇ኱㝔࣭⌮㸧◊✲┠ⓗࠊෆᐜ
ගྜᡂỈศゎ཯ᛂࡣࠊග໬Ꮫ⣔ ,, ࢱࣥࣃࢡ㉁㸦36,,㸧ࡢ㓟໬ഃ࡟⤖ྜࡍࡿ 0Q&D2 ࢡࣛࢫࢱ࣮࡟࠾࠸࡚⾜ࢃࢀࠊ ࡘࡢ୰㛫≧ែ㸦66㸧ࡢ཯ᛂࢧ࢖ࢡࣝࢆ୍࿘ࡍࡿࡈ࡜࡟ࠊ ࡘࡢỈศᏊࡀ㸯ࡘࡢ㓟⣲ศᏊ࡜  ࡘࡢࣉࣟࢺࣥ࡟ศゎࡉࢀࡿࠋࡇࡢ཯ᛂ࡟ࡼࡾࠊ1$'3+ ྜᡂ࡟ᚲせ࡞㟁Ꮚ࠾ࡼࡧ $73 ྜᡂ࡟ᚲせ࡞ࣉࣟࢺࣥࡀ౪⤥ࡉࢀࠊࡲࡓ࿧྾⏕࿨ࡢ⏕Ꮡ࡟ᚲ㡲࡞㓟⣲ࡀᨺฟࡉࢀࡿࠋ36,, ࡢ ; ⥺⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡾᬯ୰࡛Ᏻᐃ࡞ 6 ≧ែࡢᵓ㐀ࡀ♧ࡉࢀࠊࡲࡓ㐃⥆ࣇ࢙࣒ࢺ⛊⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡾ୰㛫≧ែࡢᵓ㐀ࡢゎ᫂ࡀ㐍ࡵࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ
0Q&D2 ࢡࣛࢫࢱ࣮ࡸ㓄఩ỈศᏊࡢࣉࣟࢺࣥ໬ᵓ㐀ࡣྠᐃࡉࢀ࡚࠾ࡽࡎࠊỈศゎࡢศᏊᶵᵓࡢ඲ㇺࡣᮍࡔ᫂࠿࡜ࡉࢀ࡚࠸࡞࠸ࠋࡲࡓࠊ0Q&D2 ࢡࣛࢫࢱ࣮ࡣගάᛶ໬࡜࿧ࡤࢀࡿගㄏ㉳㐣⛬ࢆ⤒࡚ࠊ࢔࣏ 36,, ࢱࣥࣃࢡ㉁࡟ᙧᡂࡉࢀࡿࡀࠊࡑࡢᵓ⠏ᶵᵓࡢヲ⣽࡟ࡘ࠸࡚ࡶ࡯࡜ࢇ࡝ゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊ
㸦㸯㸧0Q&D2
ࢡࣛࢫࢱ࣮࡟㓄఩ࡍࡿỈศᏊࡢࣉࣟࢺࣥ໬ᵓ㐀ࠊ࠾ࡼࡧ㸦㸰㸧0Q&D2 ࢡࣛࢫࢱ࣮ᵓ⠏ࡢึᮇ㐣⛬࡟࠾࠸࡚ග㓟໬ࡉࢀࡓ 0Qࡢ⤖ྜ఩⨨ࢆࠊTXDQWXPPHFKDQLFVPROHFXODUPHFKDQLFV㸦4000㸧ィ⟬ࢆ⏝࠸࡚ㄪ࡭ࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ

 6 ≧ែ࡟࠶ࡿ 36,, ࢱࣥࣃࢡ㉁ࡢ ; ⥺⤖ᬗᵓ㐀㸦3'% FRGH 8% 6XJD HW DO 1DWXUH 㸧࠿ࡽࠊ0Q&D2
ࢡࣛࢫࢱ࣮ࡢ࿘ᅖ c ௨ෆࡢ࢔࣑ࣀ㓟ṧᇶ࠾ࡼࡧỈศᏊࢆษࡾྲྀࡾࠊึᮇᵓ㐀࡜ࡋࡓࠋࣉࣟࢺࣥ௜ຍ࡜ࡑࡢ
ᵓ㐀᭱㐺໬ࡢᚋࠊ*DXVVLDQ ୖࡢ 21,20 ἲ࡟ࡼࡾ 4000 ィ⟬ࢆᐇ⾜ࡋࡓࠋ0Q&D2 ࢡࣛࢫࢱ࣮࠾ࡼࡧࡑ
ࡢ࿘ᅖ࡟Ꮡᅾࡍࡿ࢔࣑ࣀ㓟࠾ࡼࡧỈศᏊࢆ 40 㡿ᇦ࡜ࡋࠊࡑࢀ௨እࡢᵓ㐀ࢆ 00 㡿ᇦ࡟ᣦᐃࡋ࡚ࠊᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋᵓ㐀᭱㐺໬࡟࠾࠸࡚ࠊ40 㡿ᇦࡢཎᏊࡣࡍ࡭࡚ࣇ࣮ࣜ࡜ࡋࠊ00 㡿ᇦࡢཎᏊ࡟ࡘ࠸࡚ࡣࡑࢀࡽ
ࡢ఩⨨ࢆᅛᐃࡋࡓࠋࡲࡓࠊ40 㡿ᇦࡢィ⟬࡟ࡣ %/<3 㛵ᩘ⣔ࢆ౑⏝ࡋࠊᇶᗏ⣔࡜ࡋ࡚ &D ཬࡧ 0Q ཎᏊ࡟ࡣ/$1/'= ࢆࠊࡑࡢ௚ࡢཎᏊ࡟ࡣ * G  ࢆ⏝࠸ࡓࠋ00 㡿ᇦࡢィ⟬࡟ࡣ $PEHU ຊሙࢆ᥇⏝ࡋࡓࠋ6 ≧ែ࠾ࡼࡧ㸯㟁Ꮚ㑏ඖࡋࡓ 6 ≧ែ㸦2+ ࠾ࡼࡧ 2+ ᵓ㐀㸧࡟ࡘ࠸࡚ࠊ0Q ࡟㓄఩ࡍࡿỈศᏊ : ࡀ +2 ࡢሙྜ࡜2+íࡢሙྜ࡟ࡘ࠸࡚ィ⟬ࢆ⾜ࡗࡓࠋ 0Q&D2 ࢡࣛࢫࢱ࣮ࡢᵓ⠏ᶵᵓ࡟ࡘ࠸࡚ࡣࠊୖグࡢࣔࢹࣝ࠿ࡽ 0Q&D2 ࢡࣛࢫࢱ࣮ࢆ㝖ཤࡋࡓ࢔࣏ග໬Ꮫ
⣔ϩࢱࣥࣃࢡ㉁࡟ 0Q ⤖ྜ㒊఩㸦0Q0Q0Q0Q㸧ࡢ㸲⟠ᡤ࡟ 0Qࢆ⤖ྜࡉࡏࡓྛ⣔࡟ࡘ࠸࡚ࠊ4000ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊࡑࡢ࢚ࢿࣝࢠ࣮ࢆồࡵࡓࠋ



◊✲ᡂᯝ

㸦㸯㸧0Q&D2 ࢡࣛࢫࢱ࣮ࡢỈ㓄఩Ꮚࡢࣉࣟࢺࣥ໬ᵓ㐀㸸0Q&D2 ࢡࣛࢫࢱ࣮ࡢ 0Q ࡟㓄఩ࡍࡿỈศᏊ :ࡀ +2 ࠾ࡼࡧ⬺ࣉࣟࢺࣥ໬ࡋࡓ 2+íࡢࡑࢀࡒࢀࡢᵓ㐀ࢆᣢࡘሙྜ࡟ࡘ࠸࡚㸦ᅗ㸯㸧ࠊ6 ≧ែ࡜ 2+ ᵓ㐀࠾ࡼࡧ 2+ ᵓ㐀ࢆᣢࡘ 6 ≧ែࡢࣔࢹࣝᑐࡋ࡚ࠊ4000 ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ: ࡀ +2ࡢሙྜ࡟ࡣ 0Q2 ࡢ㓄఩㊥㞳ࡣ࠾ࡼࡑ c ࡛࠶ࡾࠊ୍᪉ࠊ2+íࡢሙྜ࡟ࡣࠊc ࡢ 0Q2 ㊥㞳ࡀᚓࡽࢀࡓ㸦ᅗ㸰㸧ࠋࡇࢀࡲ࡛ᚓࡽࢀ࡚࠸ࡿ ; ⥺⤖ᬗゎᯒࡢᐇ㦂ࢹ࣮ࢱ࡜ẚ㍑ࡍࡿ࡜ࠊ0Q2 ㊥㞳ࡢᐇ㦂್ࡣ :㸻+2- 307 -

ᅗ㸯 6 ≧ែ㸦2+ ᵓ㐀㸧࡟࠾ࡅࡿ : +2 D ࠾
ࡼࡧ : 2+í E ࡢࣔࢹࣝ
ࡢሙྜࡢィ⟬⤖ᯝ࡜࡯ࡰ୍⮴ࡋࡓࠋࡑࡢ௚ࡢỈศᏊ㸦:
::㸧࡟ࡘ࠸࡚ࡶࠊࡍ࡭࡚ c ௨ୖࡢ 0Q &D 2 ㊥㞳ࡀᐇ㦂ⓗ࡟♧ࡉࢀ࡚࠸ࡿࡇ࡜࠿ࡽࠊ6 ࠾ࡼࡧ 6 ࡢ࠸ࡎࢀࡢ୰㛫≧ែ࡟࠾࠸࡚ࡶࠊ0Q&D2 ࢡࣛࢫࢱ࣮࡟⤖ྜࡍࡿỈࡣࡍ࡭࡚ࣉࣟࢺࣥ໬ࡉࢀࡓ +2 ࡢᵓ㐀ࢆᣢࡘ࡜⤖ㄽࡉࢀࡓࠋ
㸦㸰㸧0Q&D2 ࢡࣛࢫࢱ࣮ࡢᵓ⠏㐣⛬࡟࠾ࡅࡿ 0Qࡢᅗ㸰4000 ィ⟬࡟ࡼࡾᚓࡽࢀࡓ 0Q&D2 ࢡࣛࢫࢱ࣮㸦6 ࠾ࡼࡧ 6 ≧ែ㸧࡟࠾ࡅࡿ : ࡜ 0Q
ࣃࢡ㉁࡟࠾ࡅࡿ  ࡘࡢ 0Q ⤖ྜ఩⨨ࡢࡑࢀࡒࢀ࡟ 0Q
ࡢ 0Q2 ㊥㞳࡜ ; ⥺⤖ᬗゎᯒ࡟ࡼࡿᐇ㦂್ࡢẚ㍑
ࢆ㓄⨨ࡋ࡚ᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊࡑࢀࡽࡢ࢚ࢿࣝࢠ್࣮ࢆ
⤖ྜ఩⨨㸸0Q&D2 ࢡࣛࢫࢱ࣮ࢆ㝖࠸ࡓ࢔࣏ 36,, ࢱࣥẚ㍑ࡋࡓࠋࡑࡢ⤖ᯝࠊ0Q ࢧ࢖ࢺࡀ᭱ࡶᏳᐃ࡟ 0Q㸩ࢆ⤖ྜࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ0Q㸩ࡢග㓟໬࡟ࡼࡗ࡚⏕ᡂࡍࡿ 0Q㸩ࡣࢱࣥࣃࢡ㉁ࢥࣥࣇ࢛࣓࣮ࢩࣙࣥኚ໬ࡢᚋࠊ0Q ࢧ࢖ࢺ࡟⛣ືࡋ࡚Ᏻᐃ໬ࡍࡿ
ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ㸰␒┠࡟Ᏻᐃ࡞ 0Q ⤖ྜ㒊఩ࡣ 0Q ࢧ࢖ࢺ࡛࠶ࡗࡓࡇ࡜࠿ࡽࠊ㸰ࡘ┠ࡢ 0Q࢖࢜ࣥࡀ
0Q ࢧ࢖ࢺ࡟⤖ྜࡋࠊ0Q ࢧ࢖ࢺࡢ 0Q㸩࡜㸰᰾㘒యࢆᙧᡂࡍࡿࡇ࡜ࡀ᥎



ࡉࢀࡓࠋ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

մ ᑠᯘᬛᖾࠊᔱ⏣཭୍㑻ࠊ㛗ᑿ㑈ࠊ㔝ཱྀᕦࠊ5ROHRI'+LVLQWKHUHDFWLRQRIWKHVHFRQGDU\TXLQRQHHOHFWURQDFFHSWHU4%LQSKRWRV\VWHP,,ࠊ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ࠊ࢜ࣥࣛ࢖ࣥࠊ ᖺ  ᭶  ᪥ մ ᔱ⏣཭୍㑻ࠊ໭ᓥ ஭ཎ ᬛ⨾ࠊ㛗ᑿ㑈ࠊ㔝ཱྀᕦࠊ1RYHODPLQRDFLGFRQYHUVLRQRID+LVPXWDQWRI'$VSLQSKRWRV\VWHP,,ࠊ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ࠊ࢜ࣥࣛ࢖ࣥࠊ ᖺ  ᭶  ᪥ մ ᔱ⏣཭୍㑻ࠊ㕥ᮌ೺⿱ࠊ໭ᓥ ஭ཎ ᬛ⨾ࠊ㛗ᑿ㑈ࠊᇽ๓┤ࠊ㔝ཱྀᕦࠊ0HFKDQLVPRIQRYHODPLQRDFLGFRQYHUVLRQ
RID0QFOXVWHUOLJDQGLQSKRWRV\VWHP,,ࠊ᪥ᮏ᳜≀⏕⌮Ꮫ఍ᖺ఍ࠊ࢜ࣥࣛ࢖ࣥࠊ ᖺ  ᭶  ᪥ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

մ0<DPDPRWRDQG71RJXFKL9LEUDWLRQDOVWUXFWXUHRIWKH6VWDWHRIWKHSKRWRV\QWKHWLFZDWHUR[LGL]LQJFRPSOH[DV VWXGLHG E\ TXDQWXP PHFKDQLFVPROHFXODU PHFKDQLFV FDOFXODWLRQV Phys. Chem. Chem. Phys.   ±  մ $ 6DWR < 1DNDQR 6 1DNDPXUD DQG 7 1RJXFKL 5DSLGVFDQ WLPHUHVROYHG $75)7,5 VWXG\ RQ WKHSKRWRDVVHPEO\RIWKHZDWHUR[LGL]LQJ0Q&D2FOXVWHULQSKRWRV\VWHP,,J. Phys. Chem. BLQSUHVV- 308 -

Pd(II)஧
஧᰾㘒యࢆ⏝࠸ࡿගゐ፹ⓗ C-H ሷ⣲໬཯ᛂࡢ㛤Ⓨ
Development of Photocatalytic C-H Chlorination
by a Dinuclear Pd(II) Complexࠐᮧ⏣ ្ࠊ▼஭ ࿴அ㸦ᮾி኱Ꮫ⏕⏘ᢏ⾡◊✲ᡤ㸧◊✲┠ⓗࠊෆᐜ
஧ࡘࡢᖹ㠃ᅄ㓄఩ᆺ G 㔠ᒓ㘒యࡀྥࡁྜࡗࡓ≧ែ࡛ᯫᶫࡉࢀࡓ +DOIODQWHUQ ᆺ㘒యࡣࠊྍどගບ㉳࡟ࡼࡗ࡚⏕ࡌࡿ 0HWDO0HWDOWR/LJDQG&KDUJH7UDQVIHU 00/&7  ບ㉳≧ែ࡟࠾࠸࡚㔠ᒓࣛࢪ࢝ࣝᛶࢆ♧ࡋࠊཎᏊᘬ
ࡁᢤࡁ཯ᛂࢆ㉳ࡇࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡑࡢ኱༙ࡣ㔞ㄽ཯ᛂ࡟㛵ࡍࡿሗ࿌࡛࠶ࡾࠊゐ፹཯ᛂ࡟ᒎ
㛤ࡉࢀࡓ౛ࡣࡁࢃࡵ࡚ᑡ࡞࠸ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ+DOIODQWHUQ ᆺ 3G ,,  ஧᰾㘒యࡢ 00/&7 ບ㉳≧ែ࡟࠾ࡅࡿࣁࣟࢤࣥᘬࡁᢤࡁࢆ㘽࡜ࡍࡿࠊ᪂ወගゐ፹ⓗ &̽+ ࣁࣟࢤࣥ໬཯ᛂࡢ㛤Ⓨࢆ⾜ࡗࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ
+DOIODQWHUQ ᆺ 3G ,,  ஧᰾㘒య⁐ᾮ࡟ᑐࡋࠊ✀ࠎࡢⅣ໬Ỉ⣲ᇶ㉁ࢆస⏝ࡉࡏࠊྍどග㸦%OXH/('VOLUU 

QP㸧ࢆ↷ᑕࡋ࡚཯ᛂࢆ᥈⣴ࡋࡓࠋࡑࡢᚋࠊ3G ,,  ※ࠊ⁐፹ࠊῧຍ๣ࠊ↷ᑕἼ㛗࡞࡝ࡢ཯ᛂ᮲௳ࢆ᭱㐺໬ࡋࡓࠋࡇࢀࡽ࡜୪⾜ࡋ࡚ࠊ3G ,,  ஧᰾㘒యࡢᇶᗏ࠾ࡼࡧບ㉳≧ែ࡟࠾ࡅࡿ㟁Ꮚ≧ែࢆᐦᗘỗ㛵ᩘἲ㸦')7㸧࠾ࡼࡧ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲ㸦7'')7㸧࡟ࡼࡾࡑࢀࡒࢀゎᯒࡋࡓࠋィ⟬࡟ࡣࠊ*DXVVLDQ ࣃࢵࢣ࣮ࢪࢆ⏝࠸ࠊ0ỗ㛵ᩘ࠾ࡼࡧ 6'' 3G * GS  +&12  ᇶᗏ㛵ᩘ⣔ࢆ㐺⏝ࡋࡓࠋ



◊✲ᡂᯝ
཯ᛂ᮲௳ࢆ✀ࠎ᳨ウࡋࡓ⤖ᯝࠊ࣋ࣥࢰ>K@࢟ࣀࣜࣥ࡟ᑐࡋ࡚㐺ษ࡞ 3G ,,  ※ࠊᅄሷ໬Ⅳ⣲ࠊ࠾ࡼࡧ㖟ሷࢆస⏝ࡉࡏࠊྍどගࢆ↷ᑕࡍࡿࡇ࡜࡟ࡼࡾࠊ࢔࣮ࣜࣝ &̽+ ⤖ྜࡢゐ፹ⓗሷ⣲໬཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋᑐ↷ᐇ㦂ࡼࡾࠊᮏ཯ᛂ࡟ࡣྍどග࠾ࡼࡧ 3G ,,  ※ࡀᚲ㡲࡛࠶ࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋࡲࡓࠊ✀ࠎࡢᐇ㦂࠾ࡼࡧ⌮ㄽゎᯒࡢ⤖ᯝࡼࡾࠊᮏ཯ᛂ࡟ࡣ⣔୰Ⓨ⏕ࡍࡿ +DOIODQWHUQ ᆺ 3G ,,  ஧᰾㘒యࡢ 00/&7 ບ㉳≧ែࡀ㛵୚ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋᚑ᮶ࡢ 3G ,,  ゐ፹࡟ࡼࡿ⇕ⓗ &̽+ ࣁࣟࢤࣥ໬཯ᛂ࡛ࡣ୍⯡࡟ࠊࣁࣟࢤࣥཎᏊ
ࢆྵࡴᙉຊ࡞㓟໬๣ࡢῧຍࡀᚲせ࡜ࡉࢀ࡚ࡁࡓࠋ୍᪉ࠊᮏ཯ᛂࡣࠊ

࿴࡞᮲௳ୗ࡛㐍⾜ࡋࠊᏳ౯࡛ྲྀࡾᢅ࠸

ᐜ᫆࡞ࣁࣟࢤࣥ໬Ⅳ໬Ỉ⣲㢮ࢆࣁࣟࢤࣥ※࡜ࡋ࡚฼⏝ྍ⬟࡟ࡍࡿࡇ࡜࠿ࡽព⩏῝࠸ࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬๽⤂ீࠊὠ➃ᓫඖࠊᮧ⏣្ࠊ▼஭࿴அ ᪥ᮏ໬Ꮫ఍➨  ᫓Ꮨᖺ఍㸦࢜ࣥࣛ࢖ࣥ㸧ࠊ ‫ۻ‬ᮧ⏣្ࠊὠ➃ᓫඖࠊ▼஭࿴அ ➨  ᅇ᭷ᶵ㔠ᒓ໬Ꮫウㄽ఍㸦࢜ࣥࣛ࢖ࣥ㸧ࠊ㸦ணᐃ㸧   ௚  ௳ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬0HQJIHL:DQJ.HL0XUDWD<RVXNH.RLNH.D]X\XNL,VKLL&KHP(XU-2021LQSUHVV‫ۻ‬.D]X\XNL,VKLL-XQ\D:DGD.HL0XUDWD-3K\V&KHP/HWW2020
‫ۻ‬.HL0XUDWD<RVXNH.RLNH.D]X\XNL,VKLL&KHP&RPPXQ2020

- 309 -

」㞧࡛ከᵝ࡞ศᏊᵓ㐀࡜㟁Ꮚ≧ែ࠾ࡼࡧ໬Ꮫ཯ᛂ࡟㛵ࡍࡿ◊✲
Theoretical study for complex and heterogeneous molecular andelectronic structures and their chemical reactions‫ࠊ୍Ⰻ ⏣⚟ۑ‬㧗ᯇ ᫭ᙪ㸦ி㒔኱Ꮫ ᐇ㦂࡜⌮ㄽィ⟬⛉Ꮫࡢ࢖ࣥࢱ࣮ࣉࣞ࢖࡟ࡼࡿゐ፹࣭㟁ụࡢඖ⣲ᡓ␎◊✲ᣐⅬ㸧
1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ㄢ㢟࡛ࡣࠊ㔞Ꮚ໬Ꮫィ⟬ࢆᇶ┙ᡭἲ࡜ࡋࠊᅛయ⾲㠃࡜྾╔ศᏊࡸྜ㔠ࢡࣛࢫࢱ࣮ࡢࡼ࠺࡞ከᡂศ࠿

ࡽᵓᡂࡉࢀࡿศᏊ⣔ࡢᵓ㐀ࠊ㟁Ꮚ≧ែࠊ໬Ꮫ཯ᛂ࡟㛵ࡍࡿ◊✲ࠊཬࡧࠊ㟁Ꮚບ㉳≧ែ࡜࢖࢜ࣥ໬ࡸ㟁Ꮚ௜ຍ≧ែࡢࡼ࠺࡞ከᵝ࡞㟁Ꮚ≧ែࡀ㛵୚ࡍࡿࠊศᏊ⣔ࡢග≀ᛶࡸග໬Ꮫ཯ᛂࡢ◊✲ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋᮏᖺࡣࠊ
㸯) 」ྜ㔠ᒓཬࡧ」ྜ㔠ᒓ㓟໬≀⾲㠃ࡢ㟁Ꮚ≧ែ࡜ศᏊ྾╔ᶵᵓࡢゎ᫂ࠊ㸰㸧࢔࣑ࣝࢼ࡟ᢸᣢࡉࢀࡓⓑ㔠ゐ፹࡟ࡼࡿ࢚ࢳࣞࣥỈ⣲໬཯ᛂࡢ in situ 㝧Ꮚ㠀ᙎᛶᩓ஘ᐃࡢᖐᒓ࡜ゎᯒࠊ㸱㸧ᑐ㏆ఝࢡࣛࢫࢱ࣮ᒎ㛤ἲࡢ㛤Ⓨࢆ⾜ࡗࡓࠋࡇࡇ࡛ࡣ㸰) ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲศᏊ⣔ࡢィ⟬࡟ࡣ Gaussian 09/16 ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ SAC-CI ἲ࡜ DFT/TDDFT ཬࡧ OpenMolCas ࡟ᐇ⿦ࡉࢀ

࡚࠸ࡿ CASSCF/CASPT2 ἲࠊMolPro ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ Full-CI ἲࢆ⏝࠸ࡓࠋ㓟໬≀ᅛయ⾲㠃ཬࡧ࢔࣑ࣝࢼ࡟
ᢸᣢⓑ㔠⣔ࡢィ⟬࡟ࡣࠊᖹ㠃Ἴᇶᗏ࡟ࡼࡿ࿘ᮇቃ⏺᮲௳ࡢ DFT ィ⟬ࢆ VASP ࣉࣟࢢ࣒ࣛ࡟ࡼࡾ⾜ࡗࡓࠋ
OpenMP ཬࡧ MPI ࡟ࡼࡿ୪ิィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝ
3.1. in situ 㝧Ꮚ㠀ᙎᛶᩓ஘ᐃཬࡧ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ࢔࣑ࣝࢼ㸭ⓑ㔠ゐ፹ୖࡢỈ⣲✀ࡢྠᐃ࡜ࡑࡢάᛶ

Ỉ⣲✀(H)ࡣࠊゐ፹཯ᛂ࡟࠾࠸࡚᭱ࡶ㔜せ࡞୰㛫యࡢ୍ࡘ࡛࠶ࡿࠋⅣ⣲ከ㔜⤖ྜࡸ㓟໬≀ᐁ⬟ᇶࢆỈ⣲໬ࡍࡿࡓࡵ࡟ࡣࠊ㓟໬≀⾲㠃࡟ᢸᣢࡉࢀࡓ㔠ᒓᚤ⢏Ꮚゐ፹࡟ࡼࡿ H2 ࡢάᛶ໬ࡀᗈࡃ⏝࠸ࡽࢀ࡚࠾ࡾࠊỈ⣲✀୰㛫యࡢᛶ㉁ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣࠊ཯ᛂࡢຠ⋡໬ࡸ᪂ࡓ࡞཯ᛂタィ࡟Ḟ࠿ࡏ࡞࠸ࠋࡋ࠿ࡋࠊỈ⣲✀୰㛫ࡢ┤᥋ほࡣᅔ㞴࡛࠶ࡾࠊ⏕ᡂ≀࠿ࡽ୰㛫యࡸ཯ᛂ⤒㊰ࢆ᥎࡜ඹྠ࡛ࠊin situ 㝧Ꮚ㠀ᙎᛶᩓ஘ࡍࡿ஦ࡀ୍⯡ⓗ࡛࠶ࡿࠋ௒ᅇᡃࠎࡣࠊᐇ㦂ࢢ࣮ࣝࣉᐃ࡜ DFT ィ⟬࡟ࡼࡾࠊᐇ㝿ࡢ཯ᛂ⣔ࡢ࢔࣑ࣝࢼ㸭ⓑ㔠ゐ፹ୖ࡟Ꮡᅾࡍࡿ

Ỉ⣲✀ࡢྠᐃ࡟ᡂຌࡋࡓࠋࡉࡽ࡟ࠊ࢚ࢳࣞࣥࡢỈ⣲໬཯ᛂ࡟ᑐࡍࡿࠊࡑࢀࡽỈ⣲✀୰㛫యࡢάᛶࢆ㆟ㄽࡋࡓࠋᅗ㸯࡟♧ࡍࡼ࠺࡟ࠊȖAl2O3 (110)⾲㠃ୖ࡟ Pt (111)ࢆᢸᣢࡋࡓࣔࢹࣝࢆసᡂࡋࡓࠋ3 ḟඖ࿘ᮇቃ⏺᮲௳ࢆㄢࡋ࡚࠸ࡿࡓࡵࠊPt ࡣᲬ≧ࡢᵓ㐀࡜࡞ࡿࠋ༢఩ࢭࣝ࡟ࡣ Pt14(Al2O3)16 ࢆྵࡴࠋྍ⬟ᛶࡢ࠶ࡿ 10 ࠿ᡤࡢ྾╔ࢧ࢖ࢺ࡟ H ࢆ྾╔ࡉࡏࡓࠋᗏࡢᒙࢆᅛᐃࡋࠊᵓ㐀᭱㐺໬࡜᣺ືᩘࡢィ⟬ࢆ⾜ࡗࡓࠋィ⟬࡟ࡣ PAW ἲࠊPW91 ỗ㛵ᩘࢆ⏝࠸ࠊᖹ㠃Ἴࡢ࢝ࢵࢺ࢜ࣇࡣ 600 eVࠊk-point mesh ࡣ 2î2î ࢆ⏝࠸ࡓࠋ㝧Ꮚ㠀ᙎᛶᩓ஘ (inelastic neutron scattering: INS)ࢫ࣌ࢡࢺࣝࡢᙉᗘࡣḟᘧࡢࡼ࠺࡟ィ⟬ࡉࢀࡿࠋ
,

Z

³ G4


ª­
º
4
§ Z· ½
H S  X  4  * Z « ®H[S ¨
H[S¸ ¾  »
0 Z
© N7 ¹ ¿¬« ¯¼»
ࡇࡇ࡛ࠊM ࡀᩓ஘ཎᏊࡢ㉁㔞ࠊω ࡀほ(1)ࡋ࡚࠸ࡿ࣮ࣔࢻࡢ᣺ືᩘ࡛<u2>ࡣࡑࡢཎᏊᗙᶆࡢᖹᆒ஧஌ኚ఩ࠊG(ω)ࡀ᣺ື≧ែࡢᐦᗘ࡛࠶ࡿࠋࡇࡇ࡛ࡣ྾╔Ỉ⣲✀ࡢ⃰ᗘࢆ⪃៖ࡋ࡚࠸࡞࠸ࡓࡵࠊG(ω)౫Ꮡᛶࡣ⌧ࢀ࡞࠸ࠋINS- 310 -

ࢫ࣌ࢡࢺࣝᙉᗘࡣᩓ஘ཎᏊࡢ㉁㔞࡟཯ẚ౛ࡍࡿࡓࡵࠊỈ⣲✀ࡀ㛵ಀࡍࡿ᣺ືࢆ㑅ᢥⓗ࡟ほ࡛ࡁࡿࠋࡉࢀࡓ INS ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋᐇ㦂ࡣ H2 ὀධ๓ࠊH2 ὀධᚋࠊ࢚ࢳࣞࣥὀධᚋࡢ

ᅗ㸯࡟ィ⟬⤖ᯝཬࡧほኚ໬ࢆ♧ࡋ࡚࠸ࡿࠋࢫ࣌ࢡࢺࣝࡢኚ໬ࡀィ⟬࡟ࡼࡾᖐᒓࡉࢀࡓỈ⣲✀ࡢ⏕ᡂ㸭ᾘ㈝࡟ᑐᛂࡋ࡚࠸ࡿࠋỈ⣲ࡣPt ୖ࡛άᛶ໬ࡉࢀࡿ࡜ࡀࠊAlO-H ✀ࡀቑຍࡋ࡚࠸ࡿ஦ࡣ࢔࣑ࣝࢼୖ࡬ࡢỈ⣲ࡢࢫࣆ࣮ࣝ࢜ࣂ࣮ࡀほࡉࢀࡓ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊAlO-H ✀ࡣⓑ㔠ୖ࡟㏫࡟⛣ືࡋ࢚ࢳࣞࣥỈ⣲໬࡟ᐤ୚ࡋࡓࠋࡘࡲࡾࠊάᛶỈ⣲✀ࡀ࢔࣑ࣝࢼୖ࡟㈓ⶶࡉࢀࡿ஦ࡀศ࠿ࡗࡓࠋࡲࡓࠊedge ࡟྾╔ࡋࡓỈ⣲ࡣỈ⣲໬཯ᛂᚋ࡟ࡶほࡉࢀࡓ஦࠿ࡽࠊά

ᛶࡀప࠸࡜⪃࠼ࡽࢀࡿࠋ
ᮏ◊✲ࡣࠊ኱ᙉᗘ㝧Ꮚຍ㏿ჾ᪋タ J-PARC ࡜ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮RCCS ࡢ኱つᶍ᪋タࢆ౑ࡗࡓඹྠ◊✲࡟
ࡼࡾࠊゐ፹ࡢ᪂ࡓ࡞ほᡭἲࠊ◊✲᪉ἲࢆᣅࡃࡶࡢ࡛࠶ࡿࠋ

ᅗ 1㸬(a) Pt14(Al2O3)16 ィ⟬ࣔࢹࣝ㸦࿘ᮇቃ⏺㸧(b) ィ⟬࡟ࡼࡾࢩ࣑࣮ࣗࣞࢩࣙࣥࡋࡓ INS ࢫ࣌ࢡࢺࣝ (c) ほࡉࢀࡓ INS ࢫ࣌ࢡࢺࣝ࡜ࡑࡢᖐᒓࠋ

4

Ⓨ⾲ᐇ⦼

‫ ۻ‬㧗ᯇ᫭ᙪ㸪⚟⏣Ⰻ୍ࠕ࣌ࣟࣈࢫ࢝࢖ࢺ㓟໬≀ Sr3Fe2O7 ཬࡧ SrFeO3 (001)㠃࡟࠾ࡅࡿ❅⣲㓟໬≀ࡢ㓟໬࣭྾ⶶ࣓࢝ࢽࢬ࣒ࠖ➨ 126 ᅇゐ፹ウㄽ఍㸪2020 ᖺ 9 ᭶㸪࢜ࣥࣛ࢖ࣥ

5

ฟ∧ᐇ⦼

‫ ۻ‬6<DPD]RH$<DPDPRWR6+RVRNDZD5)XNXGD.+DUD01DNDPXUD..DPD]DZD77VXNXGD+<RVKLGD
77DQDND³,GHQWLILFDWLRQRI+\GURJHQ6SHFLHVRQ3W$O2E\LQVLWX,QHODVWLF1HXWURQ6FDWWHULQJDQGWKHLU5HDFWLYLW\ZLWK(WK\OHQH´&DWDO\VLV6FLHQFH 7HFKQRORJ\11±  ‫ ۻ‬$7DNDPDWVX.7DPDL6+RVRNDZD77DQDND0(KDUD5)XNXGD³2[LGDWLRQDQG6WRUDJH0HFKDQLVPVIRU
1LWURJHQ 2[LGHV RQ 9DULRXVO\ 7HUPLQDWHG   6XUIDFHV RI 6U)H2 íį DQG 6U)H2íį 3HURYVNLWHV´ $&6 $SSOLHG
0DWHULDOV ,QWHUIDFHV13±  - 311 -


Investigation of organic reaction mechanism using
computational chemistryŧ ¸ã, ðċ º¬, ŧċ ÍŨďŅ¢û} yĕĜÒũ1ĕĜđĎ¶®ŋŐûr·ÁùŝÝû3č½2;,.èô°Ë3ćŃĎĽê4ª !č½&.>tà/š®ĄÏľġ+"/4İÐ/ 1¡®0&.°ì:î3ř®ì×#<?>ŌÀtĳĎ2Ċ<?>èô°Ë3ŔÔÌ3Üŕĺ¡0&.9)?<3ìüđ%?.>
ĕĜĸı4Ë3ŔÔÌčĆ2°ìŝA,.!>èô°Ë3ŁĨ1ĽêBđĎ0&.
^ogo]q63ŗ®3Ë3Ëôò3ĽêBĶ,*8*ôĲÌ®r«āăÑ63½ś
Bxē2*ßļË3śčBđĎ0&*ĕĜ3tĈ0&.)3ËôòĽêBĶ,*Ď1¶űèôòŎ°2.^ogo\oJVIq3ŬwÊūš®ī3¯¤ĲÌ4ª 1
Ń{3Ď01,.*Ć¤/4Č;19301,.> &&Ń{3w/)?<04tĻ
ĔĒ'>īì9ÚĖ%?.>Ń{3ĩĐ/> 1970 ÀH. C. Brown <4øîĎ1¹D\Iq3¯¤1

v/4^ogo\oJVIq4Ď1òŎB0,.>0xÅB½ś&)3ïÕ0&.Ř÷Ħ%?*ŗ®3^ogo]q5)3ł»63ËBÚĖ&* (£ 1) ZnboIpŖŗ D 
(TFA-d) BĊ*Ë2.²2¹Ę
D1òŎBè'>^ogo\oJVIqčĉOH
OH
CF3COOD LiAlH4
Other+ Isotopomers
D +&.>§24ĉÑă3öą4Ġ&!1>
Et2O
0 ºC
4(/>µş24ĉÑă3öą ,
:
:
37
26
37
.>$3µť|µ¹ĘòŎBÖ-Ţ£Ū. TFA 3^ogo]q63ËĎJVIq63ŀ0&.Ċ%?*ė(a)R
ő4éË2Ţ¿ķì.>$0BzÎ&
NH
N
n
OAr2
CF3SO3H
ŔÔÌ3Ňÿ2-.Ĥí&*O
Ar1 O
CH2Cl2ßļèô°Ë0&.ňÆŗ§2">XZ
Ar1,2: aromatic rings
R: Substituentsm`[pESK^nqł»3P`[pESK^pn = 0,1(b)qł»63ËBčĻ&)3Ë3tĳÌ0Ë
COOMe
X1
ôò2-.ĽêBĶtà/Ũ£ū (a)ũ8-IKS
X1
O
N O
N
CF3SO3H
doaqŤ3ąĎÑË3ôòBñĿ&Ũ£ū
O
n
n O N
CH2Cl22(b)ũ«āăÑ3cmWZbHsj0&.èĊ0İ
X2
X2
<?>boIpG^qă63øîË3Ë
(c)
F
Nu
RO
ôòBĤí&* (£ū (c))
RO
Nu–
2

O
O

2

ĕĜàûľġàû

O

£ū. ~

F

O
O

O
F

3ĕĜ¹ń0&*ßļ°Ëį·ÁùŝÝûBĊ*š®G]oLsØÝòŎçŒľġ24 Gaussian16 5 GRRM14 cpNmjBĊ&*8*®ŋŐûBĊ*ŦĤÁš®
G]oLsľġ24 Molpro cpNmjBĊ&*ğtć®°û2;>Ëŋŉ3ľġ24ĕĜĸıæ*°ľġcpNmjBĊGaussian16 8*4 MOPAC 2;,.ľġ&*BĊ&.ěBĶ,.>¨œęĄÏćŃľġ;5Zq]oìĹõ2ŝ&.4i]STª° D. Truhlar <2;,.śč%?* POLYRATE BĊNosc2;,.śč%?* GAUSSRATE BEqTsbFsQ0&.
Gaussian16 Bř®°ľġ2Ċ&.>±´ŕÂĽê24ĕĜĸıæ*hoObŏŚlqXJopû2;>ŕÂĝŜÙħcpNmjBĊ.>

- 316 -

Cl3C

3

O

ĕĜÑì

O –
D

O
O

D

CCl3

+

ľġ2Œ&*dqRqĀ­3Ëĥ2.ŁĨ1ōÁCClþ´µťBĶ,*0$@cpZqË3ýÌĚ4 7)$
CCl
O
D O
O
D O
O
CCl
D
O
CCl
3©ř/>$0,*äÀÁ¦&*^ogoODO£Ŭ]qł»37 GLK\GURPHWKDQRQDSKWKDOHQH B
Ñ& £Ŭ )?<63 7)$G 3Ë3ŔÔÌB£ŭ. ĪŊ¾3óÃ£µťĎ2É>0092®°û2;,.)3ŔÔÌBľġ&*éË4œęĄÏÈ3ĪŊ¾2;,.Ë3ŔÔÌú´%?.>0$0ã<21,.>Ũ£ŭũé¥ņ3§^ogo]q;=9ō:2ŢĎJVIq60¨'>$0
Ė%?*
3

3

3

3

 8*XZm`[pESK^nqł»3Ëôò0&.µť5ľġ2;>Ľê3īìĞĦu3cpZqBĪ.dqPoJVIqčĉ&)3JVIqå1>cpZqB"*PJVIqBčĉÄ Ĭ!ĈË2;,.ZnDnsokTqŤĉÑ'>TqYjËôòã<21,*Ũ£Ůũ8*ŰIKSdoaqŤ3ĉÑË2.Jo_lEo¥3ýÌ3ōÁ»%?*\Zp¥3Į2;,.ª !ÇţB".=$3ýÌË3ÑBú´&.>$0Bã<2&*Ũ£ůũ

O
OMe
Me H
ΔG

kcal/mol
Me N
O
X
=
H,
X
=
H
(1’)
1
2

O
X = NO , X = H (6’)
1

Ar1
N

Ar1 O

OAr2

H
Ar1-3: aromatic rings

Ar1

H
H
N

OAr2
O

H

+H+
-H+

H
N

Ar3

O

H

X1

NH

Ar1

N Me
O

MeO

7.4
7.3
8.0

O

O

Triarylmethanes

19.4
13.4
16.0

O
H

X2

X2

22.6
18.1
20.9

Me
X1

O

OAr2

2

NH

n
Intramolecular
reactionor Ar3-H
addition2

X1 = H, X2 = NO2 (7’)

R

0.0
0.0
0.0
Me

£Ů. PJVIqwŜBĪ>Ëôò

Me
N
O

H

O

Me
Me N

OMe

O

O
H

OMe

O
X1

X2

O
X1

X2

£ů. lYoBĊ*Jo_ksZ3ýÌ3ËUEDNmj

čĸµĭ8*4z´ňÆŗBĊ&*XZm`[pESK^nqł»3ZnDnsokTq63¨ÛËŧ¸ã áéĴ°ğ   À 2³Ĳ¥Bè'>fQbCVPoOnqŤ3Ñ0  >  

;5   JWcnqN2;

 QeMZo3Ľêðċº¬¼ëŠtĢ ŞÞĵ âã áéĴ°ğ   ÀĂµĭ8*4z´Óģ1) Enhancement of the carbamate activation rate enabled syntheses of tetracyclic benzolactams: 8-oxoberbines andtheir 5- and 7-membered C-ring homologues. Hiroaki Kurouchi, Org. Biomol. Chem., 2021, 19, 653-658.
2) Diprotonative stabilization of ring-opened carbocationic intermediate: conversion of tetrahydroisoquinoline totriarylmethanes. Hiroaki Kurouchi, Chem. Commun., 2020, 56, 8313-8316.

- 317 -







Computational catalyst design and analysis of organic luminescentmaterials() (I) 
+ * ! 0 &
1 2'

3 ./%&/4



%&$#



Å¤Êw¸l'aÇWmaa!Æ'^$OÈ´$¿yÑªzÉm_o¹©"$Å¤·'ÇWmc ÆMº¹Í$£¦ ¡(
&%$£¦|£¦r ¿ÌË(I)¸l"$R¯)JLÏ/IA@,«_a $ÇWmY#$ '¢ $%&-(Ém_o¹©7><,-)TP?K1GC' (1) 6L8NZ?K1GC=:2

N4: Gaussian 16 (rev. C.01) (2) FN3N+L5<NI: GRRM (developer’s version)PSI4 (ver. 1.3.2)Orca(ver. 4.2.1)pa#Q%$§XÆp$«Á¥¹©E;I'Y Ém_o¹©'Å¤¬'³®¹©##%$¼ ÆqÐÆ'¾
$ ¹©k|'»[k|$°#%$Å¤tÀÎm·'³%&¿|£¦rË , ¸l"$R¯)JLÏ)I0I@,«_a'f¯)I2LÀ'$)HI@,«_cc 'Â ah½¯h" 1+& ÇWm 6,0HV  @5>*LÇWm ;DQWSKRVÄ$aW¯M§XÆ~ieµ#%

Æ$ '#$ ')7 ¹©'Å¤·'³­@,«u\Å¤@,«hD9Ih'bs$   $ÇWmÀ B2:<ÀÑÆÈ´$  ] g  S} %#­' ¶ÇWm;3+L'³ÆdO'¢g  R¯)JLÏ)I0I@,«_a $§XÆpÅ¤

- 318 -

 ",)  





 

v ` Ã² {x U² ± ³R¯)JLÏ)I0I@,«_a"$j¯)HI@,«_cW¯"§XÆ c ´ _oV¨  nyV .LG+L)























7DNDKDVKL5.XERWD.,WR+³$LUDQGPRLVWXUHVWDEOH;DQWSKRVOLJDWHGSDOODGLXPGLDON\OFRPSOH[DVD
SUHFDWDO\VWIRUFURVVFRXSOLQJUHDFWLRQV´&KHP&RPPXQ±
6HNL 7 ,GD . 6DWR + $RQR 6 6DNDNL 6 ,WR + ³$XURSKLOLFLW\PHGLDWHG &RQVWUXFWLRQ RI (PLVVLYH
3RURXV0ROHFXODU&U\VWDOVDV9HUVDWLOH+RVWVIRU/LTXLGDQG6ROLG*XHVWV´&KHP(XU-±
6HNL70DVKLPR7,WR+³&U\VWDO-XPSLQJRI6LPSOH+\GURFDUERQV&RROLQJ,QGXFHG6DOLHQW(IIHFWRI
%LV 7UL DQG 7HWUDSKHQ\OHWKHQH WKURXJK $QLVRWURSLF /DWWLFH 'LPHQVLRQ &KDQJHV ZLWKRXW 7KHUPDO 3KDVH
7UDQVLWLRQV´&KHP/HWW±
7DJXFKL-0DWVXXUD66HNL7,WR+³6\QWKHVLVDQG7XQDEOH2SWLFDO3URSHUWLHVRI&1&KHODWHG%RUDWH
/XPLQRSKRUHV'HULYHGIURP3RWDVVLXP$F\OWULIOXRURERUDWHV´&KHP(XU-±
+D\DPD . .RMLPD 5 .XERWD . ,WR + ³6\QWKHVLV RI &KLUDO 1+HWHURF\FOLF $OO\OERURQDWHV YLD WKH(QDQWLRVHOHFWLYH%RU\ODWLYH'HDURPDWL]DWLRQRI3\UUROHV´2UJ/HWW±,ZDPRWR + +D\DVKL < 2]DZD < ,WR + ³6LO\OJURXSGLUHFWHG /LQHDUVHOHFWLYH $OO\ODWLRQ RI &DUERQ\O&RPSRXQGVZLWK7ULVXEVWLWXWHG$OO\OERURQDWHV8VLQJD&RSSHU , &DWDO\VW´$&6&DWDO±
6HNL77R\RVKLPD1,WR+³0L[HGFU\VWDOIRUPDWLRQRIWZRJROGLVRF\DQLGHFRPSOH[HVZLWKYDULRXVUDWLRVIRUFRQWLQXRXVWXQLQJRISKRWRSK\VLFDOSURSHUWLHV´'DOWRQ7UDQV±
$NL\DPD 6 1RPXUD 6 .XERWD . ,WR + ³&RSSHU , &DWDO\]HG %RU\O 6XEVWLWXWLRQ RI 7ULIOXRURPHWK\O$OOHQHVIRUWKH6\QWKHVLVRI%RU\O6XEVWLWXWHGJHP'LIOXRURGLHQHV´-2UJ&KHP±
6HNL 7 )HQJ & .DVKL\DPD . 6DNDPRWR 6 7DNDVDNL < 6DVDNL 7 7DNDPL]DZD 6 ,WR +
³3KRWROXPLQHVFHQW)HUURHODVWLF0ROHFXODU&U\VWDOV´$QJHZ&KHP,QW(G±
6HR7.XERWD.,WR+³6HOHFWLYH0HFKDQRFKHPLFDO0RQRDU\ODWLRQRI8QELDVHG'LEURPRDUHQHVE\,QVLWX&U\VWDOOL]DWLRQ´-$P&KHP6RF±
6KLVKLGR58HVXJL07DNDKDVKL5LNXUR0LWD7,VKL\DPD7.XERWD.,WR+³*HQHUDO6\QWKHVLVRI 7ULDON\O DQG 'LDON\ODU\OVLO\OERUDQHV 9HUVDWLOH 6LOLFRQ 1XFOHRSKLOHV LQ 2UJDQLF 6\QWKHVLV´- $P &KHP
6RF±
3DQJ</HH-:.XERWD.,WR+³6ROLG6WDWH5DGLFDO&í+7ULIOXRURPHWK\ODWLRQ5HDFWLRQV8VLQJ%DOO
0LOOLQJDQG3LH]RHOHFWULF0DWHULDOV´$QJHZ&KHP,QW(G±
.XERWD . 7DNDKDVKL 5 8HVXJL 0 ,WR + ³$ *ORYHER[ DQG 6FKOHQNOLQHIUHH 3URWRFRO IRU 6ROLGVWDWH&1 &URVVFRXSOLQJ 5HDFWLRQV 8VLQJ 0HFKDQRFKHPLVWU\´$&6 6XVWDLQDEOH &KHP (QJ
±
+D\DPD . 7DNDKDVKL 5LNXUR .XERWD . ,WR + ³&RSSHU , &DWDO\]HG 6WHUHRVHOHFWLYH 6LO\ODWLYH
'HDURPDWL]DWLRQRI,QGROHVDQG3\UUROHVXVLQJ6LO\OERURQDWHV´&KHP/HWW±
-LQ 0 $QGR 5 -HOOHQ 0 - *DUFLD*DULED\ 0 $ ,WR + ³(QFDSVXODWLQJ 1+HWHURF\FOLF &DUEHQH
%LQXFOHDU7UDQVLWLRQ0HWDO&RPSOH[HVDVD1HZ3ODWIRUPIRU0ROHFXODU5RWDWLRQLQ&U\VWDOOLQH6ROLG6WDWH´-
$P&KHP6RF±
0DWVXXUD67DJXFKL-6HNL7,WR+³6\QWKHVLVDQG2SWLFDO3URSHUWLHVRI&16ZDSSHG%RUDQLOV'HULYHG
IURP3RWDVVLXP$F\OWULIOXRURERUDWHV´%XOO&KHP6RF-SQ-XVW$FFHSWHG$NL\DPD 6 2\DPD 1 (QGR 7 .XERWD . ,WR + ³$ &RSSHU , &DWDO\]HG 5DGLFDO 5HOD\ 5HDFWLRQ(QDEOLQJ WKH ,QWHUPROHFXODU $ON\OERU\ODWLRQ RI 8QDFWLYDWHG 2OHILQV´- $P &KHP 6RF
±
6HR 7 7R\RVKLPD 1 .XERWD . ,WR + ³7DFNOLQJ 6ROXELOLW\ ,VVXHV LQ 2UJDQLF 6\QWKHVLV 6ROLG6WDWH&URVV&RXSOLQJRI,QVROXEOH$U\O+DOLGHV´-$P&KHP6RF±
.DWR.6HNL7,WR+³ ,VRF\DQRDQWKUDFHQH JROG , &RPSOH[HV([KLELWLQJ7ZR0RGHVRI&U\VWDO-XPSV
E\'LIIHUHQW6WUXFWXUH&KDQJH0HFKDQLVPV´,QRUJ&KHP-XVW$FFHSWHG
,ZDPRWR+2]DZD<7DNHQRXFKL<,PDPRWR7,WR+³%DFNERQH0RGLILHG&6\PPHWULFDO&KLUDO%LVSKRVSKLQH 7064XLQR[3  $V\PPHWULF %RU\ODWLRQ RI 5DFHPLF $OO\O (OHFWURSKLOHV´- $P &KHP
6RF±
.XERWD.7R\RVKLPD10LXUD'-LDQJ-0DHGD6-LQ0,WR+³,QWURGXFWLRQRID/XPLQRSKRUHLQWR *HQHULF 3RO\PHUV YLD 0HFKDQRUDGLFDO &RXSOLQJ ZLWK D 3UHIOXRUHVFHQW 5HDJHQW´$QJHZ &KHP ,QW
(G-XVW$FFHSWHG
.XERWD.0LXUD'7DNHXFKL72VDNL6,WR+³6\QWKHVLVRI&KLUDOĮ$PLQR7HUWLDU\%RURQDWHVYLDWKH
&DWDO\WLF(QDQWLRVHOHFWLYH1XFOHRSKLOLF%RU\ODWLRQRI'LDON\O.HWLPLQHV´$&6&DWDO±

- 319 -

᭤ࡆኚᙧ࡟㛵ࡍࡿᾮᬗᏳᐃᛶࡢศᏊືຊᏛ࡟ࡼࡿ◊✲0ROHFXODU'\QDPLFV6WXG\IRUWKH'HIRUPDWLRQ 
DQG,QVWDELOLW\LQ/LTXLG&U\VWDO ‫ۑ‬ᆏᮏ 㐨᫛㸦ᮾி㎰ᕤ኱Ꮫ㸧◊✲┠ⓗ㸪ෆᐜ
ࢫ࣓ࢡࢸ࢕ࢵࢡᾮᬗࡣᒙᵓᡂࢆྲྀࡿࡓࡵ㸪ᶵᲔⓗኚᙧ࡟ࡼࡾᒙࡢ᭤⋡ࡀ⮫⏺್࡟㐩ࡍࡿ࡜㸪ᒙᵓ㐀ࡣࢺ࣏ࣟࢪ࣮Ḟ㝗ࡢⓎ⏕࡜ඹ࡟ᔂቯࡍࡿ㸬ࡋࡓࡀࡗ࡚㸪ኚᙧ࡟ᑐࡍࡿᒙ⛛ᗎࡢᏳᐃᛶࡢ☜❧࠾ࡼࡧḞ㝗ࡢᢚไࡣ㸪ࡇࢀࡽࡢศ㔝࡟ᛂ⏝ࡍࡿ࡟࠶ࡓࡾ኱ࡁ࡞ㄢ㢟࡛࠶ࡿ㸬ᮏ◊✲࡛ࡣ㸪ᾮᬗࡢ᭤ࡆኚᙧ࡟క࠺ࡇࢀࡽࡢ⛛ᗎᵓ㐀࡬ࡢᙳ㡪࡟ࡘ࠸࡚㸪࣓ࢰࢫࢣ࣮࡛ࣝࡢศᏊືຊᏛࡢどⅬ࠿ࡽᢅ࠺ࡇ࡜࡟ࡼࡾ㸪᭤ࡆ࡟ᑐࡍࡿᾮᬗ㓄ྥ⛛ᗎࡢᏳᐃ໬ࢆ⌮ㄽⓗ࡟᳨ウࡍࡿ㸬 ᖺᗘࡣ㸪&% ᾮᬗศᏊࡢ⢒ど໬ࣔࢹࣝࢆ⏝࠸࡚࣓ࣛࣛᵓ㐀ࢆ⏕ᡂࡋ㸪ศᏊືຊᏛࣉࣟࢢ࣒࡛ࣛ࠶ࡿ *URPDFV ࢆ⏝࠸࡚᭤ࡆኚᙧࡢィ⟬ࢆ⾜࠸㸪࣓ࣛࣛᒙࡀᔂቯࡋࢺ࣏ࣟࢪ࢝ࣝḞ㝗ࢆ⏕ᡂࡍࡿࡲ࡛ࡢ㐣⛬ࢆㄪ࡭ࡓ㸬 ᖺᗘ࡟㸪ࡉࡽ࡟ෆᐜࢆ඘ᐇࡉࡏ࡚ㄽᩥࢆసᡂࡋ࡚ᰝㄞ௜ࡁㄽᩥ㞧ㄅ࡬ᢞ✏࣭ฟ∧ࡋࡓ 㸬ࡲࡓ㸪⢒ど໬ຊሙࡢ࣮࣋ࢫ࡜࡞ࡿ㸪ኚᙧࢩ࣑࣮ࣗࣞࢩࣙࣥࡀྍ⬟࡞඲ཎᏊศᏊຊሙࡢ⢭ᗘࢆ㧗ࡵࡿࡓࡵ㸪ỗ⏝ຊሙ࡟⿵ṇࢆ࠿ࡅࡿࡇ࡜࡛ᢳฟࡋࡓ㸬 ᖺᗘࡣ㸪ୖグ࡛ㄝ᫂ࡋࡓᢳฟࡋࡓ඲ཎᏊศᏊຊ
ሙࢆᇶ࡟ከ┠ⓗ᭱㐺໬ᡭἲࢆ⏝࠸࡚⢒ど໬ຊሙࡢᢳฟࢆ⾜ࡗࡓ㸬ᑟฟࡉࢀࡓࣔࢹࣝࡣ㸪ᗙᒅኚᙧ㸪ࢫ࣓ࢡࢸ࢕ࢵࢡᒙࡢᔂቯ㸪ࢹ࢕ࢫࢡࣜࢿ࣮ࢩࣙࣥᑐࢆక࠺㌿఩Ḟ㝗⏕ᡂ࡜࠸ࡗࡓ᪤▱ࡢ≉ᛶࢆ෌⌧ࡋ࡚࠾ࡾ㸪ࢺ࣏ࣟࢪ࢝ࣝḞ㝗ࡢ⌮ㄽࡸᐇ㦂࡜୍⮴ࡋࡓ㸬ࡇࢀࡽࡢᢳฟᡭἲཬࡧᚓࡽࢀࡓࣔࢹࣝ࡟㛵ࡋ࡚ㄽᩥᢞ✏ࢆ⾜ࡗࡓ㸬◊✲᪉ἲ㸪ィ⟬᪉ἲ
3DUHWRVHW ࡟ᇶ࡙ࡃከ┠ⓗ᭱㐺໬ࣇ࣮࣒࣮ࣞ࣡ࢡࢆ㛤Ⓨࡋ㸪Ḟ㝗⏕ᡂ᫬ࡢศᏊᥥീࢆྵࡴศᏊືຊᏛࡢࡓࡵࡢ⢒ど໬ຊሙࢆᑟฟࡋࡓ㸬┠ⓗ㛵ᩘ࡟ࡣ㸪ືᚄศᕸ㛵ᩘࡢ௚࡟㸪ᾮᬗࡢ⛛ᗎኚᩘ࡜ᒙᔂቯࡢ⮫⏺ゅࢆ᥇⏝ࡋ㸪ࡑࢀࡽࡢᛂ⟅㠃ࢆ࢞࢘ࢫ㐣⛬࡟ࡼࡾ᥎ᐃࡋࡓ㸬ࡲࡓ㸪᥈⣴✵㛫ࢆศᏊࡢ KHDGWDLO ᑐ⛠ᛶࡢ㧗࠸㒊ศ࡜ప࠸㒊ศ࡟ศࡅ㸪ྛࢧࣈࢻ࣓࢖ࣥࡢᛂ⟅㠃࡟ᇶ࡙࠸࡚㸪*$ ࢆ⏝࠸࡚ࣃ࣮ࣞࢺ᭱㐺ゎࢆồࡵ㸪 ศᏊࡢ KHDGWDLO ᑐ⛠ᛶࡢ㧗࠸ຊሙ࡜ప࠸ຊሙࢆࡑࢀࡒࢀ㑅ᢥࡋࡓ㸬



◊✲ᡂᯝ

ᚓࡽࢀࡓຊሙࢆ⏝࠸࡚㸪ኚᙧࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋ㸪⏕ᡂࡉࢀࡿḞ㝗ࡢ✀㢮ࢆㄪ࡭ࡓ㸬⏕ᡂࡉࢀࡿḞ㝗ࡢ✀㢮ࡣ㸪ᵓᡂศᏊࡢ KHDGWDLO ᑐ⛠ᛶ࡟౫Ꮡࡍࡿ㸬⢒ど໬ຊሙࡢᮎ➃⢏Ꮚ࡛࠶ࡿ & 1 ⢏Ꮚཬࡧ $/ ⢏Ꮚࡢ/HQQDUG-RQHV ຊሙࡢ࢚ࢿࣝࢠ࣮ࣃ࣓࣮ࣛࢱࡢẚ⋡ U ࣅ&1í&1ࣅ$/í$/ ࡜ࡋ࡚ KHDGWDLO ᑐ⛠ᛶࢆᐃ⩏ࡋࡓሙྜ㸪ᅗ ࡟♧ࡍ㏻ࡾ㸪KHDGWDLO ᑐ⛠ᛶࡀ㧗࠸㸦ᅗ  D  E  F 㸧࡯࡝㸪GLVFOLQDWLRQ ࢆక࠺ %XUJHUVYHFWRUE  ࢆࡶࡘ㌿఩Ḟ㝗ࡀᨭ㓄ⓗ࡛࠶ࡿ㸬୍᪉㸪KHDGWDLO ᑐ⛠ᛶࡀప࠸㸦ᅗ  G  H  I 㸧࡯࡝㸪ᒙࡢษ᩿࡟ࡼࡿ %XUJHUVYHFWRUE ࢆࡶࡘ㌿఩Ḟ㝗ࡢⓎ⏕ࡀᨭ㓄ⓗ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡿ㸬ࡇࢀࡼࡾᗙᒅ࡟ࡼࡗ࡚⏕ࡌࡿࢺ࣏ࣟࢪ࢝ࣝḞ㝗ࡢᛶ㉁ࢆỴᐃࡍࡿศᏊຊሙࡢᨭ㓄ᅉᏊ࡜ࡋ࡚㸪ศᏊࡢ KHDGWDLO ᑐ⛠ᛶࡀ㔜せ࡞ᅉᏊ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ୖグࡢኚᙧ࡟㐺ࡋࡓࢫ࣓ࢡࢸ࢕ࢵࢡᾮᬗࡢ⢒ど໬ຊሙ࡟㛵ࡍࡿከ┠ⓗ᭱㐺໬࡟ࡼࡿᢳฟᡭἲ㸪ཬࡧᢳฟࡋ

ࡓຊሙࢆ⏝࠸ࡓᗙᒅ୙Ᏻᐃᛶ࡜Ḟ㝗Ⓨ⏕࡟㛵ࡋ࡚ᰝㄞ௜ࡁㄽᩥ࡟ᢞ✏୰࡛࠶ࡿ㸬௒ᚋࡣ㸪ࢺ࣏ࣟࢪ࢝ࣝḞ㝗- 320 -

ࡢ⏕ᡂ࡟⮳ࡿ๓ẁ㝵࡟ࡘ࠸࡚ࡢኚᙧ࡟ࡘ࠸࡚ㄪ࡭ࡿ㸬≉࡟㸪⥺ᙧᙎᛶኚᙧ࠿ࡽረᛶኚᙧ࡬ࡢ⛣⾜ࡣ㸪ࢩ࢙ࣈࣟࣥ㡬Ⅼ࡛ࡢ㓄ྥ⛛ᗎࡢ⼥ゎࡀཎᅉ࡛࠶ࡿ࡜⪃࠼ࡽࢀ㸪㡬Ⅼ㒊࡛ࡢᛂຊࡸ㓄ྥ⛛ᗎ≧ែ࡟ࡘ࠸᳨࡚ウࡍࡿ㸬ࡇࢀ࡟ࡼࡾ㸪㔠ᒓ࡜ࡣ␗࡞ࡿ␗᪉ᛶ⢓ᙎᛶᣲືࢆ♧ࡍࢯࣇࢺ࣐ࢱ࣮ᅛ᭷ࡢኚᙧ⌧㇟ࢆ᫂ࡽ࠿࡟ࡋ࡚࠸ࡃ㸬 ཧ⪃ᩥ⊩ 06DNDPRWRDQG,+DQDVDNL-DSDQHVH-RXUQDORI$SSOLHG3K\VLFV 6' 6''&  ࠙ᅗ㸯ࠚ6QDSVKRWVRIGLVORFDWLRQVRIWKHV\PPHWULFDQGDV\PPHWULFIRUFHILHOGV7KHKHDGWDLOV\PPHWU\UDWLR
U DQGIRU D  E  F  G  H DQG I ZKHUHU ࣅ&1í&1ࣅ$/í$/

- 321 -









Computer-aided antibody design (  





)



Æ1ÇJBI~# lv/f%ª$ng# /Ìng
%ÐSkØ"Ôa1Y /;L?5/w«1­ $Û«x§x°qÚ+
wq¾dx1ÇJBI\Î ®o1w«$Ç l#T×/ 1Òµ  /
À·%MV$  {Ò#.¥2
 ,4.-5KG?@/5>69)90I1)E(*AJ;90$M.C<NJ;oGKÐb"C4HbR¹'&3K<.Æ´ÀYÜ¦V[~º$'&Ì¬¥Å& À·#R©ÍÕu1wq1¾/w«$\1zÌÀ·%HLb0 /wq#¬/Ç¾1­ Ç¹Ý`l#,/¦t×\#X ¸U´²j¿Ül ,7& "!$pË1× wq¾dx$»±1zo

6$56&R9 $AK=3:#¬*Ç¹Ý`l1× \#.¥2AK=3
:$/ÄN#ÉO½/ $dÁÙ0/ pµ#c#Ê}0 /[%$r17CEJ7FL#,.¡Î"y Ój ,&ÉOj$

AK=3:#¬Ç¹Ý`l1 $<4>C58$P 1y ,4.-5KG?@/5>69)O/J;ow«%«¼#

wq#,.im|/, #W/$Z³1QÂ#%Þ s'6L@E;#,/Ç l$·%))]£$Ö¯.¤^$r-`(/ %ª Ì{Ò%eß %È$w«#¬«¼$W$Z³_º/ÉO$Ôa1Ç¹Ý`l p¨²#,.\w«$Z³/Å$ÉO«#¬00Ç¹Ý`l ÃÑAG9DLhÏ 635 #,/wq $¦t×\1
 -#Ì{Ò%¢$w« *HUPOLQH w« #¬*Ç

ll1



 ?8%=H2'D:9),4,4 !#&"$oÌ{Ò%
 l#¶1ng1A«µ#%Ç¹Ý`l+ÜW`l"DL= IKl*@Zw«$3C¯$4Ll1 6L@E;#,/4LmY1V#p¨²/ $4L £¨ ·1HkÒ/w«$ÆdÁ %² Þ )4L¢u$w«#¬00Ç¹Ý`l1 $4L$|Ú1So;L?5$4LË$
6XSHUFKDUJLQJÃÑYb#+3C1½+1ÉW/s0/Ë/$Ë#,.FK;L?5 *)3 +w«$QÌT )Y $'¦- 322 -

':1L®Z;#Ê}0 /  6XSHUFKDUJLQJ #,.²L/lU"Çdx%Î- #0 " /K=EL3#&¿¾#%VfsÛn·×)B;Ð(|ZzÝ¾±PÙ#&¼ $ 6XSHUFKDUJLQJ

£"¶O &Ú(¼&(­  ,4 !#&"$J;o*URPDFV (W§¬]v{137 )K0K>H &kr©SN]va_w¾±(z¸3K<.Æ{&_q &+$500P]v 7,33*,K  01D&O(§Øt¡]v_q &*HQ)) #%|\Ï]×· *DXVVLDQ (§Îb(¸o

5RVHWWD (W§V]v]v71*K¾±(z¢xyiMd »liM!¾±P3K<.ÆQÔÈ(µ¾±(¸o¾±²¼Ö3URG\0'7UDM0'7$6.0'$QDO\VLV3\URVHWWD0DWSORWOLE 
3\WKRQ F*>FG" LQKRXVH Õ«&¼5LH³(^§

 7P>6J;?8%=HL+ozÝ#&3K<.Æ£ÁX®}Ç¢ÒyÞ'6&ß,7&635 (§'6& 
3K<.Æ¢xys( &  &,7& ²hy` ²hT+K3H=L"+K8J=Lsb¢_w¬<FCL3(e  &635 Ê
Ã<FCL3( &  &'$g¯<FCL3¾±#% $'&<FCL3(É&3K<.Æ¿¾!Ó( &  & 
 ,4.-5KG?@/5>69)90I1)E(*AJ;90$M.C<
NJ;o:;DLFLI@H²h¶(VA*.JDLFLI@HÉ¬²h»l(3K<.Æ]vÂÄÍ($ o

6$56&R9 ?J6)L2Ñ¦m¶ UN&pj'&sªV{]va_
w¾±#&É¼(¸sª#%?J6)L2ËÈ iM¤½uoa "&($  ,4.-5KG?@/5>69)O/J;ol  *gÉO / c#Î-" /w«1DI × 0

ÉOÞ ²#¤ /%>1p ,&l$¬Ñ -Hk635 #,/¦t×$¿Ý`\$mY L;I@ÉW ǻ+ 1Gµ#z/ÉO LK@ÉW ǻ6 1z
/ÉO 0$¦t×?G;#*%>1¤ " ÉO/ Î-"0ÉO#¬-#Ç¹Ý`l1z 7CEJ7FL$x§d$ÉW 0_
p?G;$4C1Î- #
 ?8%=H2'D:9),4,4 !#&"$- 323 -)H<-¨c9C*KV{°VËo

o

71*K¾±(z¿¾('6& #%²s(  MiM&   $¢xy iMsªV  {&²h»l UN]v
a_w¾±² $sª#% ÂÄÏUN &Ë & ²h»l&($ 

4Ll#,.w«$'É­#$ wq¾ÄN1h ­##q+1*3C1o

ÉO½ ¿²LÇ¹Ý`l#,.¿²L$Ø$%w«ÃÑ$q+z / ÃÑ1 HL4 L$z pÞIi #¡¨/'Á1\)× DIwq*q+1~& /-w«q+1~&/!

wq¾ÁI^/ £y0,7& ¨²$mYm|2%w|" 0m|u$¦t×¥]#*"ÉWo-0"  Î-   ?

"



t ´QB3F  µÓ R¶ ¢}±9 Q O µ}X m,Ì Q³3¦t×${·³µv#b 3 HL$UuDx/´  . 4 4°W`7L 
 1q E«QB3F)e ¨[Ä 7

t ´Ì Q³l4L 6XSHUFKDUJLQJ w«$ÆdÁ\´   . x§2¦47L  À XÌ PQJ sQB3Ft ´oÌ fX m,Ì Q$SSOLFDWLRQRIȕKDLUSLQVWUXFWXUHRI9++&'5IRUSHSWLGHGHVLJQV À· !(`ngg * Ã- À  cv }QJ sQB3FÌ Q³6WUXFWXUDO DQDO\VLV RI D SHSWLGH IUDJPHQW JUDIWHG RQWR WKH$GKLURQVFDIIROG´  . Ì(`-À-  À &= aQ²O µ}b§ N`J sQB3F  ¡" 8

t ´n" 6 NB ª¢Ì Q³7KH0ROHFXODU%DVLVRI+RZ613LQ/,FDGKHULQ$IIHFWHG&DQFHU
0HWDVWDVLV´  . Ì(`-À-  À  V rjJ sQB3F

3(4K Ì Q³Ç¹Ý`7CEJ7FL1×

 &'5*UDIWLQJ #,/| 9++ # /Ç<¹$\ ´  . ÌÆÆÚ`-À-À  ¡" 8

 &= aQ²5Ó MQ¼X J sQB3F t ´n" 

6 NB ª¢Ì Q³0ROHFXODUEDVLVRILQFUHDVHGULVNRIFRORUHFWDOFDQFHUPHWDVWDVLVFDXVHGE\
613VLQ/,FDGKHULQ´  . ÌÆÆÚ`-À-  À  XÌPQJ sQB3Ft ´oÌ fX m,Ì Q³9++ w« ȕKDLUSLQ

j &'5 1©×A lË$W´  . ÌÇÆ`-À- À









 .HLVXNH .DVDKDUD    $NL 7DQDEH 5DLML .DZDGH 6DWRUX 1DJDWRLVKL .RXKHL 7VXPRWR ³$QLRQ

VROYDWLRQ HQKDQFHG E\ SRVLWLYH VXSHUFKDUJLQJ PXWDWLRQV SUHVHUYHV WKHUPDO VWDELOLW\ RI DQ DQWLERG\ LQ D ZLGH S+
UDQJH´  

- 324 -

 &KLKRNR<RVKLPXUD6DWRUX1DJDWRLVKL <DVXR.RGDPD7DNDR8QR0DNRWR.LWDGH.KRRQWHH&KRQJ7DNDWD +LURPL 2VKLXPL +LURPL 0XUDRND 6DWRVKL <DPDVKLWD <XLFKL .DZDL 6KXLFKL 2KNXER .RXKHL
7VXPRWR ³7KHUPRG\QDPLF 'LVVHFWLRQ RI 3RWHQF\ DQG 6HOHFWLYLW\ RI &\WRVROLF +VS ,QKLELWRUV´      0LVDNL,VKLL0DNRWR1DNDNLGR-RVH00&DDYHLUR &-2NXPXUD7RVKLDNL0DUX\DPD.HYLQ(QW]PLQJHU.RXKHL7VXPRWR³6WUXFWXUDO%DVLVIRU$QWLJHQ5HFRJQLWLRQE\0HWK\ODWHG/\VLQH6SHFLILF$QWLERGLHV´   -XOLD.RHKOHU/HPDQ%ULDQ':HLW]QHU6WHYHQ0/HZLV-DUHG$GROI%U\IRJOH1DZVDG$ODP5HEHFFD)$OIRUG

0HODQLH $SUDKDPLDQ 'DYLG %DNHU .\OH $ %DUORZ 3DWULFN %DUWK %HQMDPLQ %DVDQWD %ULDQ - %HQGHU .ULVWLQ%ODFNORFN -DXPH %RQHW 6FRWW ( %R\NHQ 3KLO %UDGOH\ &KULV %\VWURII 3DWULFN &RQZD\ 6HWK &RRSHU %UXQR (&RUUHLD%ULDQ&RYHQWU\5KLMX'DV5HQp0'H-RQJ)UDQN'L0DLR/RUQD'VLOYD5RODQG'XQEUDFN$OH[DQGHU6)RUG %UDQGRQ )UHQ] 'DUZLQ < )X &DOHE *HQLHVVH /XNDV] *ROGVFKPLGW 5DJXO *RZWKDPDQ -HIIUH\ - *UD\'RPLQLN*URQW6KDURQ*XII\6FRWW+RURZLW]3R6VX+XDQJ7KRPDV+XEHU7LP0-DFREV-HOLD]NR5-HOLD]NRY'DYLG.-RKQVRQ.DOOL.DSSHO-RKQ.DUDQLFRODV+DPHG.KDN]DG.DUHQ5.KDU6DJDU'.KDUH)LUDV.KDWLE
$OLVD .KUDPXVKLQ ,QGLJR & .LQJ 5REHUW .OHIIQHU %ULDQ .RHSQLFN 7DQMD .RUWHPPH *HRUJ .XHQ]H %ULDQ.XKOPDQ  -DVRQ:/DERQWH-DVRQ./DL*LGHRQ/DSLGRWK$QGUHZ/HDYHU)D\6WHIIHQ/LQGHUW7KRPDV/LQVN\1LU/RQGRQ-RVHSK+/XELQ6HUJH\/\VNRY-DFN0DJXLUH/DUV0DOPVWU|P(QULTXH0DUFRV2UO\
0DUFX1LFKRODV$0DU]H-HQV0HLOHU5RFFR0RUHWWL9LNUDP.KLSSOH0XOOLJDQ6DQWUXSWL1HUOL&KULVWRIIHU1RUQ
6KDQHÏ &RQFK~LU1RDK2OOLNDLQHQ6HUJH\2YFKLQQLNRY0LFKDHO63DFHOOD;LQJMLH3DQ+DKQEHRP3DUN5\DQ(
3DYORYLF] 0DQDVL 3HWKH %ULDQ * 3LHUFH .DOD %KDUDWK 3LOOD %DUDN 5DYHK 3 'RXJODV 5HQIUHZ 6KRXU\D 6 5R\%XUPDQ$OL]D5XEHQVWHLQ0DULRQ)6DXHU$QGUHDV6FKHFN:LOOLDP6FKLHI2UD6FKXHOHU)XUPDQ<XYDO6HGDQ$OH[DQGHU06HY\1LNRODRV*6JRXUDNLV/HL6KL-XVWLQ%6LHJHO'DQLHO$GULDQR6LOYD6KDQQRQ6PLWK<LIDQ
6RQJ$PHOLH6WHLQ0DULD6]HJHG\)UDQN'7HHWV6XPPHU%7K\PH5D\<X5XHL:DQJ$QGUHZ:DWNLQV/LRU=LPPHUPDQ5LFKDUG%RQQHDX³0DFURPROHFXODUPRGHOLQJDQGGHVLJQLQ5RVHWWDUHFHQWPHWKRGVDQGIUDPHZRUNV´       

 .RXKHL 7VXPRWR ³(QJLQHHULQJ 6WDELOLW\ 9LVFRVLW\ DQG ,PPXQRJHQLFLW\ RI $QWLERGLHV E\&RPSXWDWLRQDO'HVLJQ´      5DLML .DZDGH  

 .RXKHL 7VXPRWR ³+RZ WKH SURWRQDWLRQ VWDWH RI D SKRVSKRU\ODWHG DPLQR DFLGJRYHUQVPROHFXODUUHFRJQLWLRQLQVLJKWVIURPFODVVLFDOPROHFXODUG\QDPLFVVLPXODWLRQV´    -XPSHL0RULPRWR.LP- 6DWRUX1DJDWRLVKL.RXKHL7VXPRWR6KLQVXNH6DQGR³3HUUHVLGXH

3URJUDPRI0XOWLSOH%DFNERQH'LKHGUDO$QJOHVRIȕ3HSWRLGVYLD%DFNERQH6XEVWLWXWLRQV´      .XURGD 7VXPRWR  ,NHXFKLHWDO .DZDGHHWDO y.DZDNDPLHWDO y+LZDWDVKLHWDO y.DQHGDHWDO y- 325 -

཯ᛂ⤒㊰⮬ື᥈⣴ἲࡢ㛤Ⓨ࡜ᛂ⏝
Development and Application of Automated Reaction Path Search
Methods‫ۑ‬๓⏣⌮㸪ཎῲ♸㸪ᕷ㔝ᬛஓ㸪㛗㇂ᕝኴ♸㸪㕥ᮌᮘ೔㸪ᮡᒣెዉ⨾㸪ఀ⸨⌶☻㸪ୖ⏣୍㈗㸪
ᒸ⏣ᣅ᫂㸪ṇᮧኴ୍㸪Ṋෆ㑈♸㸪ྡ⏿ኍᚿ㸪ᯇᮏⓡኴ㸪⚄ྡ⯟㸪⃝ᮏ࿴☻㸪⏣⏿㝧ኴ㑻㸪භ㎷ᬗ኱㸦໭ᾏ㐨኱Ꮫ㸧1◊✲ෆᐜᮏ◊✲࡛ࡣ㸪ศᏊ࠾ࡼࡧ≀㉁ࡢ໬Ꮫ཯ᛂࡢ⌮ゎ࡜ணࢆ┠ⓗ࡜ࡋ࡚㸪཯ᛂ⤒㊰⮬ື᥈⣴ἲࡢ㛤Ⓨ࡜ᛂ⏝ࢆᐇ᪋ࡍࡿ㸬ᙜࢢ࣮ࣝࣉ࡛㛤Ⓨࡋ࡚ࡁࡓ཯ᛂ⤒㊰⮬ື᥈⣴ἲࡢ୍ࡘ࡛࠶ࡿேᕤຊㄏ㉳཯ᛂ㸦AFIR㸧ἲࡣ㸪཯ᛂࢧ࢖ࢺྠኈࢆᢲࡋ௜ࡅࡿ㸪ཪࡣᘬࡁ㞳ࡍ㸪࡜࠸࠺༢⣧᧯స࡟ࡼࡗ࡚཯ᛂ⤒㊰ࢆồࡵࡿࡇ࡜ࡀ࡛ࡁࡿ㸬୚࠼ࡽࢀࡓึᮇᵓ㐀࠿ࡽࡇࡢ༢⣧సᴗࢆ⧞ࡾ㏉ࡍࡇ࡜࡛㸪ᮍ▱ᵓ㐀࠾ࡼࡧᮍ▱⤒㊰ࢆྵࡴ㸪཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡ
ࢆ⮬ືᵓ⠏ࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿ㸬ࡲࡓ㸪࢔ࣝࢦࣜࢬ࣒ࡢ༢⣧ࡉ࠿ࡽ㸪」㞧࡞཯ᛂ࡬ࡢ㐺⏝ᛶࡀ㠀ᖖ࡟㧗ࡃ㸪ࡇࢀࡲ࡛࡟᭷ᶵ཯ᛂ㸪ග཯ᛂ㸪㓝⣲཯ᛂ㸪⾲㠃཯ᛂ㸪⤖ᬗᵓ㐀┦㌿⛣࡞࡝ࡢᗈ⠊࡞໬Ꮫ཯ᛂ࡬࡜ỗ⏝໬ࡀᐇ⌧ࡋ࡚࠸ࡿ㸬ࡉࡽ࡟㸪ᚓࡽࢀࡿ」㞧཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡ࡟㐺⏝ࡋᚓࡿ㏿ᗘᐃᩘ⾜ิ⦰⣙㸦RCMC㸧ἲࢆ㛤Ⓨࡋ㸪RCMC ἲ࡜ AFIR ἲࢆ⤌ࡳྜࢃࡏࡓ㏿ᗘㄽࢼࣅࢤ࣮ࢩࣙࣥ௜ࡁ཯ᛂ⤒㊰⮬ື᥈⣴ࡶྍ⬟࡛࠶ࡿ㸬⌧ᅾ㸪⏕య⣔࡞࡝࡬ࡢ᭦࡞ࡿỗ⏝໬ࢆ┠ᣦࡋ࡚㛤Ⓨ◊✲ࢆ㐍ࡵ࡚࠸ࡿ㸬ࡲࡓ㸪ᐇ㦂ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲࡟ࡼࡾ㸪ᡭἲࡢᛂ⏝ࡶ⢭ຊⓗ࡟ᒎ㛤ࡋ࡚࠸ࡿ㸬ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬㈨※ࢆ฼⏝ࡋ࡚㸪᭷ᶵ཯ᛂ㸪ග཯ᛂ㸪㓝⣲཯ᛂ㸪⾲㠃཯ᛂ㸪⤖ᬗᵓ㐀┦㌿⛣࡬ࡢᛂ⏝◊✲ࢆຍ㏿ࡋࡓ࠸࡜⪃࠼࡚࠸ࡿ㸬᭷ᶵ཯ᛂࡸග཯ᛂ࡞࡝㸪ࡍ࡛࡟ᛂ⏝ᐇ⦼ࡢ࠶ࡿ཯ᛂ⣔࡟ࡘ࠸࡚ࡣ㸪ᐇ㦂ࢢ࣮ࣝࣉ࡜ࡢඹྠ◊✲ࢆ᥎㐍ࡍࡿ࡜࡜ࡶ࡟㸪ᐇ㦂࡟ඛ❧ࡗࡓணࢆᐇ⌧ࡋ࡚࠸ࡃࡇ࡜ࢆ┠ᣦࡍ㸬ࡲࡓ㸪⤖ᬗ┦㌿⛣ࡸ㓝⣲཯ᛂ࡜࠸ࡗࡓ」㞧⣔࡟ࡘ࠸࡚ࡣ㸪ᐇ㦂ࢹ࣮ࢱࡢゎᯒ
ࢆ㏻ࡌ࡚ࡑࡢ㐺⏝ᛶࢆ᳨ドࡍࡿ㸬᫖ᖺᗘࡣ㸪௨ୗࡢ 3 ࡘࡢㄢ㢟࡟ࡘ࠸᳨࡚ウࡋࡓ㸬
1-1. ศ๭እᤄἲ࡜஺ᕪⅬ᥈⣴ࢆ⏝࠸ࡓ㟁Ꮚ⛣ື཯ᛂ㏿ᗘィ⟬ἲ㟁Ꮚ⛣ື㸦ET㸧཯ᛂࡣ໬Ꮫ཯ᛂࡢ㔜せ࡞ᇶ♏ⓗ㐣⛬࡛࠶ࡿ㸬Ab initio ศᏊືຊᏛィ⟬࡟ࡼࡿ཯ᛂゎᯒࡣ㧗⢭ᗘࡔࡀィ⟬ࢥࢫࢺࡀ㧗ࡃ㸪཯ᛂࡢ⌮ㄽⓗࢫࢡ࣮ࣜࢽࣥࢢ࡛ࡢ฼⏝ࡣ㞴ࡋ࠸㸬ࡑࡇ࡛࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ
࣮᭤㠃㸦PES㸧࡟ᇶ࡙ࡃ⡆౽࡞ゎᯒࡀࢫࢡ࣮ࣜࢽࣥࢢ࡛ࡣ᭷⏝࡛࠶ࡿ㸬PES ࡟ᇶ࡙ࡃ ET ཯ᛂゎᯒ࡛ࡣ㸪ከᩘࡢ PES ࡢ࠺ࡕ ET ๓ᚋ 2 ≧ែࢆグ㏙ࡍࡿࡇ࡜ࡀㄢ㢟࡜࡞ࡿ㸬ᮏ◊✲࡛ࡣ ONIOM ἲ[2]ࡢศ๭እᤄィ⟬࡟╔┠ࡋ㸪ศ๭ࡋࡓྛ⣔ࡢ㟁Ꮚ≧ែࢆኚ࠼ࡿࡇ࡜࡟ࡼࡿ㸪ET ๓ᚋ 2 ≧ែࡢ⡆౽࡞ィ⟬ἲࡢ㛤Ⓨࢆ┠ⓗ࡜ࡋࡓ㸬
1-2. ㉸㧗ᅽୗ࡟࠾ࡅࡿ 14 ᪘࡟㓟໬≀⤖ᬗᵓ㐀ࡢ⣔⤫ⓗ᥈⣴⤖ᬗᵓ㐀᥈⣴ᡭἲ࡛࠶ࡿ PBC/AFIR ἲ࡟㸪ᅽຊ᮲௳ࢆ⪃៖ࡋࡓ᥈⣴ᶵ⬟ࡀᐇ⿦ࡋࡓ㸬ᮏ◊✲࡛ࡣ㸪ࡑࡢࢣ࣮ࢫࢫࢱࢹ࢕࡜ࡋ࡚㸪14 ᪘஧㓟໬≀ࢆᑐ㇟࡟ 1 Ẽᅽ࠾ࡼࡧ 100 ୓Ẽᅽࡢྛ᮲௳ୗ࡛ࡑࢀࡒࢀ⤖ᬗᵓ㐀᥈⣴ࢆ⾜࠸㸪ྛ⤌ᡂ࡟ࡘ࠸࡚⤖ᬗ┦ࡢᏳᐃᛶࡢᅽຊ౫Ꮡᛶࢆ⣔⤫ⓗ࡟ゎᯒࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓ㸬

1-3. ࢡࣛ࢖ࢮࣥ㌿఩࡟ᑐࡍࡿ཯ᛂ㞀ቨࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜ࡑࡢ໬Ꮫⓗ࠾ࡼࡧᩘ್ⓗ᳨ド཯ᛂ㛤Ⓨ࡛ࡣ㸪ᵝࠎ࡞཯ᛂ≀㉁ࡸ཯ᛂ᮲௳ࡢ⤌ࡳྜࢃࡏࢆࢫࢡ࣮ࣜࢽࣥࢢࡍࡿᚲせࡀ࠶ࡿ㸬ࡇࡇ࡛㸪DFT- 326 -

ィ⟬࡞࡝࡛ᚓࡽࢀࡓ཯ᛂ㞀ቨࡸ཯ᛂ࢚ࢿࣝࢠ࣮࡞࡝ࡢ᝟ሗ࡟ᇶ࡙࠸ࡓ཯ᛂࢫࢡ࣮ࣜࢽࣥࢢࡣ㸪ᐇ㦂ࢥࢫࢺࡢ๐ῶ࡟᭷ຠ࡛࠶ࡿ㸬ࡋ࠿ࡋ㸪௦ࢃࡾ࡟ィ⟬ࢥࢫࢺࢆせࡍࡿࡓࡵ㸪ᑡ࡞࠸ヨ⾜ᅇᩘ࡛ࢫࢡ࣮ࣜࢽࣥࢢ࡛ࡁࡿᡭ
ἲࡢ㛤Ⓨࡀᚲせ࡛࠶ࡿ㸬ࡇࡢ࡜ࡁ㸪ྛᡭἲࡢᛶ⬟ࢆ༶ᗙ࡟ホ౯࡛ࡁࡿࢹ࣮ࢱࢭࢵࢺࡀ࠶ࡿ࡜㠀ᖖ࡟౽฼࡛࠶
ࡿ㸬ࡑࡇ࡛ᮏ◊✲࡛ࡣ㸪ࢡࣛ࢖ࢮࣥ㌿఩཯ᛂ࡟╔┠ࡋ㸪཯ᛂ㞀ቨࡢࢹ࣮ࢱࢭࢵࢺࢆィ⟬࡛సᡂࡋࡓ㸬ࡲࡓ㸪㑇ఏⓗ࢔ࣝࢦࣜࢬ࣒㸦GA㸧ࢆ⏝࠸ࡓࢫࢡ࣮ࣜࢽࣥࢢᡭἲࢆᐇ⿦ࡋ㸪ᚓࡽࢀࡓࢹ࣮ࢱࢭࢵࢺࢆ⏝࠸࡚ࡑࡢᛶ⬟ࢆホ౯࡛ࡁࡿ࠿᳨ドࡋࡓ㸬2◊✲᪉ἲ㸪ィ⟬᪉ἲ

2-1. ศ๭እᤄἲ࡜஺ᕪⅬ᥈⣴ࢆ⏝࠸ࡓ㟁Ꮚ⛣ື཯ᛂ㏿ᗘィ⟬ἲᮏᡭἲ࡛ࡣ㸪ጞ≧ែ㸦ET ๓㸧ࡢ࢚ࢿࣝࢠ࣮ࡣ㸪ࢻࢼ࣮ศᏊࡢ㑏ඖ≧ែࡢ࢚ࢿࣝࢠ࣮࡜஧ศᏊࡢ㘒యࡢ㓟໬≧ែࡢ࢚ࢿࣝࢠ࣮ࡢ࿴࠿ࡽ㸪ࢻࢼ࣮ศᏊࡢ㓟໬≧ែࡢ࢚ࢿࣝࢠ࣮ࢆᕪࡋᘬࡃࡇ࡜࡛ィ⟬ࡉࢀࡿ㸬୍᪉㸪⤊≧ែ㸦ET ᚋ㸧ࡢ࢚ࢿࣝࢠ࣮ࡣ㸪࢔ࢡࢭࣉࢱ࣮ศᏊࡢ㑏ඖ≧ែࡢ࢚ࢿࣝࢠ࣮࡜஧ศᏊࡢ㘒యࡢ㓟໬≧ែࡢ࢚ࢿࣝ
ࢠ࣮ࡢ࿴࠿ࡽ㸪࢔ࢡࢭࣉࢱ࣮ศᏊࡢ㓟໬≧ែࡢ࢚ࢿࣝࢠ࣮ࢆᕪࡋᘬ࠸ࡓᙧ࡛ィ⟬ࡉࢀࡿ㸬ࡇࢀࡽࡢ࢚ࢿࣝࢠ
࣮㛵ᩘࡢ໙㓄࡜࣊ࢩ࢔ࣥࡣ㸪㊊ࡋᘬࡁࡍࡿ PES ࡢ໙㓄ࡸ࣊ࢩ࢔ࣥ࠿ࡽᐜ᫆࡟ィ⟬࡛ࡁࡿ㸬ᮏᡭἲࢆ㸪㔠ᒓ㘒య[M(L)n]3+࡜[M(L)n]2+ࡢ㛫ࡢ⮬ᕫ㟁Ꮚ஺᥮཯ᛂ࡬㐺⏝ࡋࡓ㸬ࡲࡎ㸪㔠ᒓ㘒యࡢ 2 ౯࡜ 3౯ࡢ࢝ࢳ࢜ࣥ༢㔞య࡟ࡘ࠸࡚㸪GRRM ࣉࣟࢢ࣒ࣛ㸦㛤Ⓨ⪅∧㸧࡟ࡼࡿᵓ㐀᥈⣴ࢆ⾜ࡗࡓ㸬ḟ࡟㸪஧㔞య࡟ୖグࡢศ๭እᤄἲࢆ㐺⏝ࡋ㸪ET ๓ᚋࡢ 2 ≧ែࢆィ⟬ࡋ࡞ࡀࡽ㸪
GRRM ࡟ࡼࡾ஺ᕪ㡿ᇦෆᴟᑠᵓ㐀ࢆ᭱㐺໬ࡋࡓ㸬ࡇࡢᵓ㐀ࢆ㑄⛣≧ែ࡜ࡋ㸪᭱Ᏻᐃ࡞ 2 ౯࡜ 3 ౯ࡢ༢㔞యࡢ࢚ࢿࣝࢠ࣮ࡢ࿴ࢆᇶ‽࡜ࡍࡿάᛶ໬࢚ࢿࣝࢠ࣮ࢆ㸪㑄⛣≧ែ⌮ㄽࡢ㏿ᗘᘧ࡟௦ධࡋ࡚㟁Ꮚ⛣ື཯ᛂࡢ㏿ᗘᐃᩘ kET ࢆィ⟬ࡋࡓ㸬㟁Ꮚ≧ែィ⟬࡟ࡣ㸪Gaussian16
ࡢ DFT ィ⟬ࢆ⏝࠸ࡓ㸬ỗ㛵ᩘࡣ UωB97X-D㸪ᇶᗏ㛵ᩘࡣ㔠ᒓཎᏊ࡟ SDD㸪ࡑࡢ௚ࡢཎᏊ࡟ 6-31+G*ࢆ⏝࠸ࡓ㸬Ỉ⁐ᾮ࡟ࡼࡿ⁐፹ຠᯝࡢ⪃៖࡟ࡣ C-PCM ἲࢆ⏝࠸ࡓ㸬
2-2. ㉸㧗ᅽୗ࡟࠾ࡅࡿ 14 ᪘࡟㓟໬≀⤖ᬗᵓ㐀ࡢ⣔⤫ⓗ᥈⣴㟁Ꮚ≧ែィ⟬࡟ࡣ SIESTA ࣉࣟࢢ࣒ࣛ㸦ver 4.0㸧ࢆ౑⏝ࡋ㸪GGA-PBE ỗ㛵ᩘ࠾ࡼࡧ DZP ᇶᗏࢆ⏝࠸ࡓ㸬⤖ᬗᵓ㐀᥈⣴࡟ࡣ㛤Ⓨ⪅∧ GRRM ࣉࣟࢢ࣒ࣛ࡟ᐇ⿦ࡉࢀࡓ PBC/AFIR ἲࢆ⏝࠸㸪1 Ẽᅽ㸦P = 1 atm㸧࠾ࡼࡧ 100
୓Ẽᅽ㸦P = 1000000 atm㸧ࡢྛ᮲௳ࢆ⪃៖ࡋ࡚⾜ࡗࡓ㸬⤖ᬗࡢ⤌ᡂࡣ㸪㸯ࣘࢽࢵࢺࢭࣝ࠶ࡓࡾ 2 ༢఩࠾ࡼࡧ 3༢఩ࡢሙྜ㸪ࡍ࡞ࢃࡕ㸪A2O4㸪A3O6㸦A = C㸪Si㸪Ge㸧ࢆ⪃៖ࡋ㸪⤖ᬗࡢ✵㛫⩌ࡢᑐ⛠ᛶ࡟ࡣไ㝈ࢆㄢࡉࡎ᥈
⣴ࢆ⾜ࡗࡓ㸬ᚓࡽࢀࡓ඲ᵓ㐀ࡣయ✚ࢆ 2 ಸ࡟ቑࡸࡋࡓ
ࢫ࣮ࣃ࣮ࢭ࡛ࣝᵓ㐀᭱㐺໬ࢆ⾜࠸㸪Ᏻᐃᵓ㐀࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓ㸬

2-3. ࢡࣛ࢖ࢮࣥ㌿఩࡟ᑐࡍࡿ཯ᛂ㞀ቨࢹ࣮ࢱ࣮࣋ࢫࡢ
ᵓ⠏࡜ࡑࡢ໬Ꮫⓗ࠾ࡼࡧᩘ್ⓗ᳨ド⨨᥮࢔ࣜࣝࣅࢽ࢚࣮ࣝࢸࣝࡢ 5 ⟠ᡤࡢỈ⣲ࢆ 10 ✀㢮ࡢ⨨᥮ᇶ࡛⨨᥮ࡋ㸪10 ୓㏻ࡾࡢศᏊࢆ⏕ᡂࡋࡓ㸦ᅗ㸯㸧㸬 ᅗ㸯㸬཯ᛂ㞀ቨࢹ࣮ࢱ࣮࣋ࢫ࡟⏝࠸ࡓ࢔ࣜࣝࣅࢽ
ྛศᏊࡢࢡࣛ࢖ࢮࣥ㌿఩࡟࠾ࡅࡿ཯ᛂ㞀ቨࢆ㛤Ⓨ⪅∧࢚࣮ࣝࢸࣝศᏊࡢ⨨᥮఩⨨࡜⨨᥮ᇶ㸬

- 327 -

GRRM ࣉࣟࢢ࣒ࣛ࡟ᐇ⿦ࡉࢀࡓேᕤຊㄏ㉳཯ᛂἲࢆ⏝࠸࡚ㄪ࡭㸪཯ᛂ㞀ቨࡢࢹ࣮ࢱࢭࢵࢺࢆసᡂࡋࡓ㸬࡞࠾㸪ィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣ
Gaussian 16㸪ィ⟬ᡭἲ࡟ࡣ PM7 ࢆ⏝࠸ࡓ㸬ࡲࡓ㸪ྛศᏊࡢ཯ᛂฟⓎ≀࣭㑄⛣≧ែ㛫ࡢ┦ᑐⓗ࡞Ᏻᐃᛶࢆ⪃៖ࡋ㸪㞀ቨࢆ෌ィ⟬㸦ᶆ‽໬㸧ࡋࡓࢹ࣮ࢱࢭࢵࢺࡶసᡂࡋࡓ㸬

3

◊✲ᡂᯝ

3-1. ศ๭እᤄἲ࡜஺ᕪⅬ᥈⣴ࢆ⏝࠸ࡓ㟁Ꮚ⛣ື཯ᛂ㏿ᗘィ⟬ἲᮏᡭἲࢆ⏝࠸࡚ィ⟬ࡋࡓ kET ࡣ㸪ᐇ㦂್ࡢഴྥࢆᐃᛶⓗ࡟෌⌧ࡋࡓ㸦ᅗ㸰㸧㸬୍⯡࡟㸪㟁Ꮚ⛣ື๓ᚋࡢ㟁Ꮚ≧ែࢆᣦᐃࡋ࡚ィ⟬ࢆᐇ⾜ࡍ ᅗ㸰㸬㟁Ꮚ⛣ື㏿ᗘᐃᩘ kET㸦ᑐᩘ್㸧ࡿࡇ࡜ࡣᐜ࡛᫆ࡣ࡞࠸ࡀ㸪ᮏᡭἲࡣᵓ㐀ศ๭࡟ࡼࡗ࡚㠀ᖖ࡟⡆౽࡟ ࡢᐇ㦂್㸦ᶓ㍈㸧࡜ᮏᡭἲ࡟ࡼࡿィ㟁Ꮚ≧ែࡢᣦᐃࡀ⾜࠼ࡿ㸬ࡑࡢࡓࡵ㸪௒ᚋ㸪ࡼࡾ」㞧࡞㟁Ꮚ⛣ື཯ ⟬್㸦⦪㍈㸧ࡢ┦㛵㸬ᛂ࡬ࡢᒎ㛤ࡀᮇᚅ࡛ࡁࡿ㸬ࡲࡓ㸪㟁Ꮚ≧ែࢆ⮬ື࡛ᣦᐃࡍࡿࡇ࡜ࡶ
ᐜ᫆࡟ᐇ⌧࡛ࡁࡿࡓࡵ㸪ET ࢆ࣮࢟ࢫࢸࢵࣉ࡜ࡍࡿ໬Ꮫ཯ᛂࡢ⌮ㄽⓗࢫࢡ࣮ࣜࢽࣥࢢࡸ཯ᛂタィ࡬ࡢᛂ⏝ࡀྍ⬟࡛࠶ࡿ㸬ᮏᡂᯝ࡟ࡘ࠸࡚
ࡣ㸪⌧ᅾㄽᩥࢆ‽ഛ୰࡛࠶ࡿ㸬

3-2. ㉸㧗ᅽୗ࡟࠾ࡅࡿ 14 ᪘࡟㓟໬≀⤖ᬗᵓ㐀ࡢ⣔⤫ⓗ᥈⣴ᮏィ⟬࡟ࡼࡾ㸪᪂ወᵓ㐀ࢆྵࡴ 800 ಶ௨ୖࡢᏳᐃᵓ㐀ࡀᚓࡽࢀࡓ
㸦ᅗ㸱㸧㸬CO2㸪SiO2㸪GeO2 ࡢྛ⤌ᡂ࡟ࡘ࠸࡚㸪1 Ẽᅽୗ࡛ࡣࡑࢀࡒ
ࢀ 219 ಶ㸪102 ಶ㸪148 ಶ㸪100 ୓Ẽᅽୗ࡛ࡣࡑࢀࡒࢀ 147 ಶ㸪63 ಶ㸪
76 ಶࡢᏳᐃᵓ㐀ࢆᚓࡓ㸬ࡇࢀࡽࡢ᥈⣴⤖ᯝࡣᐇ㦂ⓗ࡟᪤▱ࡢ஦ᐇࢆࡼࡃ෌⌧ࡋ࡚࠾ࡾ㸪ᮍ▱ࡢ⤖ᬗ┦ࢆ᥈⣴ࡍࡿᡭἲ࡜ࡋ࡚ࡢ᭷⏝ᛶࡀ☜࠿ࡵࡽࢀࡓ㸬ࡉࡽ࡟ᅽຊ࡟ᑐࡍࡿ⤖ᬗᵓ㐀ࡢ┦ᑐⓗᏳᐃᛶࢆヲࡋࡃㄪ࡭ࡿࡓࡵ㸪ᚓࡽࢀࡓ⤖ᬗᵓ㐀࡟ᑐࡋ࡚ 1 Ẽᅽ࠿ࡽ 100 ୓Ẽᅽࡢ㛫࡛Ẽᅽࢆ₞ቑῶࡉࡏࡓᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠸㸪୺せ࡞⤖ᬗᵓ㐀ࡢ࢚ࣥࢱࣝࣆ࣮ࡢ᥎⛣ࢆ㏣㊧ࡋࡓ㸬㧗ᅽ᮲௳࡛ࡣ㧗ᐦᗘ࣭㧗㓄఩ࡢ⤖ᬗᵓ㐀ࡀ┦ᑐⓗ࡟Ᏻᐃ࡜࡞ࡿഴྥࡀほᐹࡉࢀࡓ࡯࠿㸪㉸㧗ᅽࢆ᥃ࡅࡿࡇ࡜࡛㧗࿘ᮇࡢඖ⣲ࡢᛶ㉁ࢆⓎ⌧ࡍࡿᵝᏊࡀほᐹࡉࢀࡓ㸬ᮏᡂᯝ࡟ࡘ࠸࡚ࡣ㸪RSC Advances ㄅ࡟࡚බ⾲ࡋࡓ㸬
3-3. ࢡࣛ࢖ࢮࣥ㌿఩࡟ᑐࡍࡿ཯ᛂ㞀ቨࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜ࡑࡢ໬Ꮫⓗ࠾ࡼࡧᩘ್ⓗ᳨ドィ⟬࡟ࡼࡾ 99072 ศᏊ࡛ࢡࣛ࢖ࢮࣥ㌿఩ࡢ TS ࢆᚓࡓ㸬ྛศᏊ࡟࠾
ࡅࡿ཯ᛂ㞀ቨࢆィ⟬࣭ᶆ‽໬ࡋ㸪2 ࡘࡢࢹ࣮ࢱࢭࢵࢺࢆᚓࡓ㸬ࡇࢀࡽ ᅗ㸱㸬ᮏᡭἲ࡟ࡼࡗ࡚ᚓࡓ㸪ᖖᅽ࠾ࡢ⤖ᯝࢆ㸪໬Ꮫⓗ࣭ᩘ್ⓗ࡞ほⅬ࠿ࡽゎᯒࡋࡓ㸬ࡲࡎ㸪ྛࢹ࣮ࢱࢭ ࡼࡧ 100 ୓Ẽᅽ࡛ࡢ CO2㸪SiO2㸪GeO2
ࢵࢺ࡟࠾࠸࡚㞀ቨࢆᑠࡉࡃࡍࡿ⨨᥮ᇶࡢ✀㢮ࡸᛶ㉁ࢆゎᯒࡋࡓ㸬ࡑ ⤖ᬗࡢ࢚ࢿࣝࢠ࣮࡜య✚ࡢ┦㛵㸬

- 328 -

ࡢ⤖ᯝ㸪࠸ࡎࢀࡢࢹ࣮ࢱࢭࢵࢺ࡛ࡶ X1 ࡜ X4㸪X5 ࡟㟁Ꮚ౪୚ᇶ㸪ཬࡧ X2 ࡜ X3 ࡟㟁ᏊồᘬᇶࡀᏑᅾࡍࡿ࡜
㞀ቨࡀᑠࡉࡃ࡞ࡿഴྥࡀ☜ㄆࡉࢀࡓ㸬ࡲࡓ㸪㞀ቨࡢᶆ‽໬࡟ࡼࡾ㸪ᮃࡲࡋ࠸⨨᥮ᇶࡢලయⓗ࡞✀㢮ࡀኚ໬ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ḟ࡟㸪ྛࢹ࣮ࢱࢭࢵࢺ࡟ᑐࡋ࡚ GA ࢆ⏝࠸ࡓ⨨᥮ᇶࢫࢡ࣮ࣜࢽࣥࢢࢆ⾜࠸㸪ࡑࡢᛶ⬟ࢆホ౯ࡋࡓ㸬ලయⓗ࡟ࡣ㸪㝈ࡽࢀࡓヨ⾜ᅇᩘ࡛཯ᛂ㞀ቨࡢᑠࡉࡉࡀୖ఩ 100 ಶࡢศᏊࢆ GA ࡀⓎぢ࡛ࡁࡿ☜⋡ࢆㄪ࡭ࡓ㸬᳨ウࡢ⤖ᯝ㸪࠸ࡎࢀࡢࢹ࣮ࢱࢭࢵࢺ࡟ᑐࡋ࡚ࡶ㸪100 ᅇࡢヨ⾜࡛ 80%๓ᚋࡢ☜⋡㸪200 ᅇࡢヨ⾜࡟࠾࠸࡚ࡣ 90%ࢆ㉺࠼ࡿ☜⋡࡛㸪GA ࡣᑐ㇟ࡢศᏊࢆⓎぢ࡛ࡁࡓ㸬ୖグࡢ⤖ᯝ࣭ゎᯒ࡟ࡼࡾ㸪ᚓࡽࢀࡓࢹ࣮ࢱ
ࢭࢵࢺࡀ᭷⏝࡞ࢹ࣮ࢱࢭࢵࢺ࡛࠶ࡿࡇ࡜㸪ࡑࡋ࡚ࢫࢡ࣮ࣜࢽࣥࢢᡭἲࡢᛶ⬟ホ౯࡟฼⏝࡛ࡁࡿィ⟬ୖࡢṇゎ࡜ࡋ࡚ᶵ⬟ࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸬ᮏᡂᯝ࡟ࡘ࠸࡚ࡣ㸪⌧ᅾㄽᩥࢆ‽ഛ୰࡛࠶ࡿ㸬

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] ࣏ࢫࢱ࣮Ⓨ⾲, ࠐභ㎷ᬗ኱, ᩧ⏣ㅬ୍㑻, ๓⏣⌮, ࠕศ๭እᤄἲ࡜஺ᕪⅬ᥈⣴ࢆ⏝࠸ࡿ㟁Ꮚ⛣ື཯ᛂ㏿ᗘࡢ⡆౽ィ⟬ࠖ, ࠗ➨ 23 ᅇ⌮ㄽ໬Ꮫウㄽ఍࠘, 2P28, ࢜ࣥࣛ࢖ࣥ, 2021 ᖺ 5 ᭶[2] ★ ࠐྡ⏿ ኍᚿ, 㧗ᮌ ∾ே, ᩧ⏣ ㅬ୍㑻, ๓⏣ ⌮,ࠕ㉸㧗ᅽୗ࡟࠾ࡅࡿ 14 ᪘஧㓟໬≀(CO2, SiO2, GeO2)ࡢ⤖ᬗᵓ㐀ࡢ⣔⤫ⓗ᥈⣴ࠖ, ࠗ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ 2020࠘, P13, ࢜ࣥࣛ࢖ࣥ, 2020
ᖺ9᭶[3] ࠐᒸ⏣ᣅ᫂, ๓⏣ ⌮ࠕࢡࣛ࢖ࢮࣥ㌿఩࡟ᑐࡍࡿ཯ᛂ㞀ቨࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜ࡑࡢ໬Ꮫⓗ࠾ࡼࡧᩘ್ⓗ᳨ドࠖࠗ➨ 23 ᅇ ⌮ㄽ໬Ꮫウㄽ఍࠘㸪2P27㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪2021 ᖺ 5 ᭶㸪࣏ࢫࢱ࣮Ⓨ⾲5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

>@ ★$0XWVXML.6DLWDDQG60DHGDLQSUHSDUDWLRQ>@ ★+2NDGDDQG60DHGDLQSUHSDUDWLRQ>@ ★+1DEDWD07DNDJL.6DLWDDQG60DHGD56&$GY2020
>@ 7,WR<+DUDEXFKLDQG60DHGD3K\V&KHP&KHP3K\V2020>@ 70LWD<+DUDEXFKLDQG60DHGD&KHP6FL2020
>@ ★<2WDFKL$6DWRK<+DUDEXFKLDQG77DNHWVXJX-&RPSXW&KHP2020
>@ 1$L]DZD<+DUDEXFKL60DHGDDQG<-3X1DW&RPPXQ2020>@ 5/5H\HV06DWR7,ZDL.6X]XNL60DHGDDQG06DZDPXUD6FLHQFH2020>@ &g]HQ76DWRKDQG60DHGD-&RPSXW&KHP2020
>@ 07DNDJLDQG60DHGD$&62PHJD2020
>@ 0+DWDQDND7<RVKLPXUDDQG60DHGD7RS2UJDQRPHW&KHP2020
>@ 70DWVXQR06RPH\D66DWR60DHGDDQG+,VREH$QJHZ&KHP,QW(G2020
[13] < .LWDJDZD 6 :DGD 0 ' - ,VODP . 6DLWD 0 *RQ . )XVKLPL . 7DQDND 6 0DHGD < +DVHJDZD&RPPXQ&KHP2020
>@ .0DWVXRND1.RPDPL0.RMLPD70LWD.6X]XNL60DHGD7<RVKLQRDQG60DWVXQDJD-$P&KHP
6RF2021

- 329 -



 DFT 

DFT study on reaction mechanism of small molecule activation bytransition metal catalyst
$&*+

"'









#

 .()/P[O^1+µqhm³7ZI^y*3R]G^sÏµb¶'+jÎ&+¾Àf+X;ICW|«¨+hmÆ,{&)"/
ÓÙ+Æ,¢Ñ)(+h¢ºß114%3 hmu*%±p³*¦i»){'%ÚÖ
³*, h¢ºß,i»)

3',¹ ."h¢ºß'%¬q°*k q}È¶+ze')#%3 "#% h¢ºß*a§)zß5Ö%ÒÖ)Æ5¡¥ 3ËÌ5lÝ !415u&ÚÖi»\S[.&´h3Ã×3 ÒÍ)zß+-'$L8:UBÔ¸©&3h¢ºß'·Õ

UB+ÚÖ*02®¤Ê43 L8:UB°+®¤,wq°+ L8:*ÓÙ ;T^IYGZ[)5#%3+"/ ¦i»)9J[={'%pª4%3L8:UBÔ¸©
1+ÒÖhmÆÆ+d$'%7VKr1437VK,cÐÄ ß Áß)(+zß'%×2 !+~Ü³×&3| 7VK,¿Ì&¡¥4%3 ½Ø*39J[=@BG!+ÇÛ¡R]DB,Å&3"#%¦i»)ËÌ&0

2ot¼Þx+7VK+Ã×'4%3 v L8:UBÓÙ+_?G@^M>GQ]E8R+D[5Ö%µqhm³*7VK*Èn&3'É4"+¾Èn&,  Ö437VK+°&

¾'%

7ZI^,



¯¤{'%NH]<A[7V^

+Q6ZF~Ü5"4,µ¾R]DB&~Ü³*Â4 Æ+£­'5%37ZI^y+²`
4"R]DB&, P[O^ *  +§g&:<AW*Èn4%5 *:<A

W,  $+R]G^'  $+µ5Ö%7VK*Èn43+Àf&, R]G^'µ+ÙË7KH&++h*02cb43." d



5J"3';4H+Àf£43

'/#%3'1 '¶J4"+ÙËR]G^{')3'¤43Ðpa&,

'+jÎ&+_?G+7VK'+µqhm³Èn+Àf[y5Ó1*

3'5Õ³'"½* 4"  $+7VK+°& -Q6ZF~Ü5"P[O^1+7ZI^y+Àf[y+OÓ*·5º%"
 ×G°*3 ¾*03  Th+X;ICWOÓ0&  mÇhdPÜ*3U

':]1^hÆ8:^+Ff;T^

IYGZ[N+|*,¤ºß+Ò~ÚÖ×&3¤,º*03®¤ÁÚ3]+>>^9J[=ºß&2 ¤5~Ü³*Th  3¾AB8W+Ã×.

- 330 -

#%3 ¬`*ÏÈ)i¥5Ö%¾5
3¾AB8W5y®

3',~Ü³*¤5Th×¾'%5ÖI.)ng&[»xu\Ô&+¾TÖ*%Ø¢³&3 NH]193¤,

3'«14%3"#%NH]193T°+y¥'[»,r0&ØÞl+¡Ë5Ö%±~4%" j+¤Àf*°Õ 3'
3*03¤Th¿Àf+X;ICW,^=I7+X;ICW'ÄRh©+Èh,NH]19

vhmj*03ÇO.IG]193*03

3'Å&)

)/%¤+Th*%02)

i¥28G+

1+7

0&41+i¥+¾28>[*3¤Àf+)

4,Ò[i¥©*03ÇTh*-º%,.3'z"143 ×¾°&@³"¾5P¿ +Th¿[»5²c 3"/*¨¬)¸ÛÃ×'4%" Ö³)¾+"/*,
1)3¨'~Ü+ÙË5Å""¾P¿Ã×&3 1*

4"i¥©+¾»Û5¬h 3*, ¾AQ+¶JhmÆ+ ´h-×&3 vP¿4"

 NH]193+=F[ >1L,, ; )H,, &O &2 / @ ; 11¶GLHWK\OGLD]RQRQDQH

GLWKLRODWR/ ELV GLSKHQ\OSKRVSKLQR HWKDQH @, ×G°&;8]>AB  Thh5¾ 3
 ThÀf,>^UG+§g&~Ü³*^2 ¤hÆ©°V©'%¼143 ¤hÆ©+  my¥O&, ¤hÆ¼B

 NH]193+0!*'  +)*°V*B­ 3'4 1*  +Th¿+[»5$'r³*4" ¾TÊB'
X;ICW,Ó1*4%)1* UHY+Ff*±~4%)
 Å©*03  Th+X;ICW5OÓ 3 Àf Ó9J[='Àf

+pa&, .#Í, E×¾ß=F['Ì5 +/$lÀf[y5OÓ 31* ¾¤©1+R]

G^DÂ+¿Ûm'589V>B*§ 3HY+Ff 0&HY+v+E8:^+Ff5±~ 3 ,-!, P[O^1+µqhm³7ZI^y*3R]G^sÏµb¶'+jÎ&+¾Àf+X;ICWZT 9LHQQD DELQLWLR '+/1,0#1e9$63f"1,0 
6J>ALaFN]e')7f5O=Wb<MC
F

3URMHFWRUDXJPHQWHGZDYH 3$: E&0*.

3HUGHZ%XUNH(UQ]HUKRIe3%(f3DQaLa

[^

".!1 K_ eDE cF cfO.
c

9<4V

2G

=Y$0

0RQNKRUVW3DFNN &0 (+5

?H`7 H`7".K_5ORS8 @ 7L2ef-%).eD cE cF cfKUXc:B\I ×G°*3 ¾*03  Th+X;ICWOÓ0&  mÇhdPÜ*3U

':]1^hÆ8:^+Ff (%+l,   R]0ZW5Ö%{"y¥,   +kr³ÇÎ5Å""  ÃW5Ö ´h"Y´W,y¥ ´h*§%  !%µ9J[=,¹5w$3"/   5Ö"

- 331 -

 %
 P[O^1+µqhm³7ZI^y*3R]G^sÏµb¶'+jÎ&+¾Àf+X;ICW
W

l*02

h6E^'+jÎ&+µqhm³7ZI^y+ÀfkÝ5²`"9J[=

Í -B87R, :<AW°V©17ZI^'+µqhm³Èn*3&3'4"l4"BP^Ò¹ÇÉ, m+y-Í5$B87RR]G^sÏµb¶*0#%]43'/#"R]G^sÏµb¶, hd)¾AB8W.Æm³AB8W
5X,ËÀfAB8W&×)ÏS5K" '«14%3+R]G^sÏµb¶hÆµg¾&+µqhmÀf*%-[» 3',eÑ."l*02 '+V+jÎ7VKy5£ 3ze}4"  $Õ,R]G^b¶'++ZÖ&3R]G^b¶Àf, ªdB87R+
Àf&q14"41(%+R]G^b¶Àf*%Ç+¤mJ7G?>5M%ÀfÆ*b¶ 3  $Õ,,Ç02-+ÆÎ*dt*_¯43"/ mÀf5 (%+¤

ÆÎ¤*m"R]G^,+ÆÎ½*03P[O^+ÆÎ1P[O^'+µb¶*ÒÚ&3
|u 7VK¦+i¥hÆ&43(!5r³*o Àf'·Õ+¾M

R]G^<7P^0*0#%¿ 3(!5±~ 3',hÆÆÎÀf+ØO*$)3.
"

+pa&,

Q6D7G*s³ÀfkÝ5o(%+ÀfÍÄR³²'5

" C)3Q6D7G 8ZB .",B87R28G02²ÀfÍ5²c 3i»,3
41*$%-|uo» 3Ã×3
(a)

ρ(H) = 0.38

(b)

Ti
H
C

ρ(H) = 0.00

NO

ρ(H) = 0.00
ρ(H) = 0.00
TS-7a7b’ρ(H) = 0.00

2.64 eVρ(H) = 0.00

7a

ΔE

ΔE

TS-7a7b0.74 eV

0.00 eV

7a’

7b0.00 eV*CH3C(NH)COO–
+
2*H+
+
e–

–0.37 eV

*CH3C(NH)COO–
+
2*H+
+
e–

*CH3C(NH2)COO–
+
*H+

7b’
–0.35 eV
*CH3C(NH2)COO–+*H+ (QHUJ\SURILOHZLWKVSLQGHQVLWLHV \HOORZ IRU1+ERQGIRUPDWLRQ D 3URWRQFRXSOHGHOHFWURQWUDQVIHUDQG E 
K\GURJHQDWRPWUDQVIHU ×G°*3 ¾*03  Th+X;ICWOÓ0&  mÇhdPÜ*3U

':]1^hÆ8:^+Ff- 332 -

l5Ö%vÀP¿4"pa" ©0& ©*03  Th+Àf[y5OÓ"Àf[y, A* ©*03¤Th'·Õ*      *03ÇhdPÜ&#"+ÇhdPÜ,  $+¤Lµ5X, +  28G'+m*03¾¤©+y
0&HY*03R]G^DÂ*03¤hÆ©+y&3Ëw+w )"/ NH]193'C)2,Ëy+ÌÎ¼B5%&,)  ¾ 28>[5 %T·&

3R]G^5DÂHY+HY¹, Àf9J[='!+ÀfÍ*¬)Ff5Ö"3'
4" )/% ¤ThÀf&, HY¹)(02¿¿³&2 1*ÀfÍ²À§* ¤Àf&,¹++ÖÒÚ&3." R]G^©')3 U
HY.", v*3'ÀfÍ²)3'4"X 5HDFWLRQHQHUJ\DQGEDUULHUKHLJKWRI+±+ERQGFOHDYDJHDQGS.DRIWKHFRQMXJDWHGDFLGRIWKHXVHGEDVH
5HDFWLRQHQHUJ\ %DUULHUKHLJKW


±



±

&RQMXJDWHDFLG

S.D H[S ±D >1L)H+@ >+32+2@ ĺ>1L)H+@ >+32+2@





+32 E >1L)H+@&+&22±ĺ>1L)H+@&+&22+





&+&22+





±

G >1L)H+@  +2 ĺ>1L)H+@ > +2 +2@





+2

±





±



±



±

F >1L)H+@ >+32+2@ ĺ>1L)H+@ >+32+2@








H >1L)H+@>+2&O@ ĺ>1L)H+@ +2&O

¿Æ



.",³

,VHJDZD 0 ³(OHFWURFKHPLFDO $ODQLQH )RUPDWLRQ DW ,QWHUIDFH EHWZHHQ 7L2   DQG :DWHU IURP %LRPDVV'HULYHG
3\UXYLF$FLG´,QVWLWXWH,QWHUHVW6HPLQDU6HULHV,&1(5.\XVKX8QLYHUVLW\6HSWHPEHU;dPX.",³  2JR6.LVKLPD7<DWDEH70L\D]DZD.<DPDVDNL50DWVXPRWR7$QGR7.LNNDZD0,VHJDZD
0<RRQ.6+D\DPL6³1L)H@>)H)H@DQG>)H@K\GURJHQDVHPRGHOVIURPLVRPHUV´6FL$GYHDD]  ,VHJDZD06WD\NRY$0<DPDXFKL³3URWRQ&RXSOHG(OHFWURQ7UDQVIHULQ(OHFWURFKHPLFDO$ODQLQH)RUPDWLRQ
IURP %LRPDVV'HULYHG 3\UXYLF $FLG 0HFKDQLVP RI &DWDO\WLF 5HDFWLRQ DW ,QWHUIDFH EHWZHHQ 7L2   DQG :DWHU´
DFFHSWHG  ,VHJDZD06KDUPD$3KRWRFKHPLFDO&RQYHUVLRQRI&2WR&2E\D5H&RPSOH[³7KHRUHWLFDO,QVLJKWVLQWRWKH)RUPDWLRQRI&2DQG+&2±IURPDQ([SHULPHQWDOO\'HWHFWHG&DUERQDWH&RPSOH[´LQUHYLHZ- 333 -

ᶵᲔᏛ⩦ࢆ⏝࠸ࡓప⇕ఏᑟ⋡࣍࢖ࢫ࣮ࣛᆺ⇕㟁ኚ᥮ᮦᩱࡢ᥈⣴
Explore for low thermal conductivity Heusler-type thermoelectricmaterials using machine learning‫ۑ‬ᐑᓮ ⚽ಇ㸦ྡྂᒇᕤᴗ኱Ꮫ㸧1◊✲┠ⓗ
500Υ௨ୖࡢ㧗࡛㧗࠸⇕㟁ኚ᥮ᛶ⬟ࢆᣢࡘᮦᩱ࡛࠶ࡿࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ࡣ 1970 ᖺ௦࠿ࡽ┒ࢇ࡟◊✲ࡉࢀ࡚࠾ࡾࠊᕤሙ⏝᤼⇕Ⓨ㟁ࢩࢫࢸ࣒࡞࡝࡛ᐇ⏝໬ࡀ㐍ࡵࡽࢀ࡚ࡁࡲࡋࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡇࡢᮦᩱ࡟࠾
ࡅࡿ㧗࠸⇕㟁ኚ᥮ᛶ⬟ࡣࠊ⤖ᬗ୰࡟Ꮡᅾࡍࡿ㝽㛫㸦✵Ꮝ㸧࡟ཎᏊࡀḞ㝗࡜ࡋ࡚౵ධࡍࡿࡇ࡜࡟㛵ಀࡋ࡚࠸ࡿ
ࡇ࡜ࡀ⌮ㄽⓗ࡟ணゝࡉࢀ࡚ࡁࡓࡶࡢࡢࠊࡑࡢḞ㝗ཎᏊࡢᏑᅾࡣࡇࢀࡲ࡛࡟☜ㄆࡉࢀ࡚ࡁࡓࡶࡢࡢࠊḞ㝗ཎᏊ
࿘㎶ࡢヲ⣽࡞ᵓ㐀ࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠿ࡗࡓࠋࡑࡢࡓࡵࠊḞ㝗ཎᏊ࿘㎶ࡢヲ⣽࡞ᵓ㐀ࢆ▱ࡿࡇ࡜ࡀ࡛ࡁࢀ
ࡤࠊࡇࡢᮦᩱࡢ㧗࠸⇕㟁ኚ᥮ᛶ⬟ࡢࡋࡃࡳࡀ᫂ࡽ࠿࡟࡞ࡾࠊ᪂ࡋ࠸ᮦᩱ㛤Ⓨᡭἲࡢᥦ᱌࡟ࡘ࡞ࡀࡿ࡜ᮇᚅࡉ
ࢀ࡚ࡁࡓࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊ㧗࠸⇕㟁ኚ᥮ᛶ⬟ࢆ᭷ࡍࡿࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ NiZrSn ྜ㔠࡟ὀ┠ࡋࠊḞ㝗ཎᏊ࿘㎶ࡢᒁᡤⓗ࡞⤖ᬗᵓ㐀ࡢኚ໬ࢆ➨୍ཎ⌮ィ⟬࡟ࡼࡾ᫂ࡽ࠿࡟ࡍࡿ࡜࡜ࡶ࡟ࠊᨺᑕගࢆ⏝࠸ࡓ㹖⥺྾཰ᚤ⣽ᵓ㐀(XAFS)ἲ࡟ࡼࡾ┤᥋ほ2ࡋࠊ୧⪅ࡢẚ㍑ࢆ⾜ࡗࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲṇ☜࡞Ḟ㝗ཎᏊ࿘㎶ࡢཎᏊ఩⨨ࢆㄪ࡭ࡿࡓࡵ࡟ࡣ⣙ 100 ཎᏊ࡜࠸࠺ከࡃࡢཎᏊࢆྵࢇࡔྜ㔠ࢆィ⟬ࡍࡿᚲせࡀ࠶ࡿࠋࡑࡇ࡛ࠊ⮬↛⛉Ꮫ◊✲ᶵᵓ࣭ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮ࢆ⏝࠸ࡓ኱つᶍ࡞ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋィ⟬ࢥ࣮ࢻ࡟ࡣᨃ࣏ࢸࣥࢩࣕࣝἲࢆ⏝࠸࡚ VASP-code ࡟ࡼࡾィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝ
ᅗ 1 ࡟ᮏ◊✲࡛⏝࠸ࡓḞ㝗ࡀᏑᅾࡋ࡞࠸⌮᝿ⓗ࡞ࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ NiZSn ྜ㔠࠾ࡼࡧ✵Ꮝ࡟ Ni ཎᏊࢆ౵ධࡉࡏࡓḞ㝗ཎᏊࢆྵࡴ NiZrSn ໬ྜ≀ࡢ⤖ᬗᵓ㐀ࢆ♧ࡍࠋィ⟬ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊḞ㝗ཎᏊ࿘㎶ࡢཎᏊࡣࠊ1 %⛬ᗘࠊṍࢇ࡛࠸ࡿᵓ㐀࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋᅗ  Ḟ㝗ࡀᏑᅾࡋ࡞࠸⌮᝿ⓗ࡞ࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ 1L=U6Q ྜ㔠㸦ᕥ㸧ࠋࢥࣥࣆ࣮ࣗࢱ࣮ࢩ࣑࣮ࣗࣞࢩ
ࣙࣥ࡟ࡼࡾண

ࡉࢀࡓ✵Ꮝ࡟ 1L ཎᏊࡀ౵ධࡍࡿࡇ࡜࡟ࡼࡾ⤖ᬗᵓ㐀ࡢ୍㒊ࡀṍࢇࡔࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ

≀ 1L=U6Q ྜ㔠㸦୰ኸ㸧࡜ཎᏊ఩⨨ࡢࡎࢀ㸦ྑ㸧ࠋ

- 334 -

ࡲࡓࠊྜ㔠୰࡟ྵࡲࢀ࡚࠸ࡿ௵ពࡢඖ⣲ࡢ࿘㎶ཎᏊࡢ⤖ᬗᏛⓗ࡞᝟ሗࢆㄪ࡭ࡿࡇ࡜ࡀ࡛ࡁࡿᨺᑕග X ⥺ࢆ฼⏝ࡋࡓ X ⥺྾཰ᚤ⣽ᵓ㐀㸦XAFS)ࢆ

ᐃࡋࡓ⤖ᯝࠊᅗ 2 ࡟♧ࡍࡼ࠺࡟ඛࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾண

ࢀࡓḞ㝗ཎᏊ࿘㎶ࡢṍࢆ⪃៖ࡋࡓࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ NiZrSn ྜ㔠ࡢ⌮ㄽⓗ࡞ XAFSࡉᐃࡢ⤖ᯝ࡜࡯ࡰ୍

⮴ࡋ࡚࠾ࡾࠊࡇࡢྜ㔠࡛ࡣḞ㝗ཎᏊ࿘㎶ࡢ⤖ᬗᵓ㐀࡟ṍࡀ⏕ࡌ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬
ྜ≀࡟࠾࠸࡚Ḟ㝗ཎᏊ࿘㎶ࡢṍࢆᐇ㦂ⓗ࡟┤᥋ほ⬟ࡘࡲࡾࠕᮦᩱ୰࡟

ࡋࡓࡢࡣୡ⏺ึ࡛࠶ࡾࠊࡇࡢṍࡢᏑᅾࡀ㧗࠸⇕㟁ኚ᥮ᛶᗘᕪࢆຍ࠼ࡓ㝿࡟኱ࡁ࡞㟁ᅽࢆ⏕ࡳฟࡍࡀ⇕ࡣఏ࠼࡟ࡃࡃࡍࡿࠖࠊ࡜࠸࠺ࡋࡃࡳ࡟㛵୚ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

ᅗ  ࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ 1L=U6Q ྜ㔠ࡢ =U ࠾ࡼࡧ 1L. ྾཰➃࡟࠾ࡅࡿ ;$)6
࡟ࡼࡾ࿘㎶ࡢ⤖ᬗᵓ㐀ࡀṍࢆ⪃៖ࡋࡓ㝿ࡢ ;$)6ᐃࡢᐇ㦂್࡜Ḟ㝗ཎᏊᐃࡢ⌮ㄽ್ࠋ

 ⬺Ⅳ⣲♫఍ࡢ⛣⾜࡜ᣢ⥆ྍ⬟࡞♫఍ࡢᐇ⌧ࡢࡓࡵ࡟ࠊ⌧ᅾࠊᤞ࡚ࡽࢀ࡚࠸ࡿ᤼⇕ࢆຠ࡟ά⏝ࡍࡿࡇ࡜ࡀ
࡛ࡁࡿ⇕㟁ኚ᥮Ⓨ㟁ᢏ⾡ࡢ᭦࡞ࡿ㧗ᛶ⬟໬ࡀᮃࡲࢀ࡚࠸ࡿࠋࡑࡢᐇ⌧ࡢࡓࡵ࡟ࡣ᪂ᮦᩱࡢ㛤Ⓨࡀᚲせ୙ྍḞ࡛࠶ࡿࠋ௒ᅇࠊほᐹ࡟ᡂຌࡋࡓ⇕㟁ኚ᥮ᮦᩱ୰ࡢḞ㝗ཎᏊ࿘㎶ࡢṍࡢほᐹࡣࠊ᪂ࡋ࠸⇕㟁ኚ᥮ᮦᩱࡢᐇ⌧࡟ᙺ❧ࡘࡶࡢ࡛࠶ࡾࠊ௒ᚋࠊࡇࡢṍࡢᵓ㐀ࢆ✚ᴟⓗ࡟ά⏝ࡋࡓࡼࡾ㧗ᛶ⬟࡞᪂ࡓ࡞⇕㟁ኚ᥮ᮦᩱࡢᐇ⌧ࡀᮇᚅ࡛ࡁࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

★࣍࢖ࢫ࣮ࣛᆺ )H9[$Oí[ ⣔ྜ㔠ࡢ S ᆺ⇕㟁≉ᛶ࡟ཬࡰࡍ 7L5H ඹ⨨᥮ຠᯝῦ஭ ⴌⱑᐇࠊᐑᓮ ⚽ಇࠊΏ㑔 ཌ௓ࠊす㔝 ὒ୍ ᖺᗘ᪥ᮏ⇕㟁Ꮫ఍Ꮫ⾡ㅮ₇఍★࣍࢖ࢫ࣮ࣛᆺ &R0Q6Lí[$O[ ໬ྜ≀ࡢ⇕㟁≉ᛶ࡜㟁Ꮚᵓ㐀ᐑᓮ ⚽ಇࠊ㛵⏣ ዲᕼࠊΏ㑔 ཌ௓ࠊᱜᗞ ⿱ᘺࠊす㔝 ὒ୍ ᖺᗘ᪥ᮏ⇕㟁Ꮫ఍Ꮫ⾡ㅮ₇఍★࣍࢖ࢫ࣮ࣛᆺ )H[5H[9$O ໬ྜ≀ࡢ⇕㟁≉ᛶ࡜㟁Ꮚᵓ㐀ᐑᓮ ⚽ಇࠊῦ஭ ⴌⱑᐇࠊΏ㑔 ཌ௓ࠊಖ஭ ᫭ࠊ㧗ᮌ ᗣከࠊす㔝 ὒ୍  ᖺᗘ⛅Ꮨ᪥ᮏ㔠ᒓᏛ఍Ꮫ⾡
ㅮ₇఍

5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

★³3URELQJ/RFDO'LVWRUWLRQDURXQG6WUXFWXUDO'HIHFWVLQKDOI+HXVOHUWKHUPRHOHFWULF1L=U6Q$OOR\´+LGHWRVKL 0L\D]DNL 2VPDQ 0XUDW 2]NHQGLU 6HOHQ *XQD\GLQ .RVXNH :DWDQDEH .D]XR 6RGD <RLFKL 1LVKLQR 
6FLHQWLILF5HSRUWV  - 335 -

★³/RFDOVWUXFWXUHDQGDWRPLFG\QDPLFVLQ)H9$O+HXVOHUW\SHWKHUPRHOHFWULFPDWHULDO7KHHIIHFWRIKHDY\HOHPHQWGRSLQJ´..LPXUD.<DPDPRWR.+D\DVKL67VXWVXL1+DSSR6<DPD]RH+0L\D]DNL61DNDJDPL-5
6WHOOKRUQ6+RVRNDZD70DWVXVKLWD+7DMLUL$.5$QJDQG<1LVKLQR3K\V5HY%

- 336 -







Mechanistic Investigations of Organic Reactions
by Experimental and Theoretical Combination○滝田 良、渡邉 康平、金井 求、大井 未来、三ツ沼 治信、真島 壮平、上村 祐伍、生長 幸之助、古田 将大、山次 健三、野崎 多実子、坂井 健太郎、平尾 祐樹、巽 俊文、
藤田 大樹、澤崎 鷹、山根 三奈、藤吉 浩平、山梨 祐輝、田辺 駿、梶野 英俊、
藤後 貴也、高橋 和希、中尾 裕康、彭 雪、陳 虹宇、花田 華世（東大院薬）
熊谷
1

直哉、野田

秀俊（微生物化学研究所）

研究目的·×Ý$ză©Õ!æ ¡¨¤/Í-'#±!uÆ¥~Å#ØÞ/Öªė~Îøôß#"*,½!râ#Ê¥/ÆÑöä!uV6I@U/´+"-

2

SV6EaW6E·×Ý" - DFT ôß$Gaussian 16*% GRRM 14Reaction Plus ! /nÑî!ôß²Å$f"ωB97X-D, M06-2X áB3LYP ! #ÄČ°/nÑĂÚË§ *% IRC ôß"*¢+.áÐ¨á! #¼ÿ" ¼ÿ¶ā~ *%«}ò¸/î

3

SV3;

3.1 Â/ćâÇ-ĉóìĕ³Âć~¤
?9\_?

-

$

VDZ:Z;=G
cÂe"

-ĉó

ìĕ³Âć~¤${þ.|ÌÕ"O3K_Z÷m/d-/ñt·¤¾¼"

»õæ¹

;]F\_Zė!

+ĉ 1 p 3 p#<19ZČd-ć~Õj{ĄrÕëď¾¼Ù.

ě. ĉóÂć~¤#¤åû#ÁýÆ¥Ü¦.ĉ VDZ:Z;=GĊm" GRRM (@HF/LanL2DZ) "*,çéÕ"¼ÿ/­ã
ě"`o¶¼ÿ (INT1) + DFT ôß (@M06-2X/SDD&6-311+G*/SMD(water)//
M06-2X/SDD&6-31+G*/SMD(water)) "*,»õ¤åû/ÙX_GQ]A]#ć~Õj{"*,Ð

- 337 -

 INT2 /åÒÖÕ#O3K_Zm (INT4) /|Ì*d `²y¤¦.-àĆk#0Y_Z~)M0Y_Z4_EZ#Ð¨$ÞmĎ! +Ę Æ¥~4JZ8_/£ð·¤yÐ¨É/Ð-!Ęă©Õ"Āî-úÇ/´+"
3.2 Þmă©Õ"0[_]Ĕ/d - 1,3-4]1]#LG\S:J=2U~¤Nanyang Technological University íáeÂâ~HFY2U (NaH) X2$+\GURPDJQHVLWDWLRQSDWKZD\~S:J=2U (MgI2) +ÔÐ

thf2.10 Mg

1]ù#¤$ă©Õ" 1,4-LG\S:J=2U~Āî-/ñ

1.74

R2 [Mg]
+
R1

R3

R1

S:J=2ULGYGÜ 1,3-4]

Mg+2generated in situ
from Na+-MgI2

R2

qh ¯¬:Z_P#s×Ý"

R1

2.09

thf

H



1.21

1.34

1.22



1.41

thf

1.92

R2
•

+
R3

H

2.56
1.79

2.15

1.81

H

1.74
2.07

thf

Mg 1.93H
H 1.891.90
Mg 2.12 thf

1.91

2.57

1.43

1.22

2.10

ΔG‡
thf +5.0

2.29

H

1.31 1.32(–10.3)

H

1.39

1.25

1.39



R1
E

1.74

Mg 1.94H
H 1.88
1.90
Mg

2.07

Mg 1.90 1.94
thfH(–40.9)
H
2.11
1.94
Mg
2.53

1.91

1.75

cat. CuCN
E+

H

H
1.74

1.91

H H1.89
ΔG‡
1.95
Mg 2.11 thf +16.2

+
R3

H

1.89

R2
•

[Mg]

R3

thf

1.95

TSA-1

INTA-2

TSA-2

(0.0)

(16.2)(–24.7)(–19.7)

H

1.73

H

INTA-1•1.90
Mg 2.07
H 1.88thfH
Mg 1.95

1.93
2.10

INTA-3(–30.0)

DEFenyne = 5.1 kcal/mol
DEFMgH2 = 3.2 kcal/mol%+\GURPDJQHVLWDWLRQSDWKZD\tÐ0[IZS:J=2UÜ

1.75

H

thf2.09 Mg$ĉócÜ#ÃĐx#

H H1.90
1.95
Mg
thf

¤"*,Þmă©Õ"è®0[_]

2.87

1.90
2.10

thf

H

1.32 1.32

2.14

1.49

1.79
1.87

1.34

(–42.4)

1.93

2.96

1.43
1.21

Mg 1.92
H
1.91
H
1.90
Mg 2.10 thf
•

2.08

thf

1.92

Mg

1.25

H

INTB-1

TSB-1

(0.0)

(22.2)/d - :Z_P#w*,áe
Ð- MgH2 ÜÆ¥Ü

2.81 1.95
1.42

H

1.74

1.74

H

H

ΔG‡
+22.2

2.11

1.74

Mg

1.89

1.89

H

H

2.09

thf

1.92

1.35

INTB-2(–20.2)

DEFenyne = 18.8 kcal/mol
DEFMgH2 = 2.0 kcal/mol-ê+.1,3-4]1]ù#¤åû 2. 1,3-4]1]#LG\S:J=2U~¤#öä"  DFT ôß (@ωB97X-D/6-311++G**/SMD(THF)//ωB97X-D/6-31++G**Ě/Ñ »õ0[IZ
S:J=2UÜ/d - 1,4-LG\S:J=2U~¤$ 2A "Ù* " 2 ÀčĀî-`²0Z7]ąk*,Āî-4,1-LG\S:J=2U~¤$*,Ę Æ¥~4JZ8_/£ð- ( 2B)
.$ĂÚË§ TSB-1 " 1,3-4]1]ù#¡"£ð!¿&4JZ8_ (DEF)  ' -´+!#i#åû(Áý·¤#Ę ¤¥^kèă©¥ïj+.
3.3 ĉ0Z7ZH1F[]#ÃĐÕ0TK~¤" -~ă©¥
1B7<CY>]-5-5]/0Z7ZH1F[]wĖm-ó¤"

\>2Uĉó$Ó!

- ~  ă © ¥  Ô Í       ĉ H 1 F [ ]  Č d  - Ï ~ ¾ ¼ / DFT ô ßę@UM06/SDD&6-311++G(2d,p)/SMD//UB3LYP-D3(BJ)/SDD&6-31G(d)Ě"*»õĉH1F[]#¼ÿ$g#ĊmČd-gºĉH1F[] ¤$aĈēRE]=WZ4JZ8_µĒbĀîĉH1F[]"

(\>2U# ½"?N\Ï~#Æ¥~4JZ8_$u"l v´ĉó#

$?N\eċm+#ükÛ#4JZ8_Ďđ"Ę

Curtin–Hammett #¾¼"*,5ZFÈâ+#Ï~/å¤Āî-/´+

4 K%X$>@ :DWDQDEH.7DNDJL0:DWDQDEH$0XUDWD67DNLWD52UJ%LRPRO&KHP
>@ :DQJ%/L<3DQJ-+:DWDQDEH.7DNLWD5&KLED6$QJHZ&KHP,QW(G
>@ 7DN5.$PHPL\D)1RGD+6KLEDVDNL0&KHP6FL'2,'6&)
>@ 1DJDVKLPD12]DZD6)XUXWD02L0+RUL<7RPLWD76RKPD<.DQDL06FL$GY
HDEF

- 338 -



 DNA 

Theoretical analysis of the repair mechanism of UV-induced DNA
damage for blue-light photoreceptors) %. 1

1 #$"!  2' - 2 

2

/1 

#$2 ,0Ɠţ¯Áã¤ŦŁŷB2@¯ÌùƇŘb|nbgvzX,ņRU@'TƠ¯ÌùƇŘ(PLs)Bb|nb(CRYs)GBOEũƇŘB2@z xYmqfrb^ko(FAD)WĖ4Tz }ivbŷA&SƟ
FAD ,Ɠţ¯WÁã4T0BAģ%DĥšWŀķ4TƠ
PLs GřÙşEQSČ«2: DNA
W¨ù4TĥšWŀķ2ƟĐ CRYs GġĳFŀŤõĄPƜƘFŉĪĀņDCEƎ2@'T0B,ņRU@'TƠPLs B CRYs G FAD F§Ė;/AD.ƟĦƆ¶PĦĢſ,Ƙ 2@'T,ƟCRYs G DNA ¨ùĥšWŀķ2D'Ơ8FĸĽG'.>+ēR+E1U@'T,ƟŻîď:EÅá1U: DASH Ñb|nb
(CRY-DASH)GFŎƘF CRY BĿDSƟPLs BÅģE C ęœƗÒEòƗÒWĖ2@'D'0BPĭýƅ¡FYtƈĨÓ, PLs EQSƘ 2@'TİDC+R DNA ¨ùĥšWĖ4TBŠ)RU:Ơ
2+2Ɵ
Űƚŗ²*QHĺ¤²E*'@řÙşČ«2:Ěƌ DNA F¨ùĭýWŊ1D'0B,ÔÈ1UƟķÐE
*'@O8FĸĽGēR+AGD'ƠĐƟřÙşEQT DNA FČ«EGÛK+EŎƘEµƘ4T0B,A-ƟƐSÄ(yfÖÓƍE[2+2]Ĺ¾»Àü,ĺ3:eb{iÑyfƋ¤(CPD)BƐSÄ(yfÖÓƍE>F±ĖŞÄ,õĄ1UT(6-4)¯Ļĳ((6-4)PP),&TƠ CPD B(6-4)PP G CPD ¯ÌùƇŘ (CPD-PLs)*QH(6-4)¯ÌùƇŘ ((6-4)-PLs)EQ=@8U9UĴĿłE¨ù1UTƠ(6-4)-PLs EQT(6-4)PP F¨ùšGƔìE¢'()ƟCPD EĩJ@(6-4)PP GőĲ×ĿŲŀš,ƔìEƛ'İ+RƟ÷ƛ¼ĶD¨ùWƃĄ4T()A(6-4)PPF¨ùĥĢFŮēGƉūA&TƠ0UKAÚ.FůŖŋß*QHâƚEQTŮĞ,ƁNRU@-:,ƟķÐ
AO(6-4)PP F¨ùĥĢEGĘŮēFİ,Ú.Ĩ1U@'TƠĚŇŐAGƟ(i) PLs FřÙşČ« DNA FŞÄĥĢFŮēƟ(ii) CRY-DASH ,D7řÙşČ« DNA F¨ùĥšWŀķ2D'F+Ɵ*QH(iii) (6-4)-PLs EQT(6-4)PP F¨ùĥĢF°ãFŮēWŃĉ2:Ơ

2 #$+&(i) PLs FřÙşČ« DNA FŞÄĥĢFŮēE>'@G CPD-PLs B CPD WÇMřÙşČ« DNA FŪÄ¤Eå2@µÝ½¹ßůŖ*QHijZpbgeeWâđ2:ƠPLs ,řÙşČ«2:
DNA WŞÄ4TƏEČ«ƅ¡,Ěƌ DNA +RÙUTzlycB'(ķŶ,ĺ3@'T0B, X şŞĔĢſŮĞEQSēR+B1U@'TƠĚŇŐAGƟijZpbgeeWļ'@Ɵ0Fzlyc,CFQ(Eĺ3@'TF+WŢĽ]saFŭİ+RŮĞ2:ƠK:ƟCPD ,zlyc4TƏECFYtƈĨÓ,Ǝ2@'TF+WēR+E4T:NEz cnµÝŹƂĬƝFMOƞWļ
'@ CPD BÉÎFYtƈĨÓƍFń¥ļ]saFŮĞOâđ2:Ơ
(ii) CRY-DASH ,D7řÙşČ« DNA F¨ùĥšWŀķ2D'F+WēR+E4T:NƟK5 PLs EQTřÙşČ« DNA F¨ùĥĢFūA&T FAD +RČ«ƅ¡IF¯ŲŸƒÝŌ½ÀüEŅŃ2:Ơivbŷ- 339 -

F¯ŲŸƒÝŌ½ÀüWŮĞ4T()AQ.¸ļ1U@'T_gĸŴEÓ?'@ƒÝŌ½ÀüžïFŭ
İ+RŮĞWƁN:Ơ_gĸŴWļ'@ƒÝŌ½ÀüžïWŖ´4T:NEGƒÝÍÝBz bdoÍÝWŬŏOTûū,&TƠĚŇŐAGƟCRYs B PLs BOEz }ivbŷA&SƟÅ3zXWõĄ2@'T0B+Rz bdoÍÝGÅōïA&TBá2ƟƒÝÍÝEFLŅŃ2:ƠƒÝÍÝWůŖŋßłćĬEQSŬŏOT:NEƟĚŇŐAG CRY-DASH B CPD WÇMĚƌ DNA FŪÄ¤Eå
2@µÝ½¹ßůŖWâđ2ƟøRU:ŪĎFgpl|elnEå2@ Configuration interaction singlesƝCISƞ
ĬWâđ2:ƠCIS QSøRU:ĳĸƋW¸ļ2 Generalized Mulliken-Hush ĬWļ'@ƒÝÍÝWŬŏO=:ƠÅģFůŖW CRY-DASH F×Ŀ¤(Glu395Met)Eå2@Oâđ2Ɵ8U9UF©Wĩź2:Ơ1REƟ
CRY-DASH B CPD-PLs F CPD WÇMĚƌ DNA FŪÄ¤Eå2@µÝ½¹ßůŖWâđ2Ɵ8U9UF
ŞÄģðFĩźOŧ=:Ơ
(iii) (6-4)-PLs EQT(6-4)PP F¨ùĥĢF°ãWēR+E4T:NƟquantum mechanics/molecular mechanics(QM/MM)Ĭ*QH QM/MM µÝ½¹ßůŖ (QM/MM-MD)W(6-4)-PLs B(6-4)PP WÇMřÙşČ« DNA FŪÄ¤Eå2@âđ2:Ơ(6-4)PP F¨ùEG(6-4)-PLs E§Þ1U@'T>FwgkfF|n¾ĵā,ƉūA&TBċį1U@'T:NƟ>FwgkfEƎ2@Š)(T4J@F|n¾ĵāFŜLÄV
6WŠĂ2ÃŎůŖWâđ2:Ơ

ĚŇŐAGƟµÝ½¹ßůŖE GROMACS-5.0.4 B GROMACS-5.1.4ƟijZpbgeeE GROMACS-5.0.4 B PLUMED-2.4.0ƟQM/MM-MD ůŖE GROMACS-4.5.5 B ORCA-4.0.1.2ƟQM/MM ůŖ
E GAUSSIAN16Ɵ82@ CIS ůŖ*QH FMO ĬEG GAMESS ver. Dec. 2014 W¦ļ2:Ơ

3#$(i)E>'@ƟCPD WÇMřÙşČ« DNA FLB

CPD-PLs ,ŻªEÞÐ4TĜAzlycF
Ÿ-P41WŢĽ]saFŭİ+Rĩź2:ŞğƟřÙşČ« DNA FÉÎE CPD-PLs ,ÞÐ2@'TBzlyc,ĺ3P4.DT0BWē
R+E2:ƝĚŮĞAG*Q8 6 kJ/mol ōïƟÏ 1ƞ
Ơ
1RE8FĸĽWēR+E4T:NE CPD BÉÎ
FYtƈĨÓƍFń¥ļ]saWŖ´2:Şğ$CPD-PLs FivbŷŨƕEÞÐ4TħE (#$%'(#$%' "!'),!*-/;"!'),!*-/;ëƒ2@'TYtƈĨÓ(Arg B Lys), CPD Bó 8 .ń¥ļ2@'T0BWēR+E2:Ơ2:, .63:295=&+=@Ɵ0URFŞğG CPD ,ivbŷŨƕEÞÐ4TYtƈĨÓEQ=@Ěƌ DNA +Rñ=òS´
1U@'TÂšýWŊË2@'TƠ(ii)E>'@GƒÝÍÝF©GƟCRY-DASH FƊĺÑAG 5.3 meVƟCRY-DASH F×Ŀ¤AG 5.1 meV B8
U9UŬŏORU:Ơ1RE®ŧŇŐA CPD-PLs Eå2@ÅģFŮĞ,D1U@*SƟ8FŞğG 4.5 meV
A&=:Ơ2:,=@ƟůŖŋßEQS CRY-DASH G CPD-PLs BÅōïFƒÝŌ½ÀüýWĖ2@'T0
B,Ŋ1UƟĚŇŐA»):×Ŀ(Gln395Met)GƒÝŌ½žïEGöƖW)D'0BOēR+E2:ƠâƏ

- 340 -

Eą%,âđ2:âƚ+RO CRY-DASH GĚƌ DNA F¨ùĭýWŊN2:0B+RƟâƚłEO CRYDASH G¿µDƒÝŌ½ÀüýWĖ2@'T0B,ňűA-:ƠK:ƟƒÝÍÝ,CFQ(DÕÄEÛ-D©WŊ4F+WųJ:ŞğƟFAD FYmqƅ¡, CPD EŻĊ2@'TB-E©,Û-.DT¬ÆWŊ2:Ơ0F0BG0UKA®ŧŇŐAį1U@':Ymqƅ¡WŝĽ2@ƒÝ, FAD +RČ«ƅ¡IŌ½
2@'TB'(0BWčĈ4TŞğA&TƠ1RE CRY-DASH B PLs FĚƌ DNA BFŞÄģðWĩź2:ŞğƟPLs AGĚƌ DNA Bàá2:ÖĤWõĄ2:FEå2@ƟCRY-DASH AGÅģFÖĤFõĄ,àáA&=:ƠFŞğQS CRY-DASH GřÙşČ« DNA F¨ùE¿µDƒÝŌ½ÀüýWĖ2@'@OĚƌ DNA WàáEŞÄ4T0B,A-D':NEĚƌ DNA W¨ùA-D'ÂšýWŊË2@'TƠ(iii)E>'@GG3NEƟÿá2:>FwgkfF|n¾ĵāE*'@ FAD +R(6-4)PP IƒÝ,Ō½2:F<FĢſW QM/MM ĬWļ'@ĕƄ¾2:Ơ8URFĢſW·ėĢſB2@ QM/MM-MD ůŖW
âđ2:ŞğƟĚŇŐAŮĞ2:e[f[u]F(6-4)-PLs E*/T 365 ľŃFwgkf(His365)F"N¡B!N ¡,BOE|n¾1U@'TĵāE*'@ His365 +R(6-4)PP IF|nŌ½Wŭį2:Ơ
ĐƟHis365 F"N ¡FLK:G!N ¡FL,|n¾2@'TĵāAGĴúłDÀüWŭį4T0B,
A-D+=:0B+RƟæD.BO His365 F"N ¡B!N ¡,BOE|n¾1U@'Tûū,&T0B
WēR+E2:Ơ2+2Ɵ|nŌ½,ĺ3:F<Eď:EĴúłDÀüWŭį4T0B,A-D+=::NƟĚŇŐAG|nŌ½,ĺ3:F<E(6-4)PP +R FAD IFŽƒÝŌ½Àü,ĺ3TBá2Ɵ8
FĜA QM/MM-MD ůŖWâđ2:ŞğƟ¨ùÀü,Ɓŧ2:Ơ1RE0FB-^`hiĢſFõĄ
Oŭį1U:Ơ®ŧŇŐEQ=@Ɵ0F^`hiƍ¤FĖı,ŵŴ1U@-:,ēňDŮŕ,øRU@*R5ƟĚŇŐG^`hiƍ¤WŝĽ4T¨ùĥĢWčĈ4TŞğWø:Ơ8F÷Ɵ2 ÌŃF FAD +R(6-4)PP IFƒÝŌ½,ĺ3T0BA¨ùÀü,1RE®EƁŧ2ƟĕśłE³H(6-4)PP +R FAD IƒÝ,ĆT0BA(6-4)PP ,ıČ«DyfÖÓEĆTÀüFŭįEĄº2:ƝÏ 2ƞ
Ơ1REÃĢſF]saêFŭİ+ROż2:Àü,Ÿ-P4'0BWňű2:Ơ0F¨ùĥĢG®ŧŇŐEQ=@ two-photon
mechanism B2@į1U@*SƟĚŇŐFŞğG two-photon mechanism FÜôýWčĈ4TŞğA&TƠ

8   14/;  - 341 -

7<03

4

*(

#£ťŒƙƟŔ

ÌĒĚĺĳĳĸßƟ^ Z

#ŚéƑíƟ£ťŒƙƟƟ Ɵ Ɵ ƟèĄăƟç­ĮíƟŔÌĒĚĺĳĳĸßƟ^ ZƝƞ#äþƙƟéĽØƟ£ťŒƙƟèĄăƟç­ĮíƟŔ  ÌuZ^Ǝƀ¾ße~f[Ɵ^ Z

#äþƙƟ£ťŒƙƟĝěĠīƟèĄăƟç­ĮíƟŔ  Ì  ¾ßz\gi Ɵ^ Z
#ç­ĮíƟƋÝĺÊŋßß Ŕ  ÌÛƟ^ Z5

(

.1DNDPXUD66XJLXUD)$UDRND6$\D<7DNDQLVKL*:DWDQDEH56DWR<6KLJHWD+0DHGD2UJ/HWW
  
56DWR<0RUL50DWVXL12NLPRWR-<DPDPRWR07DLML%LRSK\V3K\VLFRELRO  <7HUDL50DWVXPXUD56DWR6,ZDL-<DPDPRWR1XFO$FLG5HV  <+DNHWD00L\DVXH<.RED\DVKL56DWR<6KLJHWD1<DVXGD17DPDL+0DHGD-$P&KHP6RF
  





















- 342 -

0XOWLVFDOHPRGHOLQJRILQWHUVWHOODUUDGLFDOVSHFLHVRQZDWHULFH
żW. M. C. Sameera (Institute of Low Temperature Science, Hokkaido University)

1 Introduction
The fundamental building blocks of molecules that lead to the origin of life in the Universe can be formed on cosmic
icy dust grains in the cold interstellar medium (ISM). For a quantitative understanding of the chemical evolution towards
complex molecules, it is essential to know the behavior of relatively small radical species on icy grains at low temperatures(e.g., 10 K). However, elementary processes such as adsorption, diffusion, and chemical reactions when encountering
each other are still unknown and treated as “black box” in the astrochemical models in predicting the chemical evolution
in the Universe. We use a multidisciplinary approach to overcome this limitation, where we will connect computational
chemistry, surface science, and low-temperature sciences to study the radical processes on ice. Computational methods
determine reaction paths in a broad sense to explain the reaction mechanisms for forming complex organic molecules in
the ISM, and guide the experimentalists to gain a broad viewpoint on designing their experiments and instrumentation toachieve the real situation in the ISM. This refined knowledge will fulfill a long-awaited gap in the quantitative
determination of the radical adsorption, diffusion, and chemical reactions at low temperatures.

2 Methods
The ONIOM(QM:MM) method, as implemented in the Gaussian16 program and the SICTWO interface, was used
for structure optimization. The wB97X-D functional and def2-TZVP basis sets were used for the ONIOM high-layer,
while the AMBER or AMOEBA09 force fields were employed for the ONIOM low-layer. Ice cluster models were used
to represent amorphous solid water (ASW). Vibrational frequency calculations were performed to confirm the nature of
the optimized local minimum (no imaginary frequency) or transition state (one imaginary frequency) and to calculate
zero-point energies. Excited-state calculations were performed using the TD-DFT method, where wB97X-D functionaland def2-TZVP basis sets in the Gaussian16 program were used for all atoms. Conical intersections between the excitedstate potential energy surfaces were calculated using the GRRM17 program.

3 Results
CH3O radical on ices: ONIOM(QM:MM) method was used for calculating binding energies of the CH3O radical
on ASW,1 where a range of binding energies (0.10-0.50 eV) was observed, and the average binding energy was 0.32 eV.
An energy decomposition analysis indicated that the electrostaticinteractions and Pauli repulsions between the CH3O radical and ice
control the binding energy. Computed binding energies from the
ONIOM(DFT:MM) and DFT methods are in agreement, suggesting that
the ONIOM(DFT:MM) method gives accurate binding energies.
However, computed binding energies from the ONIOM(DFT:AMBER)- 343 -

and ONIOM(DFT:AMOEBA09) differ, and therefore the chosen force field matters.
OH radical on ices: Laboratory experiments and quantum chemistry was used for calculating OH radical on ASW.2
Our experiments created OH radical on water ice by photodissociation of H2O at interstellar conditions. The wB97XD/def2-TZVP level of theory was used for calculating
ground and excited-state potential energy surfaces. DFT
calculations rationalized the mechanism for the OH
desorption on ice throught one-photon absorption of the OH(H2O)n complex. This phenomenon is sensitive to theinteractions between the OH radical and the water molecules
at the binding site.
When the OH radical meets an electron on ice, an OH
anion can be formed. ONIOM(DFT:MM) calculations
suggested that the OH anion reacts with H2O molecules on ice. Then, the OH anion can be diffused into ice bulk throughthe proton hole transfer, giving rise to the negative current.3 This phenomenon was confirmed by laboratory experiments.

4

Talks and Posters W. M. C. Sameera, Radical species on interstellar ices: a quantum mechanics/molecular mechanics study, CICO-

VICO Fall 2020 Workshop, Chalmers University, Sweden. (Talk)
 W. M. C. Sameera, Advances and challenges in modeling reaction mechanisms, Department of Chemistry School ofLife Sciences, University of Sussex, UK. (Talk)
 W. M. C. Sameera, On the mechanistic puzzles of homogeneous catalysis. Institute for Materials Chemistry andEngineering, Kyushu University, Japan. (Talk)
 W. M. C. Sameera, OH anions and OH radicals on amorphous ice: a combined experimental and quantum chemical

study, The 2nd ICReDD International Symposium, Hokkaido University, Japan. (Poster)5

Publications

 (1) W. M. C. Sameera, B. Senevirathne, S. Andersson, M. Al-lbadi, H. Hidaka, A. Kouchi, G. Nyman, N. Watanabe, J.

Phy. Chem. A, 2021, 125, 1, 387-393.
 (2) A. Miyazaki, N. Watanabe, W. M. C. Sameera, Y. Nakai, M. Tsuge, T. Hama, H. Hidaka, A. Kouchi, Phys. Rev.

Lett. A, 2020, 102, 052822.
 (3) K. Kitajima, Y. Nakai, W. M. C. Sameera, M. Tsuge, A. Miyazaki, H. Hidaka, A. Kouchi, N. Watanabe, J. Phys.

Chem. Lett. 2021, 12, 1, 704-710.
 (5) Y. Takeda, W. M. C. Sameera, S. Minakata, Acc. Chem. Res. 2020, 53, 1686-1702.
 (6) Y. Ohki, K. Ishihara, M. Yaoi, M. Tada, W. M. C. Sameera, R. E. Cramerd, Chem. Commun. 2020, 56, 8035-

8038.
 (7) K. Ishihara, Y. Araki, M. Tada, T. Takayama, Y. Sakai, W. M. C. Sameera, Y. Ohki, Chem. Eur. J. 2020, 26, 9537-

9546.

- 344 -

ࢣ࢖㓟⣔⁐⼥యࡼࡾ⏕ࡎࡿ &D6L2 ⤖ᬗ࡟࠾ࡅࡿ 6L2㘒యᵓ㐀࡬ཬࡰࡍ
ᅛ⁐ඖ⣲ࡢᙳ㡪
(IIHFWRIGRSHGHOHPHQWVRQORFDOVWUXFWXUHRIWHWUDKHGUDO6L2LQ &D6L2FU\VWDOSUHFLSLWDWHGIURPVLOLFDWHPHOW‫ۑ‬㕥ᮌ ㈼⣖ࠊ⡿㇂ ᐋဢ㸦኱㜰኱Ꮫ㸧1◊✲┠ⓗࢣ࢖㓟ࢆ୺ᡂศ࡜ࡍࡿ㓟໬≀ࡣࠊྛ✀ࢭ࣓ࣥࢺࡸ࢞ࣛࢫᮦᩱ࡞࡝ከᒱ࡟ࢃࡓࡗ࡚౑⏝ࡉࢀࠊࡲࡓ㔠ᒓ〇㘐ࡢศ㔝࡛ࡣࠊ⁐⼥㔠ᒓ୰ࡢ୙⣧≀ࢆྲྀࡾ㝖ࡃࢫࣛࢢࡢ୺ᡂศ࡛࠶ࡿࠋ6L2 㛫ࡢ⤖ྜࡣ㧗࡛ࡶᙉ࠸ඹ᭷⤖ྜᛶࢆ♧ࡋࠊ>6L2@ࡢṇᅄ㠃యᵓ㐀ࢆᏳᐃ࡟ᙧᡂࡍࡿࠋ⤖ᬗ୰࡛ࡣ>6L2@㘒యࡀつ๎ṇࡋࡃ㓄ิࡍࡿ୍᪉ࠊ⼥
య୰࡛ࡣ」ᩘࡢ>6L2@ྠኈࡀ㓟⣲ࢆ௓ࡋ࡚㐃⤖ࡋྜ࠸ࠊ3 ḟඖⓗ࡟୙つ๎࡞⥙┠ᵓ㐀ࢆᙧᡂࡍࡿࠋ≉࡟ࠊࢣ࢖㓟ሷ⣔ࡢ⁐⼥ࢫࣛࢢ୰࡟⤖ᬗࢆᯒฟࡉࡏࡿࣉࣟࢭࢫ࡛ࡣᵓ㐀ᙧᡂ࣓࢝ࢽࢬ࣒ࡢヲࡋ࠸⌮ゎࡀᚲせ࡛࠶ࡿࠋ
➹⪅ࡣࡇࢀࡲ࡛ࠊCa2+࢖࢜ࣥ࡟ࡼࡗ࡚>6L2@㘒యྠኈࡢ㐃⤖ࡀ඲࡚ษ᩿ࡉࢀࠊᏙ❧ࡋࡓ>6L2@㘒య࡜ Ca2+࠿ࡽᡂࡿࢲ࢖࢝ࣝࢩ࣒࢘ࢩࣜࢣ࣮ࢺ㸦Ca2SiO4㸧໬ྜ≀ࡢ㧗┦㸦Į㸪භ᪉ᬗ㸧࡟࠾ࡅࡿศᏊᵓ㐀ࢆゎ᫂ࡍࡿࡓࡵࡢ◊✲ࢆ⾜ࡗ࡚ࡁࡓ[1-4]ࠋྠ໬ྜ≀ࡣࠊ㕲㗰〇㘐࡟࠾࠸࡚⁐㕲୰ࡢࣜࣥ㸦P㸧ࢆ㓟໬㝖ཤࡍࡿ⬺ࣜࣥᕤ⛬࡛
⁐⼥ࢫࣛࢢ୰࡟ᯒฟࡋࠊP ᡂศࢆ㧗⃰ᗘ࡟ᅛ⁐ࡍࡿᙺ๭ࢆᢸ࠺㔜せ࡞໬ྜ≀࡛࠶ࡿࠋ㕲㗰ᮦᩱࡢ㧗ရ㉁໬ࡢ
ࡓࡵ࡟⬺ࣜࣥຠ⋡ࡢྥୖࡀồࡵࡽࢀ࡚࠸ࡿࡀࠊࡑࡢࡓࡵ࡟ࡣ⁐⼥ࢫࣛࢢ࠿ࡽᯒฟࡍࡿ &D6L2 ⤖ᬗ࡬␗✀ඖ⣲ࡀᅛ⁐ࡋࡓ㝿ࡢ>6L2@㘒యࡢศᏊᵓ㐀࡜ࡑࡢᏳᐃᛶ࡟㛵ࡍࡿ▱ぢࡀᚲせ࡛࠶ࡿࠋ
ㄢ㢟௦⾲⪅ࡣ᭱㏆ࠊ⌮໬Ꮫ◊✲ᡤࡢࢩࣥࢡࣟࢺࣟࣥ 63ULQJ ࡟࠾࠸࡚㧗࢚ࢿࣝࢠ࣮; ⥺ࢆ౑⏝ࡋࠊ⁐⼥ࢫࣛࢢ୰࠿ࡽᬗฟࡍࡿ Ca2SiO4 ໬ྜ≀ࡢ⤖ᬗᵓ㐀ࢆ㧗

ࡑࡢሙ X ⥺ᅇᢡ࡟ࡼࡗ࡚┤᥋ྠᐃࡍࡿ◊✲ࢆ⾜ࡗࡓ[3-4]ࠋࡑࡢ⤖ᯝࠊ⬺ࣜࣥᕤ⛬࡛Ⓨ⏕ࡍࡿ 6L2&D2)H2[32 ⣔ࡢ⁐⼥ࢫࣛࢢ࠿ࡽࡣ Į ┦ࡢ Ca2SiO4 ໬ྜ≀ࡀᯒฟࡍࡿࡀࠊࡑࡢ⤖ᬗᵓ㐀ࡣ⣧≀㉁ࡼࡾࡶ᱁Ꮚᐃᩘࡀ⦰ᑠࡋ࡚࠾ࡾࠊ)H ࠾ࡼࡧ 3 ᡂศࡀ⤖ᬗ୰࡟ᅛ⁐ࡋ࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ⁐⼥ࢫࣛࢢ࠿ࡽᯒฟࡍࡿ Į&D6L2 ⤖ᬗ࡟࠾࠸࡚ࡇࢀࡽࡢ␗✀ඖ⣲ࡀ>6L2@㘒యࡢ㓄ྥ≧ែ࡟ཬࡰࡍᙳ㡪ࡣ᫂ࡽ࠿࡛࡞࠸ࠋࡓࡔࡋࠊࡇࡢ>6L2@㘒యࡢ㓄ྥᏳᐃᛶࡀ &D6L2 ⤖ᬗ࡬ࡢࣜࣥᅛ⁐ᗘࢆᕥྑࡍࡿࡢ࡛ࠊࣜࣥᅛ⁐ᗘࡢ㧗࠸ Į&D6L2 ࡢ⤖ᬗᵓ㐀ࡢタィࡢࡓࡵ࡟ࡣୖグࢆゎ᫂ࡍࡿᚲせࡀ࠶ࡿࠋ
ᮏㄢ㢟࡛ࡣࠊVASP ࢆ⏝࠸ࡓᐦᗘỗ㛵ᩘἲ࡟ࡼࡿ➨୍ཎ⌮ィ⟬࠾ࡼࡧศᏊືຊᏛ㸦MD㸧ィ⟬ࢆᐇ᪋ࡋࠊĮ
Ca2SiO4 ⤖ᬗ୰࡬␗✀ඖ⣲ࢆ⨨᥮ᅛ⁐ࡉࡏࡓሙྜࡢ>6L2@㘒యࡢศᏊᵓ㐀࡜㓄ྥᛶࠊ࡞ࡽࡧ࡟㧗࡟࠾ࡅࡿ Į

┦ᅛ⁐య⤖ᬗࡢᵓ㐀Ᏻᐃᛶ࡟ࡘ࠸᳨࡚ウࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ㐣ཤ࡟ Mumme ࡽ[5]࡟ࡼࡾሗ࿌ࡉࢀࡓ Į&D6L2 ࡢᵓ㐀᝟ሗࢆᇶ࡟༢఩᱁Ꮚࣔࢹࣝࢆసᡂࡋࠊḟ࡟ࡇࢀࢆᣑᙇࡋ࡚ᩘⓒಶࡢཎᏊ࠿ࡽᡂࡿࢫ࣮ࣃ࣮ࢭࣝࢆసᡂࡋࡓࠋࡇࡢࢫ࣮ࣃ࣮ࢭࣝ࡬୍㒊ࡢ &Dࢆ )H࡬⨨᥮ࡋࠊࡲࡓ୍㒊ࡢ>6L2@㘒య୰ࡢ 6L ཎᏊࢆ 3 ཎᏊ࡬⨨᥮ࡋ࡚>32@㘒య࡜ࡋࠊ>32@㘒యࡢ᭱㏆᥋఩⨨࡟࠶ࡿ &Dࢆ✵Ꮝ࡜ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊ)H ࠾ࡼࡧ 3 ཎᏊࢆᅛ⁐ࡋࡓึᮇᵓ㐀ࣔࢹࣝࢆసᡂࡋࡓࠋࡇࡢᵓ㐀ࣔࢹࣝ࡟ᑐࡋ
࡚ࠊ➨୍ཎ⌮ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬࡞ࡽࡧ࡟ 0' ィ⟬ࢆᐇ⾜ࡋࠊ᭱Ᏻᐃ࡜࡞ࡿཎᏊ㓄⨨࠾ࡼࡧᅛ⁐࡟ᑐࡍࡿ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࡢィ⟬ࢆ⾜ࡗࡓࠋ➨୍ཎ⌮ィ⟬ࢯࣇࢺ࢙࢘࢔࡜ࡋ࡚ VASP 5.3.3 ࢆ᥇⏝ࡋࡓࠋ㟁Ꮚᐦᗘ࡟ࡣᐦᗘ໙㓄㏆ఝ㸦GGA㸧ࢆ⏝࠸ࠊᇶᗏ㛵ᩘࡣᖹ㠃Ἴࠊ஺᥮┦㛵ỗ㛵ᩘࡣ Perdew-Burke-Ernzerhof ᆺ࡜ࡋࡓࠋィ⟬࡛ᢅ࠺౯㟁Ꮚࡣࠊ2 ࡛ࡣ  㟁Ꮚ㸦VS㸧ࠊ 6L ࡛ࡣ  㟁Ꮚ㸦VS㸧ࠊ &D ࡛ࡣ  㟁Ꮚ㸦VSV㸧ࠊ)H ࡛ࡣ- 345 - 㟁Ꮚ㸦VSVG㸧
ࠊ3 ࡛ࡣ  㟁Ꮚ㸦VS㸧࡜ࡋࡓࠋ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ࡣ 450 eV ࡜ࡋࠊศᩓຊ⿵ṇ࡟
ࡣ Grimme ࡢ DFT-D3 ࢆ㐺⏝ࡋࡓࠋ➨୍ཎ⌮ MD ィ⟬ࡣ᫬㛫้ࡳᖜࢆ 1.0fs ࡜ࡋ࡚ NVT ୍ᐃࡢ࢔ࣥࢧࣥࣈࣝ
᮲௳ୗ࡛ᐇ⾜ࡋࠊ300K㹼1800K ࡢྛᗘ࡛ࡑࢀࡒࢀ 5ps ಖᣢࡋ࡚ᖹ⾮໬ࡉࡏࡓࠋࡲࡓࠊ␗✀ඖ⣲ࡢᅛ⁐࡟ᑐࡍࡿ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬㸦ο‫ܨ‬㸧ࡣࠊ౛࠼ࡤ Fe ᅛ⁐ࡢሙྜࠊḟࡢᘧ(1)࡟ࡼࡗ࡚⟬ฟࡋࡓࠋο‫ ܨ‬ൌ οܷ െ ܶοܵ, οܷ ൌ ܷେୟమሺభషೣሻ୊ୣమೣୗ୧୓ర െ ሺͳ െ ‫ݔ‬ሻܷେୟమୗ୧୓ర െ ‫ܷݔ‬୊ୣమ ୗ୧୓ర , οܵ ൌ െܴሼሺͳ െ ‫ݔ‬ሻሺͳ െ ‫ݔ‬ሻ ൅ ‫ݔݔ‬ሽ. (1)ܷେୟమሺభషೣሻ୊ୣమೣୗ୧୓ర 㸪ܷେୟమୗ୧୓ర 㸪ܷ୊ୣమ ୗ୧୓ర ࡣࡑࢀࡒࢀࠊĮ&D6L2 ୰ࡢ &D ཎᏊࡢ୍㒊ࢆ )H ཎᏊ࡬⨨᥮ࡋࡓ⤖ᬗࠊඖࡢ Į&D6L2 ⤖ᬗࠊĮ&D6L2 ୰ࡢ &D ཎᏊ඲࡚ࢆ )H ཎᏊ࡬⨨᥮ࡋࡓ⤖ᬗࡢᙧᡂ࢚ࢿࣝࢠ࣮ࢆ⾲ࡋࠊ7 ࡣᗘࠊ

5 ࡣẼయᐃᩘࠊ[ ࡣ⨨᥮ᗘࢆ⾲ࡍࠋο‫ࡢܨ‬ṇ㈇࠾ࡼࡧ኱ࡁࡉ࡟ࡼࡗ࡚ࠊ␗✀ඖ⣲ࡢᅛ⁐ࡋ᫆ࡉࢆホ౯ࡋࡓࠋ3◊✲ᡂᯝࡲࡎࠊĮ&D6L2 ⤖ᬗࡢ༢఩᱁Ꮚࢆ îî ಸ࡟ᣑᙇࡋࠊ&D ཎᏊ  ಶࢆ )H ཎᏊ࡬ࠊࡲࡓ  ಶࡢ 6L ཎᏊࢆ 3 ཎᏊ࡬⨨᥮ࡍࡿࡇ࡜࡟ࡼࡗ࡚ )H3 ࢆྠ᫬࡟ᅛ⁐ࡋࡓ Į&D6L2 ⤖ᬗࡢึᮇᵓ㐀ࣔࢹࣝࢆసᡂࡋࡓࠋ᱁Ꮚᐃᩘࢆ
➼᪉ⓗ࡟ኚ໬ࡉࡏࠊ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚ . ࡛ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓ⤖ᯝࠊ⣧≀㉁ࡢ Į&D6L2 ⤖ᬗࡼࡾࡶࡸ
ࡸ⦰ᑠࡋࡓ᱁Ꮚᐃᩘ࡟࠾࠸࡚⤖ᬗᙧᡂ࢚ࢿࣝࢠ࣮ࡀᴟᑠ್ࢆ♧ࡋࠊ᭱Ᏻᐃ࡜࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋᵓ㐀᭱㐺໬ᚋࡢ⤖ᬗᵓ㐀ࣔࢹࣝࢆᅗ  ࡟♧ࡍࡀࠊ>6L2@࡜>32@㘒యࠊ࠾
ࡼࡧ &D ࡜ )H ཎᏊࡀࠊࡑࢀࡒࢀࡢึᮇ఩⨨ࡢ㏆ഐ࡛୙つ๎࡟஘ࢀࡓ㓄⨨ࢆ♧ࡍࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢࡼ࠺࡟୙つ๎࡞ཎᏊ㓄⨨ࢆྲྀࡿഴྥࡣ Į&D6L2 ໬ྜ≀࡟≉᭷ࡢᛶ㉁࡛࠶ࡾࠊ␗✀ඖ⣲ࢆ⨨᥮ᅛ⁐ࡍࡿ࡜⤖ᬗ୰࡛㟁Ⲵศᕸࡀ୙ᆒ⾮࡜࡞ࡿࡓࡵࠊࡇࢀࢆ⦆࿴ࡍ
ࡿࡓࡵ࡟ཎᏊ㓄⨨ࡢኚ఩ࡸᅇ㌿ࡀ୙つ๎࡟⏕ࡌࡿ࡜⪃࠼ࡽࢀࡿࠋ
ḟ࡟ࠊ⬺ࣜࣥᕤ⛬ࡀ⾜ࢃࢀࡿ . ࡛ࡢ Į&D6L2 ⤖ᬗ࡬ࡢ )H   3 ᅛ⁐࡟ᑐࡍࡿ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆ⟬ฟࡋࡓ⤖ᯝࢆ⾲  ࡟♧ࡍࠋ ᅗ 1. Fe ࠾ࡼࡧ P ࢆᅛ⁐ࡋࡓ ĮCa2SiO4)H ᅛ⁐࡟ᑐࡋ࡚ࡣο‫⤯ࡢܨ‬ᑐ್ࡀᑠࡉࡃ )H ࡣᅛ⁐ࡋ㞴࠸ࡀࠊ3 ᅛ⤖ᬗ㸦Į଺ଶ ଵ ଷ଴ ଶ ଵଶ଼ 㸧ࡢᵓ㐀᭱㐺⁐࡟ᑐࡋ࡚ࡣο‫ࡀܨ‬㈇࡟኱ࡁࡃࠊ3 ࡣᅛ⁐ࡋ᫆࠸ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ

໬ᚋࡢཎᏊ㓄⨨ᅗࠋࡲࡓࠊ)H 3 ࢆྠ᫬࡟ᅛ⁐ࡋࡓሙྜࡢο‫ ࡣܨ‬3 ࡢࡳᅛ⁐ࡋࡓሙྜ࡜⾲ 1.

ྠ➼࡛࠶ࡿࡇ࡜࠿ࡽࠊĮ&D6L2 ⤖ᬗ࡬ )H ࡀணࡵᚤ㔞࡟ᅛ⁐ࡋ࡚ᑐࡍࡿ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬㸦.㸧
ࠋ࠸࡚ࡶࠊ3 ᡂศࡢᅛ⁐ࡣᏳᐃ࡟⏕ࡌᚓࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

Į&D6L2 ⤖ᬗ࡬ࡢ )H3 ᅛ⁐࡟

&U\VWDOο‫[ܨ‬kJ㺃mol-1]

Į଺ଷ ଵ ଷଶ ଵଶ଼-44.1

[1] ࠐM. Suzuki, H. Serizawa, S. Nakano, N. Umesaki, ",QVLWX SKDVHĮ଺ଷ ଷ଴ ଶ ଵଶ଼-120

GHWHUPLQDWLRQ RI SULPDU\ SUHFLSLWDWHG FRPSRXQG IURP PROWHQĮ଺ଶ ଵ ଷ଴ ଶ ଵଶ଼

-125

4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃSKRVSKRUXVFRQWDLQLQJVODJ", The 11th Int. Conf. Molten Slags, Fluxes and Salts, Feb. 21-25th, 2021, Virtual, Korea.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬2] M. Suzuki, N. Umesaki, Y. Ishii, "Highly Disordered Ionic Distribution in ĮDicalcium Silicate for Structure
Relaxation", J. Am. Ceram. Soc., submitted.

ཧ⪃ᩥ⊩>@06X]XNL61DNDQR+6HUL]DZD1 8PHVDNL ,6,-,QW9ROSS  >@06X]XNL+6HUL]DZD18PHVDNL,6,-,QW9RO SS  >@ :0XPPH/0'&UDQVZLFN%&&KDNRXPDNRV 1-E0LQHU$EK9ROSS  

- 346 -

ศᏊືຊᏛィ⟬࡟ࡼࡿ㧗᥋╔⺮ⓑ㉁ࡢỈ୰᥋╔࣓࢝ࢽࢬ࣒ࡢゎ᫂Elucidation of adhesion mechanism of highly adhesive protein in waterby molecular dynamics simulation
‫ۑ‬㕥ᮌ
1

῟ᕧࠊ➲ཎ

⣧ࠊᇼ

ඞᩄ㸦ྡྂᒇ኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧◊✲┠ⓗࠊෆᐜ
⣽⳦ $FLQHWREDFWHU6S 7RO ࡣࠊ$WD$ ࡜࿧ࡤࢀࡿ඲㛗⣙ QP ࡢᕧ኱⧄⥔≧ࢱࣥࣃࢡ㉁  ṧᇶࡢ࣏ࣜ࣌ࣉࢳࢻ㙐ࡢ  㔞యࠊศᏊ㔞 N'D ࢆ⣽⬊⾲ᒙ࡟ᣢࡗ࡚࠾ࡾࠊ$WD$ ࢆ௓ࡋ࡚ࣉࣛࢫࢳࢵࢡࠊ㔠ᒓࠊ࢞ࣛࢫ
➼ࡢᵝࠎ࡞≀㉁ࡢ⾲㠃࡟ᙉࡃ᥋╔ࡍࡿࠋ$WD$ ࡢ᥋╔ᛶࡣࠊ୺࡟ࠊࡑࡢඛ➃࡟࠶ࡿ 1KHDG ࡜࿧ࡤࢀࡿࢻ࣓࢖ࣥศᏊ㔞 N'D ࡀᢸࡗ࡚࠾ࡾࠊ1KHDG ༢⊂࡛␯Ỉᛶ࠿ࡽぶỈᛶ࡟⮳ࡿᵝࠎ࡞ᮦᩱ㠃࡟ᑐࡋ࡚Ỉ୰࡛ᙉ࠸᥋╔ᛶࢆ♧ࡍࠋ㸦ᅗ㸯㸧᥋╔ᶵᵓゎ᫂ࡢࡓࡵ࡟ࠊ
ࡇࢀࡲ࡛࡟⤖ᬗゎᯒ ୍㒊࡟ࡘ࠸࡚Ⓨ⾲῭ࡳࠊᩥ⊩  ࠊ⇕ኚᛶᐇ㦂 ᩥ⊩  ࠊ$)0࡟ࡼࡿ᥋╔ຊࡢ┤᥋ほᐹ ᰝㄞ୰ ࠊ
4&0' ࡟ࡼࡿ᥋╔᫬ࡢ⭷ཌᐃ ᢞ✏‽ഛ୰ ࢆ⾜ࡗࡓࠋࡇࢀࡽࡢᐇ㦂ࡣࠊ$WD$ࡢ᥋╔࡟㛵ࡍࡿ⌮ゎࢆ῝ࡵࡓࡀࠊศᏊࣞ
࡛࣋ࣝ㉳ࡇࡿ┦஫స⏝ࡢヲ⣽ࠊ౛࠼ࡤࠊ
ᮦᩱ⾲㠃࡟᥋╔ࡍࡿ㝿ࡢࢱࣥࣃࢡ㉁ศ
Ꮚࡢ㓄ྥࡸࢥࣥࣇ࢛࣓࣮ࢩࣙࣥኚ໬ࠊ⁐፹࡛࠶ࡿỈࡢാࡁ➼ࡢ᝟ሗࢆᥦ౪ࡍࡿ

௕‫ڭ‬

1KHDG म஘‫ر‬ऩ౫મ਀એपமାਙ॑ંघ

࡟⮳ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊᮏ◊✲ࡣࠊ᥋╔ࡢཎᏊⓗᥥ⏬ࢆ┠ⓗ࡜ࡋ࡚ࠊ1KHDG ࢻ࣓࢖ࣥࠊᮦᩱ⾲㠃ࠊỈࢆྵࡴ⣔ࡢ඲ཎᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࡁࡓࠋ
௧࿴㸰ᖺᗘࡢ᪋タ฼⏝(B)࡛ࡣࠊNhead ࡀ␯Ỉᛶࡢ࣏ࣜࢫࢳࣞࣥ㸦PS㸧⾲㠃ࡸぶỈᛶࡢ SiO2 ⾲㠃㸦ࢩࣜ࢝⾲㠃㸧࡟᥋╔ࡍࡿ㝿ࡢ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆ⇕ຊᏛ✚ศἲ࡟ࡼࡾ⟬ฟࡋࡓࠋࡲࡓࠊ୧⾲㠃࡟᥋╔ࡍࡿ㝿࡟㉳ࡇࡿศᏊ⾲㠃ࡢ࢔࣑ࣀ㓟ഃ㙐ࡢᵓ㐀ኚ໬ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊNhead ࡀ␯Ỉᛶ⾲㠃࡟ࡶぶỈᛶ⾲㠃࡟ࡶ᥋╔࡛ࡁࡿ࣓࢝ࢽࢬ࣒ࡢ୍➃ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ
㸺ཧ⪃ᩥ⊩㸼
㸯㸬Koiwai K, Hartmann MD, Linke D, Lupas AN, Hori K, J Biol Chem. 291(8), 3705-24(2016).
㸰㸬Yoshimoto S, Nakatani H, Iwasaki K, Hori K, Sci Rep. 6:28020 (2016).

2◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛ࡣࠊNhead ࡀ␯Ỉᛶࡢ࣏ࣜࢫࢳࣞࣥ㸦PS㸧⾲㠃࡜ぶỈᛶࡢ SiO2 ⾲㠃㸦ࢩࣜ࢝⾲㠃㸧࡟᥋╔ࡍࡿ㐣⛬࡟࠾ࡅࡿ⮬⏤ኚ໬ࢆ⇕ຊᏛ✚ศἲ࡟ࡼࡾồࡵࡓࠋ⏝࠸ࡓ⣔ࡣࠊPS ⾲㠃࡬ࡢ᥋╔࡛ࡣࠊ12127.5 nm3 ࡢṇ᪉ᙧࡢ PS ᇶ┙ࡢୖ࡟ 150 mM ┦ᙜࡢ NaCl ࢆྵࡴỈࡢᒙࢆ 17.5 nm ࡢཌࡉ࡛ࡢࡏࠊࡇࡢ୰࡟ Nhead ࢻ࣓࢖ࣥࢆ⨨࠸ࡓࡶࡢ࡛ࠊ⣙ 40 ୓ಶࡢཎᏊࢆྵࡴࠋ( ᅗ㸰㸦㹟㸧㸦ḟ㡫㸧ཧ↷) ୍᪉ࠊSiO2 ⾲㠃࡬ࡢ᥋╔࡛ࡣࠊSiO2
ᇶ┙ࡢࣔࢹࣝ࡜ࡋ࡚ȘᆺࡢỈᬗࢆ㑅ࡧࠊࡑࡢ㸦001㸧㠃ࢆ᥋╔㠃࡜ࡋࠊpH㸵࡟࠾ࡅࡿ᥋╔㠃ࢆ෌⌧ࡍࡿࡓࡵ࡟ࠊ
㸦001㸧㠃࡟࠶ࡿỈ㓟ᇶ㸦㸫OH㸧ࡢ࠺ࡕࡢ 13.3%ࢆࣛࣥࢲ࣒࡟㑅ࢇ࡛㈇㟁Ⲵࢆᣢࡗࡓゎ㞳ᆺ㸦㸫O㸫㸧࡜ࡋࡓࠋSiO2 ᇶ┙ࡣࢧ࢖ࢬ 12127.5 nm3 ࡢṇ᪉ᙧ࡛ࠊࡇࡢୖ࡟ 150 mM ࡢ NaCl ࢆྵࡴỈࡢᒙࢆཌࡉ 17.5 nm- 347 -

ࡢࡏ࡚ Nhead ࢻ࣓࢖ࣥࢆධࢀࠊ඲యࢧ࢖ࢬ 121225
㸦ᅗ㸰(b) ཧ↷㸧
nm3ࠊཎᏊᩘ⣙ 38 ୓ࡢ⣔ࢆᵓ⠏ࡋࡓࠋ
Nhead ࡢᇶ┙࡬ࡢ᥋╔㐣⛬࡜ࡋ࡚ࡣࠊNhead ࡢ㛗㍈㸦㸻
3 㔞యࡢ 3 ᅇᅇ㌿㍈㸧ࡀᇶ┙࡟ᆶ┤࡞ࠕ⦪ྥࡁࠖࢆ࡜ࡗ
࡚ Nhead ࡀᇶ┙࡟᥋㏆ࡍࡿ㐣⛬࡜ࠊ㛗㍈ࡀᇶ┙࡜ᖹ⾜࡟࡞ࡿࠕᶓྥࡁ࡛ࠖ᥋㏆ࡍࡿ㐣⛬ࡢ㸰ࡘࡢ㐣⛬ࢆ㑅ࢇࡔࠋ㸦ᅗ㸰ཧ↷㸧ࡑࡋ࡚ࠊࡇࡢ㸰ࡘࡢ㐣⛬࡟࠾࠸࡚ࠊNhead࡜ᇶ┙࡜ࡢ㛫ࡢ㊥㞳ࢆኚ࠼࡞ࡀࡽ MD ィ⟬ࢆ⾜࠸ࠊ୧⪅ࡢ㛫࡟ാࡃᖹᆒຊ㸦PMF㸧ࢆ⟬ฟࡋࠊࡇࢀࢆ᥋㏆⤒㊰
࡟ἢࡗ࡚✚ศࡍࡿࡇ࡜࡟ࡼࡾࠊNhead ࡜ᇶ┙ࡢ┦஫స⏝࡟ࡼࡿ⮬⏤ኚ໬ࢆ⟬ฟࡋࡓࠋMD ィ⟬ࡣࠊ඲࡚ࣉࣟࢢ࣒ࣛ GROMACS 2019.6 ࢆ⏝࠸ ࡚ ಸ ⢭ ᗘ ࡛ ⾜ ࡗ ࡓ ࠋ ຊ ሙ ࡟ ࡣ ࠊ CHARMM36m ࡜
INTERFACE㸦SiO2 ࡟ᑐࡋ࡚ࡢࡳ㸧ࢆ⏝࠸ࡓࠋᇶ┙࡜
Nhead 㛫ࡢᖹᆒຊࡢ⟬ฟ࡛ࡣࠊ୧⪅ࡢ㛫ࡢ㊥㞳㸦㊥㞳 0ࢆ୧⪅ࡢ᥋╔⮬⏤࢚ࢿࣝࢠ࣮ࡀ᭱ప࡜࡞ࡿⅬ࡜ᐃ⩏㸧ࢆ
㸫2 nm ࠿ࡽ 17 nm ࡲ࡛ 0.1 nm 㛫㝸࡛ኚ࠼࡚ࡑࢀࡒࢀ 10௕‫ڮ‬மାૌஙभ৸ਉ৕३঑গঞ‫ش‬३ঙথ॑ষढञ

௺‫ق‬D‫ك‬এজ५ॳঞথषभமା‫ق‬E‫ك‬३জढ़षभமା

ns ࡢ NPT ࢔ࣥࢧࣥࣈ࡛ࣝࡢ MD ィ⟬⾜࠸ࠊࡑࢀࡒࢀ࡟ࡘ࠸࡚᭱ึࡢ 0㸫2

ns ࡣ㝖࠸࡚ṧࡾࡢ 8

ns ࡢࢺࣛ

ࢪ࢙ࢡࢺ࣮ࣜ࠿ࡽ Nhead ࡟࠿࠿ࡿ PMF ࢆ⟬ฟࡋࡓࠋ࡞࠾ࠊࡇࡢࢺࣛࢪ࢙ࢡࢺ࣮ࣜࢆࡶ࡜࡟ࠊNhead ࡜ᇶ┙ࡢ㛫ࡢ┦஫స⏝࡟㛵ࢃࡿ࢔࣑ࣀ㓟ṧᇶࡢ≉ᐃࡶ⾜ࡗࡓࠋᖹᆒຊࡢ✚ศ࡟ࡼࡿ⮬⏤࢚ࢿࣝࢠ࣮ࡢ⟬ฟ࡛ࡣࠊྎᙧ
✚ศࢆ⏝࠸ࡓࠋ

3◊✲ᡂᯝ
ᅗ 3 ࡟⇕ຊᏛ✚ศἲ࡛ồࡵࡓ PS ᇶ┙࠾ࡼࡧ SiO2 ᇶ┙࡟ Nhead ࡀ᥋╔ࡍࡿ࡜ࡁࡢ୧⪅ࡢ㛫ࡢ㊥㞳࡟ᛂࡌࡓ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࢆ♧ࡍࠋ᥋╔⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࡢ᭱኱್㸦ྛࢢࣛࣇࡢ᭱పⅬ㸧ࡣࠊPS ᇶ┙㸺SIO2 ᇶ┙ࠊ⦪ྥࡁ㸺ᶓྥࡁ࡜࡞ࡗ࡚࠸ࡿࡀࠊࡑࡢᕪࡣࡑࢀ࡯࡝኱ࡁࡃ࡞࠸ࠋ

௕‫گ‬೸ৡ৾஋ী১द੭ैोञ‫ۃ‬KHDG ध౫મ੦ೕधभৼ൩੿৷ঽ૓ग़ॿঝॠ‫ش‬উটইॕঝ

‫ق‬ం‫ك‬এজ५ॳঞথ੦ೕधभ‫ق‬క‫ك‬6L2 ੦ೕधभৼ൩੿৷ঽ૓ग़ॿঝॠ‫ش‬উটইॕঝ॑ંघ

- 348 -

ࢮࣟ࠿ࡽྛࢢࣛࣇࡢ᭱పⅬࡲ࡛࢚ࢿࣝࢠ࣮ኚ໬ࢆ᥋╔⮬⏤࢚ࢿࣝࢠ࣮࡜ࡋ࡚ࠊࢱࣥࣃࢡ㉁ࡢ༙ᩘࡀᮦᩱ⾲㠃࡟᥋╔ࡍࡿࢱࣥࣃࢡ㉁⃰ᗘ㸦KL㸧ࢆồࡵࡿ࡜ 0.24μM㸦SiO2ࠊᶓྥࡁ㸧࠿ࡽ 3.9μM㸦PS,⦪ྥࡁ㸧࡜࡞ࡗࡓࠋ
ࣜࢰࢳ࣮࣒ࡸ࢘ࢩ⾑Ύ࢔ࣝࣈ࣑࡛ࣥࡣࠊ࣏ࣜࢫࢳࣞࣥ࡬ࡢ྾╔࡟࠾࠸࡚ࠊKL ࡣࡑࢀࡒࢀ 13μM ࡜ 26μM ࡜ሗ࿌ࡉࢀ࡚࠾ࡾ㸦African J. Biotech.10(15), pp. 3014-3021(2011)ࠊProg. Theor. Exp. Phys., 3 (2015)㸧ࠊNhead ࡢ KLࡀࠊࡇࢀࡽ࡜ẚ࡭࡚ 1 ᱆࠿ࡽ 2 ᱆ᑠࡉࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡣࠊNhead ࡢᙉ࠸᥋╔ᛶࢆ⿬௜ࡅࡿィ⟬⤖ᯝ࡛࠶ࡿࠋ
ᅗ㸱ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢕࡛ࣝࠊὀ┠ࡍ࡭ࡁⅬࡣࠊᮦᩱ⾲㠃࡬᥋㏆ࡍࡿ㐣⛬࡟࠾࠸࡚ࠊࢱࣥࣃࢡ㉁ࡢ
⬺Ỉ࿴࡟క࠺࢚ࢿࣝࢠ࣮㞀ቨ㸦⮬⏤࢚ࢿࣝࢠ࣮ࡀ୍᫬ⓗ࡟㧗ࡃ࡞ࡿⅬ㸧ࡀࣉࣟࣇ࢕ࣝୖ࡟⌧ࢀ࡚࠸࡞࠸ࡇ࡜
࡛࠶ࡿࠋᙜึࡢண᝿࡛ࡣࠊࢱࣥࣃࢡ㉁ࡢᮦᩱ⾲㠃࡬ࡢ᥋╔࡛ࡣࠊࢱࣥࣃࢡ㉁ࡢ⾲㠃ࢆそ࠺Ỉ࿴Ỉࡀྲྀࡾ㝖࠿ࢀࡿ࡜⪃࠼ࠊ⬺Ỉ࿴࡟ᚲせ࡞࢚ࢿࣝࢠ࣮ࡀ᥋╔ࡢ࢚ࢿࣝࢠ࣮㞀ቨࢆసࡿ࡜⪃࠼࡚࠸ࡓࠋࡇࡢ࢚ࢿࣝࢠ࣮㞀ቨࡢࣆ࣮ࢡࡣࠊ᥋╔఩⨨㸦㸻ࢱࣥࣃࢡ㉁࡜ᮦᩱ⾲㠃ࡀඹ࡟⬺Ỉ࿴ࡋ࡚┤᥋᥋ࡍࡿ఩⨨㸧࠿ࡽ 2-3ύ⛬ࡢ㊥㞳㸦㸻ᮦᩱࡸࢱࣥࣃࢡ㉁ࡢ⾲㠃࡟⤖ྜࡋ࡚࠸ࡿỈ࿴ỈศᏊࡢᏑᅾ఩⨨㸧࡟⌧ࢀࡿ࡜ண᝿ࡋ࡚࠸ࡓࡀࠊ௒ᅇࡢィ⟬࡛ࡣ⌧ࢀ࡚࠸࡞࠸ࠋࡇࡢࡼ࠺࡞⤖ᯝ࡜࡞ࡗࡓ⌮⏤ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊNhead ⾲㠃ࡢỈ࿴Ỉࡢ≧ែࢆゎᯒࡋ
ࡓࠋᅗ 4 ࡟࣏ࣜࢫࢳࣞࣥ࡟᥋╔ࡋࡓ≧ែ㸦᥋╔⮬⏤࢚ࢿࣝࢠ࣮᭱ప㸧࡛ Nhead ࡢ࣏ࣜࢫࢳࣞࣥ࡜᥋ࡍࡿ㠃ࡀ࡝ࡢࡼ࠺࡞Ỉ࿴≧ែ࡟࡞ࡗ࡚࠸ࡿ࠿ࢆ♧ࡍࠋࡇࡢᅗ࠿ࡽ⮬⏤࢚ࢿࣝࢠ࣮᭱ᑠࡢ᥋╔≧ែ࡟࠾࠸࡚ࡶࠊ⬺Ỉ࿴ࡉࢀࡿỈศᏊࡣࠊNhead ࡢ⾲㠃࠿ࡽ㣕ࡧฟࡋ࡚࠸ࡿ␯Ỉᛶࡢഃ㙐ࡢඛ➃௜㏆ࢆそࡗ࡚࠸ࡿ୍㒊ࡢỈศᏊ࡟㐣ࡂࡎࠊࡑࢀ௨እࡢ኱㒊ศࡢ⾲㠃࡛ࡣࠊỈ࿴≧ែࡀ⥔ᣢࡉࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡍ࡞ࢃࡕࠊNhead ࡀࠊ᭱ప㝈ࡢ⬺Ỉ࿴࡟ࡼࡾ࢚ࢿࣝࢠ࣮ࣟࢫࢆᢚ࠼࡚ᮦᩱ࡜ࡢຠ⋡ⓗ࡞᥋╔ࢆ⾜ࡗ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋ
௕‫ڰ‬மାঽ૓ग़ॿঝॠ‫ش‬ऋਈ৵धऩॊ෱௞पउऐॊ 1KHDG धএজ५ॳ
ঞথ਀એधभৼ൩੿৷‫఺ؚ‬ल‫ؚ‬1KHDGभ਷ਮ૾ଙ௕‫ق‬D‫كۑقك‬म‫ؚ‬ອ਱ऌ‫ؚ‬૯਱ऌ‫ؚ‬जोझोभଦ਱पउऐॊঽ૓ग़ॿঝ
ॠ‫ش‬ਈ৵भமାଡୗ॑ંघ‫؛‬௕‫ق‬F‫قك‬G‫ك‬म‫ؚ‬ອ਱ऌ F ‫ؚ‬૯਱ऌ
G पउऐॊ 1KHDG‫ص‬এজ५ॳঞথ
৑भமାੀએ॑ંघ‫؛‬ऒोैभ௕म
঱੶भ D ‫ ؚ‬E भ௕दீद೧ढञ৖
ী॑ఁপखञुभ‫؛‬ອ਱ऌदम‫ૻؚ‬ຎ৓ෟैऊऩ਀એ॑੅णீःী৕੔
ഈऋএজ५ॳঞথ਀એधَૉध਴એُ
भेअऩமඡ॑खथःॊ‫؛‬૯਱ऌदम‫ؚ‬1KHDG भ਀એऊैఄलলखञ‫گ‬णभঝ‫ش‬উऋ  মभଌभेअपএজ
५ॳঞথ਀એधமखथःॊ‫؛‬௕‫ق‬H‫قك‬I‫قك‬ઃᅚ‫ك‬म‫ؚ‬மାঽ૓ग़ॿঝॠ‫ش‬ਈ৵भधऌभ‫ؚ‬1KHDG धএজ५ॳঞথभமඡੀએपउऐॊ
1KHDG भ਷ਮ૾ଙ॑ંघ‫؛‬਷ਮ਷म‫ؚ‬พः஧౦‫ق‬෷ಞ‫ك‬ध࿏౦‫ق‬਷ಞ‫ك‬भૉद਀खथँॊ‫؛‬ອ਱ऌ‫ؚك۔ق‬૯਱ऌ‫كەق‬धु‫ؚ‬൓਷ਮऋକऒॊ୩ୠमী৕਀એभऺ॒भ଒ैोञ୩ୠपघऍऩःऒधऋॎऊॊ‫؛‬- 349 -

௒ᅇࡢ㹋㹂ィ⟬࡛ࡣࠊNhead ࡀぶỈᛶ⾲㠃࡟ࡶࠊ␯Ỉᛶ⾲㠃࡟ࡶ᥋╔࡛ࡁࡿ⌮⏤ࡢ୍➃ࢆㄝ᫂ࡍࡿ࡜⪃࠼ࡽࢀࡿ⤖ᯝࡶᚓࡽࢀ࡚࠸ࡿࠋ㹋㹂ィ⟬࡛ᚓࡽࢀࡓࢺࣛࢪ࢙ࢡࢺ࣮ࣜࢆゎᯒࡍࡿ࡜ࠊNhead ࡢ⾲㠃࡟࠶ࡿ୧ぶ፹ᛶ࢔࣑ࣀ㓟࡛࠶ࡿࢫࣞ࢜ࢽࣥࡀ PS ᇶ┙࡜ࡣ␯ỈᛶࡢࠊSiO2 ᇶ┙࡜ࡣỈ⣲⤖ྜࡍࡿᵝᏊࡀほᐹࡉࢀࡓࠋ㸦ᅗ㸳ཧ↷㸧ࢫࣞ࢜ࢽࣥṧᇶࡣࠊNhead ࡢศᏊ⾲㠃࡟ẚ㍑ⓗᆒ୍࡟ศᕸࡋ࡚࠾ࡾࠊࡇࡢࢫࣞ࢜ࢽࣥࡀࠊぶỈᛶࠊ␯Ỉᛶ࡝ࡕࡽࡢ⾲㠃࡜ࡢ᥋╔ࢆ፹௓ࡋ࡚࠸ࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ௒ᚋࠊศᏊ⾲㠃ࡢࢫࣞ࢜ࢽࣥ࡟ኚ␗ࢆຍ
࠼࡚ࠊ᥋╔ᛶ࡬ࡢᙳ㡪ࢆㄪ࡭ࡿᐇ㦂ࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ

௕‫ڱ‬૏஡ᄘਙभ॔঑ঀ

෷दँॊ५ঞड़ॽথभડ
ำधႧ਷ਙभএজ५ॳঞ
থ‫ط‬஡਷ਙभ 6L2 धभৼ൩੿৷Ⴇ਷ਙभএজ५ॳঞথ
पम‫ؚ‬ડำभႧ਷ਙभও
ॳঝ੦ऋ‫ؚ‬஡਷ਙभ 6L2पम‫ؚ‬ડำभ஡਷ਙभ 2+੦ऋৼ൩੿৷खथःॊ‫؛‬

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫➲ۻ‬ཎ ⣧ࠊ㕥ᮌ῟ᕧࠊ⸨ᮏ࿴ኈࠊᒸᓮ 㐍ࠊᇼඞ ᩄࠊࠕศᏊືຊᏛィ⟬࡟ࡼࡿ㧗᥋╔ᛶࢱࣥࣃࢡ㉁ AtaA
Nhead ࡢ᥋╔㐣⛬ゎᯒࠖ➨ 9 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2019ࠊ2019 ᖺ 10 ᭶‫➲ۻ‬ཎ ⣧ࠊ㕥ᮌ῟ᕧࠊ⸨ᮏ࿴ኈࠊᒸᓮ 㐍ࠊᇼ ඞᩄ ࠕ㧗᥋╔ࢱࣥࣃࢡ㉁ࡢ␯Ỉᛶ⾲㠃࡬ࡢ᥋╔㐣⛬࡟㛵ࡍࡿศᏊືຊᏛⓗゎᯒࠖࠊ⏕≀ᕤᏛ఍ⱝᡭ◊✲⪅ࡢ㞟࠸ ➨୕ᅇ࢜ࣥࣛ࢖ࣥࢭ࣑ࢼ࣮ࠊ2020 ᖺ 11 ᭶ࠊඃ⚽Ⓨ⾲㈹ཷ㈹ ( Ⓨ⾲ 31 ௳୰ 7 ྡࡀཷ㈹ )‫ۻ‬J. Sasahara, A. Suzuki, K. Fujimoto, S. Okazaki,K. Hori,ࠕAnalysis of Adhesion Process of A Highly Adhesive
Protein by

Molecular Dynamics Simulationࠖ(2020.1.9) [ྡྂᒇ኱Ꮫ ༟㉺኱Ꮫ㝔ࣉࣟࢢ࣒ࣛ ࢺࣛࣥࢫࣇ࢛

࣮࣐ࢸ࢕ࣈ໬Ꮫ⏕࿨⼥ྜ◊✲኱Ꮫ㝔ࣉࣟࢢ࣒ࣛࠊඃ⚽࣏ࢫࢱ࣮㈹(༤ኈㄢ⛬㐍Ꮫணᐃࡢಟኈㄢ⛬Ꮫ⏕ 93
ྡ୰ 6 ྡࡀཷ㈹)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ඹྠ◊✲⪅ࡢ➲ཎẶࡣࠊ2021 ᖺᗘ࡟༤ኈㄢ⛬࡟㐍Ꮫࡋ࡚࠾ࡾࠊᮏ◊✲ᡂᯝࡢ 2021 ᖺ୰ࡢᢞ✏ࢆணᐃࡋ࡚

࠸ࡿࠋ- 350 -













Computational chemistry analysis towards deeper understanding ofelectronic structures and reactivities of biological molecular systems
"



#

1 
MUm²©®Þ»-WT*Q}ÞE;704N¡ÞÚm>F:GªZj³Ò«Ä ÔÂ *$ MUm²ÚmÉ¥*½-ÆÏ*ÉÅ°Ö¤'Ç J`*Þ©®q Ö¤-Ñ$*rw¾V·)Í"¹f Ý±wZØ Å°- MUm²ZØ Å°|¡*pÇ©®-¾ÎvÞ MUm²Å°b
 PCM Éf lY-_)Í#Å°-Ö¤ *84:Å°-?G6 A
H0Um²sp¾Þ}»-Ç*©®-¾

2 !
©®q Ö¤-Ñ$*rw¾V·)Í"¹f Ý±wZØ Å°-yÞRISM É' PCM Éf lY-_)Í#Å°-Ö¤*©®PCM I¬*­U
«xÀx[UÐ¶MC9D(IEF-PCM) -©®qÖ¤-¾*Õm[nÅ°=72H3 orz pÁIEF-PCM tR')©®q\'pÁ+tMUÐ¶MC9D(C-PCM)3 ÆÏ £}l&./G}ljlKÅ° `»!
ÊUmÚmrw ¯i "T*haC-PCM ±w X[*  ¨(+*I
IEF-PCM 'ha%±wX[ Ã(+ lKÊUmÚm~PCM ¼u§h(SCF)-´"a,* ÆÏ+*(PCM-SCF )©®]IÚmÓ¸-¡* PCM-SCF " ÚmÓ¸-ºÛ¥Úm¦Ø-ÆÏ`»oS}¯× SCF(PCM-CASSCF) y-¾orz pÁ+*lÅ°* C-PCM-CASSCF
RISM-CASSCF  4 LdpÁ IEF-PCM-CASSCF -Ì}»ÈO-¾!Û¥Úm¦Ø5D<Hrw¾V·)Í"¹(DMRG)-¡Úm~-lK%Ý±wÅ°`»*+')kP}¯×-Â*j^z+*µ{(+*(IEF-

PCM-DMRG-CASSCF/CASPT2) ±w +!Iw%Çgc+$¡¨Ã){*º(+*3 
ÎËiÜe4@0:DÄ <./.BH3G1ÔÂ * ÞÉÅ°¿¥Ù  ¨(+*ß¢ÞUm K* ÞÎËiD H9(:D HE?DÚm~ Å°s=*$*ß©®ÞÝY5ÉÞÝ±wj^ÚmZØ É-´"a,*+Å°)-Ö¤ÞÎËiUmQ[n4}-°T*É}»-pÇß J. Chem. Theory Comput., 16, 8, 4865–4873 (2020).
Green Ø -¡!6--Ä

Ê-l×¦N¡-ÆÏ* IEF-PCM - orz pÁ

- 351 -

IEF-PCM-SCF/CASSCF >F1-Ö¤|¡Å°I ?G G cis-trans 3£}[| 5 Å°-¾Gaussian 16 =72H3 B3LYP/def2-SVP E?D/>,@[-( 1){(+/>s cc-pVTZ f&-¡ ::DlKÅ°-¾(À 1)cis M TS  transM')%k mCHBG:-*$trans Mk l"#[- *µ}[D H $ *  7+L'CASSCF ÆÏ+Z¥Úm¦ØÅ° * CASPT2  IEF-PCM -´"a,p ¥Ums*Å°-¾

4





Quantum many-electron theory and other new type approaches for quantum chemical calculations, 1?kn



knAn©®A, Zoom, [n4<;ÞOct. 27, 2020.


. 0$UWLILFLDO1HXUDO1HWZRUNV$SSOLHGDV0ROHFXODU:DYH)XQFWLRQ6ROYHUV¼28n *B%
SM G3=RRP-DQ



T. Yanai, Zoom, MPIPKS Dresden (March 8 – 11, 2021); Tensor product methods for strongly correlated
molecular systems, “Molecular multireference wave functions with DMRG and related methods”

5
3-<DQJ06XJL\DPD.7VXGDDQG7<DQDL³$UWLILFLDO1HXUDO1HWZRUNV$SSOLHGDV0ROHFXODU:DYH)XQFWLRQ
6ROYHUV´ -&KHP7KHRU\&RPSXW±  '2,DFVMFWFE



5<6KLPL]X7<DQDLDQG'<RNRJDZD³,PSURYHG5,60&$66&)2SWLPL]DWLRQYLD6WDWH$YHUDJH7UHDWPHQW
DQG'DPSLQJIRU&KDUDFWHUL]LQJ([FLWHG0ROHFXOHLQ6ROXWLRQZLWK0XOWLUHIHUHQFH3HUWXUEDWLRQ7KHRU\´ -&KHP
7KHRU\&RPSXW±  '2,DFVMFWFE

;*;LRQJ$6XJLXUDDQG7<DQDL³3URMHFWRU$XJPHQWHG:DYH0HWKRGZLWK*DXVV7\SH$WRPLF2UELWDO%DVLV,PSOHPHQWDWLRQRIWKH*HQHUDOL]HG*UDGLHQW$SSUR[LPDWLRQDQG0HVK*ULG4XDGUDWXUH´ -&KHP7KHRU\&RPSXW  '2,DFVMFWFF



403KXQJ0+DJDL;*;LRQJDQG7<DQDL³3RODUL]DWLRQ&RQVLVWHQW%DVLV6HWVZLWK3URMHFWRU$XJPHQWHG
:DYH0HWKRG´ 3K\V&KHP&KHP3K\V  '2,'&3$1 ,QDL '<RNRJDZD7<DQDL ³,QYHVWLJDWLQJ WKH 1RQUDGLDWLYH 'HFD\ 3DWKZD\ LQ WKH ([FLWHG 6WDWH RI 6LOHSLQ'HULYDWLYHV6WXG\ZLWK6HFRQGRUGHU0XOWLUHIHUHQFH3HUWXUEDWLRQ:DYHIXQFWLRQ7KHRU\´ -3K\V&KHP$ ±  '2,DFVMSFDF

- 352 -







Molecular dynamics simulation of diffusion coefficient ofbio-macromolecule: Effect of denaturation %

$)*(+1 !ru(qÛ,Ïi\ 9I>1ÇU-ki\*  *  «+Ui\ ^ÔQßÔQ]X  "kyWm508p-f©%* fs*½¯¬o(Ã ¨*ÄÙ ¨d Wm[Yo6@CGK6DIÝMDÞ×508Z-vkWm 9I>1Ç3K7.1;/J°m²ªÂ×² *»®%)-¸(Uk i\¼!.?HK:¸2 !'"
×508Z ÕÈØ}QYoZ^³[-Ì  ¼  508½¯( p* Fushiki &±}-¥»®%* Yeh Ë-¸
¶Ê?H2EA'*Á¯-¸9I>1Ç½¯ ÜÎ MD 4K=* GROMACS -¥BF
W¢ i\hb Yeh Ñ¥R jOg¦¹+×wÒ²l
BFW¢ i\*hbU-ÌÉ*Yeh -Í×wÒ²½¯%#ÀT *#£§z(+*V *¾*

3 !
U-M¿ß­Ú¾9I>1Ç%+(U p Z*N-ªÂc{ºet_½¯Ô- ´47< * 9I>1ÇU½¯%aµ*N ,Og

9I>1Ç3K7½¯-Ð$´×wÒ²% Yeh ÌÉ *  ,)QYoZ Óº* &vkWmÖ*l±xi\Z Óº*  ,[6]Li}Z ½¯ i}¡~¦¤fÙ $#$(+*¡~·.1;/J°m²hb`|P
¦¤P±}i\ Óº*  , 508Sn}%ÆÅ *4 &# %(!1$7

(»ÇWm )Wm[§"L}  -¬o*  IE0I+:k-0 
 %(!1$7

Wm[Yo6@CGK6DI-¥9I>1ÇU p=±x67- 353 -

;A508Sn} 5²£Å\o 0=Ý;k;Þ  

5

#

<7DPXUD$<RVKLPRUL$6XHPDWVXDQG5$NL\DPD 
5HHQWUDQWFU\VWDOOL]DWLRQRIOLNHFKDUJHGFROORLGDOSDUWLFOHVLQDQHOHFWURO\WHVROXWLRQ5HODWLRQVKLSEHWZHHQWKHVKDSHRIWKHSKDVHGLDJUDPDQGWKHHIIHFWLYHSRWHQWLDORIFROORLGDOSDUWLFOHV (3/ (XURSK\V/HWW   KWWSVGRLRUJ
$\XPL6XHPDWVXDQG5\R$NL\DPD
6ROYHQW HIIHFW IRU DQ HIIHFWLYH DWWUDFWLRQ EHWZHHQ OLNHFKDUJHG PDFURLRQV LPPHUVHG LQ DQ HOHFWURO\WH VROXWLRQ 7KHLQWHQVLILFDWLRQPHFKDQLVPRIWKHHIIHFWLYHDWWUDFWLRQFDXVHGE\WKHWUDQVODWLRQDOPRWLRQRIVROYHQWSDUWLFOHV-&KHP3K\V  KWWSVGRLRUJ <XND1DNDPXUD$NLUD<RVKLPRULDQG5\R$NL\DPD
6ROYDWLRQ HIIHFWV RQ GLIIXVLRQ SURFHVVHV RI D PDFURPROHFXOH $FFXUDF\ UHTXLUHG IRU UDGLDO GLVWULEXWLRQ IXQFWLRQ WR
FDOFXODWHGLIIXVLRQFRHIILFLHQW
-&KHP3K\V  KWWSVGRLRUJ
.HLMX6XGD$\XPL6XHPDWVXDQG5\R$NL\DPD/DWHUDOGHSOHWLRQHIIHFWRQWZRGLPHQVLRQDORUGHULQJRIEDFWHULRUKRGRSVLQVLQDOLSLGELOD\HU$WKHRUHWLFDOVWXG\EDVHG
RQDELQDU\KDUGGLVNPRGHO -&KHP3K\V   KWWSVGRLRUJ)DUKDQD$IUR]H'DLVXNH,QRXH7DPDQQD)DUKDQD7HWVX\D+LUDLZD5\R$NL\DPD$ULI.DELU.D]XNL6DGD$NLUD.DNXJR
0RQRSRODUIORFNLQJRIPLFURWXEXOHVLQFROOHFWLYHPRWLRQ%LRFKHPLFDODQG%LRSK\VLFDO5HVHDUFK&RPPXQLFDWLRQVDFFHSWHG p 7RPR\D,ZDVKLWD0DVDDNL1DJDR$NLUD<RVKLPRUL0DVDKLGH7HUD]LPDDQG5\R$NL\DPD
5HYLVLW RI DQ (YDOXDWLRQ 0HWKRG IRU WKH 'LIIXVLRQ &RHIILFLHQW RI 3URWHLQ 8VLQJ 0ROHFXODU '\QDPLFV 6LPXODWLRQV'HSHQGHQFHRI6ROYHQW9LVFRVLW\RQWKH7KLFNQHVVEHWZHHQ0DFURPROHFXOHV/RFDWHGLQ(DFK5HSOLFD&HOOVXEPLWWHG p  1$ 7 )* #.6,Q®W2&£Å-¥<¼Ç,c4<8ÖqZ'Y/¥03
Wm6@CGK6DIo9.I5IF9RO1R  - 354 -

!





Studies on the efficient mechanisms of condensed matters including
bio-systems utilizing quantum chemical and first-principles calculations.
)AYU@n+O\D@+aPE+KFC@n+JXkho`GLefTp efdc NBabETdÌm3  Îk3Ù
NBabETdÌm4ÁÃA¯)>0ß´Óu$ ´01>&0$¹<?."=tOCSR3QeJSUu/> g/ /ß´Óu$ ´01>&0$¹<?.>&3+9¨wEWbIe4   0'?×2lEWbIeXaB(#(1&021>ß´Óu$ ´01>24¦Ï·Ø1­Àz3wÂ}Av>Ê$>+9&3^GVP]
24n<#3x ·{$Õi(.>|Ä$Ûj4&3^GVP]A½fz³Ë¾#<<#2(; 0(+Zc_ ^UHMRFYDd3Æ¶·¶¬3z³¼
RFYDd4ºÜzA8ÇÚ¤Ñ0(. :y¿1¤ÑA-*3¡¥}4@@1¸·3+92µ<?>FaLRFYDd0[aRFYDd4 ÐÖ/tÖ²2;>sÒ3¡¥u0(.¢»/#1=3§A6.>&?<4@@1¢Ýq!5ÉÅ¡¥U`dNO
Q©}±£o¡¥±ÍÞ/pµ'?.>(+$,.RFYDd4¡¥}1<72¢»2".ÔÊ/>(#(Zc_ ^UHMRFYDdÝ  Þ4°·2×2h/>&3    u4ª/'!h/lªr$Ê/>   3«$Y`OK/È¶)>0%¿   «©4Æ®¶¬)>0~2FaL\e&Ûu$)>Æ®¶¬´4Jµ&BG-3S)
¼20,.D83ÙA:+<)3/Æ®¶¬´3^GVP]®$9,?.}+Æ®¶¬4¶·2µ%>+9_3K{$~2¶(aÉ·1¼/Æ®3Ç3^GVP]A²)>&04YÅ/,+|¼/4Ûu¶FaL\e¶3H{{/>   u3;Àmw3^GVP]07À
w3^GVP]2Õ(.ÀwAµ+³³·1¼Aª1,+1{ ·A?(.*?<2e(.½nA9¨wEWbIeAË¾(+ ÁL]0*3È£m2">ÖnË¾

- 355 -

tMdR6eQ3z01>ÁL]   0    2-.½fz³uOL0½fz³Ë¾
2;,.*3²A²"+   0    2-.4¡N1¯01>\T:=*3Ö·²4§V39Gw\Md/4¡N2½fz³uOL0½fz³Ë¾$oO(¦Ï·Öw3_
  A(/:Â/Ë¾/%>ÁL]   0    2-.z62b3O%y&Ö·1²A¥d(+ efW]+lgW]
 NBabETdÌm3  Îk3Ù  1c*`]Aµ.  2;,.¨wEWbIeA9+ A1¾¤A
+.H{n0(+H{n0n3ÂA  Q= 3Ë¾Aª,+
 /4½fz³uOL3p2;,.BVead*AªR3©]oAs,+
v[TdM4b24   3±Aµc Õw3<uÕ Õw24

 Aµ+«u$+4 Af-3  U¸2¼`¾k'.x {Aµ&); 2¾¤A²(1$<  QC13 
 3Ë¾Aª,+ Zc_ ^UHMRFYDd3Æ¶·¶¬3z³¼|¼/4{±½n±3in·1¤Ñ ¼w0rOUwu~4/CZaS.
ÌÍÎË¾2[ % 1c*`] 


Aµ.aª(+<uÕÕw4 

Õw/Q=C?[jÕw0(.4  Aµ+ ÁL]0*3È£m2">ÖnË¾
 Ã¤Ñ®~3ÂA[2Oe0e,bAo,+  Aµ.ÖnË¾Aª,+uOL24   Ke.Aµ+ efSZ NBabETdÌm3  Îk3Ù$Æ¶·2{$µ&>+eO2-.°Aª,+&3]}¨wEWbIe4  >82
1=Æ¶·2µ&>&04h|Ä0¥!<?>&3mf-3  CFd$E´2t¡(.>  Ak%
q%
*3m  Ah(¹(/  Îk)>»A²"+&3Ã¨wEWbIe4g$>:33 
#!3BA(&3»4h|Ä0Ix'?+-2NBabETdÌmÓ2;-3  CFd0
 CFd2¾k(+  $(  3¤ÑA0>:3$ ´3  Aq%Q=*3m  Ah(¹(/ Îk)>»A²"+$  #!3XaB$>+9&3»4h|Ä0Ix'?+~2«3>»1!  +eO2-.²"+$ f/   #!3XaB$=  #!3
XaB4­->&0$/%1#,+- 356 -

 Zc_ ^UHMRFYDd3Æ¶·¶¬3z³¼aÃ2µ%>{ ·3A¬0(.¦ÄÔ}{Ê=M{ËÈ°(+$Æ®¶¬A±F}>l¨wEWbIe3{ ·A60-²/%+&?4  uAu¯0)>²1{/>

 ÁL]0*3È£m2">ÖnË¾
5V

ÖcAz.%>&0/!&/wÂ}$/%.>#$'#>ÁL]/4XÆmZ3

SU$g)>&02;,.Â$¤'?.>&0$u#,+fy   0    /4

AZc

 

S)0(.Â$¤'?.>&0$u#,+ÖnË¾2;,.YDb362b3¾¤A­>0Á
L]0    4  ZPm ZPm21=    4Pm01>&0$<#01,+&?4
3ÖSk$+4@i3ÍA«(."=¯oµA¥!>8/ÔÊ21>½fz³uOL2;,.¿Àz3O%yAº¶(*3^kA9>0²3¿Àz$¦Ï·¢Â}'?.>&0$
u#,+Ö¨c®~2;,.*?<3z24f1Ö¨$:,.>&0$'#=U¸3wÂ}$l1,.>&0$W'?+&?4¯{$µ&>Ã²3¿Àz${2bi(&)1,.>&0AW(.> 




Iq!&$%! ]3701[68:/HQ>?=<,









- 357 -
























  

Iq!&$%! ]3701[68:/HQ>?=<,
 bjNi5/4BM
 NBabETdÌm3  Îk3Ù^.Zc_ ^UHMRFYDd3Æ¶·¶¬3z³¼^. ÁL]0*3È£m2">ÖnË¾
^.
 F_Ni5/4BM
 NBabETdÌm3  Îk3ÙmVG;R-2-9,Zc_ ^UHMRFYDd3Æ¶·¶¬3z³¼*&%"&#!" '$$ $& %%
 ÁL]0*3È£m2">ÖnË¾
*"(& % '$$%%#$









- 358 -

 

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓᅛయ࣭ᾮయ⏺㠃࡟࠾ࡅࡿศᏊᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫ
Molecular Structure and Dynamics at Solid/Liquid Interfaces using
Molecular Dynamics Simulation‫ۑ‬ᇛሯ 㐩ஓ㸦Ⲉᇛ኱ᏛᕤᏛ㒊≀㉁⛉ᏛᕤᏛ⛉㸧

1◊✲┠ⓗࠊෆᐜ
㓟໬ࢳࢱࣥ࡞࡝ࡢᛂ⏝ୖᴟࡵ࡚㔜せ࡞ᅛయ࡜Ỉ⁐ᾮ࡜ࡢ⏺㠃࡛ࡢศᏊᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࢆศᏊືຊᏛ

㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾゎ᫂ࡍࡿࠋ⾲㠃ศᏊ✀ࡸ㟁Ẽ஧㔜ᒙ࡞࡝ࡢศᏊᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࢆ᫂ࡽ࠿
࡟ࡍࡿࡇ࡜࡛ࠊ཯ᛂᶵᵓࡀ㆟ㄽࢆ࿧ࢇ࡛࠸ࡿ㉸ぶỈᛶ࡞࡝ࡢ⏺㠃⌧㇟ࡢศᏊ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࠊⲴ㟁ࡋࡓᅛᾮ⏺㠃ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲࡢᵓ⠏ࢆ┠ᣦࡍࠋࡇࢀࡲ࡛⏦ㄳ⪅ࡣ▼ⱥࡸᾏሷ⢏Ꮚ࡞࡝ࡢⲴ㟁ࡋࡓ⏺㠃࡟࠾ࡅࡿ࿴࿘ἼⓎ⏕㸦SFG㸧ࡢゎᯒࢆ⾜ࡗ࡚ࡁࡓ㸦T.
Joutsuka and A. Morita, J. Phys. Chem. C, 122, 11407–11413 (2018); S. K. Reddy, et. Al., Chem, 4, 1629–1644 (2018);
T. Joutsuka, T. Hirano, M. Sprik, and A. Morita, Phys. Chem. Chem. Phys., 20, 3040–3053 (2018).㸧
ࠋ⌧ᅾ࡛ࡣࡇࢀࡽ
ࡢ◊✲ࢆ᭦࡟Ⓨᒎࡉࡏ࡚ࠊⲴ㟁ࡋࡓ⏺㠃ࡢ➨୍ཎ⌮ィ⟬࡟ࡼࡿࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲࢆ㛤Ⓨࡋ࡚࠸ࡿࠋ
ᮏ◊✲࡛ࡣࡲࡎࠊᅛయ⾲㠃࡟࠾ࡅࡿ࠶ࡽࡺࡿࣉࣟࢺࣥ໬≧ែࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࡓࡵ࡟ constrained
density functional theory (CDFT) ἲ࡟ࡼࡿィ⟬ᡭἲࢆ☜❧ࡍࡿࠋ⁐ᾮࡢ pH ࡟ᛂࡌ࡚Ⲵ㟁ࡍࡿ࢞ࣛࢫ࣭Ỉ⏺㠃࡬ࡢᛂ⏝ࢆぢᤣ࠼࡚ࠊࢣ࢖㓟Ỉ⁐ᾮ୰ࡢ⬺ࣉࣟࢺࣥ໬㸦ࣉࣟࢺࣥ⛣ື㸧ࡢ➨୍ཎ⌮ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ
ࣙࣥࢆᐇ⾜ࡍࡿࠋ
⥆࠸࡚ࠊගゐ፹ࡢ཯ᛂᶵᵓゎ᫂ࢆ┠ᣦࡋ࡚㓟໬ࢳࢱ࣭ࣥỈ⏺㠃࡟࠾ࡅࡿ⏺㠃ᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࢆゎᯒࡍ
ࡿࠋCDFT ἲࢆ⏝࠸࡚ࠊගບ㉳ᚋ࡟⏕ᡂࡍࡿ㟁Ꮚ࡜࣮࣍ࣝࡢ࣏࣮ࣛࣟࣥࡢࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲࢆᵓ⠏ࡍࡿࠋ⏺㠃㏆ഐ࡟ࡣࠊᵝࠎ࡞⾲㠃άᛶ✀ࡢᏑᅾࡀ♧၀ࡉࢀ࡚࠸ࡿࡓࡵගບ㉳๓ᚋࡢ⏺㠃ᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࢆ᫂ࡽ
࠿࡟ࡍࡿࠋ

2

◊✲᪉ἲࠊィ⟬᪉ἲࢩ࣭ࣜ࢝Ỉ⏺㠃࡛ࡢ⬺ࣉࣟࢺࣥ໬ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࡓࡵ࡟ࠊcp2k ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࢆ⏝࠸ࡓ abinitio ศᏊືຊᏛ(MD)ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ㸦Ⓨ⾲ᐇ⦼[2, 3]ࠊฟ∧ᐇ⦼[2, 4]㸧ࢣ࢖㓟Ỉ⁐ᾮࢆࢱ࣮ࢤࢵࢺ࡜ࡋࠊCDFT ἲࢆ⏝࠸࡚ࠊpKa ࡢ⡆༢࡞ィ⟬ࢫ࣮࣒࢟ࢆᥦ᱌ࡍࡿ࡜࡜ࡶ࡟ࠊືᚄศᕸ㛵ᩘࠊ᣺ືࢫ࣌ࢡࢺࣝࠊ
཯ᛂ⤒㊰࡞࡝ࡢᵓ㐀ࡸࢲ࢖ࢼ࣑ࢡࢫࡶゎᯒࡋࡓࠋ
cp2k ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ CDFT ἲࢆ⏝࠸࡚㸪࢔ࢼࢱ࣮ࢮᆺ TiO2 ⾲㠃࡟࠾ࡅࡿගゐ፹཯ᛂᶵᵓࡢ◊✲ࢆ⾜ࡗࡓ㸦Ⓨ⾲ᐇ⦼[1, 4]ࠊฟ∧ᐇ⦼[3]㸧ࠋ௒ᅇࡣ㸪࣮࣍ࣝ⛣ື᫬ࡢ࢚ࢿࣝࢠ࣮࡜ᵓ㐀࡟╔┠ࡋࡓࠋᮏ◊✲ࡣࠊLPCVD ᐇ㦂㸦S. Yamauchi, K. Yamamoto, and S. Hatakeyama, J. Chem. Eng., 3 (2015) 28–38.㸧ࢆ⾜ࡗࡓᐇ㦂ᐙ㸦Ⲉᇛ኱Ꮫᒣෆᬛᩍᤵ㸧࡜ࡢඹྠ◊✲࡛࠶ࡾࠊᐇ㦂࡛ᛶࡢ⌮ㄽゎᯒࢆ⾜ࡗࡓࠋ- 359 -

ᐃࡉࢀࡓ (112)㠃࡟࠾ࡅࡿ㧗࠸ගゐ፹ά

3

◊✲ᡂᯝ
CDFT ἲ࡛ィ⟬ࡉࢀࡓ⬺ࣉࣟࢺࣥ໬ࡢ཯ᛂ࢚ࢿࣝࢠ࣮࡜⮬⏤࢚ࢿࣝࢠ࣮ࡣ࡜ࡶ࡟ᩘ kcal/mol ࡛ᐇ㦂⤖ᯝ࡜୍⮴ࡋࡓࡇ࡜࠿ࡽࠊᥦ᱌ࡉࢀࡓᡭἲࡢ⢭ᗘࢆ☜ㄆࡋࡓࠋࡑࢀࡔࡅ࡛࡞ࡃࠊࡋࡤࡋࡤ⬺ࣉࣟࢺࣥ໬ࡢ➨୍ཎ⌮ィ⟬࡛⏝࠸ࡽࢀࡿ㓄఩ᩘ

㸦UL ࡣࢣ࢖㓟ࡢ OD ⤖ྜ㛗࡛ࠊND ࡜ R0 ࡣࣃ࣓࣮ࣛࢱ࣮㸧࡜࠸࠺཯ᛂᗙᶆ࡟኱ࡁ࡞ࣃ࣓࣮ࣛࢱ࣮౫Ꮡᛶࡀ࠶ࡿ
ࡇ࡜ࢆ♧ࡋࠊCDFT ἲ࠾ࡼࡧ࢚ࢿࣝࢠ࣮ᕪᗙᶆࡢ᭷⏝ᛶࢆᐇドࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡇࡢࣃ࣓࣮ࣛࢱ࣮౫Ꮡᛶ
ࡢཎᅉࡣ⬺ࣉࣟࢺࣥ໬≧ែ࡟࠾ࡅࡿ㓄఩ᩘࡀⰋ࠸཯ᛂᗙᶆ࡛ࡣ࡞࠸ࡇ࡜࡟㉳ᅉࡍࡿࠋḟ࡟ࠊ࢔ࢼࢱ࣮ࢮ㓟໬ࢳࢱࣥ⾲㠃࡟࠾ࡅࡿ࣮࣍ࣝࢺࣛࢵࣉࡢ
㠃౫Ꮡᛶࢆ᫂ࡽ࠿࡟ࡋࡓࠋィ⟬ࡢ⤖ᯝࠊග࡟ࡼࡾ⏕ᡂࡋࡓ࣮࣍
ࣝࡣ(101)㠃࡛ࡣ࡞ࡃࠊ(001)㠃࡜(112)㠃ࡢ᪉ࡀỈ㓟໬㠃࡟ࢺࣛࢵࣉࡉࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ㸦ྑᅗ㸧ࡇࢀࡽࡢ⌮ㄽⓗ▱ぢ࠿ࡽࠊ(112)㠃ࡣ௚ࡢ㠃࡟ẚ࡭࡚྾╔ࡋࡓỈ࡜ࢺࣛࢵࣉࡉࢀࡓ
ṇᏍࡢᏳᐃ໬ࡀ኱ࡁ࠸ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ௨ୖࡢィ⟬࡟ຍ࠼࡚ࠊ⌧ᅾࡣ CDFT ἲࡢᛂ⏝ࡢᒎ㛤࡜᣺ືࢫ࣌ࢡࢺࣝィ⟬ᡭἲࡢ㛤Ⓨ࡟ྲྀࡾ⤌ࢇ࡛࠸ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫[ۻ‬1] ࢔ࢼࢱ࣮ࢮᆺ㓟໬ࢳࢱࣥ࡟࠾ࡅࡿගゐ፹άᛶࡢ⤖ᬗ㠃౫Ꮡᛶ㸸㟁Ꮚ≧ែィ⟬࡟ࡼࡿゎᯒ ࠊ2020 ᖺ 12 ᭶ 25 ᪥ࠊ➨ 31
ᅇ ᪥ᮏ໬Ꮫ఍㛵ᮾᨭ㒊 Ⲉᇛᆅ༊◊✲஺ὶ఍ࠊྜྷᡂၨேࠊᒣෆ

ᅗ 1 㸬 Molecular mechanism of holeᬛࠊᇛሯ㐩ஓ

migration at anatase TiO2 surfaces.

‫[ۻ‬2] ᣊ᮰ᐦᗘỗ㛵ᩘ⌮ㄽ࡟ࡼࡿࣉࣟࢺࣥ⛣ືࡢศᏊືຊᏛ
ࢩ࣑࣮ࣗࣞࢩࣙࣥࠊ2020 ᖺ 12 ᭶ 21 ᪥ࠊ≀ᛶ◊✲ᡤࢫࣃࢥࣥඹྠ฼⏝࣭CCMS ྜྠ◊✲఍ࠕィ⟬≀㉁⛉Ꮫࡢ᪂ᒎ㛤 2020ࠖ
ࠊᇛሯ㐩ஓ㸦࣏ࢫࢱ࣮㈹㸧
‫[ۻ‬3] ᣊ᮰ᐦᗘỗ㛵ᩘ⌮ㄽ࡟ࡼࡿࢣ࢖㓟Ỉ⁐ᾮ୰ࡢ⬺ࣉࣟࢺࣥ໬ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࠊ2021 ᖺ 3
᭶ 19-22 ᪥ࠊ᪥ᮏ໬Ꮫ఍ ➨ 101 ᫓Ꮨᖺ఍ࠊᇛሯ㐩ஓ‫[ۻ‬4] 㟁Ꮚ≧ែィ⟬࡟ࡼࡿ࢔ࢼࢱ࣮ࢮᆺ㓟໬ࢳࢱࣥ࡟࠾ࡅࡿගゐ፹άᛶࡢゎᯒࠊ2021 ᖺ 5 ᭶ 13-15 ᪥ࠊ➨
23 ᅇ⌮ㄽ໬Ꮫウㄽ఍ࠊྜྷᡂၨே㸪ᇛሯ㐩ஓ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1] Taiji Nishikawa, Kensuke Horiuchi, Tatsuya Joutsuka and Satoshi Yamauchi, J. Cryst. Growth, 549, 125849(2020).
‫[ۻ‬2] Tatsuya Joutsuka and Koji Ando, J. Phys. Chem. B, 124, 38, 8323–8330 (2020).
‫[ۻ‬3] Tatsuya Joutsuka, Hiroto Yoshinari, and Satoshi Yamauchi, Bull. Chem. Soc. Jpn., 94, 106–111 (2021). (Open
Access, Selected Paper, Inside Cover)‫[ۻ‬4] Tatsuya Joutsuka and Koji Ando, Chem. Lett., in press.

- 360 -











Creation of arrangement and space based on the fine control ofmolecular metal complex
!"#1 
'1$ #5C80Ë§Q¢Ë#¼¢Ë£#¼¸  Ñ[D¸iÎoTr&fq#ZqJ)]~' ¼ÇÆ"ÒÀÀ·

'OFÃ %®²ÉÚOGÞ ­«®²)¾$ÝkÙQmÔQÓy
KHÇÆDi)¦ÊÆµuÛdsIÙ$&¯³D¹ 'Øw°ÓyÔQÎDgDcªc)ZqA;@Ä%Ý·V·)KÓyV·)Â^Ñ[Óy0?35E$:6BÓy0?35EWjh£D©W£ÄÖ'®²)¾


2 





\Î¶e¹ X ºÎÄ$&t|)¨¾ÎÏdv{ÖÜDFTÝ)¨nz¤)ÆµÕTrv{ÖÜTD-DFTÝ)¨bÌ¤)Æµ!×½Æµ#Lª¬MR¨)Á±"' NBO 7 9B1?>)S¨DFT
$ TD-DFT ÆµX Gaussian16 9B1?>)S¨((Æµ¨Ö´OGÍ&ÎÏdßB3LYP/Lanl2DZ (Óy)B3LYP/6-31G(d) (NV·),7@/EÆµß
B3LYP/Lanl2DZ(Óy)B3LYP/6-311+G(d) (NV·))¨

3 



$  Óy+-Cw*.?@Øw°ÑPqe|H¿an)ÔQ}' $&ÓyKH)'»kÙQmÔQi)¾i?4=QwH¿a_)`'¡U2*36A-<EQ Èx)¾kÙQmÔQH¿a_%'2*36A-<
EQ)¦ÊÆµÁ±"' ÑPq#H¿a_ZqÇÆ)¾2*36A-Ðªi
)¾%ÔQ HÅp' )ÁY¥l¦ÊÆµ$'gÄ))K'ÜÊ!KÝ%ÓyÑ[)-Do &v]~' Óy+-C$.Ñ[£
×qÎ)©'ÀH '®²· AE>)KÓfq)Ñ[')uÛ%%¦ÊÆµ$'ËÄ)¾·fq& 6 Ófq)Ñ
[ÙQmÓ0?35EZq C@Au6 ËÄ)«ÎÏdcÆµbÌ¤Ü'
(jh30 @ÝÆµ)¾Óy%ÑPq ,#ÜMLCTÝ' )ÁYÑPq)ÇÆ' 0?35E©W£)*%'   ÜÊ 10Ý%"'Óy)¸+:6BÓy0?35EC@Au6Ag2 ' 0?35E©W£ ' )Á
Y¦ÊÆµ%©W>Ä)¾ÜFigure 1Ý
- 361 -

        &DOFXODWHGRVFLOODWRUVWUHQJWKV I 

DEVRUSWLRQVSHFWUXPDQGH[SHULPHQWDODEVRUSWLRQVSHFWUXPRI DQG  &DOFXODWHGPROHFXODURUELWDOVVLQJO\RFFXSLHG PROHFXODU RUELWDOV LQ WKH WULSOHW VWDWH  DQG FRPSDULVRQV RI FDOFXODWHG DQG H[SHULPHQWDO WUDQVLWLRQ HQHUJLHVZDYHOHQJWKV RI DQG  4

"20 

$\DNR +LQR     +LWRVKL 8EH 0LWVXKLNR 6KLRQR\D 6\QWKHVLV RI FKLUDO WHWUDKHGUDO R[RYDQDGLXP

#

"3 #FRPSOH[HVKDYLQJDQDFKLUDOXQV\PPHWULFDOOLJDQGZLWKDEXON\VXEVWLWXHQWDQGWKHFRQWURORIWKHLUPHWDOFHQWHUHGFKLUDOLW\ $SP ZHE   =KHQ /HL     ;LDR/L 3HL +LWRVKL 8EH 0LWVXKLNR 6KLRQR\D 1+HWHURF\FOLF /LJDQGV DV 5HJXODWRU RI
3KRVSKRUHVFHQFHLQ*ROG , DQG*ROG , 6LOYHU , &OXVWHUV 7KHWK  -DSDQ6RFLHW\RI&RRUGLQDWLRQ&KHPLVWU\$ ZHE 
6HSW



/HL=KHQ+LWRVKL8EH0LWVXKLNR6KLRQR\D /LJDQGHIIHFWVRQ WKHSKRWRSK\VLFDOSURSHUWLHVRI
11¶GLLVRSURS\OEHQ]LPLGD]RO\OLGHQHSURWHFWHG&FHQWHUHGKH[DJROG , FOXVWHUV-2UJDQRPHW&KHP 
 '2,MRUJDQFKHP



.HQLFKL(QGR/LX<XDQIHL+LWRVKL8EHDQG0LWVXKLNR6KLRQR\D $V\PPHWULFFRQVWUXFWLRQRIWHWUDKHGUDOFKLUDO]LQFZLWKORQJOLIHVWDELOLW\1DWXUH&RPPXQLFDWLRQV  

+LVDNR+DVKLPRWR DQG 7UDQVLWLRQPHWDO&RPSOH[HVZLWK7ULSOH%RQGVWR6L*H6QDQG3EDQG
5HOHYDQW&RPSOH[HV &KHP/HWW 

6),Creation of POM complexes with multiple bonds between typical elements and transition
metals and control of self-assembly Science Impact Ltd, 2020, 4, 33-35.

- 362 -











Divelopment of synthetic reactions based on theoretical calculations´ý íÙĠ½pĐÃġ, x° £1Ġ½pÓèġåëáàĄîèà®Ê#.1 Zealexin A1 $Äđ²
W57P6d=Df%ÁÐ#Ñ»$¯äûª$oÇqċÖÐ0Þû$w|§#ÕÖüê21iùà#W57P6d=Df%ÁÐ$Þû#1øÎ{Ý#ėā"¦4¿
fQ8

åë2 01960 ¢#9/ßĂ2º$W57P6d=Df1V

CKf%gÕdYc$W57P6d=Dfåë
$ėā"_Oc07SĠOryza sativaġ
J7GĠGlycinemaxġP8_eBDĠZea maysġ"!jÚ$māuÐ#,
)2

1¼åëČ1 zealexins %Ģ2011 ¢#Figure 1. Structures of zealexins

Fusarium graminearum 4*Å"ÁÐÞû4±éú /+ĝ2P8_eBD$W57P6d=Df\?e<cTf$HF=NcZf1(Figure 1)zealexins $Äđ%MS.' NMR FZ?Pc$Ĉð"ă¾#.0·/ #"zealexins#% zealexin B1 (Äđ¤ãÛ) 4Ĝ ìtl© 1 åë¥¸%$âìtĔö .'ôàìtĔö#ě1«%" 2008 ¢ Degenhardt /#.Õ­ñĎ 2P8_eBD$N
cZf­ĕïĠTPSġTPS6.' TPS11ñØ-\?e<cZf(ğÇÔ1ĠE,Eġ-W5cSDcobfĖĠFPPġ /-UC[df44·/#ĠScheme 1ġ
-UC[df$ôĔö%ÆÌÐč $Èď / S 1ç22016 ¢Wang/%CYP71Z18 4÷û$ÀßÒ/# TPS11
ĠZx3ġ4× ĠSġ--\?e<cZf4ÕÖ1.
#ćĄ

34 $Õ­Ð¨/2$l#zealexin A1

)2 /# Song /%P8_e

BD / stigmens CĠ4ġ
ĢFĠ5ġ &21\?e<cT
f$HF=NcZf³é
ECD FZ?Pc

zealexin ěĒÐ4ĝ/2/$ C1 $ôĔöR

Scheme 1. Proposed biosynthetic pathway of Zealexin1 4çĠScheme 1ġzealexins $ôĔö4æĉ1+#%stigmens
hI%|®1

zealexins 4Èď1

º,æ"µÊ1 zealexins $ ECD O"  /#stigmen FĠ5ġ$¡ĞÄđ%zealexin A3Ġ3ġ i 

$ 2 $Ð$ NMR FZ?Pc%Ü"1ÍĆĘ2 +ĢiÐč æĉ1 %" /zealexin

stigmens $âàôìtÄđă· ÕåëCfXcvó4áà#å- 363 -

ë4Ě

2 åëµÊĄîµÊ%+# zealexin A1 k9RfK;\h4 Lipase AK 4× z4ę 22¬ė#­­ zealexin A1 k9RfK;\h4=ac GC 4× ­ Î$ zealexin A1 4Èď
1 ôìtĔö4Ézealexin A1 (1) $BfW:h^hD`fă¾%Conflex Xe@a]TLAhE#Ā2 MMFF94s 4× þÕ­2Äđ$ ºÄđ 9Sc>h

1.0kcal/mol r}$BfW:h\h4×å Gaussian 16 Xe@a]TLAhE#Ā2 B3LYP/6-31G(d,p) dYcÄđºē4þ"
ºē2BfW:h\h%TDDFT-B3LYP/6-31G(d,p) dYc$ UV.' CD Ąî4þ ¨/2FZ?Pc%[cM\f # ¡FZ?Pc4 

3 åë­¿
2. $®Ê#.0 zealexin A1 (1) k9RfK;\h#Ąî4¶22 ECD FZ?Pc4Ă

ê, " /­$Ëy %Ü" BfW:\h³-ĄîdYc$¹"!éÂą4þ Ü"1ò¿4¨+Ąîy ÈďôìtĔöÉ%bF? sòĊ

4 ßÿõ)%n
 Yajima, A.; Shimura, M.; Saito, T.; Katsuta, R.; Ishigami, K.; Huffaker, A.; Schmelz, E. A.
“Synthetic and Determination of Absolute Configuration of Zealexin A1, a Sesquiterpenoid
Phytoalexin from Zea mays” Eur. J. Org. Chem. 2021, 1174-1178
5 ~Ïõ)%n
"- 364 -

㟼㟁ሙ୰࡟࠾ࡅࡿศᏊ࢖࢜ࣥࡢ㍺㏦ࢲ࢖ࢼ࣑ࢡࢫ
Transportation dynamics of molecular ion under electric field‫▱ ⯓⋢ۑ‬ஓࠊ℩ᡞ ❶ᩥࠊᮾ ⚽᠇㸦㔠ἑ኱Ꮫ኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ
㟼㟁ሙࡣẼ┦୰࡟ᾋ㐟ࡍࡿศᏊ࢖࢜ࣥࡢᣲືࢆไᚚࡍࡿ㝿࡟⏝࠸ࡽࢀࡿࡀࠊ㟼㟁ሙ୰࡟࠾ࡅࡿ」㞧࡞ศᏊ࢖࢜ࣥࡢᣲືࢆ⾲ࡍ⌮ㄽయ⣔ࡣᮍࡔ࡞࠸ࠋᮏ◊✲࡛ࡣ㟼㟁ሙ࡟࠾ࡅࡿศᏊ࢖࢜ࣥࡢືⓗᣲືࢆศᏊືຊᏛࢩ
࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾゎᯒࡋࠊ⌮ㄽయ⣔ࡢᵓ⠏ࢆ᭱⤊┠ᶆ࡜ࡋ࡚࠸ࡿࠋᮏᖺᗘ࡛ࡣࠊศᏊ࢖࢜ࣥ⮬యࡀ⏕ࡳฟࡍ㟼㟁ሙ࡟╔┠ࡋࠊẼ┦୰࡟ᾋ㐟ࡋࡓูࡢศᏊ࢖࢜ࣥ࡜┦஫స⏝ࡍࡿ㐣⛬ࢆ͆㏿ᗘㄽⓗ͇࡟ゎᯒࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲศᏊ࢖࢜ࣥࡢ⾪✺㐣⛬ࢆィ⟬ࡍࡿ᪉ἲ࡜ࡋ࡚⏦ㄳ⪅ࡽࡀ᫖ᖺᗘ㛤Ⓨࡋࡓ㐃⥆య̿ศᏊືຊᏛࣁ࢖ࣈࣜࢵࢺ

ἲࢆ⏝࠸ࡓ㸦Tamadate et al., JCP, 2020㸧ࠋᮏᡭἲࡣศᏊ࢖࢜ࣥ㛫ࡢ㊥㞳ࡀ༑ศ࡟㞳ࢀࡓ࡜ࡁࡣ㍺㏦᪉⛬ᘧ࡜ࡋ࡚ᣑᩓ᪉⛬ᘧࢆ㐺⏝ࡋࠊ㏆ഐࡢᣲືࢆ MD ࡟ࡼࡾゎࡃᡭἲ࡛࠶ࡿࠋලయⓗ࡟ࡣṇ࡛+7 ౯࡟ᖏ㟁ࡋࡓ࣏࢚ࣜࢳ
ࣞࣥࢢࣜࢥ࣮ࣝ㸦PEG7+㸧࡟-1 ౯ᖏ㟁ࡋࡓ஧㓟໬❅⣲㸦NO2-㸧ࢆ㐃⥆ⓗ࡟⾪✺ࡉࡏ࡚࠸ࡁࠊ+6ࠊ+5ࠊ͐ࠊ0ࡢࡼ࠺࡟ᚎࠎ࡟㝖㟁ࡉࢀ࡚࠸ࡃ㐣⛬ࢆィ⟬ࡋࠊ㝖㟁㏿ᗘࡢゎᯒࢆᐇ᪋ࡋࡓࠋ㞺ᅖẼ࢞ࢫࡣ❅⣲࢞ࢫ࡜ࡋࠊィ⟬ࡣࡍ࡭࡚⮬సࡢࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ

3◊✲ᡂᯝ
+7 ౯࡟ᖏ㟁ࡋࡓ PEG ࢖࢜ࣥࡣ㟁Ⲵྠኈࡢ཯Ⓨ࡟ࡼࡾఙᙇࡋࡓᙧ≧ࢆ♧ࡋࡓࡀࠊ㝖㟁㐣⛬࡛ࠊ཯Ⓨຊࡢᙅࡲࡾ࠿ࡽᚎࠎ࡟⌫ᙧ࡟㏆࡙࠸࡚࠸ࡃࣘࢽ࣮ࢡ࡞㝖㟁ࣉࣟࢭࢫࡀほᐹࡉࢀࡓࠋࡲࡓࠊᣑᩓ᪉⛬ᘧ࡜ࡢࣁ࢖ࣈࣜ
ࢵࢺ࡟ࡼࡾィ⟬ࡋࡓ⾪✺㏿ᗘᐃᩘࡣࠊᡃࠎࡀᐇ᪋ࡋࡓᐇ㦂⤖ᯝ࡜ẚ㍑ⓗⰋዲ࡟୍⮴ࡋ࡚࠾ࡾࠊ㠀⌫ᙧศᏊ࢖࢜ࣥ࡟ᑐࡋ࡚ࡶ㏿ᗘㄽⓗ࡞ゎᯒࡀྍ⬟࡛ࠊศᯒࣉࣟࢭࢫࡢタィ࡞࡝࡬ࡢᛂ⏝ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬T. Tamadate, T. Seto, C. J. Hogan, “Calculation of the Nanoparticle-ion attractive collision rate coefficient bycontinuum molecular dynamics hybrid simulations”, The American Association for Aerosol Research 2021, Accepted,
US, Oct 2021.
‫▱⯓⋢ ۻ‬ஓࠊ&KULVWRSKHU-+RJDQ-Uࠊᮾ⚽᠇ࠊ℩ᡞ❶ᩥࠊࠕ&RQWLQXXP0ROHFXODU'\QDPLFV

6LPXODWLRQ ἲࢆ⏝࠸ࡓ࢖࢜ࣥ㛫⾪✺㏿ᗘᐃᩘࡢ᥎⟬ࠖࠊ➨  ᅇ࢚࢔ࣟࢰࣝ⛉Ꮫ࣭ᢏ⾡◊✲ウㄽ఍ࠊ࢜ࣥ
ࣛ࢖ࣥࠊ ᖺ  ᭶5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬77DPDGDWH ++LJDVKL&-+RJDQ 76HWR³7KHFKDUJHUHGXFWLRQUDWHIRUPXOWLSO\FKDUJHGSRO\PHULRQVYLD

LRQLRQ UHFRPELQDWLRQ DW DWPRVSKHULF SUHVVXUH´ 3K\VLFDO &KHPLVWU\ DQG &KHPLFDO 3K\VLFV   5&6'2,GFSI⌧ᅾࠊ1 ሗᇳ➹୰㸦Journal of Aerosol Science ࡟ᢞ✏ணᐃ㸧

- 365 -



Computational chemistry simulation of functional materials
using nanocarbons and organic materials
$E+)E&,<E!E?> 'E ;9E5@E >E
,=0EB)%EPatrick BonnaudCA2713#"D

1 13/.
 JST COI DS1OJa~qt*0*U,>EV3NT¥j­ Þ=>/VGTÂ(Ù^& n¨Wp¢$vc(_¼&35:J¸(² ´·(Ï &ß
X±´·ÊØÛ½e©¿h¤¹Ô°%Þ 'e©¿½Å(²±YÍU¾oUÖÄ¥$´·(Áß¤¹Ô°Ä¥$! Multi-walledcarbon nanotube (MWCNT)h§±qÒlÔ°´·"£rX¤¹µ¦®±ËÅÞ ´·({Ô ßDS4-0;Þa~qt(XÛ=>/VGTÂÞe©¿K4MVQÂÞb3IMRV3NTÂ(´·ÕU[×» .VQ4L@T«twÎ´·]g´·(Ï &ßf &fs3IMRV3NT#&»³xÚ´·B+V<?90 ÞÇ­ 'xÚª ¶t±¯m¥dfs3IMRV3NT

k%º2,0Q#Û ½¹Ô°(² &ß
e©¿½É`

'x ´·Þ COI DS1OJPV7V&a~qtÐÀua$Ô° &p}/VGT=>8MVCÜMWCNTÝHP*I<ÜPAÝÛfs(¬Ì¡Í(RO)¿ÜCNT/PA RO ¿Ýy Þfs3IMRV3NT#%ÍU¾oUÖ½É`(ÁÞÛÍ UÛ¾o U\Ö ($ ßZ´·ÞRO ¿zÑ¬&i5FV2V 

Ô° ' CNT 6QSV5=>B),?VÜCNFÝ(Ãl H

PDSART(PP)i5FV2Vfs3IMRV3NT#%Ö ½É`(ÁßMWCNT lÈMWCNT h§±l ÞÓ|Ær(¬ X MWCNT (³& ³ (Chemical vapor deposition; CVD)# ¬$'&Þ³%Å'ß¬&ÆrÓ|»U[s2,Uz4ÒÞ#T9]5z4Òlm#k°67fÁ '$Þ#%h§± CVD

Ô°(ÁµÊØ&ß\} \x 6QV¶L(9]lÏm#c Þ;¤6¹?vO
¬?QVÞ#»lÅ·9]&9]¶L9]QVÉ`(Áß2 13(E:4(e©¿½É`-<´·+a~qt1QVD#È'& CNF (Ãl  PP 5FV

2V(CNF/PP)ÞT@0Ë#&B)PT1®(Å& Þcis:.fs53t3
IMRV3NT#&Åo(Áßu¨ YnH PP  5FV2V¬ÞCNT/PP Ãl5FV2
V¬ÞCNT  CNF ($!Ãl  CNT/CNF/PP Ãl5FV2V¬(% ßÖÕ&- 366 -´·Þ¿pË ET8V0¡¬$'&3{*QCIT(Bovine serum albumin; BSA)
T@0Ë(¬ßÇB;-* LAMMPSÞfs3J 5FV2V GAFF (ÞBSA CHARMM (Þfs TIP3P (¬ß%  4 5FV2V¬y ÞA X BSA(ºW² 3IMRV3NT(ÁÞ?¦ &¤q ßXÞÑfs5FV2
VºTÁ3(4& Þxµe©iª &0S5BSV ®gV#&TÁy(td±z, 3IMRV3NT(ÁÞZ$';O4-0;PÅo(ÁßMWCNT lÈCVD

&Ó|0O5VÆrh Ó|º? ¤¹_¼¢6tM6(¤& Þ@lKm#TºwIU(¬QvÕ ÜDFT

Ý#Ó|ºW¤¹_¼¢?^Þºae9]"fÅ9]Åo(Áß¦ Fe (Ó|ÆrJl² ÞTÞ8RTÞ*68RTÞFT4QO4/QÞFT4TÞETT¤6¹(¤¹_¼¢ ¤q ßÇB;-* Quantum ESPRESSOÞdH:T3LQH
 PAWÞPBE vÕ(b¬ Þ5ATfs(_,'Ç(ÁßCVD 1200 ©Û}m#Á '%Þ D$ Fe ºgrsÜfccÝ¬("O ß?Q0¬k°6XÞ(111)º5OC ¾}f(±0 5OCKQ(% ß¾}X½}¬EO 
m#(Ê ÞW½} Fe #? isUfs¬k°6(ÁW Î¤q(Áß3 13
e©¿½É`?3IMRV3NTX BSA $(D 1 µß '´·<Þ
CNT/PP

Ãl5FV2V BSA ¿$·'&#5 Þ5FV2Vº?$'ÞÞ<
CNF/PP Ãl5FV2VÞ
CNT Ãl '& CNT/CNF/PP Ãl5FV2V!?$'ÞPP 5FV2V BSA 5FV2Vº?$'ßXy3IMRV3NT(Á»ÞD 2 µª%Þ?$' CNT/CNF/PPÞCNT/PP Ãl5FV2V BSA 5FV
2Vº§·('%Þyg=O«(y'&sk'ß

D 1. (a) CNT/CNF/PP, (b) CNT/PP, (c) CNF/PP, (d) PP 5FV2V?3IMRV3NTX BSA $ß
DX¥81l$ $5g=(µß- 367 -

?$' 2 5FV2VÕ ÞCNF/PP Ãl5FV2VD 1 $'&ª%?¥p  BSA 5FV2Vº$·'Þ ­« 5y ÞPP 5FV2V BSA º$·'Xd¿?&|«&s£ßPP 5FV2V

CNT/PP 5FV2V BSA ?¯!2<ÞCNT Ãl#&¸5#%5FV2V
ºfs

%¬W %ÞCNT/PP 5FV2Vfsº(BSA ? 

$'&ß< CNT >'& CNT/CNF/PP ! CNT/PP <¸5¦& Þ<#% BSA ? $'&ßgÞCNF/PP 5FV2VÞ¸5¦Þºfsp!Õ $ BSA 5FV2Vº?&»ßD 3 µª%¸5#& PP Ñ¸M6Ò CNT/CNF/PP # CNT/PP 5FV2Vu R ¯&!Þ¢B)PT1 ¯¦¢j&¤q\&ß

D 2. (a) BSA-5FV2Vº´§·, (b) BSA «5FV2VºTÁfi´TGß

D 3. (a) CNT/CNF/PP, (b) CNT/PP, (c) CNF/PP 5FV2V&Ãl¸M6Òß
MWCNT lÈÆrÓ| Fe (±Þfcc ¬@lKm#(Ê (111)º5OCKQÜ334 }Ý(% Þº&¹fs#¤¹_¼¢&TÞ8RTÞ*68RTÞFT4QO4/QÞFT4TÞETT¤6¹?vO¬?Q
VÞj H-H »lÞC-H »lÞC-C »lÅ·9]y&9]¶L9]QVÉ`(Áßµ¤6¹?&(&W½}!¬A(_,'Ç(Áßfcc ¬#%!
bcc ¬gH:T3LQQV±vO&ÞD 4 #?fs^!
W½} xy g='¬vO& Þ'º¬(W Ç&j¬ ßD
5a µ#¹fs

9]¶L Å·? Þ¹K#%!¹Kg MWCNT ³h§ iC ¹O4/QP&µB 'ß¦D 5(b)Þ5(c)µ#¹O
4/Q"¤¹O4/Q Fe ºae9]¶L¹S\Ç»$Þ»lÅ·9]#ª '&O4/QisÏT;SAV*$ #Û}ETT(> W ¤6

- 368 -

¹fÅ¦Z&!$ßÞ? ¤6¹fÅ X¹O4/Q¤¹O4/Q Fe º Fe /Ñ$NF h(¤& Þfcc ¬H Fe ?Q0(222)¼½¹O4/QÞ#¼½¤¹O4/Q(,'µ&,HE£#&vO6Q
V(Ç ßH:T3LQQV±¹O4/Q Fe /Ñ#%! Fe ºNF Þ¤¹O4/
Q Fe º#%! Fe /ÑNF h!$ßD 4. %  Fe ºKQß(a) W½}¬A2, (b) W½}¬AXÜj¬Ý

D 5. (a) ¹fsÅ·?9], (b) ¹O4/Qºae, (c) ¤¹O4/Qºaeß4 -86


5*6
¥f`~)X- 369 -

⭷㏱㐣࣌ࣉࢳࢻ࡟ᑐࡍࡿ⣽⬊⭷⾲㠃࡬ࡢ⛣ື㐣⛬࡟ᑐࡍࡿ⌮ㄽⓗ◊✲Theoretical study on the transfer process of cell-penetrating peptide tomembrane‫ۑ‬す⃝ ᏹ᫭㸪ᰗ ᫡㍤㸪ዟཎ ༓ె㸪ྜྷᒸ ⪔స㸪ᇼ ඃኴ㸦⟃Ἴ኱Ꮫ㸧㸪㨣㢌 ᏹ௵㸦⚄ᡞ኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࡣ᪂ࡋ࠸་⸆ရ࡜ࡋ࡚ὀ┠ࢆ㞟ࡵ࡚࠸ࡿ⎔≧࣌ࣉࢳࢻࡢ⣽⬊⭷㏱㐣ᛶࢆ㸪⟬⛉Ꮫࢆ⏝࠸᳨࡚ドࡍࡿࡶࡢ࡛࠶ࡿࠋᑐ㇟࡜ࡍࡿ⣔࡟ᑐࡋ࡚㔞Ꮚ໬Ꮫィ⟬ᡭἲࡢ 1 ࡘ࡛࠶ࡿ㟁Ꮚᐦᗘᙉ᮰⦡ (DFTB) ἲ࡟ᇶ࡙ࡃศᏊ
ືຊᏛ (MD) ィ⟬ࢆ⾜࠺ࡀ㸪ṇࡋ࠸⤫ィ㔞ࢆᚓࡿ࡟ࡣࢩ࣑࣮ࣗࣞࢩࣙࣥ୰ࡢ඲࢚ࢿࣝࢠ࣮ࡀಖᏑࡋ࡚࠸ࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋࡋ࠿ࡋ㸪DFTB-MD ࡛ࡣ⤫ィᖹᆒࡢṇࡋࡉࢆಖドࡍࡿࡼ࠺࡞◊✲⤖ᯝࡣ࠶ࡲࡾከࡃ࡞࠸ࠋ
ࡑࡇ࡛㸪DFTB-MD ࡟㛵ࡋ࡚඲࢚ࢿࣝࢠ࣮ࡀಖᏑࡋ࡚࠸ࡿ࠿ࢆ᳨ドࡋ㸪ᮏᡭἲࡢጇᙜᛶ࡟ࡘ࠸᳨࡚ドࡋࡓࠋࡲࡓ㸪MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࢧࣥࣉࣜࣥࢢຠ⋡ࢆྥୖࡍࡿࡓࡵ࡟㸪ᵓ㐀ࢆᣊ᮰ࡍࡿᡭἲࡢ 1 ࡘ࡛࠶ࡿRATTLE ἲࡢຠ⋡ⓗ࡞ィ⟬ᡭἲࢆ㛤Ⓨࡋࡓࠋ2◊✲ᡂᯝᮏ◊✲࡛㛤Ⓨࡋࡓ Matrix-RATTLE ἲࢆỈศᏊ࡟㐺⏝ࡋࡓ⤖ᯝࢆ⾲ 1 ࡟♧ࡍࠋᣊ᮰᮲௳ࡣ O-H, H-H 㛫㊥㞳ࡢ 3 ⮬⏤ᗘ࡟ᑐࡋ࡚᥃ࡅ࡚࠾ࡾ㸪ࡍ࡭࡚ࡢ㊥㞳ࡀ 10-7 Å ௨ୗࡲ࡛ᣊ᮰᮲௳࡟୍⮴ࡍࡿᅇᩘ࡜㊥㞳ࡢኚ໬ࢆ♧ࡋ࡚࠸ࡿࠋ㏻ᖖࡢ RATTLE ἲ࡛ࡣ 1 ᗘ᥃ࡅࡓᣊ᮰ࡀูࡢᣊ᮰࡟
ࡼࡗ࡚ኚ᭦ࡉࢀ࡚ࡋࡲ࠺ࡓࡵ㸪඲య࡛ 27 ᅇࡢᡭ⥆ࡁࢆ࡜ࡿᚲせ⾲ 1. RATTLE ἲ࡜ Matrix-RATTLE ἲࡢỈศᏊᣊ᮰ࡢ཰᮰㐣⛬ࡀ࠶ࡗࡓࠋࡑࢀ࡟ᑐࡋ࡚㸪Matrix-RATTLE ࡛ࡣࡍ࡭࡚ࡢ⮬⏤ᗘ
ࢆ 1 ᗘ࡟ᣊ᮰ࡍࡿࡓࡵ㸪1 ᅇࡢᡭ⥆ࡁ࡛ࡍ࡭࡚ࡢ㊥㞳ࡀ 10-2 Å ⛬ᗘࡲ࡛ᣊ᮰ࡉࢀ࡚࠸ࡿࠋࡲࡓ 3 ᅇࡢ⧞ࡾ㏉ࡋᡭ⥆ࡁ࡛㸪㏻ᖖࡢ
RATTLE ἲ࡜ྠ➼ࡢᣊ᮰ࢆ᥃ࡅࡿࡇ࡜ࡀ࡛ࡁࡓࠋ
ḟ࡟࢚ࢿࣝࢠ࣮ࡢಖᏑ࡟ࡘ࠸᳨࡚ドࢆ⾜ࡗࡓࠋࡲࡎ㸪㔞Ꮚ໬Ꮫィ⟬࡛ࡢຊࡢィ⟬࡟ࡘ࠸᳨࡚ドࡋࡓࠋ㔞Ꮚ໬Ꮫィ⟬࡛ࡣຊࡣ㸪ྂ඾ MD ࡛ࡶ⌧ࢀࡿ Hellmann–Feynman ຊ࡟ຍ࠼࡚㸪Pulay ຊࡶィ⟬ࡍࡿᚲせࡀ࠶ࡿࠋPulayຊࡣཝᐦ࡟ồࡵࡿࡇ࡜ࡀ࡛ࡁ࡞࠸ࡀ㸪ኚศཎ⌮ࡢ཰᮰᮲௳ࢆཝࡋࡃࡍࡿࡇ࡜࡛㸪⌮ㄽⓗ࡟ࢮࣟ࡟ࡍࡿࡇ
࡜ࡀ࡛ࡁࡿࠋࡑࡇ࡛㸪཰᮰᮲௳ࡢ㐪࠸࡟ࡼࡿ඲࢚ࢿ
ࣝࢠ࣮ࡢಖᏑᛶ࡟ࡘ࠸᳨࡚ドࢆ⾜ࡗࡓࠋDFTB ィ⟬ࡢ཰᮰ุᐃ࡟⏝࠸ࡽࢀࡿ Mulliken 㟁Ⲵࡢኚ໬ࡢ᭱኱
್ࡀ 10-p ௨ୗ࡟࡞ࡿࡲ࡛ィ⟬ࢆ⾜ࡗࡓ⤖ᯝࢆᅗ 1 ࡟♧ࡍࠋ཰᮰᮲௳ࡀ 10-6 ࡢ࡜ࡁࡣࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬
㛫ࢆ㛗ࡃࡍࡿ࡜඲࢚ࢿࣝࢠ࣮ࡀಖᏑࡋ࡞ࡃ࡞ࡗ࡚࠸
ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡑࢀ࡟ᑐࡋ࡚㸪཰᮰᮲௳ࡀ 10-8 ࡼࡾᑠࡉ࠸࡜ࡁࡣ 500 ps ࡢࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡶ඲࢚

ᅗ ཰᮰᮲௳ࡢ㐪࠸࡟ࡼࡿ')7%0'ࢩ࣑࣮ࣗࣞࢩ
ࣙࣥ࡟ࡼࡿ඲࢚ࢿࣝࢠ࣮ࡢ᫬㛫Ⓨᒎ

- 370 -

ࢿࣝࢠ࣮ࡀ 1 kcal/mol ௨ෆ࡛ಖᏑࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡟㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ MD ィ⟬࡛ࡣཝࡋ࠸཰᮰᮲௳
ࢆ⏝࠸࡚ຊࡢィ⟬ࢆṇࡋࡃྲྀࡾᢅ࠺ᚲせࡀ࠶ࡿࠋ᭱ᚋ࡟㸪࣓ࢱࣀ࣮ࣝ 64 ศᏊ࡟ᑐࡋ࡚ DFTB-MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㐺⏝ࡋࡓ⤖ᯝࢆᅗ 2 ࡟♧ࡍࠋ཰᮰᮲௳
ࡣ 10-8 ࡜ࡋ㸪Matrix-RATTLE ἲࢆ⏝࠸ࡓ⤖ᯝࡶేࡏ࡚♧ࡋ࡚࠸ࡿࠋRATTLE ἲࢆ⏝࠸࡞࠸ሙྜ࡛ࡶ㸪᫬㛫้
ࡳࢆ 0.5 fs ࡜ࡋࡓሙྜࡣ඲࢚ࢿࣝࢠ࣮ࡢಖᏑࡀ☜ㄆ࡛ࡁࡓࠋ୍᪉㸪᫬㛫้ࡳࢆ 2.0 fs ࡜ࡋࡓሙྜࡣᣊ᮰᮲௳ࢆ
⏝࠸࡞࠸ሙྜ㸪඲࢚ࢿࣝࢠ࣮ࡣಖᏑࡋ࡞࠸ࡀ㸪ᣊ᮰᮲௳࡛࠶ࡿ RATTLE ἲࢆ⏝࠸ࡓሙྜ࡟ࡣ 2 kcal/mol ⛬ᗘࡢㄗᕪ࡛ಖᏑࡍࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋᑐ㇟࡜ࡍࡿ⣔࡟ࡶࡇࡢ⛬ᗘࡢ᫬㛫้ࡳࢆ⏝࠸ࡿࡇ࡜࡛㸪㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ MD ィ⟬࡛ࡶṇࡋࡃࢩ࣑࣮ࣗࣞࢩࣙࣥࡀ࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿࠋ
D

E

F

ᅗ ᣊ᮰᮲௳ࡢ᭷↓࡟ࡼࡿ')7%0'ィ⟬ࡢ඲࢚ࢿࣝࢠ࣮ࡢኚ໬ D IV E IV F IV

C60 ྾╔ࢱࣥࢢࢫࢸࣥ⾲㠃ࡢ➨୍ཎ⌮ィ⟬㸦㨣㢌ᏹ௵㸧
C60 ࡀ྾╔ࡋࡓࢱࣥࢢࢫࢸࣥ (W) ࠿ࡽࡢ㟁⏺㟁Ꮚᨺฟࡢ▱ぢࢆᚓࡿࡓࡵ㸪ᅗ 3(a)ࡢࡼ࠺࡞ࢫࣛࣈࣔࢹࣝࢆసᡂࡋ㸪Quantum
ESPRESSO ࡟ࡼࡿᐦᗘỗ㛵ᩘἲ (DFT) ィ⟬࠿ࡽ㸪xy 㠃ᖹᆒࢆ࡜ࡗࡓ z ㍈᪉ྥ࣏ࢸࣥࢩࣕࣝ (ᅗ X(b)) ࢆồࡵࡓࠋ㟁ሙ(Ez=-2V/Å) ࡣࣀࢥࢠࣜᆺࡢ࣏ࢸࣥࢩࣕࣝ࡜ࡋ࡚ຍ࠼ࡓࠋỗ㛵ᩘࡣ PBE ࢆ㸪ᨃ࣏ࢸࣥࢩࣕࣝἲࡣ PAW ࢆ౑⏝ࡋ㸪Ἴື㛵ᩘ࡜㟁Ⲵᐦᗘࢆᖹ㠃Ἴ࡛ᒎ㛤ࡍࡿ㝿ࡢ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ࡣ㸪
50Ry ࡜ 475Ry ࡟タᐃࡋࡓࠋK Ⅼࡣ 4x4x1 ࡟ྲྀࡗࡓࠋ
㟁ሙ↓ࡋ࡛ࢱࣥࢢࢫࢸࣥࡢࡳࡢィ⟬⤖ᯝ (㯮⥺ࡢ z=4-35Å್) ࡣ㸪W(100)㠃ࡢ௙஦㛵ᩘࡢᐇ㦂್ 4.5ࠥ4.7eV ࢆⰋࡃ෌⌧ࡋࡓࠋ㉥⥺ࡣ㸪C60 ྾╔ W(100)㠃࡟-2.0V/Å ࡢ㟁ሙࢆ࠿ࡅࡓ⤖ᯝ࡛㸪C60 ࡢእഃ࠿ࡽ㟁⏺࡟ࡼࡿ࣏ࢸࣥࢩࣕࣝࡢഴᩳࡀጞࡲࡗ
࡚࠸ࡿࠋࡇࡢࡇ࡜࠿ࡽ྾╔ࡋࡓ C60 ࡣ㔠ᒓⓗ࡟࡞ࡗ࡚࠸ࡿࡇ
࡜ࡀศ࠿ࡗࡓࠋ(ᮏィ⟬ࡣࠊᮾ኱≀ᛶ◊ࡢᰡ⃝ၨྐ༤ኈ࡜ࡢඹ
ྠ◊✲࡜ࡋ࡚⾜ࡗࡓࠋ)3ᅗ  D & ྾╔ࢱࣥࢢࢫࢸࣥࡢࢫࣛࣈࣔࢹࣝ㸪
E ] ㍈᪉ྥ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࡢィ⟬⤖ᯝ

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
>@ ‫ ۻ‬す⃝ᏹ᫭, 㔜⏣⫱↷, ͆㟁Ꮚ≧ែィ⟬࡟ᇶ࡙ࡃศᏊືຊᏛィ⟬ࡢ࢚ࢿࣝࢠ࣮ಖᏑ᳨ド࡜ᵓ᝿༊᮲௳
ࢆ⏝࠸ࡓຠ⋡໬͇, ➨ 34 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ, 2020 ᖺ 12 ᭶

4ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
>@ ‫ ۻ‬Hiroaki Nishizawa, Yasuteru Shigeta, J. Comput. Chem. to be submitted.

- 371 -

ຍỈศゎ㓝⣲ࢆ⏝࠸ࡿ㏿ᗘㄽⓗගᏛศ๭ࡢᶵᵓゎ᫂࡜ྜᡂ໬Ꮫⓗᛂ⏝
Mechanism elucidation of hydrolase-catalyzed kinetic resolution and its
synthetic applications‫ۑ‬㉥஭ ࿘ྖࠊ∾㔝 㞞⩏㸦኱㜰኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲⛉㸧1◊✲┠ⓗᙜ◊✲ࢢ࣮ࣝࣉ࡛ࡣࡇࢀࡲ࡛ࠊຍỈศゎ㓝⣲ࣜࣃ࣮ࢮ࡜ࠊ⊂⮬࡟㛤Ⓨࡋࡓ࣓ࢯ࣏࣮ࣛࢫࢩࣜ࢝ᢸᣢࣂࢼࢪ࣒࢘ゐ፹㸦VMPSࠊᅗ 1A㸧ࢆ⤌ࡳྜࢃࡏࡓືⓗ㏿ᗘㄽⓗගᏛศ๭㸦DKR㸧ࢆ㛤Ⓨࡋ࡚ࡁࡓ㹙Angew. Chem. Int.
Ed. 2006, 45, 2592; Angew. Chem. Int. Ed. 2013, 52, 3654; Green Chem. 2017, 19, 411; Angew. Chem. Int. Ed. 2018,57, 10278 ௚ከᩘ㹛ࠋᮏ DKR ἲࡣධᡭᐜ᫆࡞ࣛࢭ࣑య࢔ࣝࢥ࣮ࣝࢆ࡯ࡰ 100%ࡢ཰⋡࡛ගᏛάᛶయ࡬࡜ኚ᥮࡛
ࡁࠊ᧯సࡶᴟࡵ࡚⡆౽࡛࠶ࡿࡓࡵࠊᐇ⏝ᛶࡢ㧗࠸ᡭἲ࡛࠶ࡿ㸦ᅗ 1B㸧
ࠋ୍᪉࡛㓝⣲࡜ᅛ┦ゐ፹ࢆే⏝ࡍࡿᮏᡭἲࡣࠊゐ፹ศᏊࡀᕧ኱࠿ࡘ୙ᆒ୍⣔࡞཯ᛂ࡛࠶ࡿࡓࡵࠊ㏻ᖖࡢศගᏛⓗᡭἲ࡟ࡼࡿ཯ᛂᶵᵓࡸ❧యไᚚࡢ࣓࢝ࢽࢬ࣒ࡢゎᯒࡀᅔ㞴࡛࠶ࡾࠊ࠸ࡲࡔヲ⣽ࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋᮏᡭἲࢆ୍⯡ᛶࡢ㧗࠸୙ᩧྜᡂἲ࡜
ࡋ࡚☜❧ࡍࡿࡓࡵ࡟ࡣࠊVMPS ࡟ࡼࡿࣛࢭ࣑໬ࡢᶵᵓゎ᫂࠾ࡼࡧࠊVMPS ࡢゐ፹ᵓ㐀ࡀࣛࢭ࣑໬άᛶ࡟ཬࡰ
ࡍᙳ㡪ࡢゎ᫂ࡀ୙ྍḞ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊᙜࢢ࣮ࣝࣉࡀ᭱㏆ሗ࿌ࡋࡓ VMPS ࡜ࣜࣃ࣮ࢮࢆే⏝ࡍࡿࣉࣟࣃ
ࣝࢠࣝ࢔ࣝࢥ࣮ࣝࡢ DKR㹙S. Kawanishi, S. Oki, D. Kundu, S. Akai, Org. Lett., 2019, 21, 2978㹛࡟ࡘ࠸࡚ࠊィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢ᪋タࢆ฼⏝ࡋࡓ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾヲ⣽࡞཯ᛂᶵᵓࡢゎᯒࢆ⾜ࡗࡓࠋᅗ 1. VMPS ࡢᵓ㐀㸦A㸧࡜ VMPS㸭ࣜࣃ࣮ࢮࡢඹྠゐ፹࡟ࡼࡿືⓗ㏿ᗘㄽⓗගᏛศ๭㸦B㸧

2◊✲᪉ἲࠊィ⟬᪉ἲ
VMPS ࢆ㔞Ꮚ໬Ꮫィ⟬࡛ᢅ࠺ࡓࡵ࡟ࠊάᛶ୰ᚰࡢᵓ㐀ࢆᢳฟࡋ⡆␎໬ࡋࡓࣔࢹࣝ໬ྜ≀A ࢆ⏝࠸࡚཯ᛂᶵᵓࡢゎᯒࢆ⾜ࡗࡓࠋࣛࢭ࣑໬㑄⛣≧ែࡢ᥈⣴࡟ࡣ Gaussian ࣉࣟࢢ࣒ࣛ
09 ࠾ࡼࡧ 16 ࡢᐦᗘỗ㛵ᩘ㸦DFT㸧ἲࢆ⏝࠸ࡓࠋỗ㛵ᩘ࡟ࡣ B3LYP-D3ࠊᇶᗏ㛵ᩘ࡟ࡣ
6-31+G(d)ࢆ⏝࠸ࠊSi ࠾ࡼࡧ V ࡟ᑐࡋ࡚ࡣ Lanl2DZ ࢆ౑⏝ࡋࡓࠋᚓࡽࢀࡓ㑄⛣≧ែ࡟ᑐࡋ
GRRM14 ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ SADDLE ィ⟬࡜ Intrinsic Reaction Coordination㸦IRC㸧ィ⟬ࢆ⾜࠸ࠊࣛࢭ࣑໬ࡢ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋ- 372 -

3◊✲ᡂᯝࣉࣟࣃࣝࢠࣝ࢔ࣝࢥ࣮ࣝ  1 ࡢ '.5 ࡣࠊ9036 ࡜ࡢࣂࢼࢪࣥ㓟࢚ࢫࢸࣝ I ᙧᡂ࡟ࡼࡿࣛࢭ࣑໬࡜ࠊ

ࣜࣃ࣮ࢮ࡟ࡼࡿගᏛศ๭ࢆక࠺࢔ࢩࣝ໬ࡢ㐣⛬࡛ᵓᡂࡉࢀࡿ㸦ᅗ 㸧ࠋࡲࡓࠊI ࡀࣛࢭ࣑໬ࡍࡿ㝿࡟ >@㌿఩ࢆ⤒࡚୙㣬࿴࢔ࣝࢹࣄࢻ 3 ࡀ๪⏕ࡍࡿࠋᮏ◊✲࡛ࡣ๪཯ᛂࡢ>@㌿఩ࢆᢚไࡋ࡚⏕ᡂ≀ 2 ࡢ཰⋡ࢆྥୖࡉࡏࡿࡓࡵࡢᣦ㔪ࢆᚓࡿࡇ࡜ࢆ┠ⓗ࡟ࠊࣛࢭ࣑໬㐣⛬࡜>@㌿఩࡟ࡘ࠸࡚ ')7 ィ⟬࡟ࡼࡿゎᯒࢆ⾜ࡗࡓࠋᙜึࠊ9036 ゐ፹࡟ࡼࡿ࢔ࣝࢥ࣮ࣝ 1 ࡢࣛࢭ࣑໬ࡣࣉࣟࣃࣝࢠࣝ࢝ࢳ࢜ࣥ III ࢆ⤒⏤ࡍࡿࡶࡢ࡜᝿ᐃ
ࡋ࡚࠸ࡓࠋࡋ࠿ࡋ ')7 ィ⟬ࡢ⤖ᯝࠊ&±2 ⤖ྜ㛤⿣ࡢ㑄⛣≧ែࡣᚓࡽࢀࡎࠊ⤖ྜࡢ㛤⿣࡜ᙧᡂࡀ༠ዌⓗ࡟㐍⾜ࡍࡿ㑄⛣≧ែ IV ࢆ⤒࡚ࣛࢭ࣑໬ࡀ㐍⾜ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡲࡓࠊ')7 ィ⟬࡟ࡼࡗ࡚⁐፹ຠᯝࡸⰾ㤶⎔ୖࡢ⨨᥮ᇶຠᯝࢆ᳨ウࡋࡓ⤖ᯝࠊ>@㌿఩࡟ᑐࡋ࡚ࣛࢭ࣑໬ࢆඃඛࡉࡏࡿ࡟ࡣ㠀㓄఩ᛶࡢ㧗ᴟᛶ⁐፹ࡀ㐺ࡋ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡍࡿ⤖ᯝࢆᚓࡓࠋ

ᅗ 2. VMPS㸭ࣜࣃ࣮ࢮ࡟ࡼࡿࣉࣟࣃࣝࢠࣝ࢔ࣝࢥ࣮ࣝࡢ DKR

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ཱྀ㢌Ⓨ⾲‫ۻ‬ගᏛάᛶࣉࣟࣃࢠࣝ࢔ࣝࢥ࣮ࣝࡢࣛࢭ࣑໬཯ᛂᶵᵓࡢィ⟬⛉Ꮫⓗゎᯒࠐ∾㔝 㞞⩏ࠊ㥖ᕝ ᫴㍜ࠊ㮵ཪ ႛᖹࠊ஭ᕝ ㈗モࠊ㉥஭ ࿘ྖ➨ 70 ᅇ᪥ᮏ⸆Ꮫ఍㛵すᨭ㒊኱఍ࠊ࢜ࣥࣛ࢖ࣥ㛤ദ㸦2020 ᖺ 10 ᭶ 10 ᪥㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬M. Makino, S. Komagawa, K. Kanomata, T. Ikawa, S. Akai, manuscript in preparation.

- 373 -

Ẽ┦ศᏊࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜ศᏊ㛫┦஫స⏝ࡢ⌮ㄽⓗゎᯒ࡜࣮ࣞࢨ࣮ศග◊✲Theoretical and laser spectroscopic investigations of structures andintermolecular interactions of molecular clusters: Structural analysis
and reaction path search calculations of molecular clusters‫ۑ‬ᯇ⏣ Ḡஅ, ⸨஭ ᮒ㫽, ๓ᒣ ಇᙪ, Ᏻᮏ ෽, ᪂ᾏ Ꮥὒ ᖹ㔝 ⿱ኴ㑻㸦ᮾ໭኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉໬Ꮫᑓᨷ㸧1◊✲┠ⓗࠊෆᐜ
ศᏊࡸࢡࣛࢫࢱ࣮ࡢ࢖࢜ࣥ໬࡟ࡼࡗ࡚ㄏ㉳ࡉࢀࡿ␗ᛶ໬཯ᛂࡸゎ㞳཯ᛂ࡟ࡘ࠸࡚ࠊ㉁㔞ศᯒࠊࢧ࢖ࢬ㑅ู࣮ࣞࢨ࣮ศගࠊ࠾ࡼࡧ㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ཯ᛂ⤒㊰᥈⣴࡟ࡼࡿ◊✲ࢆᒎ㛤ࡋ࡚ࡁࡓࠋศᏊࡸࢡࣛࢫࢱ࣮ࡢ
࢖࢜ࣥ໬ㄏ㉳཯ᛂࡢ⌮ゎࡣࠊ㉁㔞ศᯒࡸᨺᑕ໬Ꮫศ㔝࡛㉳ࡇࡿ࢖࢜ࣥ໬㐣⛬࡟࠾ࡅࡿ␗ᛶ໬ࡸゎ㞳ࡢᚤどⓗ⌮ゎ࡟ࡘ࡞ࡀࡿࠋࡑࢀࡽࡢ⌮ゎࢆ┠ᶆ࡜ࡋ࡚ࠊศᏊࡸࢡࣛࢫࢱ࣮ࡢ࣮ࣞࢨ࣮ศගࢆ⾜࠺࡜࡜ࡶ࡟ࠊ⮬↛⛉Ꮫ◊✲ᶵᵓᒸᓮඹ㏻◊✲᪋タィ⟬ᶵࢆ฼⏝ࡋ࡚㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃᵓ㐀᭱㐺໬ࠊ᣺ືィ⟬ࠊNatural Bond
Orbital (NBO)ィ⟬ࠊglobal reaction route mapping (GRRM)ἲ[1]࡟ࡼࡿ཯ᛂ⤒㊰᥈⣴࡞࡝ࡢ㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗࡓࠋࡑࢀࡽ࡟ࡼࡾࠊ2-࣌ࣥࢱࣀࣥࡢ࢖࢜ࣥ໬࡟ࡼࡗ࡚ㄏ㉳ࡉࢀࡿ McLafferty ㌿఩࡟࠾࠸࡚⏕ᡂࡉࢀࡿ࢚ࣀ࣮
ࣝ୰㛫యࢆࡣࡌࡵ࡚ศගᏛⓗ࡟ほࡋࠊࡑࡢ␗ᛶ໬࠾ࡼࡧゎ㞳㐣⛬ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓ┤㙐࢔ࣝ࢝ࣥࡢ஧

㔞యṇ࢖࢜ࣥࡢᵓ㐀࡜ศᏊ㛫┦஫స⏝ࠊ࠾ࡼࡧ୰ᛶࣀࢼࣥ࡜Ỉࢡࣛࢫࢱ࣮ࡢศᏊ㛫┦஫స⏝࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 16 ࣉࣟࢢ࣒ࣛࢆ฼⏝ࡋ࡚ࠊᵓ㐀᭱㐺໬ࠊ᣺ືィ⟬ࠊNBO ィ⟬ࠊIntrinsic Reaction Coordinate (IRC) ィ⟬ࢆ⾜ࡗࡓࠋ཯ᛂ⤒㊰᥈⣴࡟ࡣࠊGRRM ἲ[1]ࢆ⏝࠸࡚᥈⣴ࢆ⾜ࡗࡓࠋ࢖࢜ࣥ໬ㄏ㉳཯ᛂࡢ᥈⣴࡛ࡣࠊࡲࡎᆶ
┤࢖࢜ࣥ໬ᵓ㐀࡟ࡘ࠸࡚ IRC ィ⟬ࢆ⾜࠸ࠋIRC ィ⟬࡛ᚓࡽࢀࡓṇ࢖࢜ࣥࡢᏳᐃᵓ㐀ࢆ཯ᛂ⤒㊰᥈⣴ࡢ㉳Ⅼ࡜ࡋ ࡚ GRRM ἲ ࡟ ࡼ ࡿ ཯ ᛂ ⤒ ㊰ ᥈ ⣴ ࢆ ⾜ ࡗ ࡓ ࠋ
FMO-PIEDA ࡟ࡼࡿ┦஫స⏝࢚ࢿࣝࢠ࣮ࡢゎᯒ࡟
ࡣࠊGAMESS-2018Sep30R3 ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

1) 2-࣌ࣥࢱࣀࣥࡢ࢖࢜ࣥ໬㐣⛬࡟࠾ࡅࡿ
McLafferty ㌿఩ࡢศගᏛⓗ◊✲
McLafferty ㌿఩ࡣࠊJ఩ࡢⅣ⣲(&J)࡟Ỉ⣲ཎᏊࢆᣢࡘࢣࢺࣥࡢ࢖࢜ࣥ໬࡟࠾࠸࡚ほࡉࢀࡿࠊ࢚ࣀ࣮ࣝ

໬ࢆక࠺ゎ㞳ᶵᵓ࡛࠶ࡿࠋ>@McLafferty ㌿఩࡟ࡘ࠸ᅗ 1 ࢖࢜ࣥ໬ࡉࢀࡓ 2-࣌ࣥࢱࣀࣥࡢ㉥እࢫ࣌ࢡࢺ

࡚ࠊࡇࢀࡲ࡛ከࡃࡢ㉁㔞ศᯒ◊✲ࡀ⾜ࢃࢀ࡚ࡁࡓࡀࠊ ࣝ࡜ᅗ୰ࡢ 2-࣌ࣥࢱࣀࣥࡢ࢚ࣀ࣮ࣝṇ࢖࢜ࣥࡢᏳᐃ
ศගᏛⓗ࡞◊✲౛ࡣ࡞࠿ࡗࡓࠋᮏ◊✲࡛ࡣࠊᵓ㐀࡟ࡘ࠸࡚ィ⟬ࡉࢀࡓ᣺ືࢫ࣌ࢡࢺࣝ

- 374 -

McLafferty ㌿఩࡟࠾ࡅࡿ␗ᛶ໬཯ᛂࡢ⌮ゎࢆ┠ⓗ࡜ࡋ࡚ࠊJ఩࡟࣓ࢳࣝᇶࢆᣢࡘ᭱ࡶ༢⣧࡞ࢣࢺ࡛ࣥ࠶ࡿ ࣌ࣥࢱࣀࣥࢆᑐ㇟࡜ࡋ࡚┿✵⣸እග࢖࢜ࣥ໬᳨ฟ㉥እゎ㞳ศගἲࢆ⏝࠸࡚ࠊ୰ᛶ࠾ࡼࡧṇ࢖࢜ࣥࡢ㉥እศග࡜㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗࡓࠋᅗ  ࡟ࠊ࣌ࣥࢱࣀࣥṇ࢖࢜ࣥࡢᐇ
࢖࢜ࣥ࡟ࡘ࠸࡚ィ⟬ࡋࡓ᣺ືࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋᐇ⦰᣺ືࣂࣥࢻࢆほࡢ㉥እࢫ࣌ࢡࢺࣝ࡜ᅗ୰ࡢᏳᐃ࡞࢚ࣀ࣮ࣝᆺ

ࡢࢫ࣌ࢡࢺࣝ࡟ࡣࠊ&+ ఙ⦰᣺ືࣂࣥࢻ࡜࡜ࡶ࡟ 2+ ఙࡉࢀࡓࠋࡇࡢ⤖ᯝࡣ࢖࢜ࣥ໬ࡉࢀࡓ࣌ࣥࢱࣀࣥ࡟࠾࠸࡚ࠊ&+ ࠿ࡽࡢỈ⣲ཎᏊࡢ⛣ື࡟ࡼࡿ࢚ࣀ࣮ࣝ໬ࡀ㉳ࡁ࡚࠸ࡿࡇ࡜ࢆ♧ࡍࠋࡇࡢࡼ࠺࡟ McLafferty ㌿⛣࡟ࡼࡗ࡚⏕ᡂࡉࢀࡿ࢚ࣀ࣮ࣝṇ࢖࢜ࣥࢆศගᏛⓗ࡟ࡣࡌࡵ࡚ほࡋࡓࠋࡇࡢ㉥እศගࡢ⤖ᯝ࡜࡜ࡶ࡟㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ཯ᛂ⤒㊰᥈⣴࡟ࡼࡾࠊ2-࣌ࣥࢱࣀࣥࡢ࢖࢜ࣥ໬࡟࠾ࡅࡿ McLafferty ㌿⛣ࡢẁ㝵ⓗ࡞␗ᛶ໬࡜ࡑࡢᚋࡢゎ㞳㐣⛬ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
2) ࡑࡢ௚
ୖグ࡜ྠᵝ࡟㉥እศග࡜㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾࠊࣉࣟࣃࣥࢪ࣮࢜ࣝࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂࠊ࣌ࣥࢱࣥࢆ
ྵࡴ࢔ࣝ࢝ࣥ஧㔞యṇ࢖࢜ࣥࡢᵓ㐀ゎᯒࠊ୰ᛶࣀࢼࣥ࡜Ỉࡢ┦஫స⏝࡟ࡘ࠸࡚ࡢ◊✲ࡀ⥅⥆୰࡛࠶ࡿࠋ

ཧ⪃ᩥ⊩ >@  .2KQRDQG60DHGD&KHP3K\V/HWW.2KQRDQG60DHGD-3K\V&KHP$60DHGDDQG.2KQR-3K\V&KHP$  >@  1001LEEHULQJ-$P6RF
0DVV6SHFWURP  

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ ࣥ࢝ࣝ࢔  ۻ‬2 㔞యṇ࢖࢜ࣥ࡟࠾ࡅࡿỈ⣲ศᏊ⬺㞳๓㥑యࡢ㉥እศග◊✲:ศᏊ㛫 H-H ‽ඹ᭷⤖ྜࡢᙧᡂࠊᏳᮏ෽ࠊᯇ⏣Ḡஅࠊ⸨஭ᮒ㫽ࠊ➨ 14 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019 ᖺ 9 ᭶‫   ۻ‬,QIUDUHGVSHFWURVFRSLFREVHUYDWLRQRIWKH0F/DIIHUW\UHDUUDQJHPHQWLQLRQL]HGSHQWDQRQH<RVKL\XNL0DWVXGD
5\R<DVXPRWR$VXND)XMLL,QWHUQDWLRQDO6\PSRVLXPRQ0ROHFXODU6SHFWURVFRS\ᖺ᭶ Ⓨ⾲ணᐃ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫   ۻ‬,QIUDUHG VSHFWURVFRSLF REVHUYDWLRQ RI WKH 0F/DIIHUW\ UHDUUDQJHPHQW LQ LRQL]HG SHQWDQRQH 5 <DVXPRWR <
0DWVXGD$)XMLL3K\V&KHP&KHP3K\V  ‫  ۻ‬0LJUDWLRQV DQG FDWDO\WLF DFWLRQ RI ZDWHU PROHFXOHV LQ WKH LRQL]HG IRUPDPLGH +2  FOXVWHU < 0DWVXGD <+LUDQR60L]XWDQL'6DNDL$)XMLL60DHGD.2KQR-3K\V&KHP$    8QGHUVWDQGLQJ)HUPLUHVRQDQFHVLQWKHFRPSOH[YLEUDWLRQDOVSHFWUDRIWKHPHWK\OJURXSVLQPHWK\ODPLQHV45 +XDQJ7(QGR60LVKUD%=KDQJ/:&KHQ$)XMLL/-LDQJ*13DWZDUL<0DWVXGD-/.XR3K\V &KHP&KHP3K\V  ‫   ۻ‬6HPLFRYDOHQWERQGHGSHQWDQHGLPHUFDWLRQZKLFKLVDUHDFWLRQLQWHUPHGLDWHRIFRXSOLQJUHDFWLRQV7(QGR<
0DWVXGD5<DVXPRWR$)XMLL.7DNDKDVKL ᇳ➹୰‫   ۻ‬0LJUDWLRQVDQGFDWDO\WLFDFWLRQRIZDWHUPROHFXOHVLQWKHLRQL]HGIRUPDPLGH +2 FOXVWHU ௬㢟 <0DWVXGD<+LUDQR$)XMLL 㔞Ꮚ໬Ꮫィ⟬ࢆᐇ⾜୰‫   ۻ‬,5VSHFWURVFRSLFLQYHVWLJDWLRQRISURSDQGLROFDWLRQRQLWVDFLGLF&+ERQG ௬㢟 <0DWVXGD$0DWVXXUD++DULJD\D$)XMLL ◊✲ࡀ㐍⾜୰‫   ۻ‬,5VSHFWURVFRSLFVWXG\RIDONDQHGLPHUFDWLRQV ௬㢟 5<DVXPRWR<0DWVXGD$)XMLL ◊✲ࡀ㐍⾜୰

- 375 -

㧗ᴟᛶᾮᬗ໬ྜ≀ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ 2
Molecular Dynamics Simulation of Highly Polar Liquid Crystalline
Compounds 2żዟᮧὈᚿ㸦஑ᕞ኱Ꮫඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧◊✲┠ⓗ᭱㏆ࠊᡃࠎࡣࢪ࢜࢟ࢧࣥᇶࢆ᭷ࡍࡿࣇࢵ⣲⣔ᮦᩱ࡛࠶ࡿ ',2 )LJ ࡀࠊẚㄏ㟁⋡ࡀ⣙  ࢆ♧ࡍᾮᬗ┦࡛࠶ࡿࠕ03 ┦ࠖࢆⓎ⌧ࡍࡿᾮᬗᮦᩱ࡛࠶ࡿࡇ࡜ࢆぢฟ
ࡋࠊ'6&ᐃࠊ೫ග㢧ᚤ㙾ほᐹࠊ;5'ᐃࠊศᴟ཯㌿㟁ὶᐃࠊ6+*ᐃࠊㄏ㟁⦆࿴

ᐃࢆ㥑౑ࡍࡿࡇ࡜࡛ࠊ୍ぢࢿ࣐ࢳࢵࢡ┦ࡢࡼ࠺࡟᣺ࡿ⯙࠺ 03 ┦ࡀ཯㌿ᑐ⛠ᛶࡢ◚ࢀࡓᴟᛶᵓ㐀ࢆࡶࡘᙉㄏ㟁ᛶᾮᬗ࡛࠶ࡿ࡜ᥦၐࡋࡓ  ࠋ᭱㏆ୡ⏺୰࡛㢮ఝࡍࡿᾮᬗࡀぢฟࡉࢀ࡚࠾ࡾࠊ

Fig. 1 C3DIO ࡢ໬Ꮫᵓ㐀ᘧ࡜ MD ࢩ࣑࣮ࣗࣞࢩࣙ

ࡇࢀࡽࡢᾮᬗ┦ࡣᙉㄏ㟁ࢿ࣐ࢳࢵࢡ┦࡜࠸࠺᪂ࡋ࠸ᾮ

࡛ࣥࡢ඲ཎᏊࣔࢹࣝ

ᬗ┦࡛࠶ࡿࡇ࡜ࡀㄆࡵࡽࢀࡘࡘ࠶ࡿࠋ௒ᚋࠊ',2 ࡀ♧ࡍᕧ኱ศᴟ≉ᛶࢆ⏝࠸ࡓḟୡ௦ᾮᬗࢹ࢕ࢫࣉࣞ࢖ࠊ࢟
ࣕࣃࢩࢱ࣮ࠊㄏ㟁࢔ࢡࢳ࢚࣮ࣗࢱ࡞࡝ࠊ᪂ࡋ࠸ᶵ⬟ᮦᩱ࡬ࡢᛂ⏝ࡀྍ⬟࡟࡞ࡿ࡜ᮇᚅࡉࢀࠊከᩘࡢ௻ᴗ࡜ࡢ
ඹྠ◊✲ࢆ✚ᴟⓗ࡟᥎㐍ࡋ࡚࠸ࡿࠋࡋ࠿ࡋࠊ࡞ࡐ³',2ࡢศᏊᵓ㐀´ࡔ࡜ᙉㄏ㟁ࢿ࣐ࢳࢵࢡ┦ࡀⓎ⌧ࡍࡿࡢ࠿ࠊ
',2 ࡢ≉Ṧ࡞ศᏊᙧ≧࠿ࠊᒁᡤⓗ࡞ศᏊ㛫┦஫స⏝࠿ࠊ࠶ࡿ࠸ࡣ୧⪅ࡢ༠ྠຠᯝ࡟ࡼࡿࡶࡢ࠿඲ࡃゎ࡛᫂ࡁ࡚࠸࡞࠸ࠋ ᖺᗘᚋᮇ࡟ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢ᪋タ฼⏝% ࡛᥇ᢥࡋ࡚࠸ࡓࡔࡁࠊ',2  ศᏊࠊ඲ཎᏊᩘ⣙Fig. 2 ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ィ⟬ࡉࢀࡓ DIO1728 ศᏊ࡛ᵓᡂࡉࢀࡿࢩࢫࢸ࣒ࡢ␗࡞ࡿ ᗘ࡟࠾ࡅࡿ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(p2)ࡢ₇⟬᫬㛫౫Ꮡᛶࠋ ୓ಶ࡟ࡼࡿ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ
᪋ࡋࠊ㠀ᾮᬗ≧ែ࠿ࡽ␗࡞ࡿ

ᗘ࡛ᾮᬗ┦ࡢⓎ⌧ࢆヨࡳࡓ࡜ࡇࢁࠊᾮᬗ┦ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥᑐ
㇟࡜ࡋ࡚ࡣ㞴ࡋ࠸኱ࡁ࡞ศᏊ࡛࠶ࡿ࡟ࡶಀࢃࡽࡎࠊᐇ
㦂ⓗ࡟ᾮᬗ┦ࢆ♧ࡍᗘ㡿ᇦ࡟࠾࠸࡚ࠊᾮᬗࡢ㓄ྥᗘࢆ⾲ࡍ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮6 S ࡀቑ኱ࡋ )LJ  ࠊ཰᮰ࡋࡓ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮ࡢ

ᗘ౫Ꮡᛶࢆࣉࣟࢵࢺ

ࡋࡓ⤖ᯝࠊࢿ࣐ࢳࢵࢡ┦ࡢ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮6 S࡜ྠᵝࡢ≉ᚩࡢ

ᗘ౫Ꮡᛶࢆ♧ࡍ࡜ඹ࡟ࠊᐇ㦂ⓗ࡞ᾮᬗ┦➼᪉┦㌿⛣Ⅼ 71, ࡜ࡢᗘࡢࢬࣞࡀ ႏ⛬ᗘ࡜ᑠ

Fig. 3 ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ィ⟬ࡉࢀࡓ DIO1728 ศᏊ࡛ᵓᡂࡉࢀࡿࢩࢫࢸ࣒ࡢ
࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(p2)ࡢ ᗘ౫ᏑᛶࠋTNIࡣᐇ㦂ⓗ࡟ ᐃࡉࢀࡓ DIO ࡢᾮᬗ┦-➼᪉┦㌿⛣Ⅼ- 376 -

ࡉ࠸ㄗᕪ࡛ᾮᬗ┦➼᪉┦㌿⛣Ⅼࢆィ⟬ᶵୖ࡛෌⌧ࡍࡿࡇ࡜࡟ᡂຌࡋࡓ )LJ  ࠋ୍᪉࡛ࠊ₇⟬⤖ᯝ࠿ࡽᚓࡽࢀࡓ
ᾮᬗ┦ࡣ ',2 ࡢ 03 ┦≉᭷ࡢ཯㌿ᑐ⛠ᛶࡢ◚ࢀ࡟ࡼࡿ⮬Ⓨศᴟࢆព࿡ࡍࡿ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮6 S ࡢቑ኱ࡣ☜ㄆࡉࢀ࡚࠾ࡽࡎ )LJ  ࠊᙉㄏ㟁ࢿ࣐ࢳࢵࢡᾮᬗࢆィ⟬ᶵୖ࡟෌⌧ࡍࡿ࡜࠸࠺ᮏ◊✲ࡢ┠ᶆࡣᐇ⌧ࡉࢀ࡚࠸࡞࠸ࠋ
ᾮᬗศᏊࡢྥࡁࡢ཯㌿ࢲ࢖ࢼ࣑ࢡࢫࢆ☜ㄆࡍࡿࡓࡵࠊ
㓄ྥ࣋ࢡࢺࣝࡀ࡯ࡰ ; ㍈᪉ྥ࡟ᙧᡂࡉࢀࡓᾮᬗ⣔ )LJ࡟࠾࠸࡚ࠊ; ㍈࡟ᑐࡍࡿ⣔࡟ྵࡲࢀࡿ  ศᏊࡢ㓄ྥࡢ཯㌿ࡢ㢖ᗘࢆ☜ㄆࡋࡓࠋࡑࡢ⤖ᯝࠊ)LJ  ࡟♧ࡍᵝ࡟ ;Fig. 4 ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ィ㍈࡟ᑐࡍࡿゅᗘࡀ࡯ࡰ཯㌿ࡍࡿศᏊࡀぢࡘࡅࡽࢀࡓࠋࡋ

⟬ࡉࢀࡓ DIO1728 ศᏊ࡛ᵓᡂࡉࢀࡿࢩࢫࢸ࣒࡟

࠿ࡋࠊࡑࡢ㢖ᗘࡣ QV ₇⟬ࡋࡓ  ศᏊ࠶ࡓࡾ  ᅇ࡛

࠾ࡅࡿࠊ360Υ࡛⏕ᡂࡉࢀࡓࢿ࣐ࢳࢵࢡᾮᬗⓗ࡞࠶ࡾࠊᾮᬗ≧ែ࡟࠾ࡅࡿศᏊࡢྥࡁࡢᣢ⥆᫬㛫ࡣ㓄ྥࢆ཯ᫎࡍࡿ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(p2)࡜ࠊ

î QV ࡜ศᏊືຊᏛィ⟬ࡢ₇⟬᫬㛫ࡼࡾࡶ཯㌿ᑐ⛠ᛶࡢ◚ࢀ࡟ࡼࡿ⮬Ⓨศᴟࢆ཯ᫎࡍࡿ࢜

㛗࠸ࡇ࡜ࠊࡍ࡞ࢃࡕࣛࣥࢲ࣒࡞≧ែ࠿ࡽ⮬Ⓨⓗ࡟ᙉㄏ㟁࣮ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(p1)ࡢ₇⟬᫬㛫౫Ꮡᛶࠋࢿ࣐ࢳࢵࢡᾮᬗࢆ෌⌧ࡍࡿ࡟ࡣ₇⟬᫬㛫ࡀ኱ᖜ࡟㊊ࡾ࡞࠸࡜᝿ᐃࡉࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
ᮏ◊✲࡛ࡣࠊ௨ୖࡢ≧ἣࢆ㋃ࡲ࠼࡞ࡀࡽࠊᘬࡁ⥆ࡁ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥἲࢆ⏝࠸࡚ࠊ03 ┦ࢆィ⟬ᶵୖ࡟෌⌧ࡋࠊศᏊ㛫࡟㟁Ẽⓗ࡞᩺ຊࡀ᝿ᐃࡉࢀࡿ࡟
ࡶಀࢃࡽࡎࠊఱᨾ ',2 ศᏊࡔ࡜ศᏊศᴟࡀᥞࡗ࡚ᕧどⓗ࡟཯㌿ᑐ⛠ᛶࡀ◚ࢀࡿࡢ࠿ࠊࡑࡢᶵᵓࡢゎ᫂ࢆ┠ᣦࡋࡓࠋ

Fig. 5 ₇⟬࡟ࡼࡾࢿ࣐ࢳࢵࢡᾮᬗࢆⓎ⌧ࡋࡓ≉࡟௒ᖺᗘࡣ཯㌿ᑐ⛠ᛶࡢ◚ࢀලྜࡀ␗࡞ࡿᾮᬗ┦ࢆᙉ

1728 ಶࡢ DIO ศᏊไⓗ࡟ィ⟬ᶵୖ࡟෌⌧ࡍࡿࡇ࡜ࢆヨࡳࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡣศᏊ㞟ྜయࡢືⓗᵓ㐀ࢆཎᏊ࡛ࣞ࣋ࣝ෌⌧ࡍࡿᴟࡵ࡚᭷ຠ࡞ᡭἲ࡛࠶ࡾࠊ₇⟬㏿ᗘࡢྥୖ࡟కࡗ࡚ཎᏊᩘ  ୓ࢆ㉸ࡍ⣔࡬ࡶᗈࡃ㐺⏝ࡉࢀࡘࡘ࠶ࡿࠋࡇࡢࡇ࡜ࡣࠊ㉸ศᏊࡸᾮᬗ࡜࠸ࡗࡓከࡃ
ࡢศᏊ㛫ࡢ」㞧࡞┦஫స⏝࡟ᇶ࡙࠸ࡓඹྠⓗ࡞⮬ᕫ⤌⧊

Fig. 6 360Υ࡛ DIO ࡀࢿ࣐ࢳࢵࢡᾮᬗࢆⓎ⌧ࡋࡓ໬ࡢᶵᵓࢆゎ᫂ࡍࡿࡢ࡟ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡀ᫬࡟ࠊDIO ศᏊ 1 ศᏊࡢ㛗㍈ࡢྥࡁࡀ X ㍈࡟ᑐ฼⏝ྍ⬟࡟࡞ࡗ࡚ࡁࡓࡇ࡜ࢆព࿡ࡍࡿࠋᮏ◊✲࡛ࡣẚㄏࡋ࡚཯㌿ࡋࡓ౛ࠋࡇࡢࡼ࠺࡞཯㌿ࡀほᐹࡉࢀࡿ㟁⋡ࡀ㸯୓ࢆ㉸࠼ࡿᴟࡵ࡚≉Ṧ࡞ᾮᬗᮦᩱࡢ≀ᛶⓎ⌧ᶵ㢖ᗘࡣ 600 ns ࡢ₇⟬࡛⣙ 10%ࠋᵓࡢゎ᫂ࢆ┠ᣦࡋࡓࠋ ᖺᚋᮇࡢศᏊືຊᏛࢩ࣑ࣗࣞ
࣮ࢩ࡛ࣙࣥࠊᡃࠎࡣ࢔ࣝ࢟ࣝ㙐㛗ࡀ␗࡞ࡿ㸲✀㢮ࡢ ',2 ࡢ࠺ࡕࠊ₇⟬ᑐ㇟࡜ࡋ࡚᭱ࡶᐇ㦂ⓗ࡞◊✲ࡀ㐍⾜ࡋࠊ࠿ࡘ ႏ࠿ࡽ ႏ࡜ᗈ࠸

ᗘ⠊ᅖ࡛ 03 ┦ࢆⓎ⌧ࡋࡓ࢔ࣝ࢟ࣝ㙐ࡢⅣ⣲ᩘࡀ  ࡢ &',2 ࢆ㑅ᐃࡋࠊ&',2 ศᏊ  ಶࠊ⥲ཎᏊᩘ⣙  ୓࠿ࡽ࡞ࡿ⣔ࢆ  ࡘࡢ␗࡞ࡿ
⌧ࡍࡿࡢ࡜ྠࡌᗘ࡛ aQV ₇⟬ࡋࠊ',2 ࡀᐇ㝿࡟ᾮᬗ┦ࢆⓎᗘ㡿ᇦ࡛ࢿ࣐ࢳࢵࢡᾮᬗ࡜⪃࠼ࡽࢀࡿ㓄ྥ≧ែࢆィ⟬ᶵୖ࡟෌⌧ࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋࡇ

- 377 -

ࡢᾮᬗ≧ែࢆᚓࡿࡓࡵ࡟ᡃࠎࡣ ',2 ࡢ ; ⥺༢⤖ᬗゎᯒࡢࢹ࣮ࢱ࡟࠾ࡅࡿศᏊࡢ㔜ᚰ㛫㊥㞳ࢆᐇ㝿ࡢ  ಸ࡟タᐃࡋࡓึᮇ≧ែ࠿ࡽ₇⟬ࢆ㛤ጞࡍࡿࡇ࡜࡛ẚ㍑ⓗ▷᫬㛫࡛ᾮᬗ≧ែࢆᚓࡓࠋ ᖺᗘࡶࠊࡇࡢ⥲ศᏊᩘ⣙ ಶ࡜࠸࠺ࢫࢣ࣮ࣝࡣ⥅ᢎࡋࡓࠋ ᖺᗘࡢ⤖ᯝ࡛ሗ࿌ࡋࡓ㏻ࡾࠊᾮᬗ୰࡛ࡢศᏊࡢ཯㌿ࡢࢲ࢖ࢼ࣑ࢡࢫࡣ  QV ⛬ᗘ࡜㐜࠸ࡓࡵࠊィ⟬ᶵୖ࡛⮬Ⓨⓗ࡟཯㌿ᑐ⛠ᛶࡀ◚ࢀ࡚㧗ᴟᛶࡢᙉㄏ㟁ࢿ࣐ࢳࢵࢡᾮᬗࡀⓎ⌧ࡍࡿࡢࡣᅔ㞴࡛࠶ࡿࠋࡑࡇ࡛  ᖺᗘࡣึᮇ≧ែ࠿ࡽ཯㌿ᑐ⛠ᛶࡀ◚ࢀࡓࢿ࣐ࢳࢵࢡᾮᬗࡢⓎ⌧ࢆヨࡳࡿࠋࡑࡋ࡚Ⓨ⌧ࡋࡓᾮᬗ┦ࡢ⣔඲య࡛ࡢᖹᆒᐦᗘ࠾ࡼࡧࣞࢼ࣮ࢻ࣭ࢪ࣮ࣙࣥࢬ࣏ࢸࣥࢩࣕࣝࡢ⥲࿴ࡢᖹᆒ್ࢆẚ㍑ࡍࡿࡇ࡜࡛ࠊ᭱ࡶศᏊ㛫ࡢࣃࢵ࢟ࣥࢢࡀᐦ࡛࣏ࢸࣥࢩࣕࣝⓗ࡟Ᏻᐃ࡞ྥࡁࡢẚ⋡ࢆ᥈ࡾฟࡍࡇ࡜ࢆ┠ᶆ࡟ࡋࡓࠋࡑࡋ࡚ࠊ㠀ᑐ⛠࡛࣏ࢸࣥࢩࣕࣝࡀ᭱ࡶᏳᐃ໬ࡉࢀࡓ≧ែ࡟฿㐩ࡋࡓ᫬࡟ࠊ཯㌿ᑐ⛠ᛶࡀ◚ࢀ࡚࠸࡞࠸
⣔࡜ẚ㍑ࡋ࡚ࠊ཯㌿ᑐ⛠ᛶࡀ◚ࢀࡿࡇ࡜࡛Ᏻᐃ໬ࡋࡓ ',2 ࡢᾮᬗ≧ែࡀ㠀ᑐ⛠≧ែࢆᏳᐃ໬ࡉࡏ࡚࠸ࡿࡢ࠿ࠊ
ศᏊྠኈࡢ఩⨨㛵ಀࢆ⣽࠿ࡃ᳨ドࡍࡿࡇ࡜ࢆィ⏬ࡋࡓࠋᖹ⾮໬ࡍࡿࡲ࡛࡟ᚲせ࡞ィ⟬᫬㛫ࡣ QV ⛬ᗘ࡛࠶ࡿࡀࠊᐦᗘ࠾ࡼࡧ࣏ࢸࣥࢩࣕࣝࡢᖹᆒ್ࢆṇ☜࡟⟬ฟࡍࡿࡓࡵ࡟ィ⟬᫬㛫࡜ࡋ࡚ QV ࡣᚲせ࡜᝿ᐃࡋ࡚࠸
ࡓࠋ



◊✲ᡂᯝ
ࡇࢀࡲ࡛ࡢ 0' ィ⟬࡛ᚓࡓࢿ࣐ࢳࢵࢡ┦ࢆ᭦࡟ QV

0' ィ⟬ࢆ㐍ࡵࡓࡀࠊ⮬Ⓨⓗ࡞཯㌿ᑐ⛠ᛶࡢ◚ࢀࢆ♧၀
ࡍࡿ 6 S ࡢ್ࡣṤ࡝☜ㄆࡉࢀ࡞࠿ࡗࡓࠋࡇࢀࡣ᫖ᖺᗘ
ࡢ₇⟬⤖ᯝ࡛ &',2 ศᏊࡀᾮᬗ୰࡛ྥࡁࢆಖࡘᣢ⥆᫬㛫ࡀ QV ࡜ぢ✚ࡶࡽࢀࡓࡇ࡜࡜୍⮴ࡍࡿࠋ௒ᖺᗘࡣ
ᵝࠎ࡞≧ែ࡛ࡉࡽ࡟  QV ࡢ₇⟬ࢆ⾜ࡗࡓࡀ 6 S ࡢቑ኱ࡣほᐹࡉࢀࡎࠊࡇࢀ௨ୖ㛗࠸ィ⟬ࡣ⌧ᐇⓗ࡛࡞࠸࡜⪃࠼ࡽࢀࡓࡓࡵࠊᙉㄏ㟁ࢿ࣐ࢳࢵࢡ┦ࡢⓎ⌧ࢆ⮬Ⓨⓗ࡟෌⌧ࡍࡿࡇ࡜ࡣᅔ㞴࡜ุ᩿ࡋࡓࠋ
࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮ࡀኚ໬ࡋ࡞࠸Ᏻᐃ࡞ࢿ࣐ࢳࢵ
ࢡ┦࡟࠾ࡅࡿ➼ᅽ᮲௳࡛ࡢẚ㔜ࡢᦂࡽࡂࢆィ⟬ࡋࡓ⤖ᯝࠊࢿ࣐ࢳࢵࢡ┦ࢆ♧ࡍ . ࡛ࡣ  ࡜࠸࠺༢୍ࡢ್
ࢆ୰ᚰ࡟ẚ㔜ࡀᦂࡽࡄࡢ࡟ᑐࡋ࡚ࠊ᭦࡟పࡢ . ࡛ࡣẚ㔜ࡀ  ࡜  ࡜࠸࠺஧ࡘࡢ್ࡢ㛫ࢆ⾜ࡁ᮶ࡋ࡞ࡀࡽᦂࡽࡄࡇ࡜ࢆぢฟࡋࡓ )LJ ࠋᐦᗘࡢᦂࡽࡂ࡟క࠺

)LJ . D ࡜ . E ࡛ࡢ ',2 ࡟ࡼࡿࢿ࣐
ࢳࢵࢡ┦ࡢᐦᗘᦂࡽࡂ
ࡿ࡜ࠊ. ࡟ẚ࡭࡚㧗ᐦᗘ࡛࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮
ࡀᏳᐃ࡞≧ែ࡜ࠊ࣏ࢸࣥࢩࣕࣝⓗ࡟ࡣ኱ᕪ࡞࠸ࡀᐦᗘࡀ
ప࠸≧ែࢆྲྀࡿࡇ࡜ࡀศ࠿ࡗࡓ )LJ ࠋࡇࢀࡣ . ࡟࠾࠸࡚య✚ኚ໬ࢆక࠺ఱࡽ࠿ࡢ┦㌿⛣ࡀ㉳ࡇࡿࡇ࡜ࢆ

'HQVLW\JFP

ࣞࢼ࣮ࢻ࣭ࢪ࣮ࣙࣥࢬ࣏ࢸࣥࢩࣕࣝࡢኚ໬ࢆࣉࣟࢵࢺࡍ





.

.





♧၀ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࡀࠊ6 S ࡢ್࡟ኚ໬ࡀぢࡽࢀ













/HQDUG-RQHVSRWHQWLDO¼ N-PRO࡞࠿ࡗࡓࡇ࡜࠿ࡽᙉㄏ㟁ࢿ࣐ࢳࢵࢡ┦࡬ࡢ┦㌿⛣࡛ࡣ࡞࠸࡜⪃࠼ࡽࢀࠊ⤖ᬗ࡬ࡢ┦㌿⛣ࡢ๓㥑⌧㇟࡜⪃࠼ࡽࢀ

5 

5 

)LJ  ',2 ᾮᬗࡢ␗࡞ࡿ

ᗘ࡟࠾ࡅࡿᐦᗘࡢᦂ

ࡽࡂ࡟క࠺ࣞࢼ࣮ࢻ࣭ࢪ࣮ࣙࣥࢬ࣏ࢸࣥࢩࣕࣝ

ࡓࠋ

ࡢኚ໬

- 378 -཯㌿ᑐ⛠ᛶࡀ◚ࢀࡓᙉㄏ㟁ࢿ࣐ࢳࢵࢡ┦ࢆ෌⌧ࡍࡿࡓ
ࡵࠊ;5'ᐃ⤖ᯝ࠿ࡽᚓࡽࢀࡓ &',2 ศᏊࡢ୰࠿ࡽ┤⥺ⓗ࡞ᙧែࡢศᏊࢆ㑅ࡧࠊ୕ḟඖ✵㛫୰࡟ îî ศᏊࢆ㓄ิࡍࡿࡇ࡜࡛ึᮇ≧ែ࡜ࡋࡓࠋࡇࡢ᫬ࠊศᏊ㛫࡟㔜࡞ࡾࡀ⏕ࡌ࡞࠸㊥㞳ࢆ☜ಖࡍࡿࡓࡵ࡟ศᏊ㛫㊥㞳ࢆ⤖ᬗ᫬ࡢ⣙  ಸ⛬ᗘ࡟ᗈࡆࡿᚲせࡀ࠶ࡗࡓ )LJ ࠋึᮇᵓ㐀⦆࿴ィ⟬ࢆ  . ࡛  QV ⾜ࡗࡓ⤖ᯝࠊ᭱ึ࡟  ࡔࡗࡓ࣮࢜
ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮6 S ࡀ QV ᮍ‶࡜࠸࠺▷࠸᫬㛫࡛ ࡟పୗࡋࡓࠋࡇࡢ᫬ࠊ➼ᅽ࣭➼࢔ࣥࢧࣥࣈ࡛ࣝࡢ

₇⟬ࢆ⾜࠺ணᐃ࡛࠶ࡗࡓࡀṇᖖ࡟ᐇ⾜࡛ࡁࡎࠊᐃ✚᮲௳ Fig. 9 ྠ୍᪉ྥࡢศᏊࢆ 121212 ✚ᒙࡍࡿࡇ࡜
࡛ࡢ₇⟬࡛ࡋ࠿⾜࠼࡞࠿ࡗࡓࡢ࡛ࠊᅗ  ࡢᵝ࡞ᾮᬗ┦࡜ ࡛ᚓࡽࢀࡓึᮇᵓ㐀┿✵≧ែࡢ┦ศ㞳࡜࡞ࡗࡓࠋ┿✵ࡣ␯Ỉⓗ࡛࠶ࡾࠊ࢔ࣝ
࢟ࣝ㙐ᮎ➃ࡀ┿✵࡟᥋ࡋ࡚࠾ࡾࠊ⏺㠃࡟ᆶ┤㓄ྥࡍࡿഴྥ࡟࠶ࡿࡇ࡜ࡀࢫࢼࢵࣉࢩࣙࢵࢺ࠿ࡽ♧၀ࡉࢀࡓࠋࢆ .ࠊ. ࡜పᗘഃ࡟ࢩࣇࢺࡋ࡚ึᮇᵓ㐀⦆࿴ィ⟬ࢆ⾜ࡗࡓࡀࠊྠᵝ࡟➼ᅽ࣭➼࢔ࣥࢧࣥࣈ࡛ࣝࡢ₇⟬ࡀฟ᮶ࡎࠊQV ᚋࡢ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮6 S ࡣࡑࢀࡒࢀࠊ
 ࡜  ࡲ࡛ῶᑡࡋࠊ཯㌿ᑐ⛠ᛶࡀ◚ࢀࡓᾮᬗ┦ࢆ෌⌧ࡍࡿ௨๓࡟㓄ྥ≧ែࡀኻࢃࢀࠊᙉㄏ㟁ࢿ࣐ࢳࢵࢡ┦ࡢ෌⌧ࡣฟ᮶࡞࠿ࡗࡓࠋ௒ᚋࠊᙉㄏ㟁ࢿ࣐ࢳࢵࢡ┦ࢆ෌⌧
Fig. 10 ึᮇᵓ㐀⦆࿴ィ⟬ᚋ (500 K, 1ns) ࡢ 1728

ࡋࠊ᭦࡟ࡑࡢⓎ⌧ᶵᵓࢆゎ᫂ࡍࡿࡓࡵ࡟ࡣࠊ➼ᅽ࣭➼࢔ࣥࢧࣥࣈ࡛ࣝࡢ₇⟬࡟ຍ࠼࡚ࠊᙉㄏ㟁ࢿ࣐ࢳࢵࢡ┦ࡢ ಶࡢ DIO ศᏊࡢࢫࢼࢵࣉࢩࣙࢵࢺ
ᐇ⌧࡟ᚲせ࡞ศᏊᩘࡢ෌᳨ウࠊ౑⏝ࡍࡿຊሙࡢ᳨ウࠊᾮᬗ≧ែ࡛ࡢᐁ⬟ᇶࡢ఩⨨㛵ಀࢆ⤫ィⓗ࡟⌮ゎࡍࡿゎᯒ࡞࡝ࠊᡭἲ㠃࡛ࡢᨵၿࡀᚲせ࡜⪃࠼ࡽࢀࡿࠋ
Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
★Ỉᇛ ⿱ኴࠊඹ⼥⌧㇟࡟ᇶ࡙ࡃ㧗ᴟᛶᾮᬗ┦ࡢⓎ⌧ᗘ⠊ᅖࡢᣑ኱ ஑ᕞ኱Ꮫ⥲ྜ⌮ᕤᏛᗓ㔞Ꮚࣉࣟࢭࢫ

⌮ᕤᏛᑓᨷಟኈㄽᩥ  ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ


ཧ⪃ᩥ⊩

1) ³$ )OXLG /LTXLGဨ&U\VWDO 0DWHULDO ZLWK +LJKO\ 3RODU 2UGHU´ + 1LVKLNDZD . 6KLURVKLWD + +LJXFKL <
2NXPXUD<+DVHED6<DPDPRWR.6DJR+.LNXFKL$GYDQFHGPDWHULDOV  - 379 -

6+ χϟ΢ϱΝୱಝҡదͶ‫׈‬੓ԿͤΖϠοʖϓ͹֋൅'HYHORSLQJRIPRWLIZKLFKFDQDFWLYDWH6+GRPDLQDPRQRVSHFLILF
PDQQHUʕഗࠞ ٍཔਕʤ౨‫ښ‬୉ָ୉ָӅ޽ָ‫ڂݜܧ‬ՌԿָਫ਼ໍ޽ָ઒ߊʥɼϜʖζΠ ΠϨʤ౨‫ښ‬୉ָ޽ָ‫ڂݜܧ‬Ռώ΢ΨΦϱζωΠϨϱή઒ߊʥ߶͏݃߻ಝҡ੓Ν࣍ͯϨϱ࢐ԿοϫεϱϠοʖϓϘϕοχ͹υδ΢ϱ νϱϏέ࣯εϝϣϪʖεϥϱλϓφ 5RVHWWD Ν༽͏ͪυδ΢ϱɼ͕Γ; 0' εϝϣϪʖεϥϱ͹݃Վ ‫ڂݜ‬໪దɼ಼༲
‫ڂݜ‬໪ద νʖΰρφͳͤΖ 6UF+RPRORJ\GRPDLQʤҐԾ 6+ χϟ΢ϱʥͶଲ͢ͱɼୱಝҡదͶ݃߻ͤΖϨϱ࢐ԿϘϕοχ͹֋൅͗໪దͲ͍Ζɽ6+ χϟ΢ϱͺϨϱ࢐ԿοϫεϱΝ‫؜‬΋Ϙϕοχഓ྽ʤҐԾοϫεϱϠοʖϓʥͶଲͤΖ݃߻χϟ΢ϱͲ͍Εɼࡋ๖಼εήψϩఽୣ‫ߑؽ‬Ͷ͕͜Ζ෾ࢢؔ૮‫༽ࡠޕ‬ϋρφϭʖέͶ͕͜ΖΦρζΝ͖ͯ͠ʹΖकགྷ͵݃߻χϟ΢ϱͲ͍Ζɽ6+ χϟ΢ϱͺҲൢͶ෵਼͹οϫεϱϠοʖϓഓ྽ͶଲͤΖ݃߻੓Ν༙ͤΖ͞ͳ͗எΔΗͱ͕Εɼ‫ٱ‬Ͷ 6+ χϟ΢ϱͺࡋ๖಼Ͷ  झྪҐ৏͹ϓΟϝϨʖΝ༙͢ͱ͏Ζɽͨ͹ͪΌ 6+ χϟ΢ϱΝղͪ͢εήψϩఽୣͺ͞͹Γ͑͵ଡଲଡ͹૮‫༽ࡠޕ‬ϋρφϭʖέΝ‫ܙ‬੔͢ͱ͏Ζɽըʓͺ͞ΗͶଲ͢ͱɼ ͯ͹ 6+ χϟ΢ϱͳ͹Ί૮‫ͤ༽ࡠޕ‬Ζ
Γ͑͵οϫεϱϠοʖϓഓ྽Νࡠ੣ͤΖ͞ͳͲɼࡋ๖಼͹εήψϩఽୣΝਕҟదͶ੏‫͢ޜ‬ɼΑ͚Α͚ͺࡋ๖ଁ৫Ώ෾Կͳ‫ࡋͪͮݶ‬๖ӣໍΏࡋ๖‫ؽ‬೵Ν੏‫ͤޜ‬Ζ͞ͳΝ࠹शద͵໪దͳͤΖɽ‫಼ڂݜ‬༲ ౲ॵ͹‫ܯ‬ժͲͺɼνϱϏέ࣯͹෾ࢢઅ‫ܯ‬λϓφͲ͍Ζ 5RVHWWD Ν࢘͏ͪϘϕοχυδ΢ϱΝߨ͏ɼͨ͹‫ ޛ‬5RVHWWD ͹χρΫϱήεϝϣϪʖεϥϱΝ༽͏ͱɼυδ΢ϱͪ͢ഓ྽͗ଠ͹ 6+ χϟ΢ϱϓ
ΟϝϨʖͶଲͤΖ݃߻੓Ν༙ͤΖ͖ʹ͖͑Ν඲ՃͤΖͳ͏͑๏ਓͲ͍ͮͪɽ͖͢͢͞͹඲Ճ๑͗న઀Ͳ
͵͏͞ͳ͖Δɼ෾ࢢಊྙָεϝϣϪʖεϥϱʤҐԾ 0'ʥΝ༽͏ͪ݃߻༹ࣞ͹඲Ճ΃ҢߨͤΖ͞ͳͳͪ͢ɽ
ࠕյ͹νʖΰρφͳ͢ͱɼࡋ๖ଁ৫͵ʹͶ‫ؖ‬༫ͤΖ 3,.$NW ‫ܨ‬࿑Ͷ‫ؖ‬ΚΖ෾ࢢΓΕɼ3,. ͹ SD γϔϤωρφ͹͑ͬɼ1 ຦୼ଈ͹ 6+ χϟ΢ϱʤҐ‫ ޛ‬SDQ6+ʥΝમ୔ͪ͢ɽ ‫ڂݜ‬๏๑ɼ‫ࢋܯ‬๏๑઴յΉͲ͹ๅࠄͶͱɼ5RVHWWD ͹ FRXSOHGGHVLJQ>@@Ν༽͏ͱɼSDQ6+ ͶଲͤΖ߶͏݃߻੓Ν༙ͤΖϘϕοχഓ྽͹υδ΢ϱ͗‫׮‬྅͢ͱ͏Ζɽ͞͹‫ࢋܯ‬͹ͪΌͶɼ3URWHLQ'DWD%DQNʤ3'%ʥΓΕ SDQ6+
ͳ݃߻Ϙϕοχ͹‫݃ڠ‬ধߑଆ৚ๅΝखಚ͢ɼഓ྽ௗΝ $$ ΃ͳ৵ௗͪ͢ɽ͞ΗΝτϱϕϪʖφͳ͢ͱ࠹న͵ॵ‫غ‬ഓ྽Νɼ)OH[3HS'RFN DELQLWLR >@Ν༽͏ͪχρΫϱήεϝϣϪʖεϥϱͶΓΕ‫͢ࢋܯ‬ɼಚΔΗ
ͪߑଆΝ‫ݫ‬Ͷ &RXSOHGPRYHV Ν༽͏ͪഓ྽͹࠹నԿΝࢬͪ͢ɽಚΔΗͪഓ྽Ν࠸ౕχρΫϱήεϝϣϪ
ʖεϥϱ͢ɼ৏ҒηαΠ͹ߑଆ͹ͻΔͯ͘Ν඲Ճͪ͢ɽ
࣏ͶɼಚΔΗͪഓ྽͹ଠ͹ 6+ χϟ΢ϱͶଲͤΖ݃߻੓Ν඲ՃͤΖͪΌɼ֦ 6+ χϟ΢ϱ͹ 3'% ϓΟ΢ϩ஦͹Ϙϕοχഓ྽Νυδ΢ϱ͠Ηͪഓ྽Ͷรߍ͢ɼχρΫϱήεϝϣϪʖεϥϱΝߨ͏ಚΔΗͪφρϕηαΠ͹ߑଆ͹ͻΔͯ͘Νർֳͪ͢ɽ
֦Ϙϕοχ͹݃߻য়ସͶ͕͜Ζξ΢ψϝέηΝմੵͤΖͪΌɼ෾ࢢಊྙָ‫ࢋܯ‬λϓφ͹ *520$&6 >@- 380 -

Ν༽͏ͱ 0' εϝϣϪʖεϥϱΝࣰࢬͪ͢ɽྙ৖ͺ &+$500>@Ν࢘༽͢ɼब‫ڧغ‬ֆড়݇ͳ͢ͱ $͹ཱི๏ରϠυϩΝࡀ༽͢ɼ01D&O ড়݇ͳͪ͢ɽΦϋϩάʖ࠹ঘԿ͹‫ޛ‬ɼSV197 ͲฑߩԿɼ
QV137 ͲϕϫξέεϥϱϧϱΝߨͮͪɽ ‫ڂݜ‬੔Վ઴յΉͲ͹݃ՎͲɼυδ΢ϱͪ͢ഓ྽ͺ࠸ౕχρΫϱήΝߨͮͪࡏͶɼηαΠ͹߶͏χρΫϱήߑଆ͗ͤ΄ͱୱҲ͹ߑଆͶफ଍ͤΖ݃ՎͶ͵ͮͪɽΉͪ͞͹ഓ྽ͺɼ౵ԻథఈΩϫϨϟφϨʖΏ %LR/D\HU
,QWHUIHURPHWU\ ๑ͶΓΖ૮‫༽ࡠޕ‬଎ఈͶ͕͏ͱ΍ɼυδ΢ϱ઴͹ഓ྽ͳಋఖౕ͹਎࿪੓Ν༙ͤΖ͞ͳ͗ࣖ͠Ηͱ͏Ζɽ
࣏Ͷɼ਎࿪੓Ν LQVLOLFR Ͳ඲ՃͤΖͪΌͶɼχρΫϱήεϝϣϪʖεϥϱ͹݃ՎΝࢨඬͳͤΖ͞ͳΝࢾΊͪɽ͞͹໪దͳ͢ͱɼୱಝҡ੓͹֭ಚ͹ͪΌͶɼSDQ6+ Ґ֐͹ 6+ χϟ΢ϱͶଲͤΖ౲֚Ϙϕοχ͹਎࿪੓Ν඲Ճ͢ɼ݃߻੓Ν༙ͤΖ৖߻ͺͨ͹ഓ྽Ν‫ͤ٭ؼ‬Ζචགྷ͍͗ΖͪΌͲ͍Ζɽ۫ରద͵๏๑ͺɼχρΫϱήεϝϣϪʖεϥϱͶΓͮͱಚΔΗΖφρϕηαΠ͹ߑଆ͗ɼ݃߻͹‫͠ک‬ͶΓͮͱफ଍ͤ
Ζ͞ͳΝ‫غ‬ଶ͢ɼSDQ6+ ͳɼ݃߻੓͗ͤͲͶஎΔΗͱ͏Ζ͏͚͖ͯ͹Ϙϕοχ͹χρΫϱήεϝϣ
ϪʖεϥϱΝߨͮͪɽ͖ͨ͢͢͹݃Վɼྈंͺ૮‫ܐؖؖ‬Ͷ͵͏͞ͳ͗ɼ͏͚͖ͯ͹εϝϣϪʖεϥϱ͹݃Վࣖࠨ͠Ηͪɽ

ਦ 3DQ6+ ͳ  झ͹Ϙϕοχ͹χρΫϱήεϝϣϪʖεϥϱ͹݃Վ͞͹ཀྵ༟ͳ͢ͱɼχρΫϱήεϝϣϪʖεϥϱ͹݃Վ͹ɼॵ‫غ‬য়ସͶଲͤΖғଚ੓͹߶͠Ώɼͨ΍ͨ΍౲֚νϱϏέͶ͕͏ͱɼࣰࡏ͹૮‫༽ࡠޕ‬Ͷ͕͏ͱͺϘϕοχଈ͗ξ΢ψϝρέͶಊ͚͞ͳ͗༩૟͠Ηɼߑଆ҈ఈ੓Νࢨ޴ͤΖχρΫϱήεϝϣϪʖεϥϱΝ࢘༽ͤΖ͞ͳ͗న઀Ͳ͵͖ͮͪՆ೵੓͗ߡ͓ΔΗ
Ζɽ
͞͹մ݀ࡨͳ͢ͱɼ0' εϝϣϪʖεϥϱ͹ΠϱϔϪϧγϱϕϨϱήΝ༽͏ͪ݃߻਎࿪੓඲Ճ͵ʹ͹

- 381 -

घ๑͗ߡ͓ΔΗΖ͗ɼࠕյͺಚΔΗͪ‫ݳ‬েͶΓΕ஥໪͢ɼ͵ͧχρΫϱήߑଆ͗फ଍͢͵͖͖ͮͪɼͨ΍ͨ΍Ϙϕοχͳ 6+ χϟ΢ϱ͹૮‫༽ࡠޕ‬Ͷ͕͏ͱ֦࢔‫خ‬ͺʹ͹Γ͑͵ༀׄΝՎͪ͢ͱ͏Ζ͹͖ͳ͏ͮͪɼಝҡ੓ͨ͹΍͹Ͷͪ͏ͤΖཀྵմΝ਄ΌΖͳ͏͑๏޴੓Ͳ‫ڂݜ‬Ν਒ΌΖ͞ͳͳͪ͢ɽ
ͨ͹ͪΌͶɼΉͥϘϕοχ͹݃߻য়ସΝ֋఼࢟ͳͪ͢ XQELDVHG ͵ 0' εϝϣϪʖεϥϱΝߨ͏ɼχϟ΢ϱ৏Ͳ͹‫ڏ‬ಊΝ௒΄Ζ͞ͳͳͪ͢ɽ
*520$&6 Ν༽͏ͪ‫ࢋܯ‬͹݃ՎɼSDQ6+ ͳɼಋఖౕ͹਎࿪੓͍͗ΖͳஎΔΗͱ͏ΖϘϕοχ  झͺͨΗͩΗɼҐԾ͹Γ͑͵‫ڏ‬ಊΝࣖͪ͢ਦ 3DQ6+ ͳ݃߻੓Ν༙ͤΖ  झ͹Ϙϕοχ͹ 0' εϝϣϪʖεϥϱ͹݃Վɽ֦ਦͶ͕͏ͱɼࠪ
৏ʁϘϕοχ 1 ຦୼ଈɼӊ৏ʁϘϕοχસௗɼࠪ஦ஊʁS7\U Ґ֐͹Ϙϕοχ࢔‫خ‬સରɼӊ஦ஊʁϘϕοχ & ຦୼ଈɼࠪԾʁS7U\ɼ͹έʖϫϱϛτϱεϡϩͳ /- ϛτϱεϡϩ͹‫࣎ܨ‬รԿɼӊԾʁ֦࢔‫خ‬͹Φϋϩάʖ͹࣎ؔฑ‫ۋ‬ɼ࠹ԾஊࠪʁϧϜοϡϱχϧϱϕϫρφɼ࠹Ծஊӊʁ֦Φϋϩάʖ͹਼஍ҲལಚΔΗͪ݃ՎͶΓΖͳɼϨϱ࢐ԿοϫεϱʤS7\UʥͶΓΖ‫ر‬༫͗ΦϋϩάʖదͶ୉͘͏͞ͳ͗෾͖ͮͪɽ
ࣰࡏͶ 0' εϝϣϪʖεϥϱ͹݃ՎΝ‫ͱݡ‬΍ɼS7\U ΝϒϚρφͳͪ͢Γ͑͵‫ڏ‬ಊ΍؏଎͠Ηͱ͏ΖɽҲ๏Ͳɼʹ͹Ϙϕοχഓ྽Ͷ‫ͱؖ͢‬΍ɼοϫεϱԾླྀ͹࢔‫خ‬͹Φϋϩάʖద͵‫ر‬༫͗ɼ৏ླྀഓ྽ΓΕ΍୉͘͏͞ͳ΍ࣖࠨ͠Ηͪɽଠ͹ 6+ χϟ΢ϱ͹݃Վ΍մੵͤΖචགྷ੓ͺ͍Ζ͗ɼ6+ χϟ΢ϱͶΓΖ݃߻ͺɼϨϱ࢐Կοϫεϱ͗஦ৼͳ͵ͮͱ͕Εɼͨ͹बว࢔‫خ‬͹ഓ྽͹‫ر‬༫ͺർֳదओ͏΍͹͹ɼҲൢͶഓ྽ғଚదͶ਎࿪੓͗݀Ήͮͱ͏Ζ͞ͳ͖Δ΍ɼबวഓ྽͗ʹ͹Γ͑Ͷ݃߻Ͷ‫ر‬༫͢ͱ͏Ζ͖͗ғષͳ͢ͱ෈
໎ྐͲ͍Ζ͞ͳ͗෾͖ͮͪɽ
ͨ͹ͪΌࠕ‫ޛ‬ͺɼӇΗϜϩαϓϠυϩմੵ͵ʹΝ಍೘ͤΖ͞ͳͲɼ݃߻য়ସɼ͍Ζ͏ͺ݃߻մ཯‫ݳ‬েͶ͕͏ͱɼϘϕοχଈ͹ʹ͹Γ͑͵ߑଆ͗݃߻͹યҢয়ସͳ͢ͱଚࡑ͢ͱ͏Ζ͖Ν໎Δ͖Ͷ͢ɼ࢔‫ͨخ‬ΗͩΗ͹࣍ͯ‫ر‬༫ΝಋఈͤΖ͞ͳͲɼSDQ6+ ͹ಝҡ੓૓ड़͹ɼߑଆదϟΩωθϞΝ໎Δ͖ͶͤΖ͞ͳ
ͳͤΖɽ
 ൅නࣰ੹Ήͪͺ༩ఈ

- 382 -͵͢ ड़൝ࣰ੹Ήͪͺ༩ఈ͵͢ࢂߡช‫ݛ‬>@1RDK2OOLNDLQHQ5HQp0GH-RQJDQG7DQMD.RUWHPPH3/R6&RPSXW%LROH
>@%DUDN5DYHK1LU/RQGRQ/LRU=LPPHUPDQDQG2UD6FKXHOHU)XUPDQ3/R62QHH
>@0DUN-DPHV$EUDKDPD7HHPX0XUWRODGHWDO6RIWZDUH;>@-LQJ+XDQJ6DUDK5DXVFKHUHWDO1DW0HWKRGV

- 383 -

ᕤᴗཎᩱࢆ฼⏝ࡋࡓ⢭ᐦ໬Ꮫኚ᥮཯ᛂࡢ㛤Ⓨࢽࢵࢣࣝ㘒యୖ࡟࠾ࡅࡿ༠ዌⓗ⤖ྜ⤌᥮࠼཯ᛂࡢᶵᵓゎ᫂

'HYHORSPHQWRIKLJKVHOHFWLYHRUJDQLFWUDQVIRUPDWLRQVXVLQJIHHGVWRFNFKHPLFDOV‫⏕ۑ‬㉺ ᑙ௓ࠊᫍᮏ 㝧୍ࠊᒾᮏ ⣫᫂㸦኱㜰኱Ꮫ㸧◊✲┠ⓗ㑄⛣㔠ᒓ㘒యࡣᵝࠎ࡞᭷ᶵኚ᥮཯ᛂࢆྍ⬟࡟ࡍࡿゐ፹࡜ࡋ࡚ࠊ⌧ᅾ࡟⮳ࡿࡲ࡛᪂ࡓ࡞㘒యࡢྜᡂ࠿ࡽࠊゐ፹཯ᛂࡢ㛤Ⓨࠊ཯ᛂᶵᵓࡢゎᯒ࡞࡝㠀ᖖ࡟άⓎ࡟◊✲ࡀ࡞ࡉࢀ࡚࠸ࡿࠋ㔞Ꮚ໬Ꮫィ⟬ࡢᡭἲࡢ୍ࡘ࡛࠶ࡿᐦ
ᗘซ㛵ᩘἲ㸦')7㸧ィ⟬ࡣࠊ」㞧࡞ศᏊᵓ㐀࠿ࡘ㟁Ꮚᵓ㐀ࢆ᭷ࡍࡿ㑄⛣㔠ᒓ㘒యࡢᛶ㉁ࡢゎ᫂ࡸ཯ᛂᶵᵓゎᯒ࡟࠾࠸࡚ࠊ㢖⧚࡟⏝࠸ࡽࢀ࡚࠸ࡿࠋࡉࡽ࡟ࠊ㏆ᖺ࡛ࡣィ⟬ᶵࡢᛶ⬟ྥୖ࡟ࡼࡾࠊࡑࡢィ⟬⢭ᗘࡣ㠀ᖖ࡟㧗ࡃ࡞ࡾࠊ㑄⛣㔠ᒓゐ፹཯ᛂࢆ⏝࠸ࡓゐ፹཯ᛂ㛤Ⓨ࡟࠾࠸࡚Ḟ࠿ࡍࡇ࡜ࡢ࡛ࡁ࡞࠸ࢶ࣮ࣝ࡜࡞ࡗ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ')7 ィ⟬࡟ࡼࡾ཯ᛂ࣓࢝ࢽࢬ࣒ࢆ෌⌧ࡍࡿࡔࡅ࡛ࡣ࡞ࡃࠊ㑄⛣≧ែ࡟࠾ࡅࡿ㟁Ꮚ≧ែࢆヲ⣽࡟ㄪ࡭ࡿࡇ࡜࡛᪂ࡓ࡞཯ᛂ⌮ㄽࡢᥦ᱌ࢆ⾜࠺ࠋࡑࡢ୍౛࡜ࡋ࡚ࠊࢽࢵࢣࣝ  㘒య࡟ࡼࡿⅣ⣲㸫ࣇࢵ⣲⤖ྜษ᩿཯ᛂࡢヲ⣽࡟ࡘ࠸࡚◊✲ࢆ⾜ࡗࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬⏝ࣃࢵࢣ࣮ࢪ࡜ࡋ࡚ *DXVVLDQ UHY& ࢆ౑⏝ࡋࠊࢽࢵࢣࣝ  㘒య࡟ࡼࡿࢺࣜࣇ࣓ࣝ࢜ࣟࢳ

ࣝ࢔࣮ࣞࣥࡢ & VS ±) ⤖ྜษ᩿཯ᛂࡸࠊ࡟࠾ࡅࡿศᏊᵓ㐀࡜⮬⏤࢚ࢿࣝࢠ࣮ࢆᐦᗘซ㛵ᩘ⌮ㄽ㸦')7㸧ィ⟬࡟ࡼࡾồࡵࡓࠋࡲࡓࠊ1%2 ࢆ⏝࠸࡚㑄⛣≧ែ࡟࠾ࡅࡿ㌶㐨㛫┦஫స⏝ࢆᐃ㔞ࡋࠊ& VS ±) ⤖ྜษ᩿㐣⛬࡟࠾ࡅࡿ㟁Ꮚࡢ⛣ືࢆྵࡴヲ⣽࡞࣓࢝ࢽࢬ࣒ࢆㄪᰝࡋࡓࠋ



◊✲ᡂᯝ
஧ศᏊࡢ 1࣊ࢸࣟ⎔≧࢝ࣝ࣋ࣥ 1+& 㓄఩Ꮚࢆ᭷ࡍࡿࢽࢵࢣࣝ  㘒య࡜ࣄࢻࣟࢩࣛࣥࢆ⏝࠸ࡓࢺࣜࣇࣝ࢜

࣓ࣟࢳࣝ࢔࣮ࣞࣥࡢ & VS ̽) ⤖ྜࡢ⬺ࣇࢵ⣲Ỉ⣲໬཯ᛂࡢ཯ᛂ࣓࢝ࢽࢬ࣒ࢆ ')7 ィ⟬࡟ࡼࡾ෌⌧ࡋࡓ㸦ḟ࣮࣌ࢪୖᅗ㸧ࠋィ⟬⤖ᯝ࡜ࡋ࡚ࠊ& VS ̽) ⤖ྜࡢ㓟໬ⓗ௜ຍ࡜⥆ࡃࠊࣄࢻࣟࢩࣛࣥ࡜ࡢࢺࣛࣥࢫ࣓ࢱࣝ໬ࠊ㑏ඖⓗ⬺㞳ࢆ⤒⏤ࡍࡿ཯ᛂᶵᵓࡀጇᙜ࡞άᛶ໬࢚ࢿࣝࢠ࣮࡛♧ࡉࢀࡓࠋࡲࡓࠊᮏ཯ᛂ࡟࠾࠸࡚ & VS ̽) ⤖ྜࡢ㓟໬ⓗ௜ຍࡀᚊ㏿ẁ㝵࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡾࠊࡇࢀࡣᐇ㦂⤖ᯝ࡜ࡶ୍⮴ࡋࡓࠋ୍⯡࡟ࠊⅣ⣲㸫ࣇࢵ⣲⤖ྜࡣ㠀ᖖ࡟㧗࠸⤖ྜ࢚ࢿࣝࢠ࣮ࢆ᭷ࡍࡿࡓࡵࠊࡑࡢษ᩿ࡣᅔ㞴࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡑࡇ࡛ࠊࡇࡢ୙ά
ᛶ⤖ྜࡢษ᩿ࡀྍ⬟࡜࡞ࡗࡓせᅉࢆ᳨ドࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊ௒ᚋࡢⅣ⣲㸫ࣇࢵ⣲⤖ྜษ᩿཯ᛂ㛤Ⓨ࡟࠾࠸࡚㔜せ࡞࣓࢝ࢽࢬ࣒࡟࡞ࡾᚓࡿ࡜⪃࠼ࠊࡉࡽ࡞ࡿゎᯒࢆヨࡳࡓࠋࡲࡎࠊᮏ཯ᛂࡣ࢔࣮ࣜࣝᇶࡢࡼ࠺࡞ⰾ㤶⎔࡟⤖ྜࡋࡓ & VS ̽) ⤖ྜࡢࡳࡀษ᩿ྍ⬟࡛࠶ࡾࠊᕤᴗཎᩱ࡛࠶ࡿࣇ࣮ࣝ࢜ࣟ࢝࣎ࣥ㢮࡛ࡣ཯ᛂࡀ㐍⾜ࡋ࡞࠿ࡗࡓࠋࡑࡇ࡛ࠊࡇࡢࢽࢵࢣࣝ  ౯㘒యࡢ཯ᛂᛶࢆ᫂ࡽ࠿࡜ࡍࡿࡓࡵ࡟ࠊ㑄⛣≧ែ࡟࠾ࡅࡿ㌶㐨ゎᯒࢆ⾜ࡗࡓࠋヲ⣽࡟ࡣ⮬↛⤖ྜ㌶㐨㸦1%2㸧ゎᯒ࡜ ,QWULQVLF %RQG 2UELWDO㸦,%2㸧ゎᯒࢆ⏝࠸࡚ࠊ㑄⛣≧ែ୰ࡢ㟁Ꮚࡢὶࢀࢆᐃ㔞࣭ྍど໬ࡋࡓ㸦ୗᅗ㸧ࠋࡑࡢ⤖ᯝࠊࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ࢔࣮ࣞࣥࡢ & VS ̽) ⤖ྜࡢ㓟໬ⓗ௜ຍࡣࠊ୰ᚰ
㔠ᒓ࡛࠶ࡿࢽࢵࢣࣝࡢ G ㌶㐨ࡢ㟁Ꮚࡀ࣋ࣥࢮࣥ⎔ࡢȧ ㌶㐨࡬࡜౪୚ࡉࢀࠊ⥆ࡃࠊ࣋ࣥࢮࣥ⎔ࡢȧ㌶㐨ࡢ㟁ᏊࡀⅣ⣲㸫ࣇࢵ⣲⤖ྜࡢȪ ㌶㐨࡬࡜౪୚ࡉࢀࡿ࡜࠸ࡗࡓ㟁Ꮚࡢὶࢀ࡛ࠊ༠ዌⓗ࡟ & VS ̽) ⤖ྜࡀษ᩿ࡉࢀ

- 384 -

ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࡢࡼ࠺࡟ࠊࢽࢵࢣࣝ  㘒యࡀ┤᥋ & VS ̽) ⤖ྜࢆࡍࡿࡢ࡛ࡣ࡞ࡃࠊከᩘࡢཎᏊࡀ㛵୚ࡍࡿ༠ዌⓗ࡞㟁Ꮚࡢࡸࡾྲྀࡾ࡛㐍⾜ࡍࡿ࡜࠸࠺᪂ࡓ࡞࣓࢝ࢽࢬ࣒ࡢ♧ࡍࡇ࡜࡟ᡂຌࡋࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ












‫ۻ‬Iwamoto, H.; Imiya, M.; Ohashi, M.; Ogoshi, S. J. Am. Chem. Soc. , 142, 19360.
Iwamoto, H. Tsuruta, T. Ogoshi, S. ACS Catal. , 11, 6741.
Ishida, N.; Iwamoto, H.; Sunagawa, D. E.; Ohashi, M.; Ogoshi, S. Sythesis , DOI:
10.1055/s-0040-1705962.
Ishida, N.; Adachi, T.; Iwamoto, H.; Ohashi, M.; Ogoshi, S. Chem. Lett. , 50, 442.
Sunagawa, D. E.; Ishida, N.; Iwamoto, H.; Ohashi, M.; Fruit, C. Ogoshi, S. J. Org. Chem. , 86,
6015.
Hoshimoto, Y.; Nagai, S.; Hinogami, T.; Hazra, S.; Ogoshi, S. Asian, J. Org. Chem. , 10, 1085.
Hoshimoto, Y.; Ogoshi, S. Bull. Chem. Soc. Jpn. , 94, 327.
Yamauchi, Y.; Nagai, S.; Terada, T.; Hoshimoto, Y.; Ogoshi, S. Chem. Lett. , DOI:
10.1246/cl.210202.
Hoshimoto, Y.; Sakuraba, M.; Kinoshita, T.; Ohbo, M.: Ratanasak, M.; Hasegawa, J.; Ogoshi, S.
ChemRxiv. 2021 DOI: 10.26434/chemrxiv.14462391.v1.

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
↓ࡋ- 385 -

⏕య࣭㧗ศᏊ⮬ᕫ㞟ྜ⣔ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ

0ROHFXODU 6LPXODWLRQ RI 6HOI$VVHPEOHG V\VWHP RI %LRDQG
0DFURPROHFXOHV‫ۑ‬⠛⏣΅ࠊ⸨ᮏ࿴ኈࠊᾆ㔝
ୗᒸ

ㄹࠊ▼ᕝ

༤❶ࠊᘻᕳ

࿘ᖹࠊ⏣୰

⿱㈗ࠊ ཎ⏣ᫀ࿃ࠊ⛱ࠊ0DUN *ULIILWKVࠊ+DUL <DGDYࠊ$NKLO3UDWDS 6LQJKࠊ0D\DQN 'L[LW㸦ྡ኱㝔ᕤ㸧◊✲┠ⓗ⏕య࣭㧗ศᏊ⮬ᕫ㞟ྜ⣔ࡢ≀ᛶゎ᫂ࡢࡓࡵ࡟ࠊ኱つᶍศᏊ⣔࡟ᑐࡍࡿ㛗᫬㛫 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࡞ࡗ࡚࠸ࡿࠋᖺᗘᐇ᪋ࡋࡓㄢ㢟ࡢ୰࡛௦⾲ⓗ࡞ㄢ㢟 Ⅼ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ ⸆๣ศᏊࡢ %ᆺ⫢⅖࢘࢖ࣝࢫ࡬ࡢ㏱㐣ᶵᵓࡢ᥈⣴%ᆺ⫢⅖ࡣ㸰൨ ༓୓ேࡀ៏ᛶⓗ࡟⨯ᝈࡋ࡚࠾ࡾࠊᖺ㛫  ୓ேࡀ %ᆺ⫢⅖ࡸࡑࡢྜే⑕࡛ஸࡃ࡞ࡗ࡚࠸ࡿ
࡜ሗ࿌ࡉࢀ࡚࠸ࡿࠋࡑࡢཎᅉ࡛࠶ࡿ % ᆺ⫢⅖࢘࢖ࣝ
ࢫ +%9 ࡣࠊ࢝ࣉࢩࢻࢱࣥࣃࢡ㉁ࢲ࢖࣐࣮ࡀSJ51$ ࡜࢘࢖ࣝࢫࡢ࣏࣓࣮ࣜࣛࢮࡢ࿘ࡾ࡟㞟ࡲࡗࡓṇ஧༑㠃యᑐ⛠ᛶࡢ࢝ࣉࢩࢻࢆᇶᮏ㦵᱁࡟ᣢࡘࠋࡇࡢ࢝ࣉࢩࢻ
ෆ࡛࣏࣓࣮ࣜࣛࢮ࡟ࡼࡾ SJ51$ ࠿ࡽ㏫㌿෗ࢆ⾜࠸஧㔜ࡽࡏࢇࡢ '1$ ࢆసᡂࡍࡿ㸦ᡂ⇍㐣⛬㸧ࠋࡑࡢᚋࠊ
+%9 ࢝ࣉࢩࢻࡣ࢚࣮ࣥ࣋ࣟࣉ࡟そࢃࢀࠊ⣽⬊እ࡬࡜ฟ࡚࠸ࡃࠋ㏫㌿෗࡟ᚲせ࡞᰾㓟ࡣ࢘࢕ࣝࢫ࢝ࣉࢩࢻࡢᅗ   +%9 ඲య㸦ᕥ㸧࡜ࡑࡢ㒊ศ⣔㸦ྑ㸧ࠋ⣽Ꮝ࠿ࡽ᰾㓟ࢆྲྀࡾ㎸ࡴ㸦ᅗ 㸧ࠋࡇࡢ⣽Ꮝࡣ༙ᚄ⣙Ⴒ ࡢ⟄≧࡛࠶ࡾࠊෆ㒊࡟ᗈ࠸✵㛫ࢆ᭷ࡍࡿࠋ᰾㓟㢮ఝ⸆๣ศᏊ࡛࠶ࡿ࢚ࣥࢸ࢝ࣅࣝ୕ࣜࣥ㓟 (7973  ᅗ㸰 ࢆ㏱㐣≀㉁㸦ศᏊ㸧࡜ࡋ࡚⏝࠸ࠊᡃࠎࡣ௨๓㏱㐣ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢕࣮ࣝࢆィ⟬ࡋࠊ⣽Ꮝධཱྀ௜㏆࡟࣑ࢽ࣐࣒ࡀᏑᅾࡋࠊฟཱྀ௜㏆࡟㞀ቨࢆᣢࡘࡇ࡜ࢆሗ
࿌ࡋࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡇࡢィ⟬࡛ࡣ⣽Ꮝࡢ୰ᚰࢆ㏻
ࡿ࡜௬ᐃࡋ࡚࠾ࡾࠊ⣽Ꮝ㏻㐣ࡢ᭱ᑠ࢚ࢿࣝࢠ࣮⤒㊰࡟࡞ࡗ࡚࠸࡞࠸ࠋࡘࡲࡾࠊࡼࡾṇ☜ヲ⣽࡞㏱㐣ࢆ㆟ㄽࡍᅗ  ᢠ +%9 ⸆࢚ࣥࢸ࢝ࣅࣝࡢศᏊᵓ㐀ࡿࡓࡵ࡟ࡣࠊ⣽Ꮝࡢ㸱ḟඖࡢ⮬⏤࢚ࢿࣝࢠ࣮࣐ࢵࣉࢆ
ィ⟬ࡍࡿᚲせࡀ࠶ࡿࠋᮏ◊✲࡛ࡣ (7973ࡢ +%9 ⣽Ꮝ⮬⏤࢚ࢿࣝࢠ࣮࣐ࢵࣉࢆィ⟬ࡍࡿࠋࡇࡢ◊✲ࡢ▱ぢࡣ᪂つ⸆๣㛤Ⓨᣦ㔪ࢆ୚࠼ࡿᙺ๭࡟ຍ࠼ࠊ+%9 ࡢࣛ࢖ࣇࢧ࢖ࢡࣝࡢ㏫㌿෗ࡢึᮇ㐣⛬ࢆ᫂ࡽ࠿࡟ࡍࡿࡶࡢ࡛࠶
ࡿࠋ- 386 -

ᡂᙧຍᕤࣉࣟࢭࢫ࡟ࡼࡿ⬤ᛶᮦᩱࡢᘏᛶ໬ࡢศᏊㄽⓗゎ᫂㧗ศᏊᮦᩱࡢ౑⏝⏝㏵ࡣᵝࠎ࡛࠶ࡿࡀࠊ࡝ࡢࡼ࠺࡞⏝㏵࡛࠶ࡗ࡚ࡶᶵᲔⓗᙉᗘࡣ㔜せ࡞ᛶ㉁࡛࠶ࡿࠋ౛࠼ࡤࠊ
86%ࡢ⤯⦕య࡜ࡋ࡚౑⏝ࡉࢀ࡚࠸ࡿ㧗ศᏊᮦᩱ㸦ⓑࡲࡓࡣ㟷Ⰽࡢ㒊ศ㸧࡛ࡶࠊ౑⏝୰࡟ቯࢀ࡞࠸ࡇ࡜ࡀせồ
せ௳ࡢ୍ࡘ࡜ࡋ࡚㛤Ⓨࡀ⾜ࢃࢀ࡚࠸ࡿࠋࡑࡢࡓࡵࠊ෾ࢢ࠱͹ഓ޴੏‫ޜ‬͹Γ͑Ͷɼ੣ଆ޽ఖΝ޽෋ͤΖ͞ͳͲ߶෾ࢢࡒྋ͹‫޴ౕک‬৏͗ߨΚΗͱͪ͘ɽࡑࡢ୍ࡘ࡟ࠊࣉࣞࢫᘏఙἲ࡜࿧ࡤࢀࡿࠊࠕ㧗ศᏊᮦᩱࢆᅽ⦰ࡍࡿࡇ࡜
࡟ࡼࡾࠊ⾪ᧁ࡟ᑐࡍࡿᙉᗘࢆྥୖࡉࡏࡿ᪉ἲࠖࡀᏑᅾࡍࡿࠋࡇࡢ᪉ἲࡣࠊศᏊࡑࡢࡶࡢࢆኚ࠼ࡿࡢ࡛ࡣ࡞ࡃࠊศᏊ
㙐ࡢᵓ㐀ࢆኚ໬ࡉࡏࡿࡔࡅ࡛ᙉᗘࢆኚ໬ࡉࡏࡿࡇ࡜ࡀ࡛ࡁࡿᡭἲ࡛࠶ࡿࠋゝ࠸᪉ࢆኚ࠼ࢀࡤࠊ᪤Ꮡࡢ㧗ศᏊ࡛ࡶศᏊ㙐ࡢ㓄ྥ➼ࢆኚ࠼ࡿࡔࡅ࡛ᙉᗘࢆࢥࣥࢺ࣮ࣟࣝࡍࡿࡇ࡜ࡀ࡛ࡁࡿྍ⬟ᛶࢆ⛎ࡵ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀ
ࡽࠊ㧗ศᏊ㙐ࡢᵓ㐀࡜ᙉᗘࡢ㛵ಀᛶࡣヲ⣽࡟ゎ᫂ࡉࢀ࡚࠾ࡽࡎࠊࡲࡔ⫋ே㸦ᕤဨ㸧ࡢ຺ࠊ⤒㦂ࠊᕤኵ࡟ࡼࡿ
࡜ࡇࢁࡀ኱ࡁ࠸ࠋࡑࡇ࡛⚾ࡣ㧗ศᏊ㙐ࡢᵓ㐀࡜ᙉᗘࡢ㛵ಀᛶࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊࣉࣞࢫᘏఙἲࢆ㢟ᮦ࡟◊✲ࢆ㛤ጞࡋࡓࠋලయⓗ࡟ࡣࠊࣉࣞࢫᘏఙἲࢆ෌⌧ࡍࡿᡭἲࢆ㛤Ⓨࡋࠊ㏻ᖖ⬤ᛶ◚ቯࢆ♧ࡍ300$ ࡢ඲ཎᏊศᏊືຊᏛィ⟬࡟ࡼࡿ◚ቯࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ ⸆๣ศᏊࡢ%ᆺ⫢⅖࢘࢖ࣝࢫ࡬ࡢ㏱㐣ᶵᵓࡢ᥈⣴
+%9 ࢝ࣉࢩࢻ඲యࢆィ⟬ᑐ㇟࡜ࡍࡿሙྜࠊ⣔ࡣỈ⁐ᾮ࡞࡝ࢆྵࡵ⣙ ୓ཎᏊ࡜࡞ࡾィ⟬ࢥࢫࢺࡀ㠀ᖖ࡟㧗ࡃࠊ⮬⏤࢚ࢿࣝࢠ࣮࣐ࢵࣉィ⟬ࡣ⌧ᐇⓗ࡛ࡣ࡞࠸ࠋࡑࡇ࡛ࠊ+%9࢝ࣉࢩࢻࡀṇ஧༑㠃యᑐ⛠ᛶࢆ᭷ࡍࡿ஦
࡟╔┠ࡋࠊ+%9࢝ࣉࢩࢻࡢ㒊ศ⣔㸦ᅗྑᅗ㸧ࢆィ⟬ᑐ㇟࡜ࡋࡓࠋࡇࢀ࡟ࡼࡾࠊィ⟬⣔ࡣ඲య⣔ࡢศࡢ
ࡢ⣙ ୓ཎᏊ࡜࡞ࡾ⮬⏤࢚ࢿࣝࢠ࣮࣐ࢵࣉィ⟬ࡀྍ⬟࡜࡞ࡿࠋࡉࡽ࡟ࠊィ⟬ᑐ㇟࡜ࡍࡿ⣽Ꮝࡀ ᅇᅇ㌿ᑐ⛠ᛶࢆᣢࡘࡇ࡜ࢆ฼⏝ࡋࠊ⣽Ꮝෆࡢศࡢࡢ㡿ᇦ࡛0'ィ⟬ࢆ⾜࠸ࠊᚓࡽࢀࡓࢹ࣮ࢱࢆᑐ⛠㍈࿘ࡾ࡟ᅇ㌿ࡉࡏࡿࡇ࡜࡛⣽Ꮝ඲య࡟ࡘ࠸࡚ࡢࢹ࣮ࢱࢆᚓࡿࠋࡇࢀ࡟ࡼࡾࡉࡽ࡞ࡿィ⟬ࢥࢫࢺࡢ๐ῶࡀ࡛ࡁࡿࠋ
ᡂᙧຍᕤࣉࣟࢭࢫ࡟ࡼࡿ⬤ᛶᮦᩱࡢᘏᛶ໬ࡢศᏊㄽⓗゎ᫂ࡲࡎࠊ࢞ࣛࢫ㌿⛣ᗘࡼࡾࡶࢃࡎ࠿࡟㧗࠸ᗘ࡛⾲   ࣉࣞࢫᘏఙࢆ᪋ࡋࡓ300$࡜᪋ࡋ࡚࠸࡞࠸

࠶ࡿ. ࡛ᅽ⦰ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋᅽ

300$ࡢ⣔ࡢ᮲௳ࠋ

⦰ᚋࠊ⣔ࢆ⦆࿴ࡉࡏࡿࡓࡵ࡟. ࡛ࢩ࣑࣮ࣗࣞ

XQUROOHG

ࢩࣙࣥࢆ⾜ࡗࡓࠋࡇࡢ⦆࿴࡟ࡼࡾࠊ㧗ศᏊ㙐ࡢ㓄ྥࢆኚ໬ࡉࡏࠊᵝࠎ࡞㓄ྥᗘࢆᣢࡗࡓ⣔ࢆసᡂࡍࡿࡇ࡜ࡀྍ⬟࡜࡞ࡿࠋࡑࡢᚋࠊ.QV࡛⣔ࢆ෭༷ࡍࡿࡇ࡜࡛ࠊࣉࣞࢫᘏఙࢆࡋࡓ⣔ࢆసᡂࡋࡓࠋ

0Z0Q



0Q



7DFWLFLW\UU UP PP 

2UGHUSDUDPHWHU

ࡲࡓࠊẚ㍑ࡢࡓࡵ࡟௨ୖࡢࣉࣞࢫᘏఙࡢ᧯సࢆ⾜

7J ႏ GHQVLW\





WRWKH]D[LVࡗ࡚࠸࡞࠸⣔ XQUROOHG V\VWHP ࡶసᡂࡋࡓࠋ⾲࡟ࣉࣞࢫᘏఙࢆࡋ࡚࠸࡞࠸⣔࡜ࠊࣉࣞࢫᘏఙࢆ⾜ࡗࡓ⣔ࡢヲ⣽ᵓ㐀ࢆ♧ࡍࠋ⾲ࡢࡼ࠺࡟ࠊศᏊ㔞ศᕸࠊ࢞ࣛࢫ㌿⛣

UROOHGᗘࠊᐦᗘ➼ࡀྠ⛬ᗘ࡛ࠊ㧗ศᏊ㙐ࡢ㓄ྥࡢࡳࡀ኱ࡁࡃ␗࡞ࡗࡓ㸰ࡘࡢ⣔ࢆసᡂࡋࡓࠋ

- 387 -



◊✲ᡂᯝ


 ⸆๣ศᏊࡢ%ᆺ⫢⅖࢘࢖ࣝࢫ࡬ࡢ㏱㐣ᶵᵓࡢ᥈⣴

(7973 ࡣѸ ࡢ㟁Ⲵࢆᣢࡕࠊ⣽Ꮝࢆᙧᡂࡍࡿࢱࣥ



ࣃࢡ㉁ࡢṇ㟁Ⲵࢆᣢࡘ࢔࣑ࣀ㓟ṧᇶ࡟ᙉࡃᘬࡁ௜
ࡅࡽࢀࡿ㸦ᅗ㸧ࠋࡑࡢࡓࡵࠊ㏻ᖖࡢ0' ィ⟬࡛ࡣ
(7973 ࡀ+%9 ࢝ࣉࢩࢻ⣽Ꮝෆࡢ඲✵㛫ࢆᇙࡵࡿࡼ࠺࡞㌶㊧ࢆᚓࡿࡇ࡜ࡣ㠀ᖖ࡟ᅔ㞴࡛࠶ࡿࠋࡑࡇ
࡛ࠊ⣽Ꮝෆࡢ✵㛫ࢆ ḟඖ࣓ࢵࢩࣗ≧࡟ศ๭ࡋࠊ
(7973ࡀࡑࢀࡒࢀࡢ㡿ᇦෆ࡛㐠ືࡍࡿࡼ࠺࡟ࣇࣛ

ࢵࢺ࣎ࢺ࣒࣏ࢸࣥࢩࣕࣝࢆㄢࡋ࡚0' ィ⟬ࢆ⾜࠺ࡇ࡜࡛ࢧࣥࣉࣜࣥࢢຠ⋡ࢆ࠶ࡆࡓࠋᚓࡽࢀࡓศᕸ

ᅗ Ⲵ㟁ࡋࡓṧᇶ㸦ᕥᅗ㸧࡜࢚ࣥࢸ࢝ࣅࣝࡢ☜⋡ᐦᗘࠋᕥᅗࡢ㟷Ⰽࡣṇ㟁Ⲵࢆ㉥Ⰽࡣ㈇㟁Ⲵࢆᖏࡧࡓṧᇶࠋ

㸦ᅗ㸱ྑᅗ㸧ࡼࡾ⮬⏤࢚ࢿࣝࢠ࣮࣐ࢵࣉࢆィ⟬ࡋࡓࠋᡂᙧຍᕤࣉࣟࢭࢫ࡟ࡼࡿ⬤ᛶᮦᩱࡢᘏᛶ໬ࡢศᏊㄽⓗゎ᫂సᡂࡋࡓ㸰ࡘࡢ⣔ࢆ⏝࠸࡚ࠊ⾪ᧁ◚ቯࢩ࣑࣮ࣗࣞࢩ

ࣙࣥࢆ⾜ࡗࡓࠋࡑࡢ⾪ᧁ◚ቯࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡾồࡵࡽࢀࡓᛂຊ̿ṍࡳ᭤⥺ࢆᅗ࡟♧ࡍࠋࢢࣛࣇ
ࡼࡾࠊࣉࣞࢫᘏఙࢆࡋ࡚࠸࡞࠸⣔࡛ࡣࠊ㝆అᚋ࡟ṍࡳ◳໬ࡀ㉳ࡇࡗ࡚࠸࡞࠸ࡀࠊࣉࣞࢫᘏఙࡋࡓ⣔࡛ࡣ㝆అᚋ࡟ṍࡳ◳໬ࡀ㉳ࡇࡾࠊᛂຊࡀୖ᪼ࡋ࡚࠸ࡿࠋ
ࡘࡲࡾࠊࣉࣞࢫᘏఙࢆ᪋ࡋࡓࡇ࡜࡛ࠊ⬤ᛶࡔࡗࡓ
300$ࡀᘏᛶ࡟ኚ໬ࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡉ
ࡽ࡟ࠊ㸰ࡘࡢ⣔࡟ᑐࡋ࡚ᙎᛶ⋡ࢆィ⟬ࡋࡓ࡜ࡇࢁࠊ

ᅗ ࣉࣞࢫᘏఙࢆ᪋ࡋࡓ300$㸦㟷㸧࡜᪋ࡋࣉࣞࢫᘏఙࢆࡋࡓ⣔ࡢ᪉ࡀࣉࣞࢫᘏఙࢆࡋ࡚࠸࡞࠸
⣔ࡼࡾᙎᛶ⋡ࡀࢃࡎ࠿࡟኱ࡁࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ௨ୖࡢࡇ࡜࠿ࡽࠊࣉࣞࢫᘏఙࢆ᪋ࡍࡇ࡜

࡚࠸࡞࠸300$㸦㉥㸧ࡢᛂຊṍࡳ᭤⥺ࠋ

࡛ࠊ300$ࡣࡼࡾ◳ࡃࠊࡼࡾᘏᛶ࡟ኚ໬ࡋ࡚࠸ࡿࡇ
࡜ࡀ☜ㄆ࡛ࡁࡓࠋࡲࡓࠊ300$ࡀ࡝ࡢࡼ࠺࡟ቯࢀ࡚
࠸ࡃ࠿ࢆ☜ㄆࡍࡿࡓࡵ࡟ࠊ㝆అᚋࡢ300$ࡢࢫࢼࢵ
ࣉࢩࣙࢵࢺࢆᅗ࡟♧ࡍࠋᅗࡼࡾࠊࣉࣞࢫᘏఙࢆࡋ
࡚࠸࡞࠸⣔࡛ࡣ㝆అᚋ࡟⣔ࡢ୍㒊ࡀ኱ࡁࡃቯࢀ࡚ࡋ
ࡲ࠸ࠊ㸰ࡘ࡟◚᩿ࡋ࡚ࡋࡲࡗ࡚࠸ࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡿࠋࡑࢀ࡟ᑐࡋ࡚ࠊࣉࣞࢫᘏఙࡋࡓ⣔࡛ࡣ㸰⟠ᡤ࡯࡝࡟ᑠࡉ࠸⣽Ꮝࡀ⏕ᡂࡋ࡚࠸ࡿࡀࠊࡑࡢ⣽Ꮝࡢᡂ㛗ࡀ኱ࡁࡃ㜼ᐖࡉࢀ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡘࡲࡾࠊ
ศᏊ㙐ࡢኚ໬࡟ࡼࡿ⣽Ꮝᡂ㛗ࡢ㜼ᐖࡀࠊ⬤ᛶ࠿ࡽᘏᅗ ࣉࣞࢫᘏఙࢆ᪋ࡋࡓ300$㸦ྑ㸧࡜᪋ࡋ࡚࠸࡞࠸300$㸦ᕥ㸧ࡢ㝆అᚋࡢࢫࢼࢵࣉࢩࣙ
ࢵࢺࠋᛶ࡬ࡢኚ໬࡟࠾࠸࡚㔜せ࡛࠶ࡿ࡜࠸࠺ࡇ࡜ࢆⓎぢࡋ- 388 -

ࡓࠋࣉࣞࢫᘏఙ࡟ࡼࡿ⣽Ꮝᡂ㛗ࡀ㜼ᐖࡉࢀࡿせᅉ࡜ࡋ࡚ࠊࣉࣞࢫᘏఙࢆ⾜࠺ࡇ࡜࡛ࠊࡑࡢᚋࡢ⾪ᧁ࡟ࡼࡾ
300$ࡀᘬࡗᙇࡽࢀࡿ᪉ྥ࡟㓄ྥࡋ࡚࠸ࡿ㧗ศᏊ㙐ࡢᩘࡀቑ࠼ࡓࡇ࡜ࡀ኱ࡁ࡞せᅉ࡛࠶ࡿ࡜⪃࠼࡚࠸ࡿࠋ
Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ



մ>@ࠕ඲ཎᏊศᏊືຊᏛィ⟬࡟ࡼࡿࠊ࢞ࣛࢫ≧㧗ศᏊࡢᘏఙཬࡧᅽ⦰◚ቯࡢศᏊㄽⓗ◊✲ࠖ㸸⸨ᮏ࿴ኈࠊ▼ᕝ༤❶ࠊ‫‮‬அஓࠊᒸᓮ㐍㸦➨ᅇ㧗ศᏊウㄽ఍ࠊᖺ᭶㸧
մ>@ࠕ࢜ࣝࢺࢣ࢖㓟ࡢࣔࢹࣝ⣽⬊⭷㏱㐣⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࠖ㸸ᘻᕳ࿘ᖹࠊ୰ᮧோࠊ⸨ᮏ࿴ኈ㸦⁐ᾮ໬Ꮫ◊✲఍ⱝᡭࡢ఍࢜ࣥࣛ࢖ࣥࢩ࣏ࣥࢪ࣒࢘ࠊᖺ᭶㸧
մ>@ࠕẼᾮ⏺㠃࡟࠾ࡅࡿ༙ࣇࢵ໬Ⅳ⣲ࡢ࣑࣑࣊ࢭࣝᙧᡂࠖ㸸ཎ⏣ᫀ࿃ࠊ+DUL26<DGDYࠊ⠛⏣΅㸦➨ᅇศ
Ꮚࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍ࠊᖺ᭶㸧
մ>@ࠕᐃ㔞ⓗ⢒ど໬ຊሙ63,&$ ࡢ'1$ ࣔࢹࣝ࣊ࡢᣑᙇ  ⬡㉁ࢼࣀ⢏Ꮚࡢᵓ㐀ண ࠖ㸸⏣୰⿱㈗ࠊᐑᓮ⿱
௓ࠊ$NKLO3UDWDS6LQJKࠊ⠛⏣΅㸦➨ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍ࠊᖺ᭶㸧
մ>@ࠕ⸆๣ศᏊࡢ% ᆺ⫢⅖࢘࢖ࣝࢫ࡬ࡢ㏱㐣ᶵᵓࡢ᥈⣴ࠖ㸸ᘻᕳ࿘ᖹࠊᾆ㔝ㄹࠊ⸨ᮏ࿴ኈࠊ⠛⏣΅ࠊᒸᓮ㐍㸦➨ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍ࠊᖺ᭶㸧
մ>@ࠕᅽᘏ࡟ࡼࡿ㧗ศᏊ㙐㓄ྥไᚚࢆ᪋ࡋࡓ300$ࡢᙉᗘྥୖ࡟㛵ࡍࡿศᏊㄽࠖ㸸▼ᕝ༤❶ࠊ⸨ᮏ࿴ኈࠊ
‫‮‬அஓࠊᒸᓮ㐍㸦➨ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍ࠊᖺ᭶㸧
մ>@ࠕ඲ཎᏊศᏊືຊᏛἲ࡟ࡼࡿ⾪ᧁ◚ቯࡢ࣑ࢡࣟᥥീࠖ㸸⸨ᮏ࿴ኈࠊ▼ᕝ༤❶ࠊ‫‮‬அஓࠊᒸᓮ㐍㸦
㧗ศᏊᏛ఍ㅮ₇఍ࠊᖺ᭶㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ



մ>@3RVLWLRQ'HSHQGHQW'LIIXVLRQ&RQVWDQWRI0ROHFXOHV LQ+HWHURJHQHRXV6\VWHPVDV(YDOXDWHGE\WKH/RFDO0HDQ
6TXDUHG'LVSODFHPHQW71DJDL67VXUXPDNL58UDQR.)XMLPRWR:6KLQRGD62ND]DNL-&KHP7KHRU\&RPSXW  մ>@)UHH HQHUJ\ SURILOH RI SHUPHDWLRQ RI (QWHFDYLU WKURXJK +HSDWLWLV % YLUXV FDSVLG VWXGLHG E\ PROHFXODUG\QDPLFVFDOFXODWLRQ.)XMLPRWR0)XNDL58UDQR:6KLQRGD7,VKLNDZD.2PDJDUL<7DQDND$1DNDJDZD6
2ND]DNL3XUH$SSO&KHP  
մ>@&RQIRUPDWLRQ DQG RULHQWDWLRQ RI EUDQFKHG DF\O FKDLQV UHVSRQVLEOH IRU WKH SK\VLFDO VWDELOLW\RIGLSK\WDQR\OSKRVSKDWLG\OFKROLQH+7VXFKLNDZD72QR0<DPDJDPL<8PHJDZD:6KLQRGD00XUDWD%LRFKHPLVWU\  
մ>@([DFW ORQJUDQJH &RXORPELF HQHUJ\ FDOFXODWLRQ IRU QHW FKDUJHG V\VWHPV QHXWUDOL]HG E\ XQLIRUPO\ GLVWULEXWHGEDFNJURXQGFKDUJHXVLQJIDVWPXOWLSROHPHWKRGDQGLWVDSSOLFDWLRQWRHIILFLHQWIUHHHQHUJ\FDOFXODWLRQ58UDQR:
6KLQRGD1<RVKLL62ND]DNL-&KHP3K\V  
մ>@3LYRWDO5ROHRI,QWHUGLJLWDWLRQLQ,QWHUOHDIOHW,QWHUDFWLRQV,PSOLFDWLRQVIURP0ROHFXODU'\QDPLFV6LPXODWLRQV6
6HR00XUDWDDQG:6KLQRGD-3K\V&KHP/HWW  
մ>@(IIHFWRI3DFNLQJ'HQVLW\RQWKH6XUIDFH+\GURSKRELFLW\RIȦ)XQFWLRQDOL]HG &)&+2&+DQG2+ 6HOI
DVVHPEOHG0RQROD\HUV$0ROHFXODU'\QDPLFV6WXG\+<DGDY$.XR68UDWD:6KLQRGD-3K\V&KHP&  
մ>@S63,&$$FRDUVHJUDLQHGIRUFHILHOGIRUOLSLGPHPEUDQHVEDVHGRQDSRODUZDWHUPRGHO<0L\D]DNL62ND]DNL
DQG:6KLQRGD-&KHP7KHRU\&RPSXW  - 389 -

!


Molecular Dynamics Study on Functional Self-Assembled Soft
Materials: Analyses of Nano-Scaled Surface Structure and Dynamics! (/ +/, -

1



%



#

"$#.

"$
½}ThØ]N ß $$ThQØX(ÂÙ7/:>25-[g«v Ë *ßTh°-e+ £}&V{ +!/0EN KÚÚÄÊÕ) ¬ ,+ßªcÕ +.C1CÔ/0E}k½c,,¿r·ºZ­-x+[1] /0E}ÒMx ,+:<Ï9?/E ß'/0E-ÌÎ+:<8@;C½+ ®),*ßR¦¾"|¨y ,+[1,2]$ (½}ThØ]Nb+Th£}&Ís¬ ,*[3]ß¤~TÛ'£©¡Wj£}¨
¼ ,+¯²3CF=ß(ThØ]N&£}-È#+%ßThYWjÝMDÞ4>

ADF4BE-¨¯²-m £ 2020 su ß/0E¶f  -wqÖ ß¥b¯² 2021 s 5  ÇI¤+ÝS¢m¹ 5-[1]Þ
 ±ßÍsÐ%+ß§NÑ]}ÜThJib+Th:<ÏÄThØ]£}¯²d_+2"$*&§NÑ]}ÜTha 1  poly-2-methoxyethylacrylateÝPMEAÞ

 


-wßgeneralized amber force fieldÝGAFFÞ-nu×ÝDFTÞ
c

³G\¦Å´µDFT Å´B3LYP × 6-

31G(d,p)ct-¨mÁßÓ]up  PMEA ÚÀ-ßRESP -¨lDFT Å´

Gaussian 16 RevC.01 -ßRESP 

AmberTools 18 -¨,,mÁ¯²

 PMEA  GAFF-¨ß5 H\hÃ MD Å´-mÁ¯²oÉa 1
 PMEA Ó]u n

a 1 PMEA ThZjÏ292 ß PMEA 8 Th- MD 6CJÆ»

700 K ) 500 K $ NPT LIÏ¸` UÏ-Oß500 K z),ÏJTh- 150-2000 Th P ) )^
` ßo½Z-Á$C

TIP4P/2005 ßTh?¶]}¡ <CÎu5F&E3ßX
2 ps Æl ÒC

NPT LI 300 K $@J)Ï¸
PMEA S% LINCS -¨Parrinell-Rahman -¨V{ß¸`Îu

2 fs ßleap-flog -¨³To½¤~vß50 ns  MD Å´(£}E=&E3-mÁ¯² MD Å´- 390 -

Gromacs 2016.5 -¨mÁ

3

"$
MD Å´z), PMEA JÏ-a 2A ®Th ß4u  YGT+ßu\+wd{«nu)\ :Rz),

a 2B 

(Th PMEA µ¶]Nb/+Ïµ\hYuTm-Ä +ßC!CcKÓ¶]Ïµ­.O¨s  +ß­.O¨u\+r$+:R+ + )  PMEA ?ÒThµ¶]-Ä

ßa 3A (ßu\+\F :Rz), Thu\+ßa 3B ®ThoYK&

a 2 PMEA Th5:=4Bß(A) 1wt% +ÜThÏÝlÞTh ÝQÞ5:=4BßÝBÞTh 5:=4Bu7i}
ÝCÞPMEA  O1, O2, O3 \hThÒYuTm×PMEA J O1, O2, O3 \h a.1 -¿K¡$%

a 3 PMEA ib+ThÝAÞoYµ¶](Th^]$

PMEA ¶]E]

ÝBÞThoYK,eMu7i}Thµ¶]\})+- 391 -

,eM&\Fßw}) :R+  ßoYK,eM: M+ )ßTh

PMEA ?Ò droplet J++¹-®+ T+(Thd{£}´-mÛ3CF=>^Ð%*ß2021 suJ¯²ª¾-Å¨
+

K¼¤
>@7.DWR0<RVKLR7,FKLNDZD%6REHUDWV+2KQR0)XQDKDVKL1DW5HY0DWHU  >@0+HQPL.1DNDWVXML7,FKLNDZD+7RPLRND76DNDPRWR0<RVKLR7.DWR$GY0DWHU  7
6DNDPRWR72JDZD+1DGD.1DNDWVXML00LWDQL%6REHUDWV..DZDWD0<RVKLR+7RPLRND76DVDNL0.LPXUD0+HQPL7.DWR$GY6FL  >@07DQDND7+D\DVKLDQG60RULWD3RO\P-  07DQDND6.RED\DVKL'0XUDNDPL)$UDWVX$.DVKLZD]DNL7+RVKLEDDQG.)XNXVKLPD%XOO&KHP6RF-SQ  

4 )'
[1] ) ¬/º, 3p, ËÈ, \¦z+, F¼ÕP, Ü0x, Th4>ADF4BE-¨¿r·º
Z/0E:<8@;C +`~ÄÝOÚÞ, Zjkj2³ 86 s2, Zoom, 2021 s 3  20-22.
[2] ) ¬/º, 3p, ËÈ, \¦z+, F¼ÕP, Ü0x, ¿r·ºZ/0E:<8@;C +`~ThYWjÄÝOÚÞ, Zj2³ 101 _s2, Zoom, 2021 s 3  19-22 .
[3] ) ¬/º, ¿r·ºZ/0E¶+:<­TÖ~ThÌÎ£}/EF=D/ÝOÚÞ, 2020 sufÓfj/F? .6EF=GZB¨Vud_2, Webex, 2021 s 3  10 .
[4] ) ¬/º, ÌÎ×+ThYWjÄ©Ø"|¨ÝOÚß~yÆÞ, ³ 10 UTh4>AD
F4BE%/!'F"|¨¯²2, Zoom, 2021 s 3  9 .
[5] J[6^ßp 9ßhÄß¬/ºßÜ0xßTh4>ADF4BE-¨%FE3%
ET«¼cß³ 23 UZjkj2j§ª¾2, 0E%/E, 2021  3  6 .
[6] ) ¬/º, :<ÏTh4>ADF4BE(+Ï(£}ÄÝOÚß~yÆÞ, ³ 10U25%¯²2, Teams, 2021 s 1  29 .
[7] ) ¬/º, 3p, ËÈ, F¼ÕP, Ü0x, ¿r·ºZ/0E<\hTh$&E3ß
1D ( 3D :<8@;CThÌÎ½ÄÝ"5FÞ, ³ 34 UTh4>ADF4BEÁÅ2, Remo,
2020 s 12  15 .
[8] ) ¬/º, 3p, ËÈ, F¼ÕP, Ü0x, Confined Water inside the Nanochannels of SelfAssembled Ionic Liquid Crystal via MD and DFT SimulationsÝ"5FÞ, /0EN Workshop2020, Zoom/Remo,
2020 s 12  4 .
[9] Hy5ß¬/ºß§iaßÜ0xßThYWj(+ThØV&EÏ5C`l}Ä"ß %/!'F2Ç 2020 ° Aq, 0E%/E, 2020 s 11  11-13 Þ[10]Ð¸1ß°gI8ß¬/ºßÜ0xßC.Ñe  +ZjL|ß%/!'F2Ç 2020 ° Aq, 0E%/E, 2020 s 11  11-13 Þ
[11] hÄß¬/ºßÜ0xßL|ThYWj(+f¤3%E²«¢ Yo+×W

- 392 -

tÙß%/!'F2Ç 2020 ° Aq, 0E%/E, 2020 s 11  11-13 Þ
[12] ) ÔoßF45E $'F MD · ] (+"&#F?CÜÏÄÃÚ¥j·-ßTDA-MI workshop 2020, 0E%/Eß2020 s 11  13 .
[13]  Kyosuke Kawakita, Yoshiki Ishii, Hiroaki Koshima, Hitoshi Washizu, Analysis of the Stability ofOrganophosphate Aggregates in Oil by Molecular Dynamics, 2020 STLE Tribology Frontiers Virtual Conference, USA,
2020 s 11  9-13 .
[14] Yosuke Hamano, Hirotoshi Akiyama, Yoshiki Ishii, Hitoshi Washizu, Chemical Reactions in Zirconia and Metals
Under Friction, 2020 STLE Tribology Frontiers Virtual Conference, USA, 2020 s 11  9-13 .
[15] Ryo Matsuoka, Yoshiki Ishii, Hitoshi Washizu, Effect of Water Atmosphere on Friction of Multilayer GrapheneStudied by Reactive Molecular Dynamics, 2020 STLE Tribology Frontiers Virtual Conference, USA, 2020 s 11  913 .
[16] ) ¬/º, 3p, ËÈ, F¼ÕP, Ü0x, ¿r·ºZ/0E<\hTh4>ADF4
BEß:<8@;CÏThÌÎÄÝOÚÞ, 2020 suÜThc­£}¯²2(ÜThÅ´±j¯²2(ÜTh:<2<'F¯²2 ]^ÁÅ2, Webex, 2020 s 11  4-5 .
[17] ) ÔoßÝjÉDß/f`ßÜ0x, F45E $'F-ÂÌh"&#FÜÏÄÚ£}Un-ÝOÚÞ, 2020 suÜThc­£}¯²2(ÜThÅ´±j¯²2(
ÜTh:<2<'F¯²2 ]^ÁÅ2, Webex, 2020 s 11  4-5 .
[18] ) ¬/º, 3p, ËÈ, F¼ÕP, Ü0x, ¿r·ºZ/0E:<8@;CJTh7/:>25ÝOÚÞ, Zj¯²2»|2, Zoom, 2020 s 10  29-30 . ;¯ª¾Ê-*[19] ) ¬/ºßËÈß3pßF¼ÕPßÜ0x, Th4>ADF4BEÀ+½}/0E¾-Í +Th7/:>25, 

fj ®4E" 2020ß0E%/E, 2020 s

10  1 .;¯"5FÊ-*[20] ) ¬/º, 3p, ËÈ, F¼ÕP, Ü0x, :<8@;C-x+¿r·ºZ/0E
<\hTh4>ADF4BEÝOÚß~yÆÞ, ³ 69 UÜThÁÅ2, Webex, 2020 s 9  16-18 .
[21] ¬/º, ¿r·ºZ/0E¶+:<­TÖ~ThÌÎ£}/EF=D/Ý"5FÞ, jfÃdc >^B¨(>^¯²³ 12 U, Zoom/Slack, 2020 s 7  9 .
[22] Y. Shimizu, T. Kurokawa, H. Arai , H. Washizu, Estimation of higher order structure of model polymer using
persistent homology and machine learning, ³ 69 UÜThj2sf2,

h, 2020 s 5  27-29 ..

[23] Yoshiki ISHII, Go WATANABE, Nobuyuki MATUBAYASI, Takashi KATO, Hitoshi WASHIZU, Molecular
Modeling of Self-Organized Ionic Liquid Crystals: Nanochannel and the Hydration PropertiesÝOÚÞ, ³ 69 UÜT
hj2sf2,

5

h, 2020 s 5  27-29 .

'

[1]) Y. Ishii, N. Matubayasi, G. Watanabe, T. Kato, and H. Washizu, under review (2021).
[2]) Y. Shimizu, T. Kurokawa, H. Arai, and H. Washizu, “Higher-Order Structure of Polymer Melt Described by
Persistent Homology”, Sci. Rep. 11, 2274 (2021). DOI: 10.1038/s41598-021-80975-5 =D5&&F5L
https://www.u-hyogo.ac.jp/outline/media/press/2021/monthly/pdf/20210127.pdf- 393 -





Study of interfaces for artificial photosynthesis and inspection ofsolvers for strong electron correlation
C @K+ !J %D
L BK L -5 $N2 H
0 .#M G"(1&7:
O<) =*E ;>=  ';>=P
1 ;>98ĂÆ+  ë0$( œºƀB[pGu<ŷŗǂ*~ª%9%#8 }$4ÑƼ$ķ<Ø'ķų(śĎÍĐ9ä½ā+ġĥ<Ĉ Ï*Ćƅ$ 9 ǉ®ŏä½ā*3* MFuiÇƏÓ+ ķ*Ʋ±(68ǂÔŅ%'9ƲųŗœŰ% ǂÔ<¹¸8ķų<œā9ķųŗœŰ*ºƌúŬ²á :7<Żƶã5@Ds7ā9jV?BuRu Flo>ť¯7¶ú<Ʃ9¬ƏÓ
7īā:# 9 ²áģĖƁ(+ƫ£'ÁŌû%Ʋ±Ʈǂ*ñ Ĥ 8 ǑǂÔ*ķƲ±<Ƅ Ʋųŗœ*¬ƏÓ+ƈƿ'M`sōÿ<¸9ƬťƶãƲ±ŋ5osƲ±ŋ~ģĖ$ 9 ƏÓ*őƜƒƐ+×ƅŘ(4ŤŘýŽ74ƳƉ'ŠŨƚǈ$ 9 ĢŠŨ$+ ƏÓ*Flo>Ōû%Ə
ÓƒƐ<ŕǄ*ƍŉ7Ƅ %%4( :0$Ƹŗ#ƲųŗœŰ*¸8ą (ùƉ'ñŜƺQp]u*ĩƓ<ĔŘ(Ƅǉ®ŏB[pGuÍĐ<ÛŐ93*őƜŠŨ<ďƩ9 

2 ;>,3I?,3
ĢÊÂĝ$+ ÛęŠŨ* y*㸰ǆŚ(! #ƳŉŘ(ÊÂ9 ÙŶ½HnMRuĻ(69ıđ¯ƇĳĻ*Ƹŗ 6U7L2 *ƶãŕǄt5K Xuc6, %L92 *ǄĘÖû*ƎĦǆŚ+ *(//$1 < ǆŚ(! #+~( 9$63 <Ŕ  ŠŨĘĻ(! #+ ıŮ*ŠŨāħ$¥(Ƒƥ9

 ;>(/ ÙŶ½HnMRuĻ(69ıđ¯ƇĳĻ*ƸŗƲųŗœŰ*ƏÓt¬ƏÓ<īā9ƬťƶãƲ±ŋ5ƬťƶãosƲ±ŋ*$+ ķ*ǑǂÔƲ±(ƺ;9}ƹñ ǂÔŜƺ<ţ Ƨé*ǂÔōÿőƜ$+ĳ īƨ5M`sGlTc<÷9%ǁ*3 ñ ǂÔŜƺ<¸8ą 3*Qp]u%# àôŇŭÔ<Ŕ  3URMHFWHG+DUWUHH)RFN 3+)
Ļ5 SRVW3+) Ļ ­Ɵōÿ*Ù &, Ǝ<ĸ393*kVpũƹƵÔksUEpr 0640& Ļ ÙŶ½
HnMRu7ƭćŘ(ƵÔČê<ĹÚ9 )&&5 )XOO&RXSOHG&OXVWHU5HGXFWLRQ Ļ >;X8HMLPD7HQQR3K\V
5HY/HWW  @*Ƹŗ<Ƅ #ĥ Ō( )&&5 Ļ+ Ƥëř=(ŠŨƄ;:# 9ƭć &,Ļ*L@NŞŝ*İŉ<È39ğ®'ĄĻ$ 8 ǂÔōÿőƜ$' ƵÔKs`muU?sI¢ƴ$4¦ŔĽŚ:# 9 Ģƚǈ$+ )&&5 Ļ(ıđ¯Ƈĳ<ŵ1½;9%(68 ƐŭKMW<- 394 -

Ðê(§ł9%( )&&5 B[pGu%ıƇĳB[pGu*ŸÇû<ÉŢ%Ù &, B[pGu*ÎčĻ<ĩƓÙ &, ļ¯ƺĔ+ :%ū'ċĔƺĔÇ*ÙŶ½HnMRuļ¯ƺĔ$ƆŐ9%¡ĥ9




 

  öſ+ 6L]HH[WHQVLYH 'ƆŐ$ 8 & Ű*Ð(ß#ċĔƺĔŘ(Ì«9*(ß 7 +Ÿó(Ì«' %joTW 9 )&&5 Ļ+ ƳƉ'HnMRuŇŭÔ 7 <­Ɵũƹ%ǃŸóŇŭ(ß9MHou
ZsI<Ƅ

%(68

ǉůí*ļ¯ƺĔ<ĸ39%$9ñª'ĄĻ$ 9 ĢŠŨ$+ )&&5 Ļ*Ĵƙæ<ıđ¯Ɯ%đ¯Ɯ$ĸ39 )&&5  Ļ*Ƹŗ<Ƅ >;X 8HMLPD7HQQR - 3K\V &KHP /HWW   @ Åǎ(ţƧ8 ıđ¯B[pGu(  + )&&5*­ƟgZmaCpX%\hpWsŇŭÔ*ĐÔƘƟ9#*ũƹ<Ŕ()&&5 %*Ÿóƺ<Ŕ #Ù &, B[pGu*ďÚ<ĸ39ǃŸóŇŭ<À2)&&5 Ư¢$+#* 03, crOMHnMRuŇŭÔ
<jkou(Ċ

#

9ùƉû

9*(ß

đ¯ũ

Åǎ FCCR(2)Ļ*Ʊżũƹ%ÎčMFui

ƹ 4 +Ù' 03, ¢ēºƀ$ 8 Ơ|¤ƐŭŒË(ƫĄĻ$ 9v%# kVpFmcquW>&X 1+ @2* SHUR[R ELV R[R Ŗû*Ŷħ<Ɔǎ(ţ ĞÐ*)&&5 ­ƟgZmaCpX 13 +  wıñ(ß đ¯Ƈĳ$+:684űǒĨÐ ı 14 7*Ü{<žĀ# 9 SHUR[R Ŗû<(¸9% )&&5  Ļ7*ŜƺB[pGuP(K (ß Îč
B[pGu+ P(K $ 8 Îčơǀ+ŜƺB[pGu*ǎǊ(4ń' %¢9 Ŗ'9đ¯¢©*Ŷħ (1 %*æ+  P(K $ 8 đ¯Ƈĳ*ƙæ+ŜƺB[pGu* Ŧí$ 9%ü:9ÅǏ(¾Ű*Ŗû±B[pGu<*ǂÔŜƺĄĻ%Ķƣ9 Ģƚǈ$Ŕ 7: )&&5  Ļ%*Îč )&&5  ([ *Ŷħ+ ĄĻ*Ōû%Ɛŭ
ƋĮ7:0$*ĕŎ$Ğ4Ǉíǉ %ž
7:9 Ð ľûũƹ<Ŕ  5$637 Ļ%'05*&$637 Ļ+Ī)¾ū*Ŷħ<{# 9&&6' 7 Ļ4¾Ĭ'Ŷħ<{#

9

)&&5 Ļ

$+ǓǂÔ­Ɵū*ǉı*­ƟŇŭÔùƉ$ 9
%7 ƙæ*Ŝĵœ# 94*%ž7:
9)&&5  Ļ+ĶƣŘÐ'¢Ô*´ÝƎ<ďÚ9*(ñª'ĄĻ$ 8 *ğ®û+dsPs*É

Ɔǎ >&X 1+ @2Ŗû(ß9 )&&5 ìōÿB[pGu(ß9dsSguH( #4

Ļ*ÍĔ*Ĕ%B[pGuƉų

¥Ʀţ:# 9>(ULNVHQ HW DO - 3K\V &KHP /HWW- 395 -   @(2) SrTiO3 *ƶãŕǄtRh Xuc6, BiVO4

100*ǄĘÖû*ƎĦ
6U7L2 +ƫ£'Xu`sIĤ$ =MFui
V?BuRu%*ŕǄ(9]sXĜ85
Flo>Ōû+V]@Mûƀ*ĒƱÄÔ$8 őƜŘ'ŌûƔƳƉ'ƚǈ$ 9 0
ǉ®ŏ±<ŚċºƌúŬ*3*Xu^


sW%# 5K +ǂƃ Ŷ½}ø%'8 Ʋųİ
ƻ5 6E Xucy$* 5K$ƏÓľû¿x

80Interconversion energy (kcal/mol)Ç*²áƏÓ$ƳƉ'ģĖ$ 9 ƶãj

FCIQMC-sc-NEVPT2HF
FCCR(2)-Ex

60
DMRG-SCF

CCSD(T)

CR-CCSD(TQ)L40
RASPT2
DMRG-CASPT220
FCIQMC-CASCI

9%ş7:# 9 ĢǆŚ*¨Ź$+ Ʋų
ŗœŰ%ķųŗœŰ<!'ƶãjV?BuR
u%#ƶ6,Ʒ%*ŕǄ*Ɛŭ<ƄFCCR(2)

FCCR

0

Fl

o>Ōû*ƪ <ƎĦ 7( Ʋųİƻ%-20

5K6E Xucy$*ņØÚŜ%Á·MeHWpÅǏ ¼ŧǂÔŜƺőƜ(69>&X 1+ @2*Ɛŭ<Ƅ 

*Ŗû±B[pGu*ĶƣÅǐ( SrTiO3/Au % SrTiO3/Ag *MnbĮÇ(ĺ âăōÿÝí<ţ źƢB[pGu įƢÅ*y(Ʊż# 9MnbkVp(ßúî
ĭ$ 8 ǂÔ*ōÿÝí<Å*»*MJup(ßúňŁ$Ɔ# 9 áèyŪtǂÔèxŪ
*ōÿÝí%4( ƶãŕǄ(Ƥ"/&ǉ B[pGuè(¢ç96 (Í±#8 ƶã7²á-*ǂÔ%²á7ƶã-*ĳÕ*Ŀ:<Ʃ9]sXdsV?sIšƗ$ ƺĔ7*Ń%vƂ9 dsV?sI*ñ(! #žÞ9% 6U7L2$X $+ŕǄƤ*ǂÔè*ōÿÝí6 H9 Ƥ0$¢ç# 9*(ß 6U7L2$J $+6 H9 Ƥ0$*¢ç$ 8$J Ď½Ě684 $X Ď½Ě*Ęñ dsV?sI<Ɵ#
9%¢9 :7*Ŷħ68ǍķųŗœƏÓ%#6U7L2 <fMWģĖ%Ě*=MFuiÇƏÓ*jV?B
uR%#+ $X *ĘFlo>ť¯(ğ¦$ 9%ţÃ
:9
ı( 6U7L2 * 5K Xuc% 6E*Xuc*ôǅ<ƛ.9Åǐ 6U7L2$Xǋåǌ%6U7L2$Jǋ»ǌŕǄ*MnbkVp
ǋyǌ%âăōÿÝí(69Ķƣǋxǌ

3 *Mu^uOp(É"Á·MeHWp*ƐŭŶħ<ÅǑ(ţ 5K *1*Xu`sI$+ 5K$
8 ºƌÁ·Ɗ7:94** 5K óā9>HOcRuņǂƃ Ŷ½}ø%'8 ƵÔ·ŏ*
y<ðƟ# 9%ž7:9 6EXuc$+ 5K-*Ĕ*Í±(- 396 -

>HOcRuņƺ

{9ƬťŀÒ9 0 5K % 6E +ƾĎƱż$Ğ4ØÚ'ŶěŜ<óā9%4ţÃ:7( ƲųŗœŰ %L92 *  %  ǄĘ
Öû<MnbkVp<Ŕ ƺĔ zľû³ÔµŊƐŭǂƃİƻƐŭ<Ƅ:*ĘĻ$4 Ǆ  Ǆ684ǎH9 Ŧí*ØÚûƊ7:ǄĘÖûǂƃ¢ǀ*Xn@_sIaCuM$
9%(Ʋųŗœ  Ǆ$°$

9%

Ɛŭ(6 #ţ: Ŷħ*ƖŴ+ŲǄ*ư½x©
þ9

4

6FA



6HLLFKLUR/7HQQR³7KHIXOOFRXSOHGFOXVWHU

ÅǑ 6U7L25K6E Xuc*Mu^Opk

DSSURDFKIRUDFFXUDWHWUHDWPHQWRIVWURQJO\

Vp%Á·MeHWp

FRUUHODWHGHOHFWURQV´1HZ+RUL]RQVLQ6FLHQWLILF
6RIWZDUHIURP/HJDF\&RGHVWR0RGXODU(QYLURQPHQWV 1RYHPEHU   -HMX6RXWK.RUHD LQYLWHG RQOLQHSDUWLFLSDWLRQ
òƕëí+ :Îǔ*Æƽƞ*ĉõƝŇėÇKrYA@pM*ôǅ$ïĠ0+}Ĳ%' 

5

4A



³7RZDUGVQHDUH[DFWVROXWLRQVRIPROHFXODUHOHFWURQLFVWUXFWXUH)XOOFRXSOHGFOXVWHUUHGXFWLRQZLWKDVHFRQG
RUGHUSHUWXUEDWLYHFRUUHFWLRQ´(;X08HMLPDDQG6/7HQQR
-3K\V&KHP/HWW í  

³4XDGUDWLFDOO\FRQYHUJHQWVHOIFRQVLVWHQWILHOGRISURMHFWHG+DUWUHH)RFN´
08HMLPDDQG6/7HQQR
-&KHP3K\V   

³7KHJURXQGVWDWHHOHFWURQLFHQHUJ\RIEHQ]HQH´--(ULNVHQ 7$$QGHUVRQ -('HXVWXD .*KDQHP '+DLW 05+RIIPDQQ 6/HH '6/HYLQH ,
0DJRXODV -6KHQ 107XEPDQ .%:KDOH\ (;X <<DR 1=KDQJ $$ODYL *./&KDQ 0+HDG
*RUGRQ :/LX 33LHFXFK 66KDUPD 6/7HQQR &-8PULJDU -*DXVV-3K\V&KHP/HWW   

³7KLUGRUGHU(SVWHLQ1HVEHWSHUWXUEDWLYHFRUUHFWLRQWRWKHLQLWLDWRUDSSUR[LPDWLRQRIFRQILJXUDWLRQVSDFHTXDQWXP0RQWH&DUOR´%/DGyF]NL08HMLPDDQG6/7HQQR
-&KHP3K\V   

³6SLQSURMHFWLRQIRUTXDQWXPFRPSXWDWLRQ$ORZGHSWKDSSURDFKWRVWURQJFRUUHODWLRQ´
77VXFKLPRFKL<0RULDQG6/ 7HQQR
3K\V5HY5HVHDUFK   - 397 -

ᐇ㦂࡜ィ⟬ࡢ⼥ྜ࡟ࡼࡿẼ┦⏕యศᏊࡢ⢭ᐦᵓ㐀Ỵᐃ㸸ศᏊㄆ㆑ᶵᵓࡢゎ᫂࡟ྥࡅ࡚
3UHFLVHVWUXFWXUDOGHWHUPLQDWLRQRIJDVSKDVHELRPROHFXOHV 
E\H[SHULPHQWDQGWKHRU\WRZDUGHOXFLGDWLRQRIPROHFXODUUHFRJQLWLRQV\VWHPV‫ۑ‬ᖹ⏣ ᆂ♸㸦ᮾᕤ኱໬⏕◊㸧




◊✲┠ⓗ
⏕యෆ࡛ࡣ࠶ࡿ≉ᐃࡢ㔠ᒓ࢖࢜ࣥࡀ࢔࣑ࣀ㓟ࡸࢱࣥࣃࢡ㉁࡜≉␗ⓗ࡟⤖ྜࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡓ࡜

࠼ࡤࠊ.ࢳࣕࢿ࡛ࣝࡣ .ࡢࡳࡀࢳࣕࢿࣝࢆ㏱㐣ࡍࡿࡇ࡜ࡀ࡛ࡁࠊ1Dࡣࢳࣕࢿࣝ୰ࢆ㏱㐣ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞
࠸ࠋࡲࡓࠊࣂࣜࣀ࣐࢖ࢩࣥ㸦ᅗ D㸧ࡣ .࡜㑅ᢥⓗ࡟⤖ྜࡋࠊ⣽⬊⭷୰ࢆ㏱㐣ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿
ࡋࠊ⏕యෆ࡛ࡣከ✀ከᵝ࡞ศᏊࡀᏑᅾࡋࠊࡑࡢᙳ㡪ࡀ↓ど࡛ࡁ࡞࠸ࡓࡵࠊ࡞ࡐࡇࡢࡼ࠺࡞࢖࢜ࣥ㑅ᢥᛶࡀ⏕ࡌࡿࡢ࠿᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣᐜ࡛᫆࡞࠸ࠋ࡜ࡾࢃࡅࠊ㏻ᖖ㔠ᒓ࢖࢜ࣥࡣ⏕యෆ࡛Ỉ࿴ࡉࢀ࡚࠸ࡿࡓࡵࠊỈศᏊࡀ࢖࢜ࣥ㑅ᢥᛶ࡟࡝ࡢࡼ࠺࡞ᙳ㡪ࢆ୚࠼ࡿࡢ࠿᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣ㠀ᖖ࡟㔜せ࡛࠶ࡿࠋࡑࡇ࡛ࠊ⚾ࡓࡕࡣ෭༷࢖࢜ࣥࢺࣛࢵࣉ㉥እศගἲ࡜ᐦᗘỗ㛵ᩘ⌮ㄽ㸦')7㸧ィ⟬ࢆ⏝࠸࡚ .ࢳࣕࢿࣝ㒊ศ࣌ࣉࢳࢻ㸦ࢢࣜࢩࣥ㸫ࢳࣟࢩࣥ㸫ࢢࣜࢩࣥ㸧㸫㔠ᒓ㘒య㸦*<*0㸧࠾ࡼࡧࣂࣜࣀ࣐࢖ࢩࣥ㸫㔠ᒓ㘒య㸦900㸧࡜ࡑࡢỈ࿴ࢡࣛࢫࢱ࣮ࡢศᏊᵓ㐀ࢆゎ᫂ࡋࠊ࣑ࢡࣟ࡞Ỉ࿴ຠᯝࡢほⅬ࠿ࡽ࢖࢜ࣥㄆ㆑ᶵᵓࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ࢚ࣞࢡࢺࣟࢫࣉ࣮ࣞ࢖࢜ࣥ໬ἲ࡟ࡼࡾ┠ⓗࡢ㔠ᒓ㘒యࢆ⏕ᡂࡋࠊᅄ㔜ᴟ㉁㔞ศᯒィ㸦406㸧࡛≉ᐃࡢ࢖࢜ࣥࡢࡳࢆ㑅ูࡋࠊ . ࡲ࡛෭༷ࡋࡓඵᴟᏊ࢖࢜ࣥࢺࣛࢵࣉ࡟ᑟධࡋࡓࠋࡇࡇ࡟ỈศᏊࢆᑟධࡋࠊỈ࿴ࢡࣛࢫࢱ࣮ࢆ⏕ᡂࡋࡓࠋ஧ྎ┠ࡢ 406 ࡛┠ⓗࡢỈ࿴ࢡࣛࢫࢱ࣮ࢆ㑅ูࡋࠊ. ࡲ࡛෭༷ࡋࡓ࢖࢜ࣥࢺࣛࢵࣉෆ࡟
࢖࢜ࣥࢆᤕᤊࡋࡓࠋࡇࡇ࡟Ἴ㛗ྍኚ㉥እ࣮ࣞࢨ࣮ࢆᑟධࡋࠊ㉥እ྾཰࡟ࡼࡾᚓࡽࢀࡓゎ㞳≀ࡢ࢖࢜ࣥ㔞ࢆᚋẁࡢ㉁㔞ศᯒィ࡛ᐃࡍࡿࡇ࡜࡛㉥እ྾཰ࢫ࣌ࢡࢺࣝ࡟┦ᙜࡍࡿ㉥እගゎ㞳㸦,53'㸧ࢫ࣌ࢡࢺࣝࢆᐃࡋࡓࠋ┠ⓗࡢỈ࿴ࢡࣛࢫࢱ࣮ࡢྲྀࡾ࠺ࡿᒁᡤᏳᐃᵓ㐀ࢆ ')7 ィ⟬࡟ࡼࡾồࡵࠊ,53' ࢫ࣌ࢡࢺࣝ࡜ࡢẚ㍑࠿ࡽศ
Ꮚᵓ㐀ࢆᖐᒓࡋࡓࠋ*<*0㘒య࡛ࡣࠊỗ㛵ᩘ࡜ࡋ࡚ %/<3'ࠊᇶᗏ㛵ᩘ࡜ࡋ࡚ FFS97= /L1D.&+2
1 ࠊGHI7=933 5E&V ࢆ⏝࠸ࠊ900㘒య࡛ࡣࠊࡑࢀࡒࢀ %/<3'%-ࠊ* GS  /L1D.&+21 ࠊ
ODQOG] 5E&V ࢆ⏝࠸ࡓࠋィ⟬ࡣ 7XUERPROH ࠾ࡼࡧ *DXVVLDQ ࢆ⏝࠸࡚⾜ࡗࡓࠋ



◊✲ᡂᯝ

 ⣬㠃ࡢ㒔ྜୖࠊ900㘒యỈ࿴ࢡࣛࢫࢱ࣮ࡢ⤖ᯝࢆ⤂௓ࡍࡿࠋ෭༷࢖࢜ࣥࢺࣛࢵࣉ㉥እศගἲ࡜࿧ࡤࢀࡿ
㠉᪂ⓗ࡞ศගᢏ⾡ࢆ⏝࠸࡚ࠊ90.㘒య࡟ỈศᏊࡀ୍ࡘ௜ຍࡋࡓỈ࿴ࢡࣛࢫࢱ࣮㸦90. +2 㸧ࡢ㉥እࢫ࣌ࢡࢺࣝࢆᐃࡋࡓࠋ%/<3'%-ODQOG] 5E&V * GS  RWKHUV ࣞ࣋ࣝࡢ ')7 ィ⟬࡟ࡼࡾᚓࡽࢀࡓ⌮ㄽ㉥እࢫ࣌ࢡࢺࣝ࡜ࡢẚ㍑࠿ࡽࠊ୕✀㢮ࡢ␗ᛶయ $ࠊ%ࠊ& ࡀඹᏑࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ␗ᛶయ $ࠊ% ࡣ࡜ࡶ࡟ỈศᏊࡀ 90 ࡢࢣ࣮ࢪෆ㒊࡟ධࡾ㎸ࡳࠊỈࡢ㓟⣲ࡀ .࡜┤᥋┦஫స⏝ࡋ࡚࠸ࡿࡀࠊỈศᏊࡢ఩⨨ࡀ␗࡞- 398 -

ࡿࠋ୍᪉ࠊ␗ᛶయ & ࡣỈศᏊࡀ 90 ࡢࢣ࣮ࢪእ࡟࡜࡝ࡲࡾࠊ90 ࡢ࢝ࣝ࣎ࢽࣝ㓟⣲࡜Ỉ⣲⤖ྜࢆᙧᡂࡋ࡚࠸
ࡿࠋ␗᪉ᛶࣃ࣓࣮ࣛࢱࡢゎᯒ࠿ࡽࠊ␗ᛶయ & ࡣ⌫࡟㏆࠸ᵓ㐀ࢆࡋ࡚࠾ࡾࠊỈࡀ௜ຍࡋ࡚࠸࡞࠸ 90.㘒య࡜ẚ㍑ࡋ࡚ࡶࡼࡾࢥࣥࣃࢡࢺ࡞ᙧ≧ࢆࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࢀࡣỈศᏊࡀ୍ࡘ௜ຍࡍࡿࡇ࡜࡛
90 ࡀࡼࡾࢥࣥࣃࢡࢺ࡟࡞ࡾࠊ⬡㉁⭷୰࡛ࡢ㏱㐣ᛶࡀྥୖࡍࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋࡇࡢᡂᯝࡣ 7KH-RXUQDORI
3K\VLFDO&KHPLVWU\/HWWHUV ㄅ㸦ᰝㄞ᭷㸧࡟ᥖ㍕ࡉࢀࠊ6XSSOHPHQWDU\&RYHU ࡟㑅ฟࡉࢀ࡚࠸ࡿࠋᅗ D  ࣂࣜࣀ࣐࢖ࢩࣥ㸦90㸧ࡢศᏊᵓ㐀ᘧ㸬E 90. +2 ࡢ㉥እࢫ࣌ࢡࢺࣝ㸦ୗẁ㸧㸬ୖẁࡣ⌮ㄽ
㉥እࢫ࣌ࢡࢺࣝ㸦␗ᛶయ $–&㸧㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬.HLVXNH+LUDWD(LNR6DWR6KXQLFKL,VKLXFKL0DVDDNL)XMLL*RUGRQ5HVHDUFK&RQIHUHQFHV0ROHFXODUDQG ,RQLF
&OXVWHUV9HQWXUD%HDFK0DUULRWW9HQWXUD&$86$-DQ‫ ۻ‬኱ྂ

ᣑᘺࠊ⏣➃ ࡳࡎࡁࠊ-DPHV /LV\ࠊྜྷ᳃

⠜ྐࠊ୰㔝

ὒᩥࠊᖹ⏣

ᆂ♸ࠊ▼ෆ

ಇ୍ࠊ⸨஭

ṇ

᫂ࠊศᏊ⛉Ꮫ࢜ࣥࣛ࢖ࣥウㄽ఍ࠊ ᖺ  ᭶㸬
‫ ۻ‬᳃

ඃኴࠊᖹ⏣

ᆂ♸ࠊ▼ෆ

ಇ୍ࠊ⸨஭

ṇ᫂ࠊ$QQH =HKQDFNHU5HQWLHQࠊศᏊ⛉Ꮫ࢜ࣥࣛ࢖ࣥウㄽ఍ࠊ ᖺ  ᭶㸬‫୕ ۻ‬஭

⪽୍㑻ࠊᖹ⏣

ᆂ♸ࠊ▼ෆ ಇ୍ࠊ⸨஭

ṇ᫂ࠊศᏊ⛉Ꮫ࢜ࣥࣛ࢖ࣥウㄽ఍ࠊ ᖺ  ᭶㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ ۻ‬71HJRUR.+LUDWD-0 /LV\6,VKLXFKL DQG 0)XMLL3K\V&KHP&KHP3K\VLQSUHVV‫ ( ۻ‬6DWR . +LUDWD - 0 /LV\ 6 ,VKLXFKL DQG 0 )XMLL - 3K\V &KHP /HWW 12    6HOHFWHG DV
6XSSOHPHQWDU\ FRYHU ‫ ۻ‬. +LUDWD < 0RUL 6 ,VKLXFKL 0 )XMLL DQG $ =HKQDFNHU 3K\V &KHP &KHP 3K\V 22   
6HOHFWHGDV%DFNFRYHU3&&3+27$UWLFOHV ‫ ۻ‬52WVXND.+LUDWD<6DVDNL-0/LV\6,VKLXFKLDQG0)XMLL&KHP3K\V&KHP 21   6HOHFWHG
DV)URQW&RYHU - 399 -











Preparation and arrangement of pi-electronic systems including ioniccompounds
? A.
+
. !(; B<= 8%' 60>. C@$*&"D
1



3421
{¹ Nd½ZF rwQt!((¶£ª¿ #-+|¤Á

/-Nd!(.0~e Nd(|´Orw g*,%-v?
v/({/R¢- X-ª¿!23>vNd/[&%%|¤¾d Zx/ ¾d?Lv/¨J-+23>ºCG/!'-NdºCG/PNd½ZF ^/'

2

34#,:5#,
A² ¥ g},Gaussian 16 /P

3

34)
b

Wd;@:>7/-¾d)¾

/-¾d%%|¤¾d/Zx±)¾d?Lv»-¬¥/ H"mÂy_/-=2591/jM¾d/Zx=25µÅ183>*$=25`_Å463>EZFrx*-¾dw

a«/g] 1. _p?U®w -EZF ¾dw ¬¥*,_pw *$U®w
 -Nd¯³/¥T-23> ÀIeLfv aV/©-xSÃ] &KHP&RPPXQ  ±Ä

4/97
x5

k¸¼n khzq ·iB cs­ lKY23>uv )UXVWUDWHG/HZLV3DLU [¾d ZxLv  \ÂNd¦¬E 3><2> o  Ãª¿»²-fE¡ 9 D
 1 D/§°Ä-7
x
x

x
x





,\RGD62NDGD*.LNXFKL.<DPDNDGR52NDGD6 0RO&U\VW/LT&U\VWLQSUHVV2VKLPL]X67DNHVKL66DWR7<DPDNDGR57DWHZDNL<2NDGD6 &U\VW*URZWK'HV ±
 <DQEH70L]XJXFKL.<DPDNDGR5 2NDGD6&KHP&RPPXQ  ±
.RGDPD6$R\DPD67DQDND<,FKLMR.<RVKLGD7<DPDNDGR5 2NDGD6 0RO&U\VW/LT&U\VW±

- 400 -

ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㧗ศᏊᾮᬗ࠾ࡼࡧࣔࢹࣝᾮᬗ໬ྜ≀ࡢ⇕ఏᑟ≉ᛶゎᯒ
Analysis of thermal conductivity for liquid crystal polymers and modelcompounds using molecular dynamic simulation
‫ྂۑ‬ᒇ

⚽ᓠࠊ᳝㔝

Ⰻ௓ࠊἙ⏣

ᝆኴࠊ㉥ሯ

ၨ⣖ࠊᰗཎ

ᩄᡂ

㸦ᮾிᕤᴗ኱Ꮫ≀㉁⌮ᕤᏛ㝔㸧1◊✲┠ⓗᮏ◊✲ࡢ┠ⓗࡣࠊ඲ཎᏊศᏊືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ㧗ศᏊᾮᬗ࠾ࡼࡧ␗᪉ⓗ㓄ྥᮦᩱࡢ⇕ఏᑟ≉ᛶࡢ᳨ウ࡛࠶ࡿࠋ㏆ᖺࠊ࢚ࣞࢡࢺࣟࢽࢡࢫࢹࣂ࢖ࢫࡢ㛤Ⓨ࡟࠾࠸࡚ᨺ⇕ᛶࡢྥୖࡀồࡵࡽࢀ࡚࠸࡚ࠊ
ᡂᙧᛶ࡟ඃࢀศᏊタィࡸ」ྜ໬ࡀᐜ᫆࡞㧗ศᏊᮦᩱࡢ㧗⇕ఏᑟ໬ࡢ◊✲࡟ὀ┠ࡀ㞟ࡲࡗ࡚࠸ࡿࠋ
㧗ศᏊᮦᩱࡢ⇕ఏᑟ⋡ࢆྥୖࡉࡏࡿࡓࡵࡢศᏊタィ࡜ࡋ࡚ࠊᾮᬗᙧᡂ⬟ࢆ᭷ࡍࡿᵓ㐀༢఩㸦࣓ࢯࢤࣥ㸧ࢆ㧗ศᏊ㙐ࡢ⧞ࡾ㏉ࡋ༢఩࡟⤌ࡳ㎸ࡴࡇ࡜ࡸࠊ㧗ศᏊ㞟ྜᵓ㐀ࡢ㓄ྥไᚚࢆ฼⏝ࡍࡿࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋࣇ࢛
ࣀࣥࡢࣃ࣮ࢥ࣮ࣞࢩࣙࣥࣃࢫࡢᙧᡂࡀ⇕ఏᑟࡢせᅉ࡛࠶ࡿ࡜࠸࠺௬ᐃ࡟ᇶ࡙ࡁࠊ⇕ఏᑟ⋡ྥୖ࡟ࡣ␗᪉ⓗ࡞㓄ྥ㞟ྜᵓ㐀ࡢᙧᡂࡀ㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋᡃࠎࡣࠊ㧗ศᏊᾮᬗࡢᾮᬗ┦㓄ྥ≧ែ࡟࠾ࡅࡿ⇕ఏᑟᶵᵓࡢゎ᫂࡜㧗⇕ఏᑟᮦᩱࡢศᏊタィࡢ☜❧ࢆ┠ᣦࡋࠊ㧗ศᏊᾮᬗࠊ࠾ࡼࡧࣔࢹࣝ஧㔞యᾮᬗ㸦Figure 1 ཧ↷㸧ࡢ┦㌿⛣ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜⇕ఏᑟ⋡ࡢゎᯒࢆ⾜࠺ࠋᡃࠎࡣࠊ୺㙐ᆺ㧗ศᏊᾮᬗࡢ┦㌿⛣ᣲື࡜ࢥ࣓࣮ࣥ࣍ࢩࣙࣥ≉ᛶ࡟ࡘ࠸࡚ࠊ㔜Ỉ⣲ NMR

ᐃ࡜ᅇ㌿␗ᛶ

≧ែ㏆ఝゎᯒࢆ⤌ࡳྜࢃࡏࠊ࢔ࣝ࢟ࣝࢫ࣮࣌ࢧ࣮࡟≉᭷ࡢࢿ࣐ࢳࢵࢡ࣭ࢥ࣓࣮ࣥ࣍ࢩࣙࣥࡢᐃ㔞ⓗゎᯒࢆ⾜࠸ࠊ⇕ຊᏛ㔞ࡢഅወຠᯝࡢཎᅉࢆ᫂ࡽ࠿࡟ࡋ࡚ࡁࡓ[1]ࠋ᫂ࡽ࠿࡟ࡋࡓࢿ࣐ࢳࢵࢡ┦ࡢࢥ࣓࣮ࣥ࣍ࢩࣙࣥࢆ⏝࠸࡚ࠊ཮ᴟᏊ࣮࣓ࣔࣥࢺࠊ☢໬⋡ࡢ␗᪉ᛶࠊගᏛ␗᪉ᛶࡢᐇ㦂್ࢆ᳨ドࡋࡓࠋࡉࡽ࡟ࠊᾮᬗࡢ␗᪉┦㸫➼᪉┦㌿⛣࡟࠾ࡅࡿ≀ᛶኚ໬ࢆศᏊ㓄ྥࡸศᏊࢥ࣓࣮ࣥ࣍ࢩࣙࣥ࡞࡝ࡢศᏊࣞ࣋ࣝࡢ᝟ሗ࡜㛵㐃௜ࡅ࡚ࠊ㓄ྥ␗᪉ᛶሙ࡟࠾ࡅࡿศᏊࡢᯝࡓࡍᙺ๭ࢆᐃ㔞ⓗ࡟᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ᐇ㦂ⓗᡭἲ࡟ྜࢃࡏ࡚ศᏊࢩ࣑࣮ࣗࣞࢩࣙ
ࣥࢆ⾜࠺ᚲせࡀ࠶ࡿࠋ)LJXUH0DLQFKDLQOLTXLGFU\VWDOSRO\PHUDQGPRGHOGLPHUOLTXLGFU\VWDOV        ඹྠ◊✲⪅࡛࠶ࡿᮾிᕤᴗ኱Ꮫᕝෆࢢ࣮ࣝࣉ࡛ࡣࠊ௦⾲ⓗࢧ࣮ࣔࢺࣟࣆࢵࢡ༢㔞యᾮᬗ࡛࠶ࡿ 4-cyano-4̓

- 401 -

-alkyl-biphenyl ࡟㐺ࡋࡓຊሙࡢ㛤Ⓨࢆ⾜ࡗࡓࠋ㛤Ⓨࡋࡓಟṇ Amber ᆺຊሙࢆ⏝࠸ࡓ MD ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ
ࡣࠊ➼᪉┦࠿ࡽࢿ࣐ࢳࢵࢡ┦࡬ࡢ⮬Ⓨⓗ㌿⛣ࢆ෌⌧ࡋࠊᐦᗘࡢ

ᗘ౫Ꮡᛶࡸ┦㌿⛣

ᗘ࡞࡝ࡢᐇ㦂⤖ᯝࢆࡼࡃ෌⌧ࡋࡓ[2, 3]ࠋ㛤Ⓨࡋࡓຊሙࡣࠊᶆ‽ Amber ᆺຊሙ㛵ᩘࢆඖ࡟௨ୗࡢ 2 Ⅼࢆಟṇࡋࡓࡶࡢ࡛࠶ࡿࠋ
㸯㸬ࣅࣇ࢙ࢽࣝ㒊఩ࡢෆ㒊ᅇ㌿࣏ࢸࣥࢩࣕࣝࣃ࣓࣮ࣛࢱࡢ MP2/6-311G(d,p)ࡢ Gaussian ィ⟬⤖ᯝ࡬ࡢ㐺ྜ
㸰㸬Lennard-Jones ࣃ࣓࣮ࣛࢱ࣮ࡢㄪᩚ࡟ࡼࡿ⣔ᐦᗘࡢ෌⌧ᮏ◊✲ࡢᑐ㇟࡛࠶ࡿࣔࢹࣝᾮᬗศᏊ㸦Figure 1 ཧ↷㸧ࡢ࣓ࢯࢤࣥࡣࠊ4-cyano-4’-alkylbiphenyl ࡜ྠᵝ࡞ᵓ㐀࡞ࡢ࡛ࠊྠᵝࡢಟṇ᪉ἲࢆ⏝࠸࡚ಟṇຊሙࢆసᡂࡋࠊMD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࠋᮏ◊✲࡛ࡣࠊࡲࡎࠊ஧
㔞యᾮᬗ CBA-n ࡟ࡘ࠸࡚ࠊ࢔ࣝ࢟ࣝࢫ࣮࣌ࢧ࣮ࡢⅣ⣲ᩘ n ࡟౫Ꮡࡍࡿ┦㌿⛣ᗘࡸ⇕ຊᏛ㔞ࡢഅወຠᯝ࡟ࡘ࠸᳨࡚ウࡋࡓࠋࡲࡓࠊᾮᬗ┦ࡢᵓ㐀࡟ࡘ࠸࡚⣔ࡢ㓄ྥ⛛ᗎᗘࢆồࡵ࡚ࠊ㓄ྥᵓ㐀ࢆㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ MD ィ⟬ࡣ Gromacs2016.5 ࢆ⏝࠸࡚⾜ࡗࡓࠋࡲࡓࠊ㔞Ꮚ໬Ꮫィ⟬ࡣ Gaussian16 ࢆ⏝࠸࡚⾜ࡗࡓࠋࢩ࣑ࣗ

࣮ࣞࢩࣙࣥᑐ㇟ศᏊࡣ஧㔞యᾮᬗࡢ CBA-9 ࡜ CBA-10 ࡛࠶ࡿࠋຊሙࡣࢩ࢔ࣀࣅࣇ࢙ࢽࣝᾮᬗྥࡅ࡟ಟṇࡉࢀࡓຊሙࢆ⏝࠸ࡓࠋ࣓ࢯࢤࣥ㒊఩࡛࠶ࡿࣅࣇ࢙ࢽࣝᇶ࡟࠿࠿ࢃࡿຊሙࣃ࣓࣮ࣛࢱ࣮࡟ࡣࠊᕝෆࢢ࣮ࣝࣉࡀ㛤Ⓨࡋࡓຊሙࢆඖ࡟ಟṇࡋ࡚⏝࠸ࡓࠋ㟁Ⲵ࡟ࡣ RESP 㟁Ⲵࢆ⏝࠸ࡓࠋࢭࣝ୰ࡢศᏊᩘࢆ 128 ಶ࡜ࡋ࡚ࠊ᫬㛫้ࡳࡣ 1 fs ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋᐇ㦂್ࡼࡾపᐦᗘࡢ 0.8
g/cm3 ࡛❧᪉యࢭࣝ࡟ศᏊ㓄⨨ࢆࣛࣥࢲ࣒࡟Ⓨ⏕ࡉࡏࠊ➼᪉┦ࡢᗘ࡛ࠊNVT ᮲௳ୗ࡛⦆࿴ࡉࡏ࡚➼᪉┦ࢆసᡂࡋࡓࠋࡇࢀࢆึᮇᵓ㐀࡜ࡋ࡚ࠊNPT ࢔ࣥࢧࣥࣈ࡛ࣝࢿ࣐ࢳࢵࢡ㸫➼᪉┦㌿⛣Ⅼ㏆ഐࡢ

ᗘᩘⅬ࡛ 20ns㛫᫬㛫Ⓨᒎࡉࡏࠊࢿ࣐ࢳࢵࢡ㸫➼᪉┦ࡢ┦㌿⛣ᣲືࢆㄪ࡭ࡓࠋNPT ィ⟬࡛ࡣࠊNose-Hoover ࢧ࣮ࣔࢫࢱࢵࢺ
࡜ Parrinello-Rahman ࣂࣟࢫࢱࢵࢺࢆ⏝࠸ࠊ1 bar ࡢᅽຊୗ࡛ᐇ⾜ࡋࡓࠋ⣔ࡢ㓄ྥ࡟ࡘ࠸࡚ࡣࠊ㓄ྥ⛛ᗎᗘ P2 ࢆィ⟬ࡋ࡚ホ౯ࡋࡓࠋ㓄ྥ⛛ᗎᗘ P2 ࡣ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱࢸࣥࢯࣝ Q㸦ᘧ㸯㸧ࡢ᭱኱ᅛ᭷್࡜ࡋ࡚ᚓࡽࢀࡿࠋ

4DE

 1 
¦ PLD PLE  GDE     㸦㸯㸧
1 Lࡇࡇ࡛ࠊ P LD (D=x, y, z)ࡣศᏊ i ࡢศᏊ㍈࣋ࢡࢺࣝᡂศࠊ G DE ࡣࢡࣟࢿࢵ࣮࢝ࡢࢹࣝࢱࠊN ࡣศᏊᩘ࡛࠶ࡿࠋ
ศᏊ㍈࣋ࢡࢺࣝ࡟ࡣࠊྛศᏊ࡟ࡘ࠸࡚௨ୗࡢᘧ㸰࡛ィ⟬ࡉࢀࡿ័ᛶ࣮࣓ࣔࣥࢺࢸࣥࢯࣝ I ࡢ᭱ᑠᅛ᭷್ࢆ୚
࠼ࡿ࣋ࢡࢺࣝࢆ⏝࠸ࡓࠋ

,

§


¨ ¦ PL \L  ]L¨ L
¨ ¦ PL [L \LL¨¨  P[]¦L L L L¨©

¦ PL [L \L
L¦P ]  [
L

L


L

·
¸
L
¸
¦ PL \L ]L ¸     㸦㸰㸧
L
¸

 ¸
¦L PL [L  \L ¸¹¦ PL [L ]LL¦ PL \L ]LLࡇࡇ࡛ࠊmi ࡣཎᏊ㔞ࠊxi, yi, zi ࡣศᏊࡢ㔜ᚰᗙᶆ࡛࠶ࡿࠋ

3◊✲ᡂᯝ
CBA-10 ࡢࢿ࣐ࢳࢵࢡ㸫➼᪉┦㌿⛣Ⅼ௨ୗࡢ

ᗘ 430K ࡟࠾࠸࡚ࠊ20ns 㛫ࡢ MD ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥᚓࡽࢀ

ࡓᵓ㐀ࢆ Figure 2 ࡟♧ࡋࡓࠋCBA-10 ศᏊࡀ㓄ྥࡋ࡚࠸ࡿࡇ࡜ࡀほ
ࡓᵓ㐀ࡀほ

ࡉࢀࡓࠋ

- 402 -࡛ࡁࡿࠋCBA-9 ࡟ࡘ࠸࡚ࡶྠᵝࡢ㓄ྥࡋFigure 2. Snapshot of the orientation structure of CBA-10 obtained at 430K.
CBA-9 ࠾ࡼࡧ CBA-10 ࡟ࡘ࠸࡚ࠊࢿ࣐ࢳࢵࢡ㸫➼᪉┦㌿⛣
Ⅼ௨ୗࡢ

(a)

ᗘ࡛ MD ィ⟬࠿ࡽᚓࡽࢀࡓ㓄ྥ⛛ᗎᗘ P2 ࡢ᫬㛫ኚ

໬ࢆ Figure 3 ࡟♧ࡋࡓࠋFigure 3 ࠿ࡽࠊ᫬㛫ࡀ㐍ࡴ࡟ࡘࢀ࡚ P2ࡢ್ࡀቑຍࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋࡇࡢࡇ࡜࠿ࡽࠊศᏊࡀ㓄ྥࡋ⛛ᗎᵓ㐀ࢆ᫬㛫Ⓨᒎ࡜࡜ࡶ࡟ᙧᡂࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋCBA-9 ࡜ CBA-10 ࢆẚ㍑ࡍࡿ࡜ࠊ20ns ᚋࡢ᭱⤊᫬㛫ࡢ㓄ྥ⛛ᗎᗘࡣࠊࢫ࣮࣌ࢧ࣮ࡀഅᩘࡢ CBA-10 ࡢ᪉ࡀወᩘࡢ CBA-9ࡼࡾࡶ㧗ࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋCBA-10 ࡢ᪉ࡀ CBA-9ࡼࡾࡶ㧗㓄ྥࡋࡓ㞟ྜᵓ㐀ࢆᙧᡂࡋ࡚࠸ࡿࠋࡇࢀࡣࠊ㔜Ỉ⣲
NMR

(b)

ᐃ࡟ࡼࡿ⤖ᯝ࡜▩┪࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ

CBA-9 ࠾ࡼࡧ CBA-10 ࡟ࡘ࠸࡚ࠊࢿ࣐ࢳࢵࢡ㸫➼᪉┦㌿⛣
Ⅼ㏆ഐࡢ

ᗘ࡛ࡢ㓄ྥ⛛ᗎᗘ P2 ࡢ᭱⤊ 5ns 㛫ࡢᖹᆒ್ࢆィ⟬ࡋࠊࡑࡢᗘ౫Ꮡᛶࢆㄪ࡭ࡓࠋCBA-9 ࡛ࡣᗘࡀపୗࡍࡿ࡟

ࡘࢀ࡚㓄ྥ⛛ᗎᗘ P2 ࡀ༢ㄪ࡟㧗ࡃ࡞ࡗࡓࠋP2 ್ࡣ┦㌿⛣Ⅼ௨ୗࡢ 420K ࡢࢿ࣐ࢳࢵࢡ┦࡛ࡣ 0.27 ࡛࠶ࡾࠊNMRᐃࡢ⤖ᯝ࡜ྠ➼ࡢ್࡛࠶ࡗࡓࠋࡋ࠿ࡋࠊCBA-10 ࡛ࡣࠊ ᗘ࡟ᑐࡋ࡚㓄ྥ⛛ᗎᗘ P2 ࡢ್ࡀ୙つ๎࡟ኚ໬ࡋ࡚࠾ࡾࠊ

ᗘ࡟ࡼࡗ࡚ࡣศ

Ꮚࡀ༑ศ࡟㓄ྥࡋ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ࠸ࡃࡘ࠿ࡢ

ᗘ࡛ࡣࠊ Figure 3. Time dependence of order parameters᫬㛫Ⓨᒎ࡟ᑐࡋ࡚㓄ྥ⛛ᗎᗘ P2 ࡀᏳᐃࡋ࡚࠸࡞࠸ࡇ࡜࠿ࡽࠊ

for (a) CBA-9 and (b) CBA-10.

20ns ࡛ࡣ⣔ࡀ༑ศ࡟ᖹ⾮໬ࡋ࡚࠸࡞࠸ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
Figure 4 ࡟ࢿ࣐ࢳࢵࢡ㸫➼᪉┦㌿⛣Ⅼ㏆ഐ࡟࠾࠸࡚ᚓࡽࢀࡓᐦᗘࡢ

ᗘ౫Ꮡᛶࢆ♧ࡋࡓࠋᐦᗘࡢ್ࡣࠊࢩ࣑

࣮ࣗࣞࢩࣙࣥࡢ᭱⤊ 5ns 㛫ࡢᖹᆒ್࡛࠶ࡿࠋᅗ୰ࡢⅬ⥺ࡣᐇ㦂࡟ࡼࡗ࡚ᚓࡽࢀࡓᐦᗘ࡛࠶ࡿ[4]ࠋCBA-9 ࡟࠾࠸࡚ࠊᾮᬗ┦ࡢᐦᗘࡣᐇ㦂್࡜Ⰻ࠸୍⮴ࢆ♧ࡋ࡚࠸ࡿࡀࠊ➼᪉┦ࡢᐦᗘࡣᐇ㦂್ࡼࡾࡶᑡࡋ኱ࡁ࠸್࡜࡞ࡾࠊ
ࢿ࣐ࢳࢵࢡ┦ࡢᗘ࠿ࡽᚎࠎ࡟ῶᑡࡍࡿഴྥࡀぢࡽࢀࠊࡣࡗࡁࡾ࡜ࡋࡓ┦㌿⛣ᣲືࡣほ࡛ࡁ࡞࠿ࡗࡓࠋ

CBA-10 ࡢሙྜࠊ➼᪉┦ࡢᐦᗘࡣᐇ㦂್࡜Ⰻ࠸୍⮴ࢆ♧ࡋ࡚࠸ࡿࡀࠊࢿ࣐ࢳࢵࢡ┦ࡢᐦᗘࡣᐇ㦂್ࡼࡾࡶᑠࡉ
࠸್࡛࠶ࡗࡓࠋࡲࡓࠊᐦᗘࡢ

ᗘ౫Ꮡᛶࡶᗘୗ㝆࡟క࠸༢ㄪ࡟ቑຍࡍࡿഴྥ࡛ࠊ┦㌿⛣ᗘ࡛ࡢ኱ࡁ࡞ࢪ

ࣕࣥࣉࡣᚓࡽࢀ࡞࠿ࡗࡓࠋCBA-10 ࡢᾮᬗ┦ᵓ㐀ࡣᖹ⾮໬ࡀ୙༑ศ࡛࠶ࡿࡇ࡜ࡶ♧၀ࡉࢀࡓࠋࣔࢹࣝ஧㔞యᾮ- 403 -

ᬗࡢ┦㌿⛣ᣲືࡢ᳨ウ࡟᫬㛫ࢆせࡋࡓࡀࠊ2021 ᖺᗘ࡟࠾࠸࡚ LAMMPS ࢆ౑⏝ࡋ࡚⇕ఏᑟ⋡ࢆ᳨ウࡍࡿࠋ

(b)

(a)

Figure 4. Temperature dependence of densities for (a) CBA-9 and (b) CBA-10.

ࠕཧ⪃ᩥ⊩ࠖ
[1] Abe, A., Furuya, H., Zhou, Z., Hiejima, T., and Kobayashi, Y., Adv. Polym. Sci., 181, 121-152 (2005).
[2] Takahashi, Y., Ishikawa, R., and Kawauchi, S., J. Comput. Chem. Jpn., 14, 211-212 (2016).
[3] Sasaki, R., Takahashi, Y., Hayashi, Y., and Kawauchi, S., J. Phys. Chem. B 124, 881̽889 (2020).
[4] Abe, A., Nam, S. Y., Macromolecules, 28, 90-95(1995).

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
1. ᰗཎ ᩄᡂࠊ㕥ᮌ ඃ㍤ࠊྂᒇ ⚽ᓠࠊቑỌ ၨᗣࠊᨺᑕග X ⥺ࢆ฼⏝ࡋࡓᅛయ࣏ࣜ࢔ࢫࣃࣝࢸ࣮ࢺࣈࣟࢵ

ࢡඹ㔜ྜయࡢ஧ḟᵓ㐀㌿⛣ゎᯒࠊ➨ 69 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍㸦2020 ᖺ㸧ࠋ
2. Ώ㎶ ᬛᡂࠊྂᒇ ⚽ᓠࠊᱱ ᬡᩩࠊ୰ᔱ ೺ࠊཎᏊ㛫ຊ㢧ᚤ㙾ࢆ⏝࠸ࡓࢼࣀࣇ࢕ࢵࢩࣥࢢ࡟ࡼࡿࡽࡏࢇᵓ
㐀࣏ࣜ࢔ࢫࣃࣝࢸ࣮ࢺ୍ᮏ㙐ࡢຊᏛ≀ᛶࠊ➨ 69 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍㸦2020 ᖺ㸧ࠋ
3. ᮧୖ ㄹኴࠊᱱ ᬡᩩࠊ୰ᔱ ೺ࠊྂᒇ ⚽ᓠࠊ࣏ࣜ࢔ࢫࣃࣝࢸ࣮ࢺࢢࣛࣇࢺ໬ⷧ⭷ࡢ୺㙐ࡽࡏࢇᵓ㐀࡟㉳ᅉࡍࡿ⾲㠃㟁Ẽ≉ᛶࡢ᳨ウࠊ➨ 69 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍㸦2020 ᖺ㸧ࠋ
4. ᮧୖ ㄹኴࠊᱱ ᬡᩩࠊ୰ᔱ ೺ࠊྂᒇ ⚽ᓠࠊ⾲㠃ࢢࣛࣇࢺ໬࣏ࣜ࢔ࢫࣃࣝࢸ࣮ࢺⷧ⭷ࡢ୺㙐ࡽࡏࢇ཯㌿࡜⾲㠃㟁Ẽ≉ᛶࠊ➨ 70 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍㸦2021 ᖺ㸧ࠋ
5. Ώ㎶ ᬛᡂࠊᱱ ᬡᩩࠊ୰ᔱ ೺ࠊྂᒇ ⚽ᓠࠊཎᏊ㛫ຊ㢧ᚤ㙾ࢆ⏝࠸ࡓ࣏ࣜ࢔ࢫࣃࣝࢸ࣮ࢺ୍ᮏ㙐ࡢຊᏛ≀ᛶ࡜࣊ࣜࢵࢡࢫࢭࣥࢫࡢ┦㛵࡟㛵ࡍࡿ◊✲ࠊ➨ 70 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍㸦2021 ᖺ㸧ࠋ
6. ᑠ㔝⃝ ඃኴࠊᱱ ᬡᩩࠊ୰ᔱ ೺ࠊྂᒇ ⚽ᓠࠊཎᏊ㛫ຊ㢧ᚤ㙾ࢆ⏝࠸ࡓ࣏ࣜ㸦Ț-࣋ࣥࢪࣝ L-ࢢࣝࢱ࣓࣮ࢺ㸧ࡢȘ࣊ࣜࢵࢡࢫ୍ᮏ㙐ࡢຊᏛ≀ᛶホ౯ࠊ➨ 70 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍㸦2021 ᖺ㸧ࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
1. Akihiro Abe, Hidemine Furuya. Conformational Characteristics of Polypeptide Chains with Special Focus on the

α-Helix-Sense Inversion, Modern Applications of Flory’s “Statistical Mechanics of Chain Molecules”, ACS Symposium
Series, ACS, Vol. 1356, Chapter 5, pp. 63-87, Sept. 2020.
2. Yuki Orito, Hiroyasu Masunaga, Hidemine Furuya, Akihiro Abe, Direct determination of helix structures involvedin the screw-sense reversal of poly(β-phenylpropyl l-aspartate) by synchrotron X-ray diffraction, J. Pept. Sci., 27, e3311(2021): https://doi.org/10.1002/psc.3311- 404 -

࣐࢝ࣝࣥ࡟࠾ࡅࡿ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢศᏊືຊᏛィ⟬

Molecular dynamics study of cavitation on Kármán vortex‫ۑ‬㔝ཱྀ ༤ྖࠊὸ㔝 ඃኴ㸦ᮾி኱Ꮫ≀ᛶ◊✲ᡤ㸧1◊✲┠ⓗ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡣࠊ檿ὶ㏿ࡢᾮయ୰࡟࠾࠸࡚ࠊᒁᡤⓗ࡞ᅽ⊂ኚ໬࡟ࡼࡗ࡚䔆ࡌࡿẼἻࡢ䔆ᡂࠊᡂ敞ࠊཬࡧᾘ⁛ࢆక࠺ὶື⌧㇟࡛࠶ࡿࠋ⯪⯧ࡢ᥎㐍ჾࡸࢱ࣮࣎ᶵᲔ࡞࡝ࠊὶయᶵᲔ࡛࢟ࣕࣅࢸ࣮ࢩࣙࣥࡀⓎ䔆ࡍࡿ࡜ࠊᛶ⬟ࡢపୗࠊ㦁柚ࡸ᣺ືࠊ࢚࣮ࣟࢪࣙࣥ࡞࡝ࢆᘬࡁ㉳ࡇࡍࠋࡋࡓࡀࡗ࡚ࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢ࣓࢝ࢽࢬ࣒ࢆ
⌮ゎࡍࡿࡇ࡜ࡣࠊ┬࢚ࢿࡸ⎔ቃᝏ໬㜵㭉ࡢほⅬ࠿ࡽ狠ᖖ࡟㔜せ࡛࠶ࡿࠋ࢟ࣕࣅࢸ࣮ࢩࣙࣥࢆᢚไࡍࡿ᪉ἲ࡜
ࡋ࡚ࠊ㧗ศᏊࡸ⏺㠃άᛶ๣ࡢῧຍࡀᐇ㦂஦ᐇ࡜ࡋ࡚▱ࡽࢀ࡚࠸ࡿࠋ≀㉁ῧຍ࡟ࡼࡿὶࢀࡢไᚚ࡛ࡣࠊὶయᶵ
Ეࡢタィࢆኚ᭦ࡍࡿࡇ࡜࡞ࡃὶࢀࢆไᚚ࡛ࡁࡿࠋࡑࡢࡓࡵࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥ࡟ᑐࡍࡿ㧗ศᏊࡸ⏺㠃άᛶ๣ࡢຠᯝࡀࠊᐇ㦂ࡸࢼࣅ࢚࣭ࢫࢺ࣮ࢡࢫ㖠⛬ᘧ࡟ᇶ࡙ࡃィ⟬ᶵࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ㄪ࡭ࡽࢀ࡚ࡁࡓࠋὶ
ࢀࡢ୰࡛ࡢࠊ

ࠊ⢓ᙎᛶࠊཬࡧẼἻ᰾ࡢ┦஫స䔏ࡀ㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞

ࡀࡽࠊ࣐ࢡࣟ࡞ὶືሙ୰࡟࠾࠸࡚ࠊ㧗ศᏊࡢ㐠ືࡸࠊẼἻ᰾ࡢ䔆ᡂ࣭ᡂ敞ࡢࢲ࢖ࢼ࣑ࢡࢫࢆྲྀࡾᢅ࠺ࡇ࡜ࡣ
ᴟࡵ࡚ᅔ㞴࡞ࡓࡵࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥᢚไࡢ࣓࢝ࢽࢬ࣒ࡣᮍࡔࡼࡃࢃ࠿ࡗ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊศ⬷ື⊂Ꮫ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ࠊ㧗ศᏊࡢῧຍ࡟ࡼࡿ࢟ࣕࣅࢸ࣮ࢩࣙࣥ࡬ࡢᙳ㡪ࢆゎᯒࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
3 ḟඖࡢ MD ィ⟬࡟ࡼࡾࠊ෇ᰕ࿘ࡾࡢ࢟ࣕࣅࢸ࣮ࢩࣙࣥὶࢀࡢゎᯒࢆ⾜࠸ࠊ㧗ศᏊࡢῧຍ࡟ࡼࡿᙳ㡪ࢆㄪ࡭ࡿࠋ⁐፹ࡢ⢏Ꮚ㛫┦஫స⏝ࡣ Lennard-Jones㸦LJ㸧┦஫స⏝࡜ࡍࡿࠋ௨ୗ࡛ࡣࠊ඲࡚ࡢ≀⌮㔞ࢆ LJ ⣔࡟≉ᚩⓗ࡞࢚ࢿࣝࢠ࣮ࠊ㛗ࡉࠊ᫬㛫ࡢࢫࢣ࣮࡛ࣝ↓ḟඖ໬ࡋ࡚࠸ࡿࠋ㧗ศᏊࡣ Kremer-Grest ࣔࢹࣝࢆ⏝࠸ࡿࠋ㧗ศ= 500ࠊ㧗ศᏊ⃰ᗘࡣ = 0.0069࡜ࡍࡿࠋ෇ᰕࡣࠊࡑࡢ⾲㠃ୖ࡟ LJ ⢏ᏊࢆᅛᏊࢆᵓᡂࡍࡿࢭࢢ࣓ࣥࢺᩘࡣ
ᐃࡍࡿࡇ࡜࡛ࣔࢹࣝ໬ࡍࡿࠋ
⣔ࡣࠊ኱ࡁࡉࡀ

××= 6000 × 2000 × 100ࡢ┤᪉య࡜ࡋࠊ඲᪉ྥ࡟࿘ᮇቃ⏺᮲௳ࢆㄢࡍࠋ⣔ࡢ୍㒊࡟ࡣὶ㏿ไᚚࠊཬࡧᖹ⾮໬ࡢࡓࡵ࡟ࠊᒁᡤⓗ࡟ࣛࣥࢪࣗࣂࣥ⇕ᾎࢆ⏝࠸ࡿࠋ෇ᰕࡢ┤ᚄࡣ = 100࡛࠶ࡾࠊ୰
ᚰ㍈ࡣ ㍈࡟୪⾜࡜ࡋࠊࡑࡢ఩⨨ࡣ (1000, 1000)࡜ࡍࡿࠋὶయࡢᐦᗘࡣ = 0.4࡜ࡍࡿࠋ඲⢏Ꮚᩘࡣ
478 036 504࡛࠶ࡿࠋὶධὶయࡢ

ᗘࡣ= 2㸦㠀࢟ࣕࣅࢸ࣮ࢩࣙࣥὶࢀ㸧ࠊཬࡧ

== 1.25㸦࢟ࣕࣅࢸ࣮ࢩࣙ

ࣥὶࢀ㸧ࡢ 2 ᮲௳࡜ࡍࡿࠋ㧗ศᏊࡢຠᯝࢆㄪ࡭ࡿࡓࡵ࡟ࠊ㧗ศᏊࢆྵࡲ࡞࠸ LJ ὶయࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࡶ⾜࠺ࠋὶࢀ࡟ࡼࡿᙳ㡪ࢆㄪ࡭ࡿࡓࡵ࡟ࠊᇶ‽࡜࡞ࡿ㟼Ṇὶయ୰࡟࠾࠸࡚ࠊ㧗ศᏊࡀẼᾮ┦ቃ⏺࡟୚࠼ࡿᙳ㡪ࢆㄪ࡭ࡿࠋࡑࡢࡓࡵ࡟ࠊẼᾮඹᏑࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࠋ⣔ࡣࠊ኱ࡁࡉࡀ

××= 1000 × 250 × 250ࡢ┤

᪉య㸦LJ ὶయ࡟ࡘ࠸࡚ࡣ200 × 50 × 50㸧࡜ࡋࠊ඲᪉ྥ࡟࿘ᮇቃ⏺᮲௳ࢆㄢࡍࠋ඲యࡢᐦᗘࡣ = 0.4࡜ࡍࡿࠋ඲⢏Ꮚᩘࡣ

= 25 000 000࡛࠶ࡿࠋึᮇ᫬้࡟࠾࠸࡚ࠊ ≤/2ࢆᾮయ≧ែࠊ >࡟⢏Ꮚࢆ㓄⨨ࡍࡿࠋ⣔඲య࡟ࣛࣥࢪࣗࣂࣥ⇕ᾎࢆㄢࡋࠊ ᗘࢆ <≧ែࢆ⏕ᡂࡍࡿࡇ࡜ࡀฟ᮶ࡿࠋ
㐠ື᪉⛬ᘧࡢᩘ್✚ศ࡟ࡣ LAMMPS ࢆ⏝࠸ࡿࠋ- 405 -

/2ࢆẼయ≧ែ࡟࡞ࡿࡼ࠺

㸦⮫⏺Ⅼ ᗘ㸧࡟ಖࡘࡇ࡜࡛ࠊẼᾮඹᏑ

3

◊✲ᡂᯝ
ᅗ㸯࡟ LJ ὶయࠊཬࡧ㧗ศᏊ⁐ᾮࡢẼᾮ┦ቃ⏺ࢆ♧ࡍࠋ㧗ศᏊ⁐ᾮࡢሙྜࡣࠊึᮇ᮲௳࡟ࡼࡗ࡚ࡣࠊ⦆࿴ࡀ㠀ᖖ࡟⦆ࡸ࠿࡟࡞ࡾࠊ‽Ᏻᐃ≧ែ࡟ᩘ༓୓ࢫࢸࢵࣉ⛬ᗘࢺࣛࢵࣉ
ࡉࢀࡿሙྜࡀ࠶ࡿࠋ⮫⏺Ⅼࡢ㏆ഐࡸࠊప ࡛㢧ⴭ࡛࠶ࡿࠋ
ࡲࡓࠊẼ┦㡿ᇦ࡛ࡣࠊ㧗ศᏊࡀ⣒ࡲࡾ≧࡟Ꮡᅾࡍࡿࡓࡵࠊ
ᒁᡤⓗ࡟ᐦᗘࡀ㧗ࡃ࡞ࡿࠋᅗ㸯࡟♧ࡍ㏻ࡾࠊ㧗ศᏊࡢῧຍ
࡟ࡼࡿ┦ᖹ⾮࡬ࡢᙳ㡪ࡣ࡯࡜ࢇ࡝࡞࠸ࠋࡋࡓࡀࡗ࡚ࠊὶࢀ
ࡢ୰࡛⏕ࡌࡿ࢟ࣕࣅࢸ࣮ࢩࣙࣥ࡟ᑐࡋ࡚ࠊఱࡽ࠿ࡢᙳ㡪ࡀ࠶ࡿ࡜ࡍࢀࡤࠊ㧗ศᏊࡢࣞ࢜ࣟࢪ࣮࡟ࡼࡿࡶࡢ࡛࠶ࡿࠋ
ᅗ2ࡣ

ᗘ

= 2㸦㠀࢟ࣕࣅࢸ࣮ࢩࣙࣥὶࢀ㸧࡟࠾ࡅࡿὶࢀሙࡢࢫࢼࢵࣉࢩࣙࢵࢺ࡛࠶ࡿࠋLJ ὶయࡢሙྜࡣࠊ෇ᰕ
ࡢᚋ᪉࡟࣐࢝ࣝࣥ

ࡀⓎ⏕ࡋ

ᅗ 1 LJ ὶయ㸦㯮㸧࡜㧗ศᏊ⁐ᾮ㸦㉥㸧ࡢẼᾮ┦ቃ⏺ࠋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿ㸦ᅗ 2(a)㸧ࠋࡲࡓࠊ෇ᰕ㏆ഐࡸࠊ෇ᰕᚋ᪉ࡢ
㏆ഐࡢᐦᗘ࡜

ᗘࡀపࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡋࡓࡀ
ࡗ࡚ࠊὶධὶయࡢ ᗘࢆୗࡆࡓ
ሙྜࠊࡇࢀࡽࡢ㡿ᇦ࡛ẼἻࡀⓎ⏕ࡍࡿࡇ࡜ࡀண᝿ࡉࢀࡿࠋ
୍᪉ࠊ㧗ศᏊ⁐ᾮࡢሙྜࡣࠊ
෇ᰕ⫼ᚋࡢ࣐࢝ࣝࣥ

ࡀࡰࡸࡅ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿ㸦ᅗ2(b)㸧
ࠋᐦᗘ࡟㛵ࡋ࡚ࡣࠊLJ ὶ= ࡟࠾ࡅࡿ LJ ὶయ࡜㧗ศᏊ⁐ᾮࡢ(a, b) ᗘయࡢሙྜ࡜ྠᵝ࡟ࠊ෇ᰕ㏆ഐ ᅗ 2 ὶධὶయࡢ ᗘࡸࠊ෇ᰕᚋ᪉ࡢ ㏆ഐ࡛పࡃ࡞ ሙ ࠊ(c, d)ᐦᗘሙ ࠊཬࡧ(e, f) ᗘሙ ࡢࢫࢼࢵࣉࢩࣙࢵࢺࠋᅗ୰ࡢ㯮୸ࡗ࡚࠸ࡿ㸦ᅗ 2(d)㸧
ࠋ࡜ࡇࢁࡀࠊ ࡣ෇ᰕ࡛࠶ࡿࠋ
ᗘ࡟㛵ࡋ࡚ࡣࠊ෇ᰕ㏆ഐࠊཬࡧ෇ᰕᚋ᪉ࡢ
ᅗ3ࡣ

㏆ഐ࡛㧗ࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿ㸦ᅗ 2(f)㸧
ࠋ= 1.25࡟࠾ࡅࡿ LJ ὶయ࡜㧗ศᏊ⁐ᾮࡢ࣎࢖ࢻ⋡ࡢ✵㛫ศᕸ࡛࠶ࡿࠋLJ ὶయࡢሙྜࠊ ࡢᨺฟ࡟㐃ືࡋ࡚ࠊ෇ᰕࡢୖഃ࡜ୗഃ࠿ࡽ஺஫࡟ẼἻࡀⓎ⏕ࡍࡿ㸦ᅗ 3(a)㸧
ࠋࡋࡓࡀࡗ࡚ࠊ᫬㛫ᖹᆒࡍࡿ࡜ࠊ๤㞳ࡏࢇ᩿ᒙࡸ෌ᚠ⎔㡿ᇦ࡟ẼἻࡀศᕸࡍࡿ㸦ᅗ 3(c)㸧
ࠋ୍᪉ࠊ㧗ศᏊ⁐ᾮࡢሙྜࡣࠊLJ ὶయ࡜ẚ㍑ࡍࡿ࡜ࠊⴭࡋࡃẼἻࡢ⏕ᡂࡀᢚไࡉࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿ㸦ᅗ 3(b, d)㸧
ࠋࡲࡓࠊࡑࡢⓎ⏕఩⨨ࡀࠊ෇ᰕ㏆ഐ࡛ࡣ࡞ࡃࠊ ࡀᙧᡂࡉࢀࡿ఩⨨㸦 ≃ 1500㸧࡟ศᕸࡋ࡚࠸ࡿࠋᅗ 2(b)࡟♧ࡋࡓࡼ࠺࡟ࠊ㧗ศᏊࢆῧຍࡍࡿ࡜ࠊ ࡢᙧᡂࡀᢚไࡉ
ࢀࡿࠋࡑࡢࡓࡵࠊ๤㞳ࡏࢇ᩿ᒙ࡟࠾ࡅࡿࠊ ࡢᙧᡂ࡟ࡼࡿᅽຊపୗࡀᢚ࠼ࡽࢀࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡀᢚไࡉ
ࢀ࡚࠸ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ
㧗ศᏊࡢຠᯝࢆヲ⣽࡟ㄪ࡭ࡿࡓࡵ࡟ࠊὶࢀࡢ୰ࡢྛ఩⨨࡟࠾ࡅࡿ㧗ศᏊࡢࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࢆㄪ࡭ࡓ㸦ᅗ 4㸧ࠋ㠀࢟ࣕࣅࢸ࣮ࢩࣙࣥὶࢀ(ᅗ 4 ᕥิ)ࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥὶࢀ㸦ᅗ 4 ྑิ㸧ࡢ࡝ࡕࡽࡢሙྜ࡟࠾࠸࡚
ࡶࠊ㧗ศᏊࡣὶࢀࡢ୰࡛࡯࡜ࢇ࡝ྠࡌࡼ࠺࡞ࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࡢኚ໬ࢆࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ័ᛶ༙ᚄ

- 406 -

ࡢ᣺ࡿ⯙࠸࠿ࡽࠊ㧗ศᏊࡣ෇ᰕ㏆ഐࡢᙉ࠸ࡏࢇ᩿࡟ࡼࡗ࡚ᘬࡁఙࡤࡉࢀ
࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿ㸦ᅗ 4(a, b)㸧ࠋࡉࡽ࡟ࠊ㓄ྥ⛛ᗎ ࡀ෇ᰕᚋ᪉ࡢ ิࡢ୰࡛ኻࢃࢀ࡚࠸ࡿࡇ࡜࠿ࡽࠊᘬࡁఙࡤ
ࡉࢀࡓ㧗ศᏊࡀ

࡟ᕳࡁ㎸ࡲࢀ࡚࠸

ࡿࡇ࡜ࡶࢃ࠿ࡿ㸦ᅗ 3(c, d)㸧ࠋᐇ㝿ࠊ㠀⌫㠃ᛶ ࡢ್ࡀ 1 ࡟㏆࠸ࡓࡵࠊ㧗ศᏊࡣ⥺≧࡟ᘬࡁఙࡤࡉࢀ࡚࠸ࡿ㸦ᅗ 3(e,f)㸧ࠋࡋࡓࡀࡗ࡚ࠊ㧗ศᏊࡀ෇ᰕ㏆ഐ࡛

ᅗ 3⥺≧࡟ᘬࡁఙࡤࡉࢀࡿࡇ࡜࡟ࡼࡿࠊఙ

ࢩࣙࢵࢺ࡜(b)᫬㛫ᖹᆒࠊཬࡧ㧗ศᏊ⁐ᾮࡢ࣎࢖ࢻ⋡ࡢ(c)ࢫࢼࢵ

㛗⢓ᗘࡢቑຍࡀ ࡢᙧᡂࢆᢚไࡋࠊࡑ

ࣉࢩࣙࢵࢺ࡜(d)᫬㛫ᖹᆒࠋᅗ୰ࡢⓑ୸ࡣ෇ᰕ࡛࠶ࡿࠋ

ᗘ࡟࠾ࡅࡿ LJ ὶయࡢ࣎࢖ࢻ⋡ࡢ(a)ࢫ
ࢫࢼࢵࣉ

= .

ࡢ⤖ᯝࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢᙧᡂࡀᢚ
ไࡉࢀ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ
ࡲࡓࠊᅗ 2(f)࡟♧ࡋࡓࡼ࠺࡟ࠊ㧗ศᏊࡢῧຍ࡟ࡼࡾࠊ෇ᰕ㏆ഐࡸࠊ෇ᰕᚋ᪉ࡢ㏆ഐࡢᗘࡀቑຍࡍࡿࠋࡇࢀ

ࡣࠊ෇ᰕ㏆ഐ࡛ᘬࡁఙࡤࡉࢀࡓ㧗ศᏊ࡟⵳࠼ࡽࢀࡓᙎᛶ࢚ࢿࣝࢠ࣮࡟ࡼࡿ
ࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡇࡢᙎᛶ࢚ࢿࣝࢠ
࣮ࡣࠊ㧗ศᏊࢭࢢ࣓ࣥࢺࢆ⤖ྜࡍࡿ࣎ࣥࢻ࢚ࢿࣝࢠ࣮࡟ࡼࡿࡶࡢ࡛ࡣ࡞࠸ࠋ
ᅗ 4(g, h)࡟♧ࡍࡼ࠺࡟ࠊ㧗ศᏊࢭࢢ࣓
ࣥࢺ㛫ࡢ࣎ࣥࢻ࢚ࢿࣝࢠ࣮ࡣ㟼Ṇὶయ୰ࡢ್࡜࡯࡜ࢇ࡝ኚࢃࡽ࡞࠸ࠋ༶
ࡕࠊ㧗ศᏊࢭࢢ࣓ࣥࢺ㛫ࡢ࣎ࣥࢻ㛗ࡣࠊ㧗ศᏊࡀ⥺≧࡟ᘬࡁఙࡤࡉࢀࡿ㝿࡟࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠸㸦ᅗ 3(g, h)㸧
ࠋࡋࡓࡀࡗ࡚ࠊ㧗ศᏊࡢఙ㛗࡟ࡼࡿ࢚ࣥ
ࢺࣟࣆ࣮ᙎᛶࡀࠊὶయࡢᗘቑຍ࡟኱

ᅗ 3 ὶධὶయࡢ

ࡁࡃᙳ㡪ࡋ࡚࠸ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ ༙ᚄ

ᗘ

= , .

࡟࠾ࡅࡿ㧗ศᏊࡢ(a, b)័
័ᛶ

ࠊ(c, d) 㓄ྥ⛛ᗎ ࠊ(e, f)㠀⌫㠃ᛶ ࠊ(g, h) ࣎ࣥࢻ࢚ࢿ

㧗ศᏊࡢఙ㛗࡟ࡼࡿࠊఙ㛗⢓ᗘࡢቑࣝࢠ࣮ࡢ✵㛫ศᕸࠋຍࠊཬࡧ࢚ࣥࢺࣟࣆ࣮ᙎᛶࡢᙳ㡪࡟ࡼ࡛࠶ࡿࠋ ࡣ㧗ศᏊࡢᮎ➃㛫࣋ࢡࢺࣝࡀ ㍈᪉ྥ࡟୪⾜࡛ 1, ᆶࡗ࡚ࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡀ๻ⓗ࡟ᢚไ┤࡛-0.5ࠊࣛࣥࢲ࣒㓄ྥ࡛ 0 ࡜࡞ࡿࠋ ࡣ㧗ศᏊࡢࢭࢢ࣓ࣥࢺࡀ

ࡉࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

┤⥺≧࡟୪ࢇࡔ᫬࡟ 1ࠊ⌫≧࡟ศᕸࡋࡓ᫬࡟ 0 ࡜࡞ࡿࠋࡣ㟼Ṇὶయ୰ࡢᏙ❧㧗ศᏊࡢ័ᛶ༙ᚄ

㟼Ṇὶయ୰ࡢᏙ❧㧗ศᏊࡢ࣎ࣥࢻ࢚ࢿࣝࢠ࣮࡛࠶ࡿࠋ

- 407 -

ࡣ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪͆㡢ἼࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ͇ࣙࣥ
㸪᪥ᮏ≀⌮Ꮫ఍ 2020 ᖺ⛅Ꮨ኱఍㸪2020 ᖺ 9 ᭶㸬‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪͆㡢ἼࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ͇ࣙࣥ㸪≀ᛶ◊✲ᡤࢫࣃࢥࣥඹྠ฼⏝࣭CCMS ྜྠ◊✲఍ࠕィ⟬≀㉁⛉Ꮫࡢ᪂ᒎ㛤 2020ࠖ
㸪2020 ᖺ 12 ᭶㸬‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪͆」㞧ὶయ୰࡟࠾ࡅࡿ࣐࢝ࣝࣥ ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢศᏊືຊᏛࢩ࣑
࣮ࣗࣞࢩ͇ࣙࣥ
㸪᪥ᮏ≀⌮Ꮫ఍➨ 76 ᅇᖺḟ኱఍㸪2021 ᖺ 3 ᭶㸬

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬Y. Asano, H. Watanabe, and H. Noguchi, “Molecular dynamics simulation of soundwave propagation in a simple

fluid”, J. Chem. Phys. 153, 124504 (2020).
㸦ணᐃ㸧‫ ۻ‬Y. Asano, H. Watanabe, and H. Noguchi, “Effects of polymers on the cavitating flow around a cylinder:
A Large-scale molecular dynamics analysis”, submitted to J. Chem. Phys. (arXiv:2105.07590)- 408 -







Analysis of aggregation and dissolution of protein from the microscopic
construction


1



#'

&(

!&

)«



µ¨­B0?3-­O´

#

¨

z$

&~µ¨­p

c

dp

EJA2 

I#
#+,?Vtµ§)w

0?3-­81<&¬nµQH°hT&s¶)«z$&)&%!

0?3-­]¸#

] 1:81<¡¬nµlbQH(5->*2,?)81<U°hT$EJ)«v#©²+,?

#±+,?"Y§µQH81<UhTEJ©Pxq«(HNC-OZ)4>.;7)

3





µ¨­B¬nµQH(5->*2,?)°hTEJ##
rR

aU&

`S&¥$'&&rRPhTEJ

4)z$

µ§)wcde^W¢Ccd#`SM_Kh³©£cd|#WT#`S&(D

'

$"

µ¨­Blb§µdZ%·i+,?jups¶}g¤k¦F[ 3 o 3 { y~fG 76 \obG (,?;+?¯L)

5"  “Solvent effect for an effective attraction between like-charged macroions immersed
solution:in an electrolyte

the intensification mechanism of the effective attractioncaused by the translational motion ofsolvent particle” Ayumi Suematsu and Ryo Akiyama, AIP publishing Journal of Chemical Physics, 154(2021)034902
 2.HPxq«)µ¨­NYXµ§° hTrREJk ¦}g¤ Pd/69=@/:?fGª Vol.23, No.2, 2021 4 {(®m 94 X)
 3. “Lateral depletion effect on two-dimensional ordering of bacteriorhodopsins in a lipid bilayer: A
theoretical study based on a binary hard-disk model” Keiju Suda, Ayumi Suematsu, and Ryo Akiyama, AIP
publishing Journal of Chemical Physics, 154 (2021)- 409 -



Computations of Atomic Force Microscopy Images of Several Molecules­ PbÞJST Ðjlß§¬¥£_kÔ\ÜvÑÞDWRPLFIRUFHPLFURVFRS\$)0ßT 'É ½+* ZkÉÅ^±Rn+hL $)0 T

nÖ'É¡*-m*1D&O »ÛLZk^± $)0 T(4BCGJ4DHÅ>@§¬ ©q*9: fªl§¬z ½ Ë.*   $)0TZk4BCGJ4DH-ºnÅ'ZkÉIÌ]$)0 TÄ

* -¾*-¥£WQ£  ¹Q  U $)0Þ'$)0ßTÃO
/0HQ '$)0 TZkÉÕÊ¾ ><@5@E;J7 $ ÝÈ $)0 T'*³¶¸´c¾ØÍ«½ZkÉÕÊ¾-º /0HQ  @5@E;J
7 $)0 TZk]\l4BCGJ4DHn-'Y _kG?FÁ³Éwi%u(+ )ÃSN*)(n (Z(²ÛÏcLÁ³[yGA

J8  ¹Q '$)0 TÃOÇ!*¹Qj×|¿ ÚrÒÝZk°)+ p³¶X`$(+·*2H;18`$(+°É '% 3= P( QP 3/6ÉV

Z

Æs+-¾*$§¬ ¤.º,+ )),6+ &  sÓ¢+

+L& g\{* >@+(À~+*É Kx"(*+-¾* UÉ-¦}½**É-½*t{ ; µ´É¾ÙkÜvÑ'*½oMd*¹Qe É-a($; µ´É¾

*KÆÙkÜvÑ'*¹Q½ %¹QXÎ¯  QP ®É¨Â+#¹Q°ÉV ¼>@©q*Ðjl9:

fªl§¬z U_kÔ\ÜvÑÞ'$)0ß-¾

"GH-U$*$)0 9: J0JJ¤Ô¾T`-w '$)0 N %Zk  UÉ-¾*·\-w>@+-¹QÇ+ _£¹Q  UÉ")°É%¾T+* g+*

$)0 À $)0 zÍ3HFÔ\-m*)3HFÉ-m*x*j¹ *zÍí3HFÔ\e
3HFÉ-F* ¹Q'(¼*N]*°É ' $)0 T

%%°É e¾T+* %Z

t{+*

¹Q#1FÉÞN  ]ßÝZk!F'*4BCGJ4DH- $)0 TÃO-º°É' $)0 T¼*-ÃO*-§¬¥£



- 410 -

§¬À©t '$)0 TÃO{H=G#3HEH&|]Ã-4BCGJ4DH')h $)0 zÍÔ³¡FJ-$
+-aÞh $)0 zÍÔÁØßvZ
*_P\-$*%>@+-nÒ'$\íÁØµÅ*
+({ $)0 ÀÔ«_·Æ
*, $)0 ÀÈ`')»Zk]

DZÈ-m*x(-mt§¬hLZk '$)0 TÃO*$LÑ N Ô¹Q-ÝZk!Fa«Þ]ß" $)0 zÍÝZkXÎ5<ÉÞHß

HNÝZkXÎ-¼*$zÍ'){BÝ
Zk» 

QÝZk] Å£Å R ¹Qv}6~ í FPV 0JJ*(+*>@ t QÝZkÇ §¬t* '$)0 T4BCGJÓ¢ (º

$#V³2*" ¹Q-ÝZk!Fq,BÃ!F->@ÝZk4BCGJ4DH{Á³Ã  -E+§¬ÝZk  7KÊ<J6 (*  °)ÞN  ]ß¦ (¦"¿(Ð¹++*ÝZk&Îh(2-²o½Ky]kOmÄr $)0 ÀZk»ÛÉÞ>=Tß-au*$zÍ- ] ÂL (ÝZk}ÆÝZk(2-m*Ý-ºÎ ] ÂLr+-I [ \ 1°¯)Ã»»Ûf-À*>@ '$)0 ÀÞ'$)0 TßÝZkXÎÉ"au*$ÝZk(2-m %zÍ-r ÝZkXÎ5<ÞN  HßhÞ]   1°*
-m*ßAÆh ] ÂLr5<ÖzÍÝZk¶¥)ÝZk-u)**'-**' ( -DU]\QVNL §c-³¡FJ^-$>@a&vZ (\-$+-I [\ 1°¯)Ã\  U,'$)0 T-$






§¬p
BÇ')$¹Q-ÝZk '$)0 TÞ5#/5* '$)0 Tß-N  N  D ÝZk!F)N  E ÝZkNi '$)0 T [] ÛN*ÝZk-p

*<J6¾Ì(À©+*<J6%¨ (È`ÞPRVWSUREDEOHVSHHGYPSß PV )+zÍ­dÀÈ`ÞYVFDQß*  PV !DZÅ ÝZk5<*zÍ-É* ? ¶¥'*F¢\*'$)0 T [\ ÛN+½+

*"[] ÛN [   QP &  QP  ] Âd0µ¼(+Á³¾´+zÍ*%* Z 

ÝZk-u& *Rcw¬£F¢\: ´-DU]\QVNL §c-*+(*'¡*F¢\- À© *- 411 -

t_P\-$*{À©%¨Â*N  F N  D 
_ÛÝZkÛN)N  G +( Ý   '$)0 T [\ 
Û N   * '$)0 T [\ ÛN¨
É¼+nÖÉ°ÉYk*

Z *+

'$)0 À')¹Q'(N]*ÝZk  UÉÀN  ÝZk!FÛN '$)0 T D  ÝZk!FÐ_ÛN  F ÛNÝ* E  ÝZkNi '$)0 T [] ÛN F  ÝZkÛN G N  D  Ý '$)0 T [\ ÛN

G·*- *(§¬ '$)0 T YVFDQ 4Vl%½!*YVFDQ  YPS RcÝZk5<Í-É* ?*Rc'$)0 T¨°É½+"zÍÝZk d ¶¥*%$nÀ
%Z
Rc

KYVFDQ  YPS zÍÝZk¶¥
?

* Z

*F¢\d*$ÝZk

*z
Z

: 

@+"+!FÏ* n $)0 À%Zk-S"G·l Ý²(+*ÝZk @+*B '$)0 T-½!*È`ªMRcdF¢\´*z: +( :/6'¼"$°É-¾T NÔ* YPSYVFDQYPS RcÀG·DZd JÝZk-SF¢\: '$)0 T%µ °ÉÀÇÀÈ`ªM¾T+*

Z

Z ")'$)0)+ ÝZk%¨ (È`  8* ZnÒµ½.-{z)zRc%Z §¬´(ÇÀÈ`-O* G·¢»n®"Om

7DNDVKL 6XPLNDPD 1LNR 2LQRQHQ )HGRU 8UWHY $GDP 6 )RVWHU 7DNHVKL )XNXPD   ³7RZDUG HOXFLGDWLQJ D
UHODWLRQ EHWZHHQ FRPSXWHG DWRPLF IRUFH PLFURVFRS\ LPDJH DQG DFWXDO VWUXFWXUH XVLQJ PDFKLQH OHDUQLQJ´ 7KH VW

- 412 -

,QWHUQDWLRQDO&RQIHUHQFHRQ%LJ'DWDDQG0DFKLQH/HDUQLQJLQ0LFURVFRS\7DNDVKL 6XPLNDPD $GDP 6 )RVWHU 7DNHVKL )XNXPD   ³&RPSXWLQJ $WRPLF )RUFH 0LFURVFRS\ ,PDJHV RI
&KURPRVRPHV8VLQJ3RO\PHU6LPXODWLRQ´%LRSK\VLFDO6RFLHW\WK$QQXDO0HHWLQJ­Pb%bKÊ± p¢Þß.FV$."F/0HÈtlZkl/Þ¼LÓ9ß­PbW3¥Ók;\)_[Ë¦kQXnK$GDP6)RVWHU¡ÔCTÞßZ¸

¹Q '$)0 TÃOnÅ l/­PbW3¥Ók;\)_[Ë¦kQXnK$GDP6)RVWHU¡ÔCTÞßZ¸

¹Q '$)0 T4BCGJ4DH'*OnÅZkl/

7DNDVKL 6XPLNDPD   ³0HFKDQLVP RI LRQ SHUPHDWLRQ DQG VHOHFWLYLW\ WKURXJK WKH .  FKDQQHO $ PROHFXODU

G\QDPLFVVWXG\´)URQWLHUVRI&RPSXWDWLRQDO3K\VLFVIURPPH9WR0H9 LQYLWHGWDON ­PbÞß/?H8xd¾'*ÝÈ_kÔ\ÜvÑ]¾kl/

5?n®"Om

$6XPLQR76XPLNDPD HTXDOFRQWULEXWRU 78FKLKDVKLDQG62LNL6FL$GYHDD[  
76XPLNDPDDQG62LNL-3K\VLRO6FL  
76XPLNDPD FRUUHVSRQGLQJ $6)RVWHUDQG7)XNXPD-3K\V&KHP&  
.0LWD76XPLNDPD HTXDOFRQWULEXWRU 0,ZDPRWR<0DWVXNL.6KLJHPLDQG62LNL3URF1DWO$FDG6FL
86$H  
6 7VXMLRND $ 6XPLQR 7 6XPLNDPD + )OHFKVLJ / 3XSSXOLQ 7 7RPLWD < %DED 7 .DNXWD 7 2JRVKL +
0XUDNRVKLDQG06KLEDWD³&D0.,,LQWHJUDWHV&DVLJQDOVE\FRRSHUDWLYHSKRVSKRU\ODWLRQRIDGMDFHQWVXEXQLWV´ s£N0 .DODWKLQJDO 7 6XPLNDPD 6 2LNL DQG 6 6DLWR ³6SRQWDQHRXV YHFWRULDO LQVHUWLRQ RI D ȕKHOLFDO SHSWLGH LQWR
PHPEUDQH$WKHRUHWLFDOVWXG\XVLQJSRO\WKHRQDPLGH%´ s£N76XPLNDPD FRUUHVSRQGLQJ ))&DQRYD'=*DR$6)RVWHUDQG7)XNXPD³&RPSXWHGWKUHHGLPHQVLRQDODWRPLFIRUFHPLFURVFRS\LPDJHVRIELRSRO\PHUVXVLQJWKH-DU]\QVNLHTXDOLW\´ s£NE²[1] J. Peng et al., 1DWXUH  [2] E. Lieberman-Aiden et al., 6FLHQFH  [3] H. D. Ou et al., 6FLHQFHHDDJ  [4] T. Fukuma and R. Garcia, $&61DQR  >@%Reischl, M. Watkins, A. S. Foster, -&KHP7KHRU\&RPSXW  [6] M. Watkins, A. L. Shluger, 3K\V5HY/HWW  [7] T. Nozaki et al., 0RO&HOO  >@76XPLNDPD$6)RVWHU7)XNXPD-3K\V&KHP&  >@&-DU]\QVNL3K\V5HY/HWW  

- 413 -

㍈ᛶ࢟ࣛࣝ࡞ⓎගⰍ⣲ࡢບ㉳≧ែᵓ㐀ࡢゎ᫂
([FLWHG6WDWH6WUXFWXUHVRI$[LDOO\&KLUDO)OXRUHVFHQW'\HV‫ۑ‬㧗▼ ࿴ே㸦ᒸᒣ኱Ꮫ኱Ꮫ㝔⮬↛⛉Ꮫ◊✲⛉㸧

1◊✲┠ⓗ㏆ᖺࠊ᭷ᶵⓎගⰍ⣲ࡢ㛤Ⓨࡀ┒ࢇ࡛࠶ࡿࠋ࡯࡜ࢇ࡝ࡣ⁐ᾮࡲࡓࡣᅛయ≧ែ࡛ࡢⓎග࡛࠶ࡿࠋᐇ⏝໬ࢆ⪃៖ࡍࡿ࡜ࠊ↓⁐፹࣭ᖖୗ࡟࠾࠸࡚Ⰽ⣲ࡀᾮయ࡛࠶ࡿࡇ࡜ࡀᮃࡲࢀࡿࠋᾮయⰍ⣲ࡣࡑࡢ≉ᛶୖࠊ(1) ᡂ⭷ᛶ࡟ඃࢀࠊࡲࡓࠊ(2) ᛶ⬟ࡀ౑⏝⎔ቃ࡟౫Ꮡࡏࡎࠊ(3) 㧗ᐦᗘ໬ࠊ(4) 㠃ሬᕸࠊ(5) ᇶᯈ࡛ࡢᣳࡳ㎸ࡳࠊ(6) ẟ⣽⟶⌧㇟ࡢ฼⏝࡞࡝฼Ⅼࡀከ࠸ࠋ୍᪉ࠊ෇೫ගⓎගᛶ (CPL) ࢆ♧ࡍ᭷ᶵⰍ⣲ࡣࠊࣇࣞ࢟ࢩࣈࣝ 3D ࢹ࢕ࢫࣉࣞ࢖ࠊ
グ㘓⣲Ꮚࠊഇ㐀㜵Ṇ⏝ሬᩱ➼࡬ࡢ฼⏝ࡀぢ㎸ࡲࢀ࡚࠾ࡾࠊ㛤Ⓨ◊✲ࡀάⓎ࡛࠶ࡿࠋࡋ࠿ࡋᾮయ CPL Ⰽ⣲ࡢሗ࿌ࡣࡈࡃ㝈ࡽࢀ࡚࠸ࡓࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ㍈ᛶ࢟ࣛࣝࣅࢼࣇࢳࣝࢆᇶ┙࡜ࡍࡿᾮయ CPL Ⰽ⣲㛤Ⓨࢆ┠ᣦࡋࡓࠋࡉࡽ࡟❧యᵓ㐀࡜ CPL ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ Ⰽ⣲ೃ⿵࡜ࡋ࡚ࣅࢼࣇࢳࣝ (S)-1–9 ࢆタィࡋྜᡂࡋࡓࠋ໬ྜ≀ 8 ௨እࡣ↓⁐፹࣭ᖖୗ࡛↓Ⰽ㏱᫂࡞ᾮయ

࡛࠶ࡾࠊ⣸እගୗ࡛㟷Ⰽࡢ⺯ගࢆ♧ࡋࡓࠋ໬ྜ≀ 8 ࡣᅛయ࡛࠶ࡗࡓࠋࡇࢀࡽࡢ࠺ࡕ໬ྜ≀ 4 ࡢࡳࡀ CPL άᛶ࡛࠶ࡗࡓࠋ໬ྜ≀ 4 ࡣ࢟ࣕࣆ࣮ࣛࣜࡸࣃࢫࢶ࣮ࣝࣆ࣌ࢵࢺ࡛ᢅ࠼ࡿ࡯࡝⢓ᛶࡀపࡃࠊࡲࡓ࢔ࣝ࢟ࣝᇶࡢ㐪࠸࡟ᅉࡿ≀ᛶࡢᕪࡣᑠࡉ࠿ࡗࡓࠋ໬ྜ≀ 4 ࡢࡳࡀ CPL άᛶ࡛࠶ࡗࡓ⌮⏤ࢆ᫂ࡽ࠿࡟ࡍࡿ࡭ࡃࠊ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿゎᯒࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲᐦᗘỗ㛵ᩘἲ (CAM-B3LYP) ࡟ࡼࡾࠊᇶᗏ≧ែ࠾ࡼࡧບ㉳≧ែࡢᵓ㐀᭱㐺໬ィ⟬ࠊ᣺ືᩘゎᯒィ⟬ࠊTD ィ⟬ࢆ⾜ࡗࡓࠋᇶᗏ㛵ᩘࡣ 6-311+G(2d,p) ࢆ⏝࠸ࡓࠋィ⟬ࢯࣇࢺࡣ Gaussian16 ࢆ౑⏝ࡋࡓࠋ

3◊✲ᡂᯝ
DFT ࠾ࡼࡧ TD DFT ィ⟬࡟ࡼࡾ (S)-1–9 ࡑࢀࡒࢀࡢᇶᗏ≧ែ࡜ບ㉳≧ែ࡟࠾ࡅࡿᏳᐃᵓ㐀ࢆồࡵࠊglumࢆணࡋࡓࠋ୍౛࡜ࡋ࡚ḟ㡫࡟ࡑࢀࡒࢀࡢᵓ㐀ࢆ♧ࡍࠋᇶᗏ≧ែᵓ㐀࡟ࡘ࠸࡚ࡣࠊ࠸ࡎࢀࡶ 2 ࡘࡢࢼࣇࢱࣞ

ࣥ⎔ࡀ࠾ࡼࡑ┤஺ࡋ࡚࠾ࡾࠊ඾ᆺⓗ࡞ࣅࢼࣇࢳࣝ໬ྜ≀ࡢ≉ᚩࢆಖᣢࡋ࡚࠸ࡓࠋ୍⯡࡟ບ㉳≧ែ࡛ࡣࠊࣅࢼ
ࣇࢳࣝࡣ஧㠃ゅࡀ⊃࠸ࢩࢯ࢖ࢻᵓ㐀࡜ᗈ࠸ࢺࣛࣥࢯ࢖ࢻᵓ㐀ࢆ࡜ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ CPL ࢆ♧ࡋ- 414 -

ࡓ (S)-4a ࡣࠊࣅࢼࣇࢳࣝࡢ஧㠃ゅࡀ 120.8° ࡛࠶ࡿࢺࣛࣥࢯ࢖ࢻᵓ㐀ࡢࡳࢆ࡜ࡾࠊglum ್ࡣ +2.0 ×
10–3 ࡛࠶ࡿ࡜ண᝿ࡉࢀࡓࠋࡇࢀࡣᐇ㦂್࡜ྠ⛬ᗘ࡛࠶ࡗࡓࠋ7,7’-఩ࡢᔞ㧗࠸ࢩࣜࣝ⨨᥮ᇶࡢᙳ㡪࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ୍᪉࡛ࠊCPL ୙άᛶࡔࡗࡓ (S)-7ࡣ஧㠃ゅࡀ⊃࠸ࢩࢯ࢖ࢻᵓ㐀 (76.5°) ࡜ᗈ࠸ࢺࣛ
ࣥࢯ࢖ࢻᵓ㐀 (116.4°) ࡢ 2 ࡘࡢᏳᐃᵓ㐀ࡀᚓࡽࢀࠊࡑࢀࡒࢀࡢ glum ್ࡣ –1.0 × 10–3 ࡜ +6.6 × 10–3
࡛࠶ࡿࡇ࡜ࡀண᝿ࡉࢀࡓࠋCPL ࡢ➢ྕࡀ␗࡞ࡿ 2ࡘࡢᵓ㐀ࡀ CPL ࢆᡴࡕᾘࡋྜࡗࡓ࡜⪃࠼ࡽࢀࡓࠋ
௚ࡢ఩⨨␗ᛶయࡸ㢮⦕య (S)-1–3, 5, 6, 8–11 ࡶᇶᗏ≧ែࡢࢼࣇࢱࣞࣥ⎔ࡣ࠾ࡼࡑ┤஺ࡋ࡚࠾ࡾࠊ᫂☜࡞ᕪࡣ☜ㄆࡉࢀ࡞࠿ࡗࡓࠋບ㉳≧ែ࡛ࡣࢩࢯ࢖ࢻᵓ
㐀࡜ࢺࣛࣥࢯ࢖ࢻᵓ㐀ࡢ୧᪉ࢆ࡜ࡿ࠿ࠊࢩࢯ࢖ࢻᵓ
㐀ࡢࡳ࡛࠶ࡗ࡚ࡶᑠࡉ࡞ glum ࡋ࠿♧ࡉ࡞࠸࡜ண᝿
ࡉࢀࡓࠋࡉࡽ࡟ࠊ↓⨨᥮యࢆ⏝࠸࡚ບ㉳≧ែࡢࣅࢼࣇࢳࣝ஧㠃ゅ࡜ CPL ࡢ┦㛵ࢆㄪᰝࡋࡓ࡜ࡇࢁࠊ⨨᥮య࡜ఝࡓഴྥࢆ♧ࡋࡓࠋࡑࡢࡓࡵࠊ❧య㓄ᗙࢆไᚚࡍࢀࡤẚ㍑ⓗ㧗࠸ CPL ࢆ♧ࡍ࡜࠸࠺≉ᛶࡣࠊࣅࢼࣇࢳࣝ㢮࡟ඹ㏻ࡍࡿ஦㡯࡛࠶ࡿྍ⬟ᛶࡀ㧗࠸ࠋ௨ୖࡢィ⟬⤖ᯝࡼࡾࠊ఩⨨␗ᛶయࡢ࠺ࡕ (S)-4 ࡢࡳࡀ CPL άᛶ࡛࠶ࡗࡓࡢࡣࠊບ㉳≧ែ࡟࠾࠸࡚
glum ࡢ኱ࡁ࡞ࢺࣛࣥࢯ࢖ࢻᵓ㐀ࢆ≉␗ⓗ࡟ᙧᡂࡍࡿࡇ࡜࡟㉳ᅉࡍࡿ࡜ุ᩿ࡋࡓࠋ௒ᚋࡣࠊࡉࡽ࡟ඃࢀ
ࡓⓎග≉ᛶࢆᣢࡘⰍ⣲ࡸⰍㄪࡢ␗࡞ࡿⰍ⣲ࡢ㛤Ⓨ◊✲ࢆ⥅⥆ࡋ࡚⾜࠺ࠋ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬㧗▼ ࿴ே, ᭷ᶵྜᡂ໬Ꮫ༠఍ࠕMukaiyama Award࣭ዡບ㈹ࠖཷ㈹ㅮ₇఍, ࢟ࣛࣝࢼࣇࢱࣞࣥከ㔞య࠿ࡽᡂࡿ
෇೫ගⓎගⰍ⣲ࡢྜᡂ, 2020 ᖺ 9 ᭶ 17 ᪥.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬Kazuto Takaishi, Tomoki Matsumoto, Miyu Kawataka, Tadashi Ema. Circularly polarized luminescence liquids basedon siloxybinaphthyls: Best binaphthyl dihedral angle in the excited state. Angew. Chem. Int. Ed. 2021, 60, 9968–9972.

- 415 -

㉸▷࣮ࣞࢨ࣮ࣃࣝࢫࢆ⏝࠸ࡓࢼࣀศᏊࡢ཯ᛂືຊᏛ࢖࣓࣮ࢪࣥࢢ⌮ㄽ
5HDFWLRQG\QDPLFVWKHRU\IRUWKHLPDJLQJRIXOWUDIDVWUHDFWLRQG\QDPLFVRIQDQRPROHFXOHVżᒣᓮ 㤾㸦⌮໬Ꮫ◊✲ᡤ㸧




◊✲┠ⓗ

㏆ᖺࡢ ; ⥺⮬⏤㟁Ꮚ࣮ࣞࢨ࣮㸦;)(/㸧ࡸ㧗ḟ㧗ㄪἼⓎ⏕㸦++*㸧ග※ࡢᛴ㏿࡞㐍Ṍ࡟ࡼࡾ㸪 H9 ௨ୖࡢගᏊ࢚ࢿࣝࢠ࣮ࢆᣢࡘࣇ࢙࣒ࢺ⛊࣭࢔ࢺ⛊㌾ ; ⥺ࣃࣝࢫග※ࡀᐇ⏝໬ࡉࢀ㸪ከཎᏊศᏊࡢ཯ᛂືຊᏛ㏣㊧࡟ά⏝ࡉࢀࡿࡼ࠺࡟࡞ࡗ࡚ࡁࡓ>DF@㸬ࡲࡓ㸪⌧ᅾᘓタ୰ࡢḟୡ௦ᨺᑕග᪋タ 6/,7- ࡛ࡣ ㌾㹖⥺ࢆ⏝࠸ࡓࠕᮦᩱࡢࡑࡢሙ࢖࣓࣮ࢪࣥࢢἲࠖࢆ┠⋢࡜ࡋࡓࣅ࣮࣒ࣛ࢖ࣥᩚഛࡀ㐍ࡵࡽࢀ࡚࠸ࡿ㸬ࡇࢀࡽࡢ◊✲ࡢ኱┠ᶆࡢ୍ࡘࡣ㸪⏕య㛵㐃ศᏊࡸᶵ⬟ᛶᮦᩱࡢ཯ᛂ୰࣭ ືస୰ࡢࢲ࢖ࢼ࣑ࢡࢫࢆ┤᥋࢖࣓࣮ࢪࣥࢢࡍࡿࡇ࡜࡛࠶ࡿ㸬ࡋ࠿ࡋ㸪ࡇࢀࡽࡢ ㌾ ; ⥺ග※ࡣ㧗࠸ගᏊ࢚ࢿࣝࢠ࣮ࢆࡶࡕ㸪ศᏊࡢ࢖࢜ࣥ໬ࡸゎ㞳࡞࡝ࡢ 5DGLDWLRQGDPDJH
ࢆᐜ᫆࡟ᘬࡁ㉳ࡇࡍ>FG@㸬ࡇࡢࡓࡵ㌾ ; ⥺࢖࣓࣮ࢪࣥࢢ࡛ࡣ㸪㌾ ; ⥺↷ᑕ๓࠿ࡽ኱࡞ࡾᑠ࡞ࡾኚ㉁ࡋࡓᮦᩱ
ࡢほᐹࢆవ൤࡞ࡃࡉࢀ࡚࠾ࡾ㸪⌮ㄽ ィ⟬➼ࢆ⏝࠸࡚ኚ㉁ࡢᙳ㡪ࢆ㐺ษ࡟ホ౯ࡍࡿᚲせࡀ࠶ࡿ>HI@㸬 ࡑࡇ࡛➹⪅ࡽࡣ㸪㌾ ; ⥺↷ᑕ࡟ࡼࡿᮦᩱኚᙧࡢືຊᏛࢆ㏣㊧ࡍࡿࡇ࡜ࢆ┠ᣦࡋ࡚㸪   㹖⥺ㄏ㉳ศᏊᵓ㐀ኚᙧࡢึᮇ≧ែ࡜࡞ࡿ  㔜✵Ꮝ≧ែ࡬ࡢ┦ᑐ $XJHU 㑄⛣☜⋡㸦$XJHU ࢫ࣌ࢡࢺࣝ㸧ィ⟬ἲ࡜   ೫ගᖹᆒศᏊ
ᗙᶆ⣔ෆẆග㟁Ꮚゅᗘศᕸ㸦3$0)3$'㸧࡟ࡼࡿศᏊᵓ㐀Ỵᐃἲࢆ㛤Ⓨࡋࡓ㸬◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 2 ✵Ꮝ㓄⨨㛫┦஫స⏝(2h-CI)ἲ࡟ᇶ࡙ࡃ Auger ࢫ࣌ࢡࢺࣝィ⟬; ⥺↷ᑕ࡟ࡼࡾ㉳ࡁࡿ໬Ꮫ཯ᛂࡢጞ≧ែỴᐃ࡟ᚲせ࡞ $XJHU ࢫ࣌ࢡࢺࣝࡢィ⟬ἲࢆ㸪౯㟁Ꮚ㌶㐨࡟  ࡘࡢ✵Ꮝࢆᣢࡘ㟁Ꮚ㓄⨨ࢆࡍ࡭࡚⪃៖ࡋࡓ㓄⨨㛫┦஫స⏝ K&, ἲ >JK@࡟ᇶ࡙࠸࡚ᨵⰋ࣭ᐇ⿦ࡋࡓ㸬K&, ィ⟬࡟ࡣ㔞Ꮚ໬Ꮫィ⟬ࣃࢵࢣ࣮ࢪ 2SHQ0ROFDV>L@ࢆ⏝࠸ࡓ㸬 
3$0)3$'ᮏ◊✲࡛ࡣ&2 ศᏊࡀ ;)(/ ࣏ࣥࣉࣃࣝࢫ࡛ &V ㌶㐨࠿ࡽ࢖࢜ࣥ໬ࡉࢀࡑࡢᚋ࡟㉳ࡁࡿ $XJHU ⦆࿴࡟ࡼࡗ୍࡚㔜㡯 ı ≧ែࡢ &2㸩 ࡀ⏕ᡂࡋ㸪ࣉ࣮ࣟࣈࣃࣝࢫ࡟ࡼࡗ࡚ 2V ㌶㐨࠿ࡽ࢖࢜ࣥ໬ࡉࢀ࡚஧㔜㡯 ıı ≧ែ࡜࡞ࡗࡓ≧ែࢆ௬ᐃࡋ࡚ 3$0)3$' ࡢィ⟬ࢆ⾜ࡗࡓ㸬ࡲࡎ㸪㔞Ꮚ໬Ꮫィ⟬ࣉࣟࢢ࣒ࣛ 02/&$6

>L@࡟ᐇ⿦ࡉࢀ࡚࠸ࡿไ㝈άᛶ✵㛫ࢆ⏝࠸ࡓከཧ↷஧ḟᦤືㄽ 5$637 ࡟ࡼࡗ࡚ศᏊ㌶㐨Ἴື㛵ᩘ࡜㟁Ꮚᐦᗘࢆィ⟬ࡋࡓ 3RLVVRQ ᪉⛬ᘧࢆゎࡃࡇ࡜࡛ࠊከ㔜ᩓ஘ィ⟬࡟ᚲせ࡞ࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࢆᚓࡓ ᚓࡽࢀࡓ㟁Ꮚᐦᗘ࡜ࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࢆ⏝࠸࡚ )XOOSRWHQWLDO ከ㔜ᩓ஘ィ⟬ࣉࣟࢢ࣒ࣛ )306>M@࠾ࡼࡧࢫ࣌ࢡࢺ
ࣝィ⟬ࣉࣟࢢ࣒ࣛ 0V6SHF>N@࡟ࡼࡾ 3$0)3$' ࢆィ⟬ࡋࡓ㸬2 V ග㟁Ꮚࡢ㐠ື࢚ࢿࣝࢠ࣮ࡣ  H9㸪&2⤖ྜ㛗ࡣ ୰ᛶ &2 ศᏊࡢᖹ⾮᰾㛫㊥㞳 c ࠿ࡽ c ࡲ࡛ c ้ࡳ࡛  Ⅼィ⟬ࡋࡓ- 416 -

◊✲ᡂᯝᮏᡭἲࢆ +2 ཬࡧ &+ ศᏊ࡟㐺⏝ࡋ㸪V ✵Ꮝ≧ែ࠿

ࡽ GLFDWLRQ ≧ែ࡬ࡢ㌶㐨⦆࿴ࢆ⪃៖ࡍࡿ>F@ࡇ࡜࡛㸪S ㌶

2p-2: 40 % of
total intensityExp㐨࡟  ࡘ✵Ꮝࢆᣢࡘ RXWHUYDOHQFH S  㡿ᇦࡢ $XJHU ࢫ࣌ࢡࢺࣝࢆᐃ㔞ⓗ࡟෌⌧࡛ࡁࡓ ᅗ 㸧>@㸬 ⌧ᅾ㸪ᮏࣉ2h-CIࣟࢢ࣒ࣛࢆⰾ㤶᪘ศᏊࡢ㹖⥺ㄏ㉳ゎ㞳㐣⛬ࡢጞ≧ែྠᐃ࡬ࡢᛂ⏝ࢆ㐍ࡵ࡚࠸ࡿ>@㸬 ෆẆග㟁Ꮚゅᗘศᕸ㸦0)3$'㸧࡟ࡼࡿ  ཎᏊศᏊࡢ
㹖⥺ㄏ㉳ືຊᏛ
ᮏ◊✲࡛ᚓࡽࢀࡓ 3$0)3$' ᅗ  >@ࡢᚋ᪉ᩓ஘ᅗ 㸸 K&, ἲ࡟ࡼࡗ࡚ィ⟬ࡉࢀࡓ࢚ࢳࣞࣥ

࡜๓᪉ᩓ஘ࡢẚ Ș 5 ࢆ &2ࡢ⤖ྜ㛗 5 ࡢ㛵ᩘ࡜ࡋ࡚ᅗ

㸦&+㸧ศᏊࡢ $XJHU ࢫ࣌ࢡࢺࣝ㸦㟷㸧࡜ᐇ㦂 ࡟♧ࡍ㸬0XIILQ7LQ ㏆ఝ࡟ᇶ࡙ࡃ  ᅇᩓ஘ࡢゎᯒᘧ>@್㸦⥳㸧ࡢẚ㍑

Ș 5 㸻 D FRV N5 F 5E   N㸸ග㟁Ꮚ㐠ື㔞 㸻 H9D ᣺ືᙉᗘ
E ࣂࢵࢡࢢࣛ࢘ࣥࢻF ᣺ື఩┦࡜ࣇ࣏ࣝࢸࣥࢩࣕࣝከ㔜ᩓ஘⌮ㄽ࡛ồࡵࡓ Ș 5 >@ࢆẚ
㍑ࡍࡿࡇ࡜࡟ࡼࡾ㸪Ș 5 ࡣ࠾ࡼࡑ N5 ࡛ῶ⾶᣺ືࡋ࡚࠸ࡿࡇ࡜ࢆぢฟࡋࡓ>@㸬  ᘧ࡜ྂ඾ࢡ࣮ࣟࣥ⇿Ⓨࣔࢹࣝࢆ⤌ࡳྜࢃࡏࡿࡇ࡜࡛㸪;)(/ ࣃࣝࢫ࡟ࡼࡿከ㔜࢖࢜ࣥ໬࡛⏕ᡂࡋࡓ 2 ከ౯࢖࢜ࣥࡢゎ㞳ືຊᏛࢆᢳฟࡍࡿࡇ
࡜࡟ᡂຌࡋࡓ>@㸬ࡲࡓ㸪෇೫ග 0)3$' ࡢゎᯒᘧࢆᑟฟᅗ 㸸ࣇ࣏ࣝࢸࣥࢩࣕࣝከ㔜ᩓ஘⌮ㄽ࡟ᇶ࡙࠸

ࡋ㸪෇೫ග 0)3$' ࠿ࡽ஧ཎᏊศᏊࡢศᏊᵓ㐀ࢆỴᐃ࡛࡚ィ⟬ࡋࡓ &2ࡢ 3$0)3$'ࡁࡿࡇ࡜ࢆ♧ࡋࡓ>@㸬⌧ᅾ㸪ෆẆග㟁Ꮚࡢ࢔ࢺ⛊ 7LPH
GHOD\ ࡢᐃᘧ໬ࢆ㐍ࡵ࡚࠸ࡿ>@㸬ཧ⪃ᩥ⊩>D@2*HVVQHUHWDO $FF&KHP5HV  >E@.=LQ]HQNRHWDO6FLHQFH  >F@1%HUUDK1DW3K\V   
>G@ K. Yamazaki HW DO - &KHP 3K\V    ᅗ 㸸ࣇ࣏ࣝࢸࣥࢩࣕࣝከ㔜ᩓ஘⌮ㄽ࡟ᇶ࡙࠸࡚

>H@.1DVVHWDO 1DW&RPPXQ   ィ⟬ࡋࡓ Ș 5 㸦Ŷ㸧࡟ᑐࡍࡿ  ᅇᩓ஘ࡢゎᯒᘧ >I@K. Yamazaki HWDO-&KHP3K\V  ࡢࣇ࢕ࢵࢸ࢕ࣥࢢ ◚⥺ >J@ . 0 0LWDQL HW DO - (OHFWURQ 6SHFWURVF 5HODW3KHQRP  - 417 -

>K@/,QKHVWHUHWDO-3K\V&KHP/HWW  >L@)$TXLODQWHHWDO-&KHP3K\V  >M@.+DWDGDHWDO Phys. Rev. B 76 060102 (2007)[k] D Sébilleau et al., Comput. Phys. Commun. 182 2567 (2011)ฟ∧ᐇ⦼ࡲࡓࡣணᐃ㈐௵ⴭ⪅>@ ‫)ۻ‬2WD.+DWDGD '6HELOOHDX.8HGDDQG.<DPD]DNL ³7KHRU\RQSRODUL]DWLRQDYHUDJHGFRUHOHYHOPROHFXODUIUDPHSKRWRHOHFWURQDQJXODUGLVWULEXWLRQV,,([WUDFWLQJWKH;UD\LQGXFHGIUDJPHQWDWLRQG\QDPLFVRI FDUERQ PRQR[LGH GLFDWLRQ IURP IRUZDUG DQG EDFNZDUG LQWHQVLWLHV´ - 3K\V %   '2,DEFIG  >@ ‫ ) ۻ‬2WD . <DPD]DNL ' 6 . 8HGD DQG . +DWDGD  ³7KHRU\ RI SRODUL]DWLRQDYHUDJHG FRUHOHYHOPROHFXODUIUDPH SKRWRHOHFWURQ DQJXODU GLVWULEXWLRQV , $ )XOOSRWHQWLDO PHWKRG DQG LWV DSSOLFDWLRQ WR
GLVVRFLDWLQJFDUERQPRQR[LGHGLFDWLRQ´-3K\V%'2,DEG  >@ ‫ۻ‬6.LQRVKLWD<+DUDEXFKL<,QRNXFKL60DHGD0(KDUD.<DPD]DNL   DQG  7(EDWD ³6XEVWLWXWLRQHIIHFWRQWKHQRQUDGLDWLYHGHFD\DQGWUDQVĺFLVSKRWRLVRPHUL]DWLRQURXWHDJXLGHOLQHWRGHYHORSHIILFLHQW
FLQQDPDWHEDVHG VXQVFUHHQV´ 3K\V &KHP &KHP 3K\V   '2, '&3'  
2XWHU)URQW&RYHU ཬࡧ 3&&3+27$UWLFOHV ࡟㑅ฟ㸬>@ ,9HOD3HUp])2WD$0KDPGL<7DPXUD-5LVW10HO]HU68HUNHQ*1DOLQ1$QGHUV'<RX0.LUFKHU&-DQNH0:DLW])7ULQWHU5*XLOOHPLQ013LDQFDVWHOOL06LPRQ97'DYLV-%:LOOLDPV5'|UQHU.+DWDGD.<DPD]DNL.)HKUH3K9'HPHNKLQ.8HGD066FK|IIOHUDQG7-DKQNH
³+LJK(QHUJ\0ROHFXODU)UDPH3KRWRHOHFWURQ$QJXODU'LVWULEXWLRQV$0ROHFXODU%RQG/HQJWK5XOHU´3K\V
5HY/HWW6XEPLWWHG DU;LY>SK\VLFVDWRPSK@ >@ *.DVWLUNH)2WD'95H]YDQ066FK|HU0:HOOHU-5LVW5%ROO1$QGHUV70%DXPDQQ6
(FNDUW%(UN$'H)DQLV.)HKUH$*DWWRQ6*UXQGPDQQ3*U\FKWRO$+DUWXQJ0+RIPDQQ0,OFKHQ&-DQNH0.LUFKHU0.XQLWVNL;/L70D]]D10HO]HU-0RQWDQR90XVLF*1DOLQ<
2YFKDUHQNR$3LHU15HQQKDFN'(5LYDV5'|UQHU'5ROOHV$5XGHQNR36FKPLGW-6LHEHUW1
6WUHQJHU'7UDEHUW,9HOD3HUH]5:DJQHU7:HEHU-%:LOOLDPV3=LRONRZVNL/3K+6FKPLGW$&]DVFK<7DPXUD1+DUD.<DPD]DNL.+DWDGD)7ULQWHU  00H\HU.8HGD3K9'HPHNKLQDQG
7-DKQNH³,QYHVWLJDWLQJFKDUJHXSDQGIUDJPHQWDWLRQG\QDPLFVRIR[\JHQPROHFXOHVDIWHULQWHUDFWLRQZLWKVWURQJIUHHHOHFWURQODVHU;UD\SXOVHV´ ᢞ✏‽ഛ୰㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

>@ ‫ۻ‬żኴ⏣ ⷋᏊ࣭'LGLHU6pELOOHDX࣭ᒣᒣᓮ 㤾࣭ୖ⏣ ₩࣭⏿⏣ ᆂ௓ࠕศᏊᵓ㐀ኚ໬ࡢ㧗᫬㛫ศゎ㏣㊧࡟ྥࡅࡓኚ᭦᪉ྥᖹᆒศᏊᗙᶆ⣔ග㟁Ꮚゅᗘศᕸࡢ )XOOSRWHQWLDO ከ㔜ᩓ஘⌮ㄽ࡟ࡼࡿ◊✲ࠖ➨  ᅇ(;$)6 ウㄽ఍㸦2㸧㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᖺ  ᭶  ᪥㸬- 418 -

>@ ‫ۻ‬żᮌୗ ┿அ௓࣭ ஭ཱྀ ెဢ ࣭ⓑ⏨ᕝ ㈗ྐ࣭Ụཎ ṇ༤࣭ᒣᒣᓮ 㤾࣭ཎῲ ♸࣭๓⏣ ⌮࣭Ụᖭ Ꮥஅࠕ㉸㡢㏿ࢪ࢙ࢵࢺ࣮ࣞࢨ࣮ศග࡜㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ᱇⓶㓟ㄏᑟయࡢ㟁Ꮚ≧ែ࡜ WUDQV ĺFLV ග␗ᛶ໬࡟ཬࡰࡍ⨨᥮ᇶຠᯝࡢ◊✲ࠖศᏊ⛉Ꮫ࢜ࣥࣛ࢖ࣥウㄽ఍㸦$㸧㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᖺ  ᭶  ᪥㸬>@ ‫ۻ‬żᒣᓮ 㤾ࠕග໬Ꮫ཯ᛂࡢ㔞Ꮚ໬Ꮫ㸸ྍど࣭⣸እ㡿ᇦ࠿ࡽ ; ⥺㡿ᇦ࡬ࡢᣑᙇࠖィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔࣒㸦3&R06㸧ࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍
㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᖺ  ᭶  ᪥㸬>@ ‫ۻ‬ż.<DPD]DNL . 0LGRULNDZD ³;UD\ LQGXFHG IHPWRVHFRQG LRQL]DWLRQ NLQHWLFV RI WURSRQH &+2  DW
FDUERQ.HGJH´ ➨  ᅇ໬Ꮫ཯ᛂウㄽ఍㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᖺ  ᭶ 㸫 ᪥>@ ‫ۻ‬żᒣᓮ 㤾࣭⥳ᕝ ඞ⨾ࠕ7URSRQH ஧౯࢝ࢳ࢜ࣥ &+2 ࡟࠾ࡅࡿ㹖⥺ㄏ㉳␗ᛶ໬࣭ゎ㞳⤒㊰ࡢࢫࣆࣥ≧ែ౫Ꮡᛶࠖ➨  ᅇศᏊ⛉Ꮫウㄽ఍㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᭶ 㸫 ᪥㸬>@ ż<7DPXUD.<DPD]DNL)2WD.8HGD.+DWDGDࠕ&2 ศᏊࡢ & V ෆẆග࢖࢜ࣥ໬࡟࠾ࡅࡿ࢔ࢺ⛊ග㟁Ꮚ 7LPHGHOD\ ࡬ࡢከ㔜ᩓ஘⌮ㄽࡢᛂ⏝ࠖ➨  ᅇศᏊ⛉Ꮫウㄽ఍㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᭶ 㸫 ᪥㸬- 419 -

6WUXFWXUDOPHFKDQLVPRI7FHOODFWLYDWLRQżFloris van Eerden (Osaka University)

1 Introduction
T cells are responsible for recognizing foreign antigens, killing infected or cancerous
cells and maintaining cellular memory of previously encountered antigens. The T cell
receptor (TCR) plays a crucial role in these processes by binding to antigens (epitopes)in the context of the major histocompatibility complex (MHC). Our bodies can makehundreds of billions of different TCR protein sequences, each with specificity for one ora few agonistic peptide-MHC (pMHC) complexes. Currently the working mechanism of
the TCR remains enigmatic. Firstly, it is unclear how a TCR specifically recognizes
only a small number of agonistic pMHCs. Secondly, it is unclear how signaltransduction is initiated after the TCR does bind to an agonistic pMHC.
The first TCR structure was recently solved by cryo-EM 1. In this structure, the TCR
makes an ~135° angle with the membrane normal as shown in Figure 1. The tilted

Figure 1: Cryo-EM structure ofa TCR in complex with its CD3
co-receptor. T cell and APC
membranes are indicated by greyboxes.

conformation appears to be sub-optimal for binding to the pMHC, as binding would be only possible if the pMHC is also
bent at a 135° angle. This led us to hypothesize that the tilted orientation as seen in the structure is only one out of manydifferent possible conformations, and that the TCR possesses a greater flexibility than the cryo-EM structure suggests.
Coarse grained molecular dynamics (CGMD) simulations were performed to test whether the TCR angle is flexible, and
how TCR binding to the pMHC influences the flexibility. These simulations revealed a great degree of flexibility in thefree TCR, but much less flexibility in the pMHC-bound complex, as predicted. We further identified two glycine residues
in the TCR beta chain that are conserved in evolution (Figure 2), and which we predict act as hinge residues. To validate
these predictions, a number of mutant TCRs were designed, in which the glycine residues were mutated to less-flexible
residues. Experiments are being carried out to quantify the degree to which TCRs with mutated hinge residues canfunction in cells.

Figure 2: MSA of the putative
hinge region. The sequence of theputative hinge is well conserved
among a wide range of organisms,with the two glycines (marked inpink) being perfectly conserved.

- 420 -

2 Methods
Applicant name: Floris van Eerden
Our simulations are based on the cryo-EM structures of Dong et al. (PDB ID 6JXR) and Newell et. al (PDB ID 3QIU) 2.
For the CD3 co-receptors and the transmembrane part of the TCR, the structure of Dong et al. was used. The structure by
Newell et al served as the basis of MHC and of the extracellular parts of the TCR. We are interested in the simulation ofa TCR-MHC complex, but the extracellular part of the TCR electron densities of the Dong structure have been fitted on
the coordinates of an atypical natural killer TCR. For this reason, the TCR from the structure by and Newell et. (PDB ID
3QIU) 2 was used for the extracellular part of the TCR. This structure was incomplete and the essential missing residues
were reconstructed using Spanner 3.
Coarse grained molecular dynamics is in particular suitable for the study of large protein systems, for which thecoarse grained martini forcefield 4 was used. Gromacs versions 2019.4, 2020.6 and 2021.1 were used as the molecular
dynamics engine 5. Simulations were performed with the novel Martini 3 forcefield 6 in conjunction with Gō-potentials. Simulations were carried out as in 8 with minor modifications. In short, systems were constructed using a variety of7tools: Martinize2 (in preparation) was used to transform the protein from atomistic to coarse grained resolution using
DSSP on the fly 9. Both the TCR in conjunction with the CD3 co-receptors and the pMHC were embedded in amembrane and solvated using the Insane script 10. The simulations were carried out at normothermia (310 K) with the vrescale thermostat 11. Pressure was semi-isotropically coupled to an external bath of p = 1 bar using the Berendsenbarostat 12). A timestep of 20 fs was used in all simulations. TCR and pMHC were brought into contact by a set of
restraints between the TCR and the pMHC. The epitope was restrained within the MHC. In the simulations with pMHC,
a pore was created in the membrane containing the pMHC to allow solvent flow between the two compartments.
Simulations were run for 10 μs Ten simulations of free TCR were performed, versus three of pMHC bound TCR.
Simulations were analyzed using VMD, Pymol, and the python MDAnalysis suite. The angles were calculated between
the TCR headgroup and the transmembrane part of the TCR. MSA were generated with MAFFT 13 14.

3 Results

To investigate the difference in behaviour between free and pMHC bound TCRs, simulations of a single TCR (Figure3A) and a TCR in conjugation with a pMHC complex (Figure 3B) were performed.

- 421 -

A

B

Figure 3: Simulation boxes of free TCR (A), and pMHC engaged TCR (B). TCR (green), together with the CD3 co-receptors (yellow)
embedded in a POPC bilayer. In the right frame, the TCR is engaged with a pMHC complex, which is itself also embedded in a POPC bilayer.
For clarity the solvent and part of the membrane are not shown.

3.1. TCR without pMHC
At the start of the simulations the TCR angle is 111 degrees. The distributions of the headgroup angle (Figure 4) for free
pMHC ranges from ~75 to 160 degrees, spanning 85 degrees, and is fairly broad, but peaks around 105 degrees. FreeTCR adopts therefore a rather bent conformation.
3.2 TCR with pMHC
The distribution of pMHC bound TCR is from ~115 to 180 degrees, which means that the initial conformation of the TCR
at 111 degrees, is not sampled when the TCR is in contact with an pMHC. With a range of 65 degrees the distribution isless broad, and has a peak around 140 degrees. This means when engaged with a TCR, the TCR adopts an almost straightconformation.
Analysis of these simulations showed that the headgroup of an unengaged TCR is much more flexible than the headgroupof a pMHC bound TCR, Figure 4. This hypothesis is currently being tested in the lab, using a variety of mutants in whichsome of the hinge residues have been changed. If our hypothesis is correct, these mutants are less likely to interact andbind with a pMHC complex.

3.3 Putative hinge
Visual inspection of simulations of a single TCR in a bilayer resulted in the identification of a region that might function- 422 -

as a hinge. We hypothesized that this hinge might render the TCR with a certain flexibility, and that this flexibility
contributes to the binding of the TCR to the pMHC. Analysis of the sequence of in the potential hinge region showed thatthe sequence is well conserved in evolution. In various mammals, among which are mouse, sheep, bovines, monkeys,
apes and humans, the sequence is almost completely conserved, with the two glycines being perfectly conserved, Figure
2.

Figure 4: Normalized distributions of the angle
between the TCR headgroup and the TCR
transmembrane helices. Simulations without
MHC (blue) and with the TCR engaged with apMHC (orange). At the start of the simulations theangle is 111 degrees, as indicated by the green
vertical line. Ten simulations of free TCR were
performed, versus three of pMHC bound TCR.

4 Talks and Posters
Due to COVID-19 relevant conferences were cancelled, the following lectures were however still being given at
Osaka University:
Combined Program on Microbiology and Immunology 1, Osaka University:‘Molecular dynamics, an introduction to “computational microscopy”’ (December 15th 2020)‘Lipids, in the mix’ ( December 22nd 2020)
Chemistry-Biology Combined Major Program, Osaka University‘Molecular dynamics, an introduction to “computational microscopy”’ (January 19th 2021)‘Lipids, in the mix’ (January 26th 2020)

5 Publications
Saputri, D. S. et al. Flexible, Functional, and Familiar: Characteristics of SARS-CoV-2 Spike Protein Evolution.
Front Microbiol 11, 2112 (2020).
Teraguchi, S. et al. Methods for sequence and structural analysis of B and T cell receptor repertoires. Comput Struct
Biotechnol J 18, 2000-2011 (2020).
Van Eerden, F.J. et al. Conformational flexibility of the T cell receptor. In preparation- 423 -

6

References[@'RQJ'HWDO6WUXFWXUDOEDVLVRIDVVHPEO\RIWKHKXPDQ7FHOOUHFHSWRU±&'FRPSOH[1DWXUH  >@

1HZHOO(:HWDO6WUXFWXUDOEDVLVRIVSHFLILFLW\DQGFURVVUHDFWLYLW\LQ7FHOOUHFHSWRUVVSHFLILFIRUF\WRFKURPHF,(N-RXUQDORILPPXQRORJ\ %DOWLPRUH0G   >@/LV0HWDO%ULGJLQJWKHJDSEHWZHHQVLQJOHWHPSODWHDQGIUDJPHQWEDVHGSURWHLQVWUXFWXUHPRGHOLQJXVLQJ6SDQQHU,PPXQRPH5HVHDUFK  >@GH-RQJ'+HWDO,PSURYHG3DUDPHWHUVIRUWKH0DUWLQL&RDUVH*UDLQHG3URWHLQ)RUFH)LHOG-RXUQDORI&KHPLFDO7KHRU\DQG&RPSXWDWLRQ  >@+HVV%.XW]QHU&YDQGHU6SRHO' /LQGDKO(*520$&6K$OJRULWKPVIRU+LJKO\(IILFLHQW/RDG%DODQFHGDQG6FDODEOH
0ROHFXODU6LPXODWLRQ-RXUQDORI&KHPLFDO7KHRU\DQG&RPSXWDWLRQ  >@6RX]D3&7HWDO0DUWLQLDJHQHUDOSXUSRVHIRUFHILHOGIRUFRDUVHJUDLQHGPROHFXODUG\QDPLFV1DW0HWKRGV  >@6RX]D3&77KDOOPDLU60DUULQN6- 0HUD$GDVPH5$QDOORVWHULFSDWKZD\LQFRSSHU=LQFVXSHUR[LGHGLVPXWDVHXQUDYHOVWKH
PROHFXODUPHFKDQLVPRIWKH*$DP\RWURSKLFODWHUDOVFOHURVLVOLQNHGPXWDWLRQ7KHMRXUQDORISK\VLFDOFKHPLVWU\OHWWHUV
 >@

YDQ(HUGHQ)-0HOR01)UHGHUL[3:-03HULROH; 0DUULQN6-([FKDQJHSDWKZD\VRISODVWRTXLQRQHDQGSODVWRTXLQROLQWKHSKRWRV\VWHP,,FRPSOH[1DWXUH&RPPXQLFDWLRQV  >@.DEVFK: 6DQGHU&'LFWLRQDU\RISURWHLQVHFRQGDU\VWUXFWXUH3DWWHUQUHFRJQLWLRQRIK\GURJHQERQGHGDQGJHRPHWULFDOIHDWXUHV%LRSRO\PHUV  >@:DVVHQDDU7$,QJyOIVVRQ+,%|FNPDQQ5$7LHOHPDQ'3 0DUULQN6-&RPSXWDWLRQDO/LSLGRPLFVZLWKLQVDQH$9HUVDWLOH
7RROIRU*HQHUDWLQJ&XVWRP0HPEUDQHVIRU0ROHFXODU6LPXODWLRQV-RXUQDORI&KHPLFDO7KHRU\DQG&RPSXWDWLRQ  >@%XVVL*'RQDGLR' 3DUULQHOOR0&DQRQLFDOVDPSOLQJWKURXJKYHORFLW\UHVFDOLQJ7KH-RXUQDORI&KHPLFDO3K\VLFV
 >@%HUHQGVHQ+-&3RVWPD-30YDQ*XQVWHUHQ:)'L1ROD$ +DDN-50ROHFXODUG\QDPLFVZLWKFRXSOLQJWRDQH[WHUQDOEDWK
7KH-RXUQDORI&KHPLFDO3K\VLFV  >@.XUDNX6=PDVHN&01LVKLPXUD2 .DWRK.D/HDYHVIDFLOLWDWHVRQGHPDQGH[SORUDWLRQRIPHWD]RDQJHQHIDPLO\WUHHVRQ0$))7
VHTXHQFHDOLJQPHQWVHUYHUZLWKHQKDQFHGLQWHUDFWLYLW\1XFOHLFDFLGVUHVHDUFK::  >@.DWRK.5R]HZLFNL- <DPDGD.'0$))7RQOLQHVHUYLFHPXOWLSOHVHTXHQFHDOLJQPHQWLQWHUDFWLYHVHTXHQFHFKRLFHDQG
YLVXDOL]DWLRQ%ULHILQJVLQELRLQIRUPDWLFV  - 424 -

ࢺࣜࢳ࣒࣮࢘࣋ࢱᔂቯࡢ⏕య㧗ศᏊ࡬ࡢᙳ㡪,QIOXHQFHRIWKHWULWLXPEHWDGHFD\RQELRSRO\PHU‫ۑ‬୰ᮧ ᾈ❶㸦᰾⼥ྜ⛉Ꮫ◊✲ᡤࠊྡྂᒇ኱Ꮫ㸧⸨ཎ 㐍ࠊỈཱྀ ᭸Ꮚࠊᮤ ᾈㄽࠊᕝἼ
❳ኴࠊ⸨Ọ ⿱ᘺ㸦ி㒔ᕤⱁ⧄⥔኱Ꮫ㸧ࠊ⃝⏣ ᣅᘺࠊᅵ⏕ ᯻ࠊ▼㯮 ೺ே㸦ྡྂᒇ኱Ꮫ㸧ࠊᩪ⸨ ㄔ⣖ࠊబ⸨ Ᏺ㤿ࠊᅵ⏣ 㝧ᖹࠊ⸨⏣ ⍠㸦ᒣᙧ኱Ꮫ㸧⾲ ◊✲┠ⓗ㸳ࡘࡢ 5HD[)) ຊሙ⚟ᓥ➨୍ཎᏊຊⓎ㟁ᡤࡢᗫ⅔సᴗ࡟࠾࠸࡚ࠊࢺࣜࢳ࣒࢘ࢆྵࡴ኱
㔞ࡢởᰁỈࡢฎ⌮ࡀၥ㢟࡜࡞ࡗ࡚࠸ࡿࠋࡉࡽ࡟ࠊᑗ᮶ࡢ᰾⼥ྜⓎ㟁࡟࠾࠸࡚ࡶ⇞ᩱ࡜ࡋ࡚ࢺࣜࢳ࣒࢘ࡀ⏝࠸ࡽࢀࡿࠋࢺࣜࢳ࣒࢘࠿ࡽᨺ
ฟࡉࢀࡿș⥺ࡢ㣕⛬ࡣ▷࠸ࡓࡵእ㒊⿕᭚ࡀၥ㢟࡜࡞ࡿࡇ࡜ࡣ࡯࡜ࢇ
࡝࡞ࡃࠊෆ㒊⿕᭚࡟ᑐࡍࡿ㜵ㆤࡀ㔜せ࡜࡞ࡿࠋ࡜ࡾࢃࡅࠊș⥺࡟ࡼ
ࡿ '1$ ᦆയࡸࠊ⨨᥮ࡋࡓࢺࣜࢳ࣒࢘ࡀ࣒࣊ࣜ࢘  ࡬࡜ቯኚࡋࡓሙྜ
ࡢ '1$ ᦆയ࡞࡝ࡀၥ㢟どࡉࢀ࡚࠸ࡿࠋࡋ
࠿ࡋࠊࡑࡢᦆയࡢศᏊ࣓࢝ࢽࢬ࣒ࡣࠊᮍゎỴࡢၥ㢟࡛࠶ࡿࠋࡑࡇ࡛ࠊ⨨᥮ࢺࣜࢳ࣒࢘
ࡢ࣒࣊ࣜ࢘  ࡬ࡢቯኚ࡟క࠺ '1$ ࡢᵓ㐀ኚ໬ࢆศᏊືຊᏛ 0' ィ⟬࡛ணࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ ◊✲᪉ἲࠊィ⟬᪉ἲᅗ㸯㸬ࢩ࣑࣮ࣗࣞࢩࣙࣥࣔࢹࣝࡢ඲యᅗ࡜ࢸ࣓ࣟ࢔ᵓ㐀ィ⟬᪉ἲ㸸ᮏ◊✲࡛ࡣࠊ5HD[)) ࡜࿧ࡤࢀࡿືⓗ࡞཯ᛂຊሙࢆ⏝࠸ࡓ 0' ィ⟬࡟ࡼࡗ࡚ࠊ⨨᥮ࢺࣜࢳ࣒࢘ࡢ࣒࣊ࣜ࢘  ࡬ࡢቯኚ࡟ࡼࡾ⏕య㧗ศᏊࡢᵓ㐀ࡀኚ໬ࡍࡿ
ᣲືࢆࠊᚑ᮶ࡢྂ඾ 0' ィ⟬࡜ẚ࡭࡚ヲ⣽࡟ㄪ࡭ࡓࠋ⏕య㧗ศᏊࡢỗ⏝ྂ඾ 0'ࢩ࣑࣮ࣗࣞࢩ࣭ࣙࣥࢯࣇࢺ࢙࢘࢔
/$0036 KWWSODPPSVVDQGLDJRY ࢆ ⏝ ࠸ᅗ㸰C 㙐࡛ࡢ Ⱦ ᔂቯࡉࡏࡿࢾࢡࣞ࢜ࢳࢻࡢሙᡤ

࡚ィ⟬ࢆ⾜ࡗࡓࠋ5HD;)) ࡜ࡋ࡚⾲㸯ࡢ㸳ࡘࡢຊሙ࡛ẚ㍑ࢆ⾜ࡗࡓࠋ ィ⟬ࣔࢹࣝ㸸'1$ 㒊ศᵓ㐀ࡢᵓ㐀ኚ໬ࢆㄪ࡭ࡿࠋ'1$ 㒊ศᵓ㐀࡜ࡋ࡚ࠊࣄࢺ '1$ ࡢࢸ࣓ࣟ࢔ᵓ㐀ࢆ⏝࠸ࡿ㸦ᅗ 㸧
ࠋࡲࡓࠊ㝖ཤࡍࡿỈ⣲ཎᏊ㸦യ࡜ྡ௜ࡅࡿ㸧ࡢሙᡤࡣ⢾ࡢ  & ࡜ࡋࠊ㞄᥋ࡍࡿࣜࣥ㓟ᇶࡢ 32 ⤖ྜࡀษ᩿ࡍࡿ࠿࡝࠺࠿ࢆ☜࠿ࡵࡿ ᅗ㸰 ࠋ

- 425 - ◊✲ᡂᯝ࢔ ᖹ⾮ィ⟬࡟࠾ࡅࡿ᭱㐺࡞ຊሙࡢホ౯ࢸ࣓ࣟ࢔ᵓ㐀࡟ᑐࡋࠊ␗࡞ࡿ㸳✀㢮ࡢຊሙࢆ⏝࠸࡚ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊࡑࢀࡒࢀࡢ
⤖ᯝࢆẚ㍑ࡋࡓࠋ౑⏝ࡋࡓຊሙ࡜⤖ᯝࡢࢢࣛࣇ
࡟࠾ࡅࡿ␒ྕࡢᑐᛂ⾲ࢆ⾲  ࡟♧ࡍࠋW  ࡟࠾ࡅࡿ '1$ ࡢᵓ㐀ࠊ࠾ࡼࡧ 㹼 ࡢ W  QV  ࡟࠾ࡅࡿ '1$ ࡢᵓ㐀ࢆ 90' ࢆ⏝࠸࡚☜ㄆࡋࡓࠋຊሙ  ࡣᵓ㐀ࡀᏳᐃࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆ࡛ࡁᅗ㸱㸬ຊሙ㸯㹼㸳ࡢᖹᆒ஧஌೫ᕪࡢ᫬㛫Ⓨᒎࡓࠋ࡞࠾ࠊ ࡣࢩ࣑࣮ࣗࣞࢩࣙࣥ࣎ࢵࢡࢫෆࢆ
ᦂືࡍࡿ㐣⛬࡛ⴭࡋࡃୖ㒊࡟⛣ືࡋࠊタᐃࡋࡓ࿘ᮇቃ⏺ࢆࡲࡓࡄᙧ࡜࡞ࡗ࡚࠸ࡿࠋຊሙ  ࡛ࡣ'1$ ᵓ㐀࡟㛤⿣ࡀⓎ⏕ࡋ࡚࠸ࡿࡇ࡜ࡀ࠺࠿ࡀ
࠼ࡓࠋࡲࡓࠊຊሙ  ࡟ࡘ࠸࡚ࡶ୺㙐࡟◚⥢ࡀࡳࡽࢀࠊேయࡢ᮲௳ୗ࡛Ᏻᐃࡋ࡚࠸ࡿ࡜ࡣゝ࠸㞴࠸ࠋ௨ୖࡢࡇ࡜࠿ࡽࠊศᏊࢆどぬⓗ࡟☜ㄆࡋࡓẁ㝵࡛ࡣ  ࡢ  ✀㢮ࡢຊሙࡀඃࢀ࡚࠸ࡿ࡜
࠸࠼ࡿࠋ
'1$ ࡢศᏊᵓ㐀ࡢᏳᐃᛶࢆᐃ㔞ⓗ࡟ホ౯ࡍࡿࡓࡵ࡟ࠊᖹᆒ஧஌೫ᕪࢆ☜ㄆࡋࡓࠋ 㹼 ࡢᖹᆒ஧஌೫ᕪࡢࢢࣛࣇࢆᅗ  ࡟♧ࡍࠋຊሙ  ࡣ㹼 ⛬ᗘ࡟ᖹᆒ஧஌೫ᕪࡢቑ኱ࡀ␃ࡲࡗ࡚࠸
ࡿࡇ࡜࠿ࡽࠊᵓ㐀ࡢᏳᐃᛶࡀ⿬௜ࡅࡽࢀ࡚࠸ࡿࠋ

ᅗ㸲㸬 1;;; ࣔࢹࣝࡢᶍᘧᅗ
1 ࡣࠊ͆യ͇ࡢ࡞࠸ࡶ࡜ࡶ࡜ࡢࢸ࣓ࣟ࢔ᵓ㐀D  E ≉࡟ࠊຊሙ  ࡟ࡘ࠸࡚ࡣ QV ௨㝆ࡢᖹᆒ஧஌
೫ᕪࡀ⣙ $ ࢆ୰ᚰ࡜ࡋ࡚Ἴᙧࢆᥥ࠸࡚࠾ࡾࠊ
ேయࡢ᮲௳ୗ࡟࠸ࡿ '1$ ศᏊࡀᏳᐃࡋࡓ≧ែ࡛ᦂືࡋ࡚࠸ࡿࡇ࡜ࢆᣦࡋ♧ࡍ࡜⪃࠼ࡽࢀࡿࠋ
࢖ '1$ ษ᩿ࡢ͆യ͇ࡢሙᡤ౫Ꮡᛶș ᔂቯࡉࡏࡿ఩⨨㸦യ㸧࡟ࡘ࠸࡚ࠊ& 㙐  ␒┠ࡣᅛᐃ࡜ࡋࠊ& 㙐࡜㏫ഃࡢ ' 㙐ഃ࡛ș ᔂቯ

F  G ࡉࡏࡿ఩⨨ࢆኚ࠼ࡿࡇ࡜࡛ࠊ஧㔜㙐ษ᩿ࡢș ᔂቯࡍࡿሙᡤ࡬ࡢ౫Ꮡᛶࡢホ౯ࢆ⾜࠺ࠋ ␒┠ࢆᇶ‽ࡢ఩⨨ࢆ ; ࡜࿧ࡪࠋᇶ‽ࡢ఩⨨࠿ࡽ  ࡘࡢሷᇶศ㞳ࢀ࡚࠸ࡿ  ␒┠࡜  ␒┠ࡢ఩⨨ࢆ;í; ࡜ࡍࡿࠋയࡢሙᡤࢆᅗ㸲ࡢࡼ࠺࡞  ࢣ࣮ࢫ࡛ẚ㍑ࢆ⾜ࡗࡓࠋW QV ࡢ 1  ;í  ;  ;
ࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆᅗ  ࡟♧ࡍࠋ஧㔜㙐ษ᩿ᅗ㸳㸬QV ᚋࡢ '1$ ࡢᵓ㐀 D 1 ࡢሙྜࠊE ; ࡢሙྜࠊF ; ࡢሙྜࠊ F ; ࡢሙྜࠋ- 426 -

ࡢⓎ⏕ࢆどぬⓗ࡟☜ㄆࡍࡿࡇ࡜ࡣ࡛ࡁ࡞࠿ࡗࡓࠋࡲ
ࡓࠊࣜࣥࢆྵࡴศᏊᩘ࡟ࡘ࠸࡚ࡶࠊ1;í;  ;
ࡢࡍ࡭࡚ࡀࢩ࣑࣮ࣗࣞࢩࣙࣥ㛤ጞ࠿ࡽ⤊஢ࡲ࡛  ಶࡢࡲࡲ࡛࠶ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ௒ᅇࡢィ⟬᮲௳ୗ࡛ࡣࠊ஧㔜㙐ษ᩿ࢆⓎ⏕ࡉࡏࡿࡓࡵ࡟ࡣࠊ୍ᑐ⛬ᗘࡢയ࡛ࡣ୙༑ศ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ
࢘ '1$ ษ᩿ࡢ͆യ͇ࡢಶᩘ౫Ꮡᛶ& 㙐࡜ ' 㙐࡛ᑐ࡟࡞ࡿ఩⨨࡛ș ᔂቯࡉࡏࡿ࡜࠸
࠺᮲௳ࢆᅛᐃࡋ࡚ࠊș ᔂቯࢆⓎ⏕ࡉࡏࡿࢾࢡࣞ࢜ࢳ
ࢻࡢಶᩘࢆኚ࠼ࡿࡇ࡜࡛ࠊ஧㔜㙐ษ᩿ࡢș ᔂቯࡍࡿಶᩘ࡬ࡢ౫Ꮡᛶࡢホ౯ࢆ⾜࠺ࠋ඲ࡃയࢆධࢀ࡚࠸࡞࠸ᅗ    ࠊ  ࠊ  ࠊ  ࡢ㸲ࡘࡢࣔࢹࣝ
ࡢᶍᘧᅗ

ࡶࡢࢆ   ࡜グ㏙ࡍࡿࠋ& 㙐ࡢ  ␒┠࡜ࠊࡑࡢᑐ
㠃࡟࠶ࡿ ' 㙐ࡢࢾࢡࣞ࢜ࢳࢻ࡛șᔂቯࡉࡏࡓࡶࡢ
ሙᡤ౫Ꮡᛶࡢ ;  ࢆ  ࡜⾲⌧ࡍࡿࠋ ᑐ࠶ࡿࢾࢡࣞ࢜ࢳࢻࡢ࠺ࡕ࡛ࠊ୰ኸࡢ  ᑐࢆșᔂቯࡉࡏࡓࡶ
ࡢ࡜ࠊ ᑐ඲࡚ș ᔂቯࡉࡏࡓࡶࡢࢆ   
࡜グ㏙ࡍࡿࠋᅗ  ࡢ  ࢣ࣮ࢫ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ
ᐇ᪋ࡋ࡚ࠊẚ㍑᳨ウࢆ⾜ࡗࡓࠋW QV ᫬Ⅼ࡛ࡢ      ࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆᅗ  ࡟♧ࡍࠋᅗ   QV ᚋ࡟࠾ࡅࡿ '1$ ᵓ㐀 ᕥᅗ  ࡢሙྜࠋྑᅗ  ࡢሙྜࠋW QV ᚋ࡟࠾ࡅࡿ   ࡢ '1$ ᵓ㐀   ࡣࡉࡽ࡟  ࡘ⛬ᗘ࡟ศ๭ࡉࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡾࠊയࡢಶ
ᩘࡢቑຍ࡜ẚ౛ࡋ࡚஧㔜㙐ษ᩿ࡢⓎ⏕ᅇᩘࡀቑຍࡍࡿࡇ࡜ࡀどぬⓗ࡟☜ㄆ࡛ࡁࡿࠋᅗ  ࡼࡾࠊ   ࡣ W QV ࡛ 㹼 ಶࠊ   ࡣ 㹼 ಶ࡟ศ๭ࡉࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ    ࠾ࡼࡧ   ࡣ᭱ᚋࡲ࡛  ಶࡢࡲࡲ࡛࠶ࡿࠋࡲࡓࠊ஧㔜㙐ษ᩿ࡀ㛤ጞࡍࡿ࡜ࠊ᏶඲࡟ษ᩿ࡉࢀࡿࡲ࡛ศᏊᩘࡀ
ኚ໬ࡍࡿ๓ᚋࡢ್ࢆ⾜ࡁ᮶ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡇ
ࢀࡣࠊ'1$ ศᏊࡀࢩ࣑࣮ࣗࣞࢩࣙࣥ࣎ࢵࢡࢫ୰࡛ᦂ
ືࡍࡿࡓࡵ࡛࠶ࡿࠋඹ᭷⤖ྜࡀ୍ᗘษࢀࡿ࡜ࡑࡢࡲࡲᅗ   ࢸ࣓ࣟ࢔ᵓ㐀ษ᩿࡟ࡼࡿศ๭ᩘࡢ᫬㛫Ⓨᒎࠋയࡢ⤌ᩘࢆࠊ  ࠊ  ࠊ  ࠊ  ࡢ㸲ࡘࡢሙྜ࡟ࡘ࠸࡚ㄪ࡭ࡓࠋ

ศᏊࡀ㞳ࢀ࡚ࡋࡲ࠺ࡢ࡛ࡣ࡞ࡃࠊ෌ᗘࡃࡗࡘ࠸ࡓࡾ㞳ࢀࡓࡾࢆ⧞ࡾ㏉ࡋࠊࡸࡀ࡚᏶඲࡟ษࢀࡿࠋࡑࡢࡓࡵࠊ
  ࡛᭱ึࡢ஧㔜㙐ษ᩿ࡀⓎ⏕ࡋࡓࡢࡣ W ⣙ QV ᫬Ⅼ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋᖹᆒ஧஌೫ᕪ࡟ࡘ࠸࡚ࡶゎᯒࡋࡓࠋ   ࡀ௚  ࡘ࡜ẚ㍑ࡋ࡚ᖹᆒ஧஌೫ᕪࡀ≉࡟኱ࡁࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ཯㠃ࠊ  ࡣ     ࡜࡯࡜ࢇ࡝ᖹᆒ஧஌೫ᕪ࡟ᕪࡀ࡞࠸ࠋࡇࡢࡇ࡜࠿ࡽࠊ஧㔜㙐ษ᩿ࡀⓎ⏕ࡋ࡚ࡶࢸ࣓ࣟ࢔ '1$ ศᏊࡀᖖ࡟ᩓࡾᩓࡾ࡟࡞ࡿࢃࡅ࡛ࡣ ࡞ࡃࠊᖹᆒ஧஌೫ᕪ࡟࠶ࡲࡾᙳ㡪ࢆཬࡰࡉ࡞࠸ሙྜࡀ࠶ࡿࡇ࡜ࢆ☜ㄆ࡛ࡁࡓࠋ
ࡇࡢࡼ࠺࡟ࠊയࢆࡘࡅࡿಶᩘࢆቑࡸࡍࡇ࡜࡛஧㔜㙐ษ᩿ࢆⓎ⏕ࡉࡏࡿࡇ࡜ࡀ࡛ࡁࡓࠋ஧㔜㙐ษ᩿ࡢⓎ⏕ᅇᩘࡸⓎ⏕᫬้࡟ࡘ࠸࡚ࡶࣜࣥࢆྵࡴศᏊᩘࢆぢࡿࡇ࡜࡛☜ㄆ࡛ࡁࠊᐃ㔞ⓗ࡞ホ౯ࢆᚓࡽࢀࡓࠋW QV ࡢ᫬
Ⅼ࡛   ࡀ 㹼 ಶ࡜࡞ࡗ࡚࠸ࡿࡇ࡜࠿ࡽࠊᚲせ࡞യࡢಶᩘࡣ  ᑐࡼࡾᑡ࡞࠸࡜⪃࠼ࡽࢀࡿࠋࡑࡢࡓࡵࠊ

- 427 -

ࡼࡾಶᩘࢆῶࡽࡋࡓࢣ࣮ࢫ࡛ࡶ஧㔜㙐ษ᩿ࡀⓎ⏕ࡍࡿࡇ࡜ࡀ᥎࡛ࡁࡿࠋ㸲 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃz‫ۻ‬୰ᮧᾈ❶㸪▼㯮೺ே㸪⸨ཎ 㐍㸪㰛⏊᭸⬷㸪⡿㇂ె᫭㸪ᏳỌ༟䔆㸪୰䔗ᙬ⬷㸪ᐑᓮ ๛㸪⤎ሯᩍ㞝㸪
๢ᣢ㈗ᘯ㸪Ἴከ㔝㞝἞㸪犸⸨┿ྖ㸪㰻⸨ㄔ⣖³'1$ ࢸ࣓ࣟ࢔୰ࢹ࢜࢟ࢩ ' ࣮ࣜ࣎ࢫࡢࢺࣜࢳ࣒࢘șᔂቯ࡟ࡼࡿᵓ㐀ኚ໬ࡢ 0' ゎᯒ´ ࣉࣛࢬ࣐࣭᰾⼥ྜᏛ఍ ➨  ᅇᖺ఍㸦ⅆ㸧ࠥ㸦㔠㸧 ࢜ࣥ
ࣛ࢖ࣥ㛤ദ

z

‫⸨ۻ‬ཎ 㐍 ୰ᮧ ᾈ❶ Ỉཱྀ ᭸Ꮚ ⡿㇂ ె᫭ ᑿཪ ୍ᐇ ᏳỌ ༟⏕ ኱㇂ ᐶ᫂ 㰻⸨ ㄔ⣖ ୰⏣ ᙬᏊ ᐑᓮ ๛ ኱ሯ ᩍ㞝 ๢ᣢ ㈗ᘯ Ἴከ㔝 㞝἞ ᩧ⸨ ┿ྖ㧗ศᏊ࣭⏕యศᏊ࡬ࡢ⨨᥮ࢺࣜࢳ࣒࢘ࡢ
ቯኚຠᯝ࡟㛵ࡍࡿศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ -667 :RUNVKRS㸤 ᖺᗘ᰾⼥ྜ⛉Ꮫ◊✲ᡤ୍⯡ඹྠ◊✲ ◊✲఍ ࠕ⨨᥮ࢺࣜࢳ࣒࢘ࡢ࣒࣊ࣜ࢘  ࡬ࡢቯኚ࡟ࡼࡿ '1$ ᵓ㐀ኚ໬࡟㛵ࡍࡿ◊✲఍㸸5DGLDWLRQ(IIHFWVLQ0DWHULDOVDQG%LRORJLFDO0ROHFXOHVࠖ ࢜ࣥࣛ࢖ࣥ㛤ദ ᖺ  ᭶  ᪥㸦ཱྀ㢌Ⓨ⾲㸧z⡿㇂ ె᫭ ⸨ཎ 㐍 ୰ᮧ ᾈ❶ 㜿⸽ ྖ '1$㸫ࣛࢪ࢝ࣝ┦஫స⏝ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥゎᯒ -667 :RUNVKRS㸤 ᖺᗘ᰾⼥ྜ⛉Ꮫ◊✲ᡤ୍⯡ඹྠ◊✲ ◊✲఍ ࠕ⨨᥮ࢺࣜࢳ࣒࢘ࡢ࣒࣊ࣜ࢘ ࡬ࡢቯኚ࡟ࡼࡿ '1$ ᵓ㐀ኚ໬࡟㛵ࡍࡿ◊✲఍㸸5DGLDWLRQ(IIHFWVLQ0DWHULDOVDQG%LRORJLFDO0ROHFXOHVࠖ ࢜ࣥࣛ࢖ࣥ㛤ദ ᖺ  ᭶  ᪥㸦ཱྀ㢌Ⓨ⾲㸧z‫▼ۻ‬㯮 ೺ே ୰ᮧ ᾈ❶ ⸨ཎ 㐍 Ỉཱྀ ᭸Ꮚ /, +$2/81 ⡿㇂ ె᫭ ᏳỌ ༟⏕ 㰻⸨ ㄔ⣖ ୰⏣ᙬᏊ ᐑᓮ ๛ ኱ሯ ᩍ㞝 ๢ᣢ ㈗ᘯ Ἴከ㔝 㞝἞ ᩧ⸨ ┿ྖ '1$ ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟㐺⏝ࡍࡿ཯
ᛂຊሙ 5HD[)) ࡢẚ㍑-667:RUNVKRS㸤 ᖺᗘ᰾⼥ྜ⛉Ꮫ◊✲ᡤ୍⯡ඹྠ◊✲ ◊✲఍ࠕ⨨᥮ࢺࣜࢳ࣒࢘ࡢ࣒࣊ࣜ࢘  ࡬ࡢቯኚ࡟ࡼࡿ '1$ ᵓ㐀ኚ໬࡟㛵ࡍࡿ◊✲఍㸸5DGLDWLRQ (IIHFWV LQ 0DWHULDOV DQG%LRORJLFDO0ROHFXOHVࠖ ࢜ࣥࣛ࢖ࣥ㛤ദ ᖺ  ᭶  ᪥㸦ཱྀ㢌Ⓨ⾲㸧zᕝἼ ❳ኴ/,+$2/81 ⸨ཎ 㐍 ୰ᮧ ᾈ❶ ᑿཪ ୍ᐇ⨨᥮ࢺࣜࢳ࣒࢘ࡢ࣮࣋ࢱᔂቯ࡟ࡼࡿ㧗ศᏊࡢᵓ㐀ኚ໬࡟㛵ࡍࡿ⌮ㄽ࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ ᪥ᮏ≀⌮Ꮫ఍  ᖺ⛅Ꮨ኱఍ ࢜ࣥࣛ࢖ࣥ㛤ദ  ᖺ ᭶  ᪥㹼 ᭶  ᪥ 360 㸦࣏ࢫࢱ࣮Ⓨ⾲㸧z+DROXQ/L6XVXPX)XMLZDUD+LURDNL1DNDPXUD7RPRNR0L]XJXFKL$\DNR1DNDWD7VX\RVKL0L\D]DNL6KLQML
6DLWR $ 0ROHFXODU '\QDPLFV 6WXG\ RQ 6WUXFWXUDO &KDQJH RI 'DPDJHG 3RO\HWK\OHQH E\ %HWD'HFD\ RI
6XEVWLWXWHG 7ULWLXP XVLQJ 5HDFWLYH )RUFH )LHOG ➨  ᅇ㧗ศᏊウㄽ఍ ࢜ࣥࣛ࢖ࣥ㛤ദ  ᖺ  ᭶  ᪥
(6$ 㸦ཱྀ㢌Ⓨ⾲㸧 ฟ∧ᐇ⦼ࡲࡓࡣணᐃzᅵ⏣㝧ᖹ 㰻⸨ㄔ⣖ ୰ᮧᾈ❶ ⡿㇂ె᫭  ⸨ཎ㐍³ศᏊືຊᏛἲࢆ⏝࠸ࡓ '1$ ࢸ࣓ࣟ࢔ᵓ㐀୰ࣂࢵࢡ࣮࣎ࣥỈ⣲ࡢ⁐፹᥋ゐ⾲㠃✚ࡢホ౯´ ᪥ᮏࢩ࣑࣮ࣗࣞࢩࣙࣥᏛ఍࿴ᩥㄅ㸦ᥖ㍕Ỵᐃ㸧z+ /L 6 )XMLZDUD + 1DNDPXUD 7 0L]XJXFKL $ 1DNDWD 7 0L\D]DNL DQG 6 6DLWR ³6WUXFWXUDO FKDQJH RI
GDPDJHG SRO\HWK\OHQH E\ EHWDGHFD\ RI VXEVWLWXWHG WULWLXP XVLQJ UHDFWLYH IRUFH ILHOG´ -SQ - $SSO 3K\V 6$$%  >'2,DEEGF@z+ 1DNDPXUD + 0L\DQLVKL 7 <DVXQDJD 6 )XMLZDUD 7 0L]XJXFKL $ 1DNDWD 7 0L\D]DNL 7 2WVXND 7
.HQPRWVX < +DWDQR 6 6DLWR ³0ROHFXODU G\QDPLFV VWXG\ RQ '1$ GDPDJH E\ WULWLXP GLVLQWHJUDWLRQ´ -SQ -
$SSO3K\V6$$(  >'2,DEG@- 428 -

㔠ᒓ᭷ᶵᵓ㐀య࡟ࡼࡿỈྠ఩యศᏊㄆ㆑
0ROHFXODU5HFRJQLWLRQRI:DWHU,VRWRSHVE\0HWDí2UJDQLF)UDPHZRUNV‫⏣ۑ‬୰ ⚽ᶞ㸦ಙᕞ኱Ꮫඛ㗦ᮦᩱ◊✲ᡤ㸧◊✲┠ⓗ㔠ᒓ᭷ᶵᵓ㐀యࡢ୍✀࡛࠶ࡿ &D 㘒య >&D &2 +2@Q >@ࡣ㸪&D ཎᏊ࡟ࢫࢡ࢔ࣜࣥ㓟࢔ࢽ࢜ࣥࡀ㓄఩ࡋ㸪࠿ࡘ㸪ỈศᏊࡀ໬Ꮫⓗ࡟྾╔ F+2 ࡋࡓࣇ࣮࣒࣮ࣞ࣡ࢡᵓ㐀ࢆ᭷ࡋ࡚࠾ࡾ㸪ࡑࡢࣇ࣮࣒࣮ࣞ࣡ࢡ୰ࡢ  ḟඖࢳࣕࣥࢿࣝࡣ㸪ỈศᏊࢆ≀⌮྾╔ S+2㸸᭱኱࡛ &D ཎᏊᙜࡓࡾ  ಶ ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ ᅗ  ࠋࡇࡢ≧ែ࡟࠾ࡅࡿ &D 㘒య S+2F+2 ࡢ D ㍈᪉ྥࡢ᱁Ꮚᐃᩘ . ࢆ㸪LQVLWX;53'ᐃ࡟ࡼࡗ࡚Ỵᐃࡋࡓ࡜ࡇࢁ㸪F+2 ࡢࡳ࠿ࡽ࡞ࡿ
&D 㘒యࡼࡾࡶ㸪ࡑࡢᵓ㐀ࡀᅗ  &D 㘒య>&D &2 +2 ࣭ +2 @Q ࡢᵓ㐀཰⦰ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿
ࡗࡓࠋࡑࡇ࡛㸪$,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ DELQLWLR ศᏊືຊᏛἲ&3.VRIWZDUH>@ ࢆᐇ᪋ࡋࡓ࡜ࡇࢁ㸪S+2 ࡜F+2 ࡜ࡢ㛫࡟Ỉ⣲⤖ྜࡀᙧᡂࡉࢀ㸪F+2 ࡀ㓄఩ࡍࡿ &D ࢖࢜ࣥ࡟ᑐࡋ࡚㸪 ḟඖࢳࣕࣥࢿࣝࡢ୰ᚰ㍈࡟ᆶ┤࡞᪉ྥ࡬ࡢᘬຊࢆ⏕ࡌ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡘࡲࡾ㸪&D 㘒యࡣ S+2 ࡜ F+2 㛫ࡢỈ⣲⤖ྜᙧᡂ࡟ࡼࡿᛂ⟅≉ᛶࢆ᭷ࡋ࡚࠸ࡿࡇ࡜࡟࡞ࡿࠋࡉࡽ࡟㸪&D 㘒యࡢ D ㍈᪉ྥࡢ᱁Ꮚᐃᩘࡢ S+2 ྾╔㔞౫Ꮡᛶ . ࢆ LQVLWX;53'ᐃ࡟ࡼࡗ࡚ㄪ࡭ࡓ࡜ࡇࢁ ᅗ  㸪S+2 ྾╔㔞ࡢቑຍ࡟కࡗ࡚㸪᱁Ꮚᐃᩘ D ࡀᑠࡉࡃ࡞ࡿ

ࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡣ㸪S+2 ࡢศᏊᩘࡀከࡃ࡞ࡿ࡟ᚑࡗ࡚㸪S+2 ࡜ F+2 ࡜ࡢ㛫࡟ᙧᡂࡉࢀࡿỈ⣲⤖ྜᩘࡀቑຍࡍࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋࡑࡇ࡛㸪+2ࡼࡾࡶᙉ࠸Ỉ⣲⤖ྜࢆᙧᡂࡍࡿ '2 ࢆ &D 㘒య࡟≀⌮྾╔  . ࡉࡏࡓ࡜ࡇࢁ㸪ண᝿࡟཯ࡋ࡚㸪᱁Ꮚᐃᩘ D ࡢ཰⦰ࡣ S+2 ྾╔ࡢሙྜࡼࡾࡶᑠ
ࡉࡃ࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡇ࡛㸪ᾮయ≧ែ ࣂࣝࢡ ࡟࠾ࡅࡿ +2 ศᏊ㛫ࡢỈ⣲⤖ྜࡣ '2 ࡢࡑࢀࡼࡾࡶᙅࡃ࡞ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀ㸪ࡇࢀࡣ 'ཎᏊࡼࡾࡶ㉁㔞ࡢᑠࡉ࡞ + ཎᏊ࡟࠾ࡅࡿ఩⨨୙☜ᐃᛶࡀ኱ࡁࡃ࡞ࡿࡓࡵ࡟㸪ࣉࣟࢺࣥ࡜㓟⣲ཎᏊ㛫࡟࠾ࡅࡿỈ⣲⤖ྜ࢚ࢿࣝࢠ࣮ࡀᑠࡉࡃ࡞ࡿࡓ
ࡵ࡛࠶ࡿࠋࡍ࡞ࢃࡕ㸪ୖ㏙ࡢ S+2 ࡜ S'2 ࡢ྾╔࡟ࡼࡿ &D 㘒యࡢ཰⦰ᣲື࡟࠾ࡅࡿᕪ␗ࢆィ⟬ᅗ  ,QVLWX;53' ᐃ࡟ࡼࡿ &D 㘒యࡢ᱁Ꮚᐃᩘ D ࡢ+2 ࠾ࡼࡧ '2 ྾╔㔞౫Ꮡᛶ .

- 429 -

⛉Ꮫⓗ࡟᳨ウࡍࡿࡓࡵ࡟ࡣ㸪)H\QPDQ ࡢ⤒㊰✚ศἲ࡟ࡼࡗ࡚㸪ࡑࡢ㔞ᏊຊᏛⓗຠᯝࢆ⪃៖ࡍࡿᚲせࡀ࠶ࡿࠋࡑࡇ࡛㸪&3. ࢆእ㒊ࢥ࣮ࢻ࡜ࡍࡿ LSL VRIWZDUH >DELQLWLR ⤒㊰✚ศศᏊືຊᏛ $,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ
ࡓࡵࡢ 3\WKRQ ࢥ࣮ࢻ>@@ࢆ౑⏝ࡋ ᅗ  㸪S+2 ࡜ S'2 ࡢ྾╔࡟ࡼࡿ &D 㘒యࡢ཰⦰ᣲືࢆ $,3,0' ࡟ࡼࡗ࡚ヨ㦂ⓗ࡟᳨ウࡋࡓ࡜ࡇࢁ  . 㸪ᐇ㦂⤖ᯝ࡟ᐃᛶⓗ࡟୍⮴ࡋ㸪+2 ࡜ '2 ྾╔࡟࠾ࡅࡿ㔞ᏊຊᏛⓗຠᯝࡢᕪ␗ࡀ㸪&D 㘒య࡟Ỉྠ఩యࡢศᏊㄆ㆑⬟ࢆࡶࡓࡽࡋ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋࡋ࠿ࡋ㸪ࡇࡢ
$,3,0' ࡛ࡣ㸪ཎᏊ᰾ࢆ  ಶࡢㄪ࿴᣺ືᏊࣂࢿ࡛㐃⤖ࡉࢀࡓྂ඾ࣅ࣮ࢬ⩌࡟ࡼࡗ࡚⾲ࡍᚲせࡀ࠶ࡾ>SDWKLQWHJUDO JHQHUDOL]HG /DQJHYLQHTXDWLRQ WKHUPRVWDW 3,*/(7ἲࢆ౑⏝@㸪ྛࣅ࣮ࢬ࡟ࡘ࠸
࡚ࡢ ')7 ィ⟬ࢆ  ୪ิ࡛ィ⟬ࡍࡿᚲせࡀ࠶ࡿࡓࡵ࡟㸪ᴟࡵ࡚ィ⟬ࢥࢫࢺࡀ㧗࠸ࠋࡇࡢࡓࡵ㸪ࠕ ᖺᗘィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮᪋タ฼⏝➼ࡢබເࠖ࡟ᛂເࡋ㸪኱つᶍ࡞
$,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ
ᐇ᪋ࡍࡿࡇ࡜࡛㸪&D 㘒య࡬ࡢỈ྾╔࡟క࠺ᵓ㐀ኚᙧ࡞ࡽࡧ ࡟ Ỉ ྠ ఩ య +2 ࠾ ࡼ ࡧ'2 ࡢศᏊㄆ㆑⬟ࡢⓎ⌧࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡜ࡍࡿࡇᅗ  )H\QPDQ ࡢ⤒㊰✚ศἲ࡟ᇶ࡙ࡃỈศᏊࡢᵓ㐀⾲⌧࡜
LSL&3. ࡟ࡼࡿ $,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ

࡜ࢆ┠ⓗ࡜ࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ&3. ࡟ࡼࡗ࡚㸪>&D &2 F+2@Q ࠾ࡼࡧ>&D &2 F+2࣭S+2@Q ࡢᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓ㸦uuࢭࣝ㸧ࠋᮏィ⟬࡛ࡣ㸪%/<3 ỗ㛵ᩘ㸪'=9302/23765*7+ ᇶᗏ㛵ᩘࢆ⏝࠸㸪&XWRII  5\㸪5HO&XWRII 
 5\ ࠾ࡼࡧ 1*5,'6  ࢆ᥇⏝ࡋࡓࠋࡲࡓ㸪')7' ࡟ࡼࡗ࡚ศᩓຊ⿵ṇࢆ⾜ࡗࡓࠋୖグࡢᵓ㐀᭱㐺໬࡟ࡼࡗ࡚ᚓࡽࢀࡓᵓ㐀ࢆึᮇᵓ㐀࡜ࡋ㸪&3. ࢆእ㒊ࢥ࣮ࢻ࡜ࡍࡿ LSL VRIWZDUH ࡟ࡼࡗ࡚㸪>&D &2 F+2࣭S+2@Q ࠾ࡼࡧ>&D &2 F+2࣭S'2@Q ࡢ $,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ᮲௳ࡣ௨ୗࡢ㏻ࡾ㸸FRQVWDQWVWUHVV 167 HQVHPEOH㸪ᆶ┤ᛂຊ  03D㸪ࡏࢇ᩿ᛂຊࢮࣟ㸪 ᗘ
.㸪.㸪.㸪.㸪᫬㛫ࢫࢸࢵࣉ IV㸪ࣅ࣮ࢬᩘ  ࡲࡓࡣ 㸪ࣅ࣮ࢬᩘ࠶ࡓࡾࡢ FRUH ᩘ 㸪%/<3ỗ㛵ᩘ㸪'=9302/23765*7+ ᇶᗏ㛵ᩘࢆ⏝࠸㸪&XWRII  5\㸪5HO&XWRII  5\㸪1*5,'6 ࠋࡲࡓ㸪3,*/(7 ࣃ࣓࣮ࣛࢱ࣮ࡣ KWWSFRVPRHSIOJLWKXELRJOHPG ࡟࠾࠸࡚ྲྀᚓࡋࡓࠋ◊✲ᡂᯝᵓ㐀᭱㐺໬࡟ࡼࡗ࡚ᚓࡽࢀࡓ>&D &2 F+2@Q ࠾ࡼࡧ>&D &2 F+2࣭S+2@Q ࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆ

- 430 -ᅗ  ࡟♧ࡍࠋࡑࢀࡒࢀࡢ᱁Ꮚᐃᩘࡣ㸪>&D &2 F+2@Q㸸D E c㸪F 
c㸪>&D &2 F+2࣭S+2@Q㸸D E 
c㸪F c ࡜࡞ࡾ㸪S+2 ࡢᏑᅾ࡟ࡼࡗ
࡚ᵓ㐀ࡀ཰⦰ࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋィ⟬࡟ࡼࡾᚓࡽࢀࡓ᱁Ꮚᐃᩘ D E ࡢ⤯ᑐ್ࡣᐇ㦂⤖ᯝ ᅗ  ࡼࡾࡶࢃࡎ࠿࡟኱ࡁ࠸ࡀ㸪S+2 ࡢ྾╔࡟క࠺᱁Ꮚᐃᩘࡢኚ໬ࡢ࣮࢜ࢲ࣮ࡣᐇ
㦂⤖ᯝ࡟Ⰻࡃ୍⮴ࡋ࡚࠸ࡿࠋᐇ㦂 ᐊᅗ   &3. ࡟ࡼࡿᵓ㐀᭱㐺໬㸸 D >&D &2 F+2@Q
E >&D &2 F+2࣭S+2@Q࡟ࡼࡾ᫂ࡽ࠿࡜࡞ࡗ࡚࠸ࡿ

>&D &2 F+2࣭S+2@Q ࡢᵓ㐀ࡣṇ᪉ᬗ D EFD E  J  ࡛࠶ࡿࡀ㸪$,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ
ࣅ࣮ࢬᩘ 㸸ྂ඾ S+2 ࢆ⾜ࡗࡓ࡜ࡇࢁ㸪࠿ࡗࡓ>ᗘ . ௨ୗ࡟࠾࠸࡚┦㌿⛣ࡀ⏕ࡌ㸪J ࡜࡞ࡿࡇ࡜ࡀศᗘ  . ᅗ D ࠾ࡼࡧ  . ࡛ࡣṇ᪉ᬗ@ࠋࡇࢀࡣ㸪&D 㘒యࡢኚᙧ࡟ࡼࡗ࡚㸪ࡑࡢࣇ࣮࣒࣮ࣞ࣡ࢡ

࡜ S+2 ࡜ࡢ┦஫స⏝ࡀቑᙉࡉࢀࡓࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ୍᪉㸪>&D &2 F+2࣭S+2@Q ࠾ࡼࡧ>&D &2 F+2࣭S'2@Q ࡟ࡘ࠸࡚ࡢ $,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ ࣅ࣮ࢬᩘ 㸸㔞Ꮚ S+2 ࠾ࡼࡧ㔞Ꮚ S'2 ࢆᗘ. ࡟࡚⾜ࡗࡓ࡜ࡇࢁ㸪>&D &2 F+2࣭S'2@Q ࡛ࡣJ  ᅗ E 㸪>&D &2 F+2࣭S+2@Q ࡛ࡣ

J   ᅗ F ࡜࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢࡇ࡜ࡣ㸪&D 㘒యࡀỈྠ఩యศᏊ࡟࠾ࡅࡿ㔞Ꮚຠᯝࡢᕪ␗ࢆㄆ㆑
ࡋ࡚ᵓ㐀㌿⛣ࢆ㉳ࡇࡋ㸪࠿ࡘ㸪ࡑࡢᵓ㐀ࡀ␗࡞ࡿࡶࡢ࡟࡞ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋᅗ   $,3,0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ>FRQVWDQW VWUHVV 167 HQVHPEOH ᆶ┤ᛂຊ  03D㸪ࡏࢇ᩿ᛂຊࢮࣟ ᗘ .@࡟ࡼࡗ࡚ᚓࡽࢀࡓ &D 㘒యࡢࢫࢼࢵࣉࢩࣙࢵࢺ㸸 D ྂ඾ +2 ࡢ྾╔≧ែ E 㔞Ꮚ'2 ࡢ྾╔≧ែ ỈⰍࡣ ' ཎᏊ  F 㔞Ꮚ +2 ࡢ྾╔≧ែ E  F ࡟ࡘ࠸࡚ࡣ඲࡚ࡢࣅ࣮ࢬࢆ⾲♧ࡇࡢ㔞Ꮚຠᯝ࡟౫Ꮡࡋࡓ &D 㘒యࡢᵓ㐀㌿⛣ࢆ⌮ゎࡍࡿࡓࡵ࡟ࡣ㸪ࢩ࣑࣮ࣗࣞࢩࣙࣥࢭࣝࢧ࢖ࢬ࡟ᑐࡍࡿ
⤖ᬗᵓ㐀ࡢ౫Ꮡᛶࢆ᳨ドࡍࡿ࡜ྠ᫬࡟㸪J ࡜J ࡟࠾ࡅࡿ⤖ᬗᵓ㐀ࡢᏳᐃᛶ ⮬⏤࢚ࢿࣝࢠ࣮ ࢆホ౯ࡋ㸪ࡑࡢ㔞Ꮚຠᯝ࡟ᑐࡍࡿ౫Ꮡᛶࢆ᫂ࡽ࠿࡜ࡍࡿᚲせࡀ࠶ࡿࠋ⮬⏤࢚ࢿࣝࢠ࣮ࡢィ⟬ἲ࡜ࡋ࡚ࡣ㸪J ࢆ ࠿ࡽ ࡲ࡛ኚ໬ࡉࡏ㸪ྛᵓ㐀࡟࠾ࡅࡿ 197$,3,0' ィ⟬ࢆᐇ᪋ࡋ㸪㟼Ỉᅽࡢ࢔ࣥࢧࣥࣈࣝᖹᆒࢆィ⟬ࡍࡿ᪉ἲ ࢭࣝయ✚࡟ࡘ࠸࡚㟼Ỉᅽࢆ✚ศࡍࡿࡇ࡜࡛⣔ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࢆồࡵࡿ ࡀ⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ࡣ㸪.
௨ୗࡢప࡟࠾ࡅࡿ 167$,3,0' ィ⟬ࢆᐇ᪋ࡋ㸪㔞Ꮚຠᯝ࡜⤖ᬗᵓ㐀ࡢ┦㛵ࢆ᫂ࡽ࠿࡜ࡍࡿᚲせࡀ࠶ࡿࠋ௨

ୖࡢィ⟬ࡣᴟࡵ࡚ィ⟬ࢥࢫࢺࡀ኱ࡁࡃ࡞ࡿࡀ㸪ࠕ ᖺᗘィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮᪋タ฼⏝ࠖ࡟࠾࠸࡚ᐇ᪋ࡍ
ࡿࡇ࡜ࢆணᐃࡋ࡚࠸ࡿࠋ

- 431 -

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ࠕ ᖺᗘィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮᪋タ฼⏝࡛ࠖࡢᡂᯝࢆᚓ࡚ᚋ㸪Ⓨ⾲ࡍࡿࡇ࡜ࢆணᐃࡋ࡚࠸ࡿࠋ

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ྠࡌࡃ㸪 ᖺᗘィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮᪋タ฼⏝࡛ࠖࡢᡂᯝࢆᚓ࡚ᚋ㸪ㄽᩥ࡜ࡋ࡚ᢞ✏ࡍࡿࡇ࡜ࢆணᐃࡋ

࡚࠸ࡿࠋ

ㅰ㎡
LSLVRIWZDUH ࡢ࢖ࣥࢫࢺ࣮ࣝ࡟ࡘ࠸࡚ࡣ㸪⮬↛⛉Ꮫ◊✲ᶵᵓ ᒸᓮඹ㏻᪋タ ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ ⚄㇂ᢏ⾡⫋ဨࡢ඲㠃ⓗ࡞ࡈᨭ᥼ࢆ㡬࠸ࡓࠋࡇࡢሙࢆ࠾೉ࡾࡋ࡚ཌࡃᚚ♩ࢆ⏦ࡋୖࡆࡓ࠸ࠋཧ⪃ᩥ⊩>@ &5REODQG$:HLVV0DW5HV%XOO22  >@ 7'.KQHHWDO-3K\V&KHP152  >@ 9.DSLOHWDO&RPS3K\V&RPP236  - 432 -





Structure prediction of glycan cluster using enhanced sampling method
/ =1HB":&1G<>*I

1 <>;9ƪȅ0ÉƪŒ´>ž-&,%#Ƅ´÷)Ƅ±/YhMǨ9ƾǨ-ƲÒưƼȇPtxcO
Sz9«ƉĠƤĥŔƋ,+/Ɗŧ*8Ȉ£(= ƪȅřǶ0ǎȎ)ŕǬ,#7X ƵƲń
řǶǕŐ@07Ěŏ/řǶƄżúƏ,ǕŐ)ƠřǶ@Ūý=*Ȑƪȅ/řǶŞƽƓȈ/Ɩƞ@Ǹ7=#7-Ļ#,ĪǊéƐğǐ) =´÷Ä¿úMD (Molecular Dynamics)ǖƦ0DNA 9YhMǨ,+Ƅ´÷/ƠřǶZEbtM
U@Ë÷Ǖ¨đ)Ǡ3=ŉ¿,ĩţ) <þȞ*ƓǍƏ-ƪȅ/ƠřǶǖĢê@ě=ĩţ*(ŋĘ>= ƪȅ0ƪ@&,N|PSaƲÒ/ßǭ-:<ïŚ,PjIs*(ùä= PjIsȇǾƚ0N|PSaƲÒ*üƽé/ßǭ:1ŨƮƲÒd\`M/²řƨ-Ǫà=ȟHd}Lȍì@#7ǵč/ MD ǖƦ)Îƽ,PjIs@­(ĲƯ=/0áȐ) = Ɔǡƻ;0YhMǨ/ƠřǶŲ)Đƅ;>(=~l|Kķ MD ŭȡREMD ŭ, Replica-Exchange Molecular
Dynamics ŭ[1]Ȣ@ŀƪȅ/ÞȚ-ǼƅŶů/ƪȅ-ă(NMR _Y*ǁ=ƠřǶCRk}ȡŕǬ,Ƅ´÷řǶ@ǌƂ=ǎĹ/ƠřǶ;,=řǶw_}Ȣ/Ų-ħÀ#[2]ļ)ưƼ9FD}UǌȔ-0ïĹ/ƪȅùä!>;M{UY@ĖħŞƽ-Ȉ?%(=*ƺ;>(= ƪȅM{UY@ăǥ*# MD ǖƦ/ê× 0Ř7(ć,ƗƠ#ǖƦw_}8,žŬ) %# Ňǲ/ĻæPbFD}UȡSARS-CoV-2Ȣ-Ȉ=ƖƞžŬ@íMD
ǖƦ-:<UhEMYhMǨǌȔïĹ/ƪȅ)Ǒ?>(=Ś÷Ł;-,<ƪȅ-:=ǽǆ
ȡGlycan shieldingȢM[9Ǉ/ƅ-8āĳ-Ȉ?%(=*?%(# [3] ōǟȚ)0
C~bFD}Uƙ-ĉ={\RFD}UȡLassa virus: LASVȢ/ƪYhMǨǎÒȡGlycoprotein complex:
GPCȢ-ƔƑ= LASV 0ǏCj|K@Ğ-Ťď 5000 8/šƻ@³~n} 4 /FD}U)Ō$ŉÃ,ūƌǇ9M[0ě;>(, LASV GPC 0ÍÿƲÒRkyc\`ȡGP1Ȣ*ƿǦǵǈÒö
Rkyc\`ȡGP2Ȣ;,=m^ZEs/ Ȅ)řƨ>LASV ǌȔ/Ý/ĬË) = ¼ǳ
/ SARS-CoV-2 -ť3ǌȔƪȅ/āđȟseUæƪȅï*%#Žĝ = YhMǨ/
REV8ĆǌȔƪȅ/ėȕțǅ-Ƃ>=*ģ>=*;ōǟȚ/ǖƦăǥ*(ǿA$2 <>-2D?-2
MD Stx~Sz0LASV GPC / 3 &/w_}-ă(þĽ# 1ȢƲÒƪȅ,2ȢJ|Qs
eUæȡMan9GlcNAc2Ȣ/53ȢJ|QseUǎÒæfEk|\aæ N æƪȅƲÒ#ŰÒƪȅw_} 3Ȣ)0ÑƲÒRE`-ă(þȞƏ-Ň8´Čï*>=ƪȅ@Á# [4] ·ŋř- 433 -

Ƕw_}0ƲńřǶȡPDBID: 5VK2Ȣ-é'ħ33
ō / Ʋ Ò ƪ ȅ 0 F G k ]  } CHARMM- GUI Glycan
Modeler @ƅ(Á# Ë÷Ĺ0Ñ Ũ´÷@Ö7
111 085 Ë÷ȡ1Ȣ
244 749 Ë÷ȡ2Ȣ
260 831 Ë÷ȡ3Ȣ*,%# MD ǖƦ0CHARMM36m ¿ë* TIP3P h{vY@ƅ(300 K1 atm /ýãŎȡNPTȢ)ǉ%#
Ñƫ-ă(100 ns /ĎǋÅǖƦ@þĽ#ę1s /ǖƦ@þĽ# ­(/ MD ǖƦ0GENESIS[56]@ƅ(þĽ# â 1 - MD ǖƦ-ƅ# LASV GPC /řǶ@Ƙ

â 1. MD ǖƦ-ƅ# LASV GPC ŰÒƪȅw_}/ƠřǶ GP2 :1 GP1 av
Eƪȅ@Ñ Ƞȓƴ)ǌ3 <>)0YhMǨǹÄ2/ėȕâ 2ȡĊȢ-GPC / CË÷-ă(ũ7#Ďåĸ;ȡRMSFȢ@Ƙ ƪȅ/ŉŹ-:<ð,ǻǒ;>,*;ǌȔƪȅYhMǨǹÄ-=ėȕ0Ć*?= ƪȅ =ëÒ
-Ala202 * Gly391 ǲ/iMīº>(= >;CteȂŢé/Øǰ-0ƲÒƪȅ =#7YhMǨƪȅ/ƒĳƏ,ƓƅĈĨƏ,CteȂŢé/ǹÄ@īº(=*ƺ;>=YhMǨǌȔ/ǽǆÃőş-YhMǨǌȔ@ǑƲÒƪȅ/ėȕ@Ǡ3=#7-GP1 * GP2 avE/ŶöȒ³ǌȔƝȡSolvent
Accessible Surface Area: SASAȢ@ƪȅ =ëÒ*ŹëÒ*)ǖƦ!>;/¦;ƪȅ-:=ǽǆđ
Ò@ũ7# â 2ȡÏȢ0ð/ƈ,=lkƃȡŨ´÷-Ɠĕ= 1.4Å ;Ĭ/Ȁ´řǶ@Ŝ#ð,¦4)Ȣ@ƅ(ũ7#ÑavE/ǽǆđÒ@Ƙ ­Șè) GP1 /ǽǆđÒ GP2 :<8ȟ!/ċ0lkƃ/¦ð,=-&>(țǅ-,= /Ʋő0Ĭ GP1 :<8 GP2 avE-©-ƲÒ=*@ƘÜ(= MD ǖƦ;ě;>#ƲÒƪȅ/ƠřǶ´Čȡ10 Ub\lSz\`/ȃ.Ò? Ȣ;8GP2 avE/ȀȒ³>(=*@ƗǞ)=â 2. GPC CË÷/ RMSFȡǩȤŰÒƪȅw_}ȓȤƪȅ,ȢȡĊȢ*ð/ƈ,=lkƃ@ƅ(ũ7# GP1/GP2 avE/ǽǆđÒȡÏȢ MD ǖƦ;ě;>#ƲÒƪȅ/ƠřǶ´Čȡ10 Ub\lSz\`/ȃ.Ò? Ȣ@Ìƺ*(ƘƪȅM{UY/ĖħYhMǨǌȔ@ǑƪȅþȌ-M{UY@Ėħ(=@Ǡ3=#7-MD ǖƦ-ǒ;>=ƪȅȇPYM`ȡÑƪȅoC-ă(ȃË÷ȇǫȏ 5Å ŌŴ,;PYM`(=*ǒ,Ȣ@ũ7#â 3 /PYM`s\l0 2 Ɯȝ/M{UYĖħ>(=*@ƘÜ= &0LASV GPC @řħ

- 434 -

=l`sȡÉȄȢ/ GP1 ƲÒƪȅȡN79N99N109N167Ȣ* GP2 ƲÒƪȅȡN365N390:
1 N395Ȣ@Ö6l`s±M{UY)ļ0 3 &/l`sȡ3 ȄȢ/ GP1 ƲÒƪȅ N119 ;,=l`sȇM{UY) = ¼ƻ0 GPC §ȔȡŽ- GP2 Ȁ´Ȣ@ęƻ0 GPC ȀȡGP1 Ȁ´Ȣ@ǽǆ(= l`sȇM{UY0ĀưƼ2/¢¬-ȈǷ=-TU`N|Kȡ-DGȢ*/ƲÒȀ@Ǒ%(= ļ/l`s±M{UY0GP1 Ǖȏ-ȈǷ=|XXuȈǷƿYhMǨ 1ȡLAMP1Ȣ/ƲÒȀ@Ǒ%(= ǌȔƪȅ0M{UY@Ėħ=*)ŞƽȀ@ÃƁƏ-¤Ǥ(=*ƘÜ>#â 3. MD ǖƦ;ũ7#ƪȅ
ȇ/PYM`s\ll

`s±M{UY@ǩœ)Ƙ°æƏ,ƪȅM{UYȡȓl`sȇSCl`s±M{UYȢ/Ub\lSz\`@ÌƺƘHi`l/ŲŇę-MD ǖƦ;ě;>#ǌȔƪȅ/ƠřǶZEbtMU/Ģê@ƅ(Ĭ/Hi`lŲ@
Ǜ5# ES|P/ĬHi`lŲ)0>4)ȁ¶řǶnU/Ś ,ĩŭȆƍ>Đƅ
;>(# Ƃž)0ǌȔƪȅ/ėȕ0ƺĦ>(;MD ǖƦ;ě;>#ƪȅ/Ơř
ǶĢê@Ʊ5Ò? =*)ŲƩđ/ÕŋĘ>= ¯Ə-0MD ǖƦ;ũ7#ǌȔƪȅ/řǶĸ;SASA ¦ĜǓƏƓƅ/Ģê@UPCÅľù/ȁ¶řǶnU/ĩŭ)ũ7#UPC*
Ʊ5Ò? (Hi`l@Ų# !/ƲőLASV /ľƕHi`lŠŲ>#$),
Ļ#,Hi`l¥Ǎ/Ģê8ě=*)#ȡâ 4Ȣ
â 4. MD ǖƦ*ľù/ȁ¶řǶnU/ĩŭȡBepiPred * ElliproȢ@Ʊ5Ò?
#Hi`lŲ/Ʋő ľƕ/Hi`lƸȡÏƢ/YhMǨřǶ/ȓǃȀ´Ȣǂ²Ƃ>(=4*7*ǟȚ

ōǟȚ)0MD ǖƦ-:< LASV GPC ǌȔ-ƲÒ#ƪȅ/ǽǆÃő@Ë÷Ǖ¨đ)Ł;-# ;-MD ǖƦ;ě;>#ƪȅĢê@Ěŏ/ȁ¶řǶnU/Hi`lŲ*Ʊ5Ò? =*)ǌ
Ȕƪȅ@ƺĦ#ȟƩđHi`lŲ-ħÀ# ļ)ōǟȚ)ý(#ĮĔCRk}ǖƦ
4)#+<Ɣ,%##7ƪȅM{UY/ûýġ9ĄÙ/M{UY/ùä,+@ŗǗ=*)- 435 -

,%# ęōǟȚ/Ʋő-é'ĮĔCRk}ŭ@ƅ#Ç´,řǶĲƯ@ǉōǟȚ)ě;>#Ʋő/ôĕġ@ǚ¡=**8-ƪȅM{UY/ǖƦw_}/ƗƠ@Ƒİ4 8C%@$

ȣȢ6X\RQJ5H'RFNLQJVLPXODWLRQXVLQJ*(1(6,6DQGLWVSRVVLEOHDSSOLFDWLRQIRUJO\FDQV\VWHPVWK*O\FROLSLGRORJXHVHPLQDU %  *  ):HE 4
65+ /,"#   3('17 &$!#2-3.0     %  *  ):HE 4

5 5%@$ȣȢRe, S.; Mizuguchi, K. Glycan Cluster Shielding and Antibody Epitopes on Lassa Virus Envelop Protein. J. Phys.
Chem. B 2021, 125, 2089–2097.
A,6
[1] Sugita, Y.; Okamoto, Y. Chem. Phys. Lett. 1999, 314, 141–151.
[2] Re, S.; Nishima, W.; Miyashita, N.; Sugita, Y. Biophys. Rev. 2012, 4, 179–187.
[3] Casalino, L.; Gaieb, Z.; Goldsmith, J. A.; Hjorth, C. K.; Dommer, A. C.; Harbison, A. M.; Fogarty, C. A.; Barros, E.
P.; Taylor, B. C.; Mclellan, J. S.; Fadda, E.; Amaro, R. E. ACS Cent. Sci. 2020, 6, 1722–1734.
[4] Watanabe, Y.; Raghwani, J.; Allen, J. D.; Seabright, G. E.; Li, S.; Moser, F.; Huiskonen, J. T.; Strecker, T.; Bowden,
T. A.; Crispin, M. Proc. Natl. Acad. Sci. USA 2018, 115, 7320–7325.
[5] Jung, J.; Mori, T.; Kobayashi, C.; Matsunaga, Y.; Yoda, T.; Feig, M.; Sugita, Y. Wiley Interdiscip. Rev. Comput. Mol.
Sci. 2015, 5, 310–323[6] Kobayashi, C.; Jung, J.; Matsunaga, Y.; Mori, T.; Ando, T.; Tamura, K.; Kamiya, M.; Sugita, Y. J. Comput. Chem.
2017, 38, 2193–2206.

- 436 -

QM/MM 



Met16 

Reduction potential determination of WT and Met16X variants of
Pseudoazurin with QM/MM methodj ÀâÁrxzã

1 ±²®­¨\dy )Íµ%½¬¥¦Ç ¯U]©¦Ç ÔÆ) ¯U]©ß* ~Ívh) wO¿­¯U]©chz­n+É)pÛ)¾³Â ÜyYÎ\½)BJN×7L@0Ì)2H.=,
5IL*! 16 ZF9/>Ls+W,E?Ó »)&¯U]©
¡SÜy£ÓhÐaÜZ7L@0Ì{|Ý+R )+tm)[1-4]2H.
=,5ILÖyhzádÇ½ X ¸·ÍÇ'  ~Ívhhz­n+É)
#eËÞ QM/MM (two-layer ONIOM)+©16 Z`Ø×ÒZ)A493L 81 ª-E86N
J§Ù S-πCH-π-π ¯U]© ¡SÍÜy£Ý+R )' 
ËÞ' WT (Õ¨q)2H.=,5ILMet16PheMet16IleMet16Leu v«\gÈ´+ÃÏhG;JÊ+Ã!ÓhÐaÜZÈ´+Ã2 ±²

È´

WT, Met16Phe, Met16Leu and Met16Ile PAz gÈ´ QM/MM(two-layer ONIOM) &)ÏhÍ+©È´b Gaussian 16 (rev A.03)+^©QM Ñd¶à­dfÅ(Grume’s 3D)+Ã B3LYP/def2SVP KCJÈ´MM Ñd 8Å  explicit water +l"Amber +©È´

3 ±²È´& WT 2H.=,5IL & Met16Phe, Met16Leu, Met16Ile v«\ÓhÐaÜZ(vs.
SHE, 4.44 V)WT = 1.81 V, Met16Phe = 3.80 V, Met16Leu = 3.24 V and Met16Ile = 3.78 V 1-0I:0DJ7LF<IN #ÓhÐaÜZ WT = 260 mV, Met16Phe = 305 mV, Met16Leu = 289 mV,
Met16Ile = 275 mV (È´_x«WT ÓhÐaÜZ}àMÈ´*$uk$ Met16 v«\&($[Q!È´Ù°¹#o+ÚXgÈ´+}
PV Met16Tyr, Met16Trp, Met16Val v«\ÓhÐaÜZÈ´+Ã i¼¤[1] R. F. Abdelhamid, Y. Obara, Y. Uchida, T. Kohzuma, D. M. Dooley, D. E. Brown, H. Hori, J. Biol. Inorg.
Chem., 12, 165 (2007).
[2] T. Yamaguchi, Y. Nihei, D. Southerlands, M. Stillman, T. Kohzuma, Protein Science, 1921-1931 (2017).
[3] T. Yamaguchi, K. Akao, A. Takashina, S. Asamura, M. Unno, R. K. Szilagyi, T. Kohzuma, RSC Adv., 6,- 437 -

88358-88365 (2016).
[4] T. Yamaguchi, J. Yano, V. K. Yachandra, Y. Nihei, H. Togashi, R. K. Szilagyi, T. Kohzuma, Bull. Chem. Soc. Jpn.,
88, 1642-1652 (2015)4 ¬Ä}º!T| A. Taborosi, T. Yamaguchi, C. Sakai, K. Akao, S. Mori, T. Kohzuma: Structural and computational studies of
weak interactions at the second coordination sphere Blue Copper Protein, Pseudoazurin and its Met16X variants, The
70th Conference of Japan Society of Coordination Chemistry, 2020/09/28-30
 A. Taborosi, T. Yamaguchi, K. Wood, A. Whitten, S. Mori, T. Kohzuma: The unfolding mechanismof Pseudoazurin determined by Small Angle Neutron Scattering and Molecular Dynamics simulation, The 101st CSJ
Annual Meeting, 2021/03/19-22
 T. Yamaguchi, A. Taborosi, S. Mori, T. Kohzuma; Second Coordination Effects in Blue Copper Protein with
Combined Experimental and Computational Chemistry, The 24th International Annual Symposium on Computational
Science and Engineering, 2021/04/30
  T. Yamaguchi, K. Akao, A. Koutsioubas, H. Frielinghaus, T. Kohzuma; Structure Determiantion of theOpen-Bundle Unfolding Intermediate of Cytochrome c’ by Small Angle Neutron Scattering, The 5th International
Symposium of Quantum Beam Science, 2020/11/19

5 c¢}º!T| T. Yamaguchi, A. Taborosi, C. Sakai, K. Akao, M. Akatsu, S. Mori, T. Kohzuma: – How weak interactions works at
the second coordination sphere of protein: Structural and computational studies on the S-π, π-π and CH-π interactions
in a Blue Copper Protein, Pseudoazurin and its Met16X variants - prepared for submission
 T. Yamaguchi, A. Taborosi, K. Wood, A. Whitten, T. Kohzuma: The unfolding mechanism of Pseudoazurin and thecontribution of noncovalent weak interaction determined by Small Angle Neutron Scattering and Molecular Dynamics
simulation – manuscript in preparation
 A. Taborosi, T. Yamaguchi, S. Mori, T. Kohzuma: QM/MM study on the second sphere noncovalent interactions of
WT and Met16X Pseudoazurin - manuscript in preparation
$<DPDJXFKL<(GDQDPL7<DPDJXFKL76KLEX\D1)XND\D7.RK]XPD(IIHFWRI&DYLW\6L]HRI0HVRSRURXV
6LOLFDRQ7\SH&RSSHU6LWH*HRPHWU\LQ3VHXGRD]XULQ%XOO&KHP6RF-SQ  
7<DPDJXFKL0$NDWVX$7DERURVL7.RK]XPD8QXVXDO3URWHLQ6WDELOLW\RIWKH0HW/HX3VHXGRD]XULQ9DULDQW
&KHP/HWW  

- 438 -

จ⦰⣔࡟࠾ࡅࡿ⦆࿴࠾ࡼࡧ཯ᛂࢲ࢖ࢼ࣑ࢡࢫࡢ⌮ㄽ◊✲
Theoretical studies of relaxations and reaction dynamics
in condensed phase‫ۑ‬ᩧ⸨ ┿ྖࠊ᳃ ಇᩥࠊ⏥⏣ ಙ୍ࠊᯇᮧ ⚈ᏹࠊMAURYA Manishࠊ
KALATHINGAL MahroofࠊZHU Zhe㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧

1◊✲┠ⓗࠊෆᐜ
ᮏᖺᗘࡣࠊ1. ᫬ィࢱࣥࣃࢡ KaiC ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࠊ2. จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎࡢゎ᫂ࠊ3. 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)ບ㉳࢚ࢿࣝࢠ࣮⛣ືᶵᵓࠊ4. ᅛయ⏺㠃ୖࡢỈ⁲ࡢᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࠊ5. ࢖࢜ࣥࢳࣕࢿࣝศᏊࡢ⭷ᤄධᶵᵓࠊ࡟㛵ࡍࡿ◊✲ࢆ⾜ࡗࡓࠋ⣬㠃ࡢ㛵ಀୖࠊ1-4 ࡢ⤖ᯝࢆ௨ୗ࡟⧳ࡵࡿࠋ
1.1 ᫬ィࢱࣥࣃࢡ KaiC ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࡢゎᯒࢩ࢔ࣀࣂࢡࢸࣜ࢔ࡢᴫ᪥ࣜࢬ࣒ࡣ 3 ✀ࡢࢱࣥࣃࢡ㉁(KaiA, KaiB, KaiC)ࡢ┦஫స⏝࡟ࡼࡗ࡚⏕ࡌࡿࠋᦤືࡍ
ࡿ⎔ቃࡢ୰࡛యෆ᫬ィࡢ࿘ᮇࢆ୍ᐃ࡟ಖࡘࡇ࡜ࡣ⏕⌮ⓗ࡟㔜せ࡞ᶵ⬟࡛࠶ࡾࠊࡑࡢ࣓࢝ࢽࢬ࣒ࢆ▱ࡿ࡟ࡣࡲࡎ࿘ᮇࡢỴᐃᶵᵓࢆ▱ࡿᚲせࡀ࠶ࡿࠋ࿘ᮇࡣ㐜࠸㐣⛬࡟ࡼࡗ࡚୺࡟ᐃࡲࡿࠋࢩ࢔ࣀࣂࢡࢸࣜ࢔࡛ࡣ KaiB-KaiC
ࡢ」ྜయᙧᡂࡀࡦ࡜ࡘࡢ㐜࠸㐣⛬࡛࠶ࡿࠋࡇࡢ⤖ྜࡢ๓ẁ㝵࡛ KaiB ࡜ KaiC ࡑࢀࡒࢀࡀ⤖ྜྍ⬟࡞ᵓ㐀࡟ኚ໬ࡍࡿᚲせࡀ࠶ࡾࠊࡑࡢ࡝ࡕࡽ࠿ࡀᚊ㏿࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡇࡢⅬࠊ࠶ࡿᐇ㦂◊✲ࡣ KaiB ࡀ㐜࠸࡜୺ᙇࡋ࡚࠸ࡿࡀࠊศᏊ◊⛅ᒣ G ࡢᐇ㦂◊✲ࡣ KaiC ࡇࡑࡀ㐜࠸࡜୺ᙇࡋ࡚࠸ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣ」ྜయᙧᡂ
ࡢ཯ᛂࣔࢹࣝࢆ⏝࠸ࡓ⌮ㄽ◊✲࡛๓⪅ࡢᐇ㦂⤖ᯝࡀ KaiB ࡢᵓ㐀ኚ໬ࡢ㏿ᗘ࡜ࡣ↓㛵ಀ࡟ㄝ࡛᫂ࡁࡿࡇ࡜ࢆ
♧ࡋࠊᚋ⪅ࡢṇᙜᛶࢆ⿬௜ࡅࡿࡇ࡜ࢆ┠ᣦࡋࡓࠋࡲࡓࡉࡽ࡟ࠊKaiC ࡢᵓ㐀ኚ໬ࢆヲ⣽࡟᳨ウࡋࠊ཯ᛂࣔࢹࣝ
ࢆ」ྜయᙧᡂࡢ඲ㇺࢆㄝ࡛᫂ࡁࡿࡼ࠺࡟Ⓨᒎࡉࡏࡓࠋ
1.2 จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎ࡟㛵ࡍࡿ◊✲จ⦰ศᏊ⣔࡟࠾ࡅࡿືⓗ࡞ᦂࡽࡂࡣືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎ࡜࿧ࡤࢀࠊ໬Ꮫ཯ᛂࡸᵓ㐀ኚ໬ࢆ⌮ゎࡍࡿୖ࡛㔜せ࡛࠶ࡿࠋࡇࢀࡲ࡛⡆༢࡞⌮ㄽࣔࢹࣝ࡟ࡼࡿ◊✲ࡀ⾜ࢃࢀ࡚ࡁࡓࡀࠊཎᏊ࣭ศᏊࣞ࣋ࣝࡢᥥീࡣᮍࡔ࡟ࡼ
ࡃࢃ࠿ࡗ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊ☜⋡㐣⛬⌮ㄽ࡟ᇶ࡙ࡁࠊMD ィ⟬࡛ᚓࡽࢀࡿ⣔ࡢ᫬⣔ิ᝟ሗࢆゎᯒࡍࡿᡭἲࢆ㛤Ⓨࡋࠊจ⦰⣔ࡢ໬Ꮫ཯ᛂࡸᵓ㐀ኚ໬࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎࡢᙺ๭ࢆ୍ศᏊ㏿ᗘㄽࡢほⅬ࠿ࡽཎᏊ࣭ศᏊ࡛ࣞ࣋ࣝ᫂ࡽ࠿࡟ࡍࡿࠋ≉࡟ࢱࣥࣃࢡ㉁୍ศᏊࡢᵓ㐀ࢲ࢖ࢼ࣑ࢡࢫࡢ◊✲ࢆ⾜ࡗࡓࠋ
1.3 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟㛵ࡍࡿ◊✲⥳Ⰽ᳜≀ࡢගྜᡂ࡟࠾ࡅࡿ᭱ึࡢࢫࢸࢵࣉࡣࠊගᤕ㞟࢔ࣥࢸࢼ࡜࿧ࡤࢀࡿࢱࣥࣃࢡ㉁࡟ࡼࡿ㧗㏿࣭㧗ຠ⋡࡞ග࢚ࢿࣝࢠ࣮ࡢ྾཰࠾ࡼࡧ཯ᛂ୰ᚰ࡬ࡢఏ㐩࡛࠶ࡿࠋ⥳Ⰽ᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)ࡣᵓ㐀ࡀ」㞧࡞ࡓࡵᐇ㦂࡟ࡼࡿゎᯒࡀᅔ㞴࡛࠶ࡿࠋࡑࡇ࡛ᮏ◊✲ࡣ LHCII ࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື(EET)ࢆ⌮ㄽⓗ࡟ゎᯒࡍࡿࠋලయⓗ࡟ࡣࠊࡲࡎࠊLHCII ࢔ࣥࢸࢼෆࡢⰍ⣲ࡢᐇ㦂ࢧ࢖ࢺ࢚ࢿࣝࢠ࣮ᕪࢆ㔞Ꮚ໬Ꮫィ⟬࡛෌⌧࡛ࡁࡿ㐺ษ࡞ỗ㛵ᩘ࡜ࣃ࣓࣮ࣛࢱࢆỴᐃࡍࡿࠋࡲࡓࠊLHCII ࢔ࣥࢸࢼෆࡢⰍ⣲ࡢບ㉳࢚ࢿࣝࢠ࣮࡜ບ㉳≧ែ㛫ࡢ࢝ࢵࣉࣜࣥࢢࡢ኱ࡁࡉ࠾ࡼࡧᦂࡽࡂࢆゎᯒࡍࡿࠋࡑࢀࡒࢀࡢ≀⌮㔞࡟࠾ࡅࡿࢱࣥࣃࢡ㉁ࡢᵓ㐀ࡸᦂࡽࡂࡀ୚࠼ࡿ

- 439 -

ᙳ㡪ࢆ⪃៖ࡋ࡚ EET ࢲ࢖ࢼ࣑ࢡࢫࢆゎᯒࡋࠊࢱࣥࣃࢡ㉁ࡢᵓ㐀ࡸᦂࡽࡂ࡜㧗㏿࣭㧗ຠ⋡࡞࢚ࢿࣝࢠ࣮⛣ື࡜ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ
1.4 ᅛయ⏺㠃ୖࡢỈ⁲ࡢᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࡍࡿ◊✲ỈศᏊ㛫ࡢỈ⣲⤖ྜ࡟ࡼࡾࠊࣂࣝࢡࡢỈ୰࡟ࡣ୕ḟඖⓗ࡞Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡀᙧᡂࡉࢀࡿࠋࡑࡢࡓࡵࠊ
ᅛయ࡜Ỉࡢ⏺㠃ࡸỈ࡜✵Ẽࡢ⏺㠃ࡢ࠶ࡿ⣔ࡢỈࡢᵓ㐀ࡣࣂࣝࢡࡢ⪅࡜ࡣ኱ࡁࡃኚࢃࡿࡇ࡜ࡀᐜ᫆࡟᝿ീࡉࢀ
ࡿࠋࡉࡽ࡟ࠊࣂࣝࢡࡢỈࡣࠊ༢఩య✚ᙜࡓࡾࡢ཮ᴟᏊ࣮࣓ࣔࣥࢺࡀ኱ࡁࡃࠊỈศᏊ㛫ࡢ཮ᴟᏊ࣮࣓ࣔࣥࢺࡀ
኱ࡁ࡞ṇࡢ┦㛵ࢆࡶࡘࡓࡵ࡟ࠊ኱ࡁ࡞㟼ⓗㄏ㟁⋡ࢆࡶࡘࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊቃ⏺᮲௳ࡢ␗࡞ࡿ᭷㝈⣔ࡢᾮ⁲࡟࠾࠸࡚ࡣࠊ⣔ࡢศᴟࡢᦂࡽࡂࡢ㐪࠸ࡶண᝿ࡉࢀࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
ࢆ⏝࠸࡚ࠊᅛయ/Ỉ࠾ࡼࡧỈ/✵Ẽࡢ⏺㠃ࢆࡶࡘỈ⁲ࡢᵓ㐀ࠊᦂࡽࡂࠊࢲ࢖ࢼ࣑ࢡࢫ࡟ࡘ࠸࡚ゎᯒࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ
2.1 ᫬ィࢱࣥࣃࢡ KaiC ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࡢゎᯒࡲࡎ཯ᛂࣔࢹࣝࢆᵓ⠏ࡋࡓࠋࡇࡇ࡛ࡣ KaiC ࡀභ㔞య࡛࠶ࡿࡇ࡜ࢆ࠶ࡽࢃ࡟⪃៖ࡋࡓ༢⣧࡞཯ᛂࣔࢹࣝࢆฟ

ⓎⅬ࡜ࡋࡓࠋࡉࡽ࡟ KaiB 㛫࡟ぶ࿴ⓗ࡞┦஫స⏝ࡀാࡃࡇ࡜ࢆࣔࢹࣝ࡟⤌ࡳ㎸ࢇࡔࠋࡑࡋ࡚ࠊᐇ㦂⤖ᯝࢆ෌⌧ࡍࡿ㐺ᙜ࡞཯ᛂ㏿ᗘᐃᩘࢆ᥈⣴ࡋࠊࡑࢀࢆ⏝࠸࡚ྛ✀ࡢᐇ㦂⤖ᯝࢆㄝ᫂ࡋࡓࠋࡇࡢ᫬Ⅼࡲ࡛ࡢ཯ᛂࣔࢹࣝࡣ
KaiC ࡀᖖ࡟⤖ྜྍ⬟࡞≧ែ㸦࢔࣑ࣀ㓟ኚ␗࡛ᐇ⌧࡛ࡁࡿ㸧࡟࠶ࡿ࡜㝈ᐃⓗ࡞௬ᐃࢆ⨨࠸ࡓࡓࡵࠊḟ࡟ࠊKaiC
ࡢ⤖ྜ๓ࡢ㐣⛬ࢆヲ⣽࡟᳨ウࡋࡓᣑᙇࣔࢹࣝࢆᵓ⠏ࡋࡓࠋࡑࡋ࡚ࠊ㔝⏕ᆺ KaiC ࡜ኚ␗య KaiC ࡑࢀࡒࢀࡢ」ྜయᙧᡂ㏿ᗘࢆ෌⌧ࡍࡿ཯ᛂ㏿ᗘᐃᩘࢆ᥈⣴ࡋࠊࡑࢀࢆ⏝࠸࡚」ྜయᙧᡂࡢ཯ᛂᶵᵓࢆㄝ᫂ࡋࡓࠋ
2.2 จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎ࡟㛵ࡍࡿ◊✲໬Ꮫ཯ᛂࡸᵓ㐀ኚ໬࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎࢆゎᯒࡍࡿࡓࡵࡢ⌮ㄽᡭἲࢆ๓ᖺᗘ࡟ᘬࡁ⥆ࡁ㛤Ⓨࡋࡓࠋ☜⋡ⓗ࡟ᦂࡽࡄ㏿ᗘಀᩘࢆ⏝࠸ࡓ⌮ㄽࣔࢹࣝ࡟ᇶ࡙ࡁࠊᵓ㐀㑄⛣㐣⛬ࡢṧᏑ☜⋡㛵ᩘࡸࡑࡢ⫼ᚋ࡟Ꮡᅾࡍࡿ㏿ᗘኚㄪࡢᣦᶆࠊࡑࡋ࡚ෆ㒊≧ែ㛫ࡢᦂࡽࡂ࡜ࡢ㛵㐃ࢆゎᯒࡍࡿᡭἲ࡛࠶ࡿࠋゎᯒᡭἲࢆ㉸㛗᫬㛫㸦㸯࣑ࣜ⛊㸧ࡢࢹ࣮ࢱࡀ฼⏝ྍ⬟࡞Ỉ⁐ᾮ୰ࡢ BPTI ࢱࣥࣃࢡ㉁࡟ᛂ⏝ࡋࠊᵓ㐀㑄⛣㐣⛬࡟࠾ࡅࡿ」㞧࡞ᦂࡽࡂࡢ
ᙳ㡪ࡢศᏊㄽⓗ㉳※ࡢゎᯒࢆ㐍ࡵࡓࠋ
2.3 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟㛵ࡍࡿ◊✲ගᤕ㞟࢔ࣥࢸࢼࡢ EET ࢲ࢖ࢼ࣑ࢡࢫ࡟࠾ࡅࡿࢱࣥࣃࢡ㉁ࡢᵓ㐀ࡸᦂࡽࡂࡢᙺ๭ࢆศᏊ࡛ࣞ࣋ࣝゎ᫂ࡍࡿࡓࡵ࡟ࠊࡲࡎࠊࢡࣟࣟࣇ࢕ࣝ(Chl) a / b ࡢᇶᗏ࠾ࡼࡧບ㉳≧ែࢆ㐺ษ࡟グ㏙ࡍࡿࡇ࡜ࡀᚲせ࡜࡞ࡿࠋᡃࠎࡢࢢࣝ
࣮ࣉࡢ௨๓ࡢ◊✲࡟ᇶ࡙ࡁࠊࢱࣥࣃࢡ㉁୰ࡢ㟁Ꮚ≧ែゎᯒࡢ๓࡟ࠊ
⁐ᾮ୰ࡢࢡࣟࣟࣇ࢕ࣝ(Chl) a / b ࡢ QM/MMィ⟬࡟ࡼࡾບ㉳࢚ࢿࣝࢠ࣮࡞࡝ࢆ㐺ษ࡟෌⌧ࡍࡿ(TD)DFT ィ⟬ࡢࣃ࣓࣮ࣛࢱ㸦࡜ࡃ࡟ࠊrange separated
parameter㸧ࢆỴᐃࡋࡓࠋᮏ◊✲࡛ࡣࠊࣂࢡࢸࣜ࢜ࢡࣟࣟࣇ࢕ࣝ a ࡢ⤖ᯝࢆࡶ࡜࡟ࠊ㔞Ꮚ໬Ꮫィ⟬࡟ CAM-B3LYP
ỗ㛵ᩘࢆ౑⏝ࡍࡿࡇ࡜࡜ࡋࡓࠋ࣓ࢱࣀ࣮ࣝࠊ࢔ࢭࢺࣥࠊࡖ࢚ࢳ࢚࣮ࣝࢸࣝࡢ 3 ✀㢮ࡢ⁐፹୰ࡢ Chl a / b ࡢ㉳࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࠊᐇ㦂ࡢບ㉳࢚ࢿࣝࢠ࣮ᕪ࡜ẚ㍑ࡋ࡚ỗ㛵ᩘࡢ range separated parameter ࢆỴᐃࡋࡓࠋࡇ
ࡢ range separated parameter ࢆ⏝࠸࡚ LHCII ࡢⰍ⣲ࡢ QM/MM ບ㉳࢚ࢿࣝࢠ࣮ࢆィ⟬ࡍࡿࠋQM/MM ບ㉳࢚ࢿࣝࢠ࣮࡟ᇶ࡙ࡁࠊLHCII ୰ࡢྛⰍ⣲ࡢศᏊෆ࣭㒊ෆ㛫┦஫స⏝ࢆィ⟬ࡍࡿࡓࡵࡢࣔࢹ࣏ࣝࢸࣥࢩࣕࣝ(MMSIC)ࢆᵓ⠏ࡍࡿࠋMMSIC ἲࡣ㧗㏿࡛࠶ࡿࡓࡵࠊMMSIC-MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽࢫ࣌ࢡࢺࣝᐦᗘ࡞࡝ࡢືⓗ≉ᛶࢆィ⟬ࡍࡿࡇ࡜ࡶྍ⬟࡜࡞ࡾࠊ᭱⤊ⓗ࡟ࠊᚓࡽࢀࡓ≀⌮㔞࡟ᇶ࡙ࡁ EET ࢲ࢖ࢼ࣑ࢡࢫࢆゎ᫂ࡍࡿࡇ࡜ࡀྍ

- 440 -

⬟࡜࡞ࡿࠋ
2.4 ᅛయ⏺㠃ୖࡢỈ⁲ࡢᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࡍࡿ◊✲ᅛయ/Ỉ࠾ࡼࡧỈ/✵Ẽࡢ⏺㠃ࢆࡶࡘỈ⁲ࡢᵓ㐀ࠊᦂࡽࡂࠊࢲ࢖ࢼ࣑ࢡࢫࢆゎ᫂ࡍࡿࡓࡵࠊ2 ᒙࡢࢢࣛࣇ࢙ࣥ
ࢩ࣮ࢺࡢୖ࡟ 1000 ศᏊ࠿ࡽ࡞ࡿ 300K ࡢỈ⁲⣔ࢆసᡂࡋࠊLAMMPS ࢆ⏝࠸ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ
⾜ࡗࡓࠋࡲࡓࠊᅛయ⾲㠃࡜Ỉࡢ┦஫స⏝ࢆኚ໬ࡉࡏࡿࡇ࡜࡟ࡼࡾࠊᵓ㐀࡞࡝ࡀ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿ࠿࡟ࡘ࠸
࡚ࡶゎᯒࡋࡓࠋ

3◊✲ᡂᯝ
3.1 ᫬ィࢱࣥࣃࢡ KaiC ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࡢゎᯒࡲࡎ KaiB 㛫┦஫స⏝ࡔࡅࢆ⪃៖ࡋࡓึᮇࡢࣔࢹࣝࢆ⏝࠸ࡓゎᯒ࡟ࡼࡾࠊKaiB ࡢᵓ㐀ኚ໬ࡢ㐜ࡉࢆ୺ᙇࡍ

ࡿඛ⾜◊✲ࡢᐇ㦂⤖ᯝࡀࠊᐇ㝿ࡣ KaiB ࡢ㐜ࡉࡣ↓㛵ಀ࡟ㄝ࡛᫂ࡁࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋලయⓗ࡟ࡣ KaiB 㛫┦஫స⏝࡜ KaiB ⃰ᗘࡢ⛥ⷧᛶࡇࡑࡀ┿ࡢせᅉ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢ⤖ᯝࡣ Sci. Rep. ㄅ࡟ᥖ㍕ࡉࢀࡓࠋࡲࡓ⥆ࡃᣑᙇࣔࢹ࡛ࣝࡣ㔝⏕ᆺ KaiC ࡜ኚ␗య KaiC ࡢ㐪࠸ࡢ㉳※ࢆ᫂ࡽ࠿࡟ࡋࠊKaiC ࡀዴఱ࡟」ྜయᙧᡂ㏿ᗘࢆไᚚࡋ࡚࠸ࡿ࠿ㄝ᫂ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ࡞࠾ࡇࡇ࡛ࡶ KaiB 㛫┦஫స⏝ࡀ㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࠋࡇ
ࡢ⤖ᯝࡣ⌧ᅾᢞ✏‽ഛ୰࡛࠶ࡿࠋ
3.2 จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎ࡟㛵ࡍࡿ⌮ㄽ◊✲
BPTI ࡣ࢔࣑ࣀ㓟 58 ṧᇶ࠿ࡽ࡞ࡿ≀⌮໬Ꮫ◊✲ࡢࣔࢹࣝࢱࣥࣃࢡ㉁࡛࠶ࡾࠊNMR ⦆࿴ศᩓᐇ㦂࡟ࡼࡾࢩࢫ
ࢸ࢖ࣥṧᇶ㛫ࢪࢫࣝࣇ࢕ࢻ⤖ྜࡢ࿘ᅖࡢᵓ㐀␗ᛶ໬ࢲ࢖ࢼ࣑ࢡࢫࡀほࡉࢀ࡚࠸ࡿࠋ๓ᖺᗘࡲ࡛࡟ࠊ཯ᛂ㏿ᗘࡀ☜⋡ㄽⓗ࡟ᦂࡽࡄࣔࢹࣝ࡟ᇶ࡙ࡁࠊBPTI ࡟࠾ࡅࡿࢩࢫࢸ࢖ࣥṧᇶ㛫ࢪࢫࣝࣇ࢕ࢻ⤖ྜࡢ␗ᛶ໬ࢲ࢖ࢼ࣑
ࢡࢫ࡟࠾ࡅࡿ཯ᛂ㏿ᗘኚㄪࡢᙳ㡪ࢆ᫂ࡽ࠿࡟ࡋࡓࠋᮏᖺᗘࡣࠊ཯ᛂ㏿ᗘኚㄪࢆ≉ᚩ࡙ࡅࡿᣦᶆࢆ᪂ࡓ࡟ᑟධࡋࠊᚤどⓗ࡞ᵓ㐀≧ែࡢᦂࡽࡂ࡜ࡢ㛵㐃ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ཯ᛂ㏿ᗘࡀ☜⋡ㄽⓗ࡟ᦂࡽࡄࣔࢹࣝ࡟㛵ࡍࡿ⌮ㄽ◊✲ࡣ 90 ᖺ௦࡟ࡶ⾜ࢃࢀࡓࠋࡋ࠿ࡋࠊ཯ᛂ㏿ᗘࡢᦂࡽࡂࡢ⿬࡟࠶ࡿศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡋࡓ◊✲ࡣࡇࢀࡲ࡛
࡟࡞ࡃࠊࡑࡢព⩏ࡣ㠀ᖖ࡟኱ࡁ࠸ࠋᚓࡽࢀࡓ⤖ᯝࢆࡲ࡜ࡵࡓㄽᩥࢆᢞ✏ࡋࡓࠋ
3.3 㧗➼᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ(LHCII)࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮⛣ື࡟㛵ࡍࡿ◊✲
3 ✀㢮ࡢ⁐፹୰ࡢ Chl a / b ࡢບ㉳࢚ࢿࣝࢠ࣮ࡢィ⟬࠾ࡼࡧᐇ㦂್ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊChl a / b ࡢບ㉳࢚ࢿࣝࢠ࣮ࢆ෌⌧ࡍࡿ᭱㐺࡞ range separated parameter ࢆỴᐃࡋࡓࠋChl a / b ࡢບ㉳࢚ࢿࣝࢠ࣮ࡢ෌⌧࡟ࡣࠊᶆ‽ⓗ࡟⏝࠸ࡽࢀ࡚࠸ࡿ range separated parameter㸦0.33㸧ࡼࡾࡶᑠࡉ࡞್࡜࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ
ࡉࡽ࡟ࠊᡃࠎࡢࢢ࣮ࣝࣉ࡛௨๓࡟⾜ࡗࡓࣂࢡࢸࣜ࢜ࢡࣟࣟࣇ࢕ࣝࡢ᭱㐺࡞ range separated parameter ࡼࡾࡶࡉࡽ࡟ᑠࡉ࡞್ࡀⰋ࠸ࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡇࢀࡣࠊChl a / b ࡢඹᙺ㡿ᇦࡀࡼࡾ኱ࡁࡃࠊ㟁Ꮚࡢ㠀ᒁᅾࡀቑࡋ࡚࠸ࡿࡇ࡜ࢆ཯ᫎࡋ࡚࠸ࡿࡇ࡜࡟㛵㐃ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ⌧ᅾࠊᮏ◊✲࡛ᚓࡽࢀࡓࣃ࣓࣮ࣛࢱࢆ⏝࠸ࠊ
LHCII ࡟࠶ࡿ 14 ಶࡢ Chl a / b ࡟ᑐࡍࡿࣔࢹ࣏ࣝࢸࣥࢩࣕࣝ(MMSIC)ࣃ࣓࣮ࣛࢱࡢゎᯒࢆ㐍ࡵ࡚࠸ࡿࠋ
3.4 ᅛయ⏺㠃ୖࡢỈ⁲ࡢᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࡍࡿ◊✲ᅛయ⾲㠃ୖࡢỈ⁲ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࠊᅛయ⾲㠃࠾ࡼࡧỈ/✵Ẽ⏺㠃㏆ഐࡢỈศᏊࡢᒁᡤ
ᵓ㐀ࡣᅄ㠃యᵓ㐀࠿ࡽ኱ࡁࡃ஘ࢀ࡚࠾ࡾࠊ3 㓄఩ࡢỈศᏊࡀ᭱ࡶከ࠸ࡇ࡜ࡀண᝿㏻ࡾ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊ
ᾮయ⣔ࡸỈ⁲ࡢ୰ᚰ㒊࡛ࡣ 2 㓄఩ࡢỈศᏊࡢ๭ྜࡣ 5%⛬ᗘࡋ࠿ぢࡽࢀ࡞࠸ࡀࠊ⏺㠃ࡸ⾲㠃㏆ഐ࡛ࡣ 20%⛬ᗘ

- 441 -

ࡶᏑᅾࡋ࡚࠸ࡿࡇ࡜ࡶ᫂ࡽ࠿࡟࡞ࡗࡓࠋỈ⁲୰ࡢỈศᏊࡢ᣺ື≧ែᐦᗘࢆゎᯒࡋࡓ࡜ࡇࢁࠊ⏺㠃࣭⾲㠃㡿ᇦࡢ㓄఩ᩘࡢప࠸ỈศᏊ࡟ࡼࡾࠊỈศᏊ㛫୪㐍࣭ᅇ㌿㐠ືࡀ red shift ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋᡃࠎࡢ
ࢢ࣮ࣝࣉࡢ 2 ḟඖ㉥እࢫ࣌ࢡࢺࣝ࡟㛵ࡍࡿ௨๓ࡢィ⟬࡟ࡼࡾࠊ㓄఩ᩘࡢప࠸ศᏊࡢ࢚ࢿࣝࢠ࣮⦆࿴ࡀ㐜ࡃ࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟ࡉࢀ࡚࠸ࡿࠋ௒ᅇࡢ⤖ᯝࡣࠊ⏺㠃࣭⾲㠃㡿ᇦࡢ࢚ࢿࣝࢠ࣮⦆࿴ࡀࣂࣝࢡࡢࡶࡢࡼࡾࡶ㐜ࡃ࡞ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋࡲࡓࠊᾮ⁲ࡢ୍ศᏊ࠾ࡼࡧ㞟ᅋᅇ㌿⦆࿴ࡢゎᯒ࠿ࡽࠊᡃࠎࡢỈࢡࣛࢫࢱ࣮࡟࠾ࡅ
ࡿྠᵝࡢゎᯒ⤖ᯝ࡜ྠᵝ࡟ࠊỈศᏊࡢ཮ᴟᏊ࣮࣓ࣔࣥࢺ㛫ࡢ㈇ࡢ┦㛵࡟ࡼࡾࠊ㞟ᅋᅇ㌿⦆࿴ࡣ୍ศᏊᅇ㌿⦆࿴ࡼࡾࡶ㏿࠸ࡇ࡜ࡶ☜ㄆࡉࢀࡓࠋlibration 㐠ື࡟㛵ࡍࡿ SFG ࢫ࣌ࢡࢺࣝࡀᐇ㦂ⓗ࡟ㄪ࡭ࡽࢀ࡚࠾ࡾࠊlibration࡟㛵ࡍࡿศᏊ㛫┦஫స⏝ࡀ್Ⰻࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࡀࠊࡑࡢࡼ࠺࡞ゎ㔘ࡀ㛫㐪࠼࡚࠸ࡿࡇ࡜ࢆ᫂
ࡽ࠿࡟ࡋࡓࠋࡉࡽ࡟ࠊᅛయ⾲㠃࡟ᑐࡍࡿỈ⁲ࡢ඲཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ୪⾜࣭ᆶ┤ᡂศࡢᦂࡽࡂࡸ⦆࿴࡟ࡘ࠸
࡚ࡶゎᯒࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊᆶ┤ᡂศ࡛ࡣࠊ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ┦ẅ࡟ࡼࡾࡑࡢ⦆࿴࡟ࡣ㸦libration 㐠ື࡟⏤᮶ࡍࡿ㸧㢧ⴭ࡞᣺ືᡂศࡀぢࡽࢀࡿࡇ࡜࡞࡝ࡶ᫂ࡽ࠿࡟ࡋࡓࠋᮏ◊✲࡛ࡣࠊࢢࣛࣇ࢙ࣥୖࡢỈ⁲ࡢศᏊ㛫㐠ື࡟ᑐࡍࡿ⡆༢࡞ࣔࢹࣝⓗィ⟬ࢆ⾜ࡗࡓࠋࡇࢀ࡟ࡼࡾࠊࡇࢀࡲ࡛ᐇ㦂ࡸィ⟬࡛ࡶ᫂ࡽ࠿࡟ࡉࢀ࡚࠸࡞࠿ࡗ
ࡓࣂࣝࢡ࡟࠾ࡅࡿࢲ࢖ࢼ࣑ࢡࢫ࡜ࡢ㐪࠸ࢆ᫂☜࡟♧ࡋࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬S-i Koda, “Numerical inference of the molecular origin of the cyanobacterial circadian rhythm”, iTHEMS

Biology Seminar, Online, Jan 28 (2021).
‫ ۻ‬ᯇᮧ ⚈ᏹ, ᩧ⸨ ┿ྖ, ͆☜⋡ⓗ࡟ᦂࡽࡄ㏿ᗘಀᩘ࡟ᇶ࡙ࡃࢱࣥࣃࢡ㉁ࡢᵓ㐀ືຊᏛゎᯒ͇, ➨ 23 ᅇ⌮ㄽ໬Ꮫウㄽ఍, ࢜ࣥࣛ࢖ࣥ, 2021 ᖺ 5 ᭶, ࣏ࢫࢱ࣮.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬S.-i. Koda and S. Saito, An alternative interpretation of the slow KaiB-KaiC binding of the cyanobacterial clock

proteins, Sci. Rep. 10, 10439 (7 pages) (2020).
C. R. Baiz , B. Báasiak, J. Bredenbeck, M. Cho, J.-H Choi, S. A. Corcelli, A. G. Dijkstra, C.-J. Feng, S. Garrett-Roe,
N.-H. Ge, M. W. D. Hanson-Heine, J. D. Hirst, T. L. C. Jansen, K. Kwac, K. J. Kubarych, C. H. Londergan, H.
Maekawa, M. Reppert, S. Saito, S. Roy, J. L. Skinner, G. Stock, J. E. Straub, M. C. Thielges, K. Tominaga, A.
Tokmakoff, H. Torii, L. Wang, L. J. Webb, and M. T. Zanni, Vibrational frequency map, vibrational spectroscopy, andintermolecular interaction, Chem. Rev. 120, 7152-7218 (2020).
‫ ۻ‬Y. Nam, M. Kalathingal, S. Saito, and J. Y. Lee, Tautomeric effect of histidine on ȕ-sheet formation of amyloid
beta 1í40: 2D-IR simulations, Biophys. J. 119, 831-842 (2020).
‫ ۻ‬N. Moritsugu, T. Nara, S.-i. Koda, K. Tominaga, and S. Saito, Molecular mechanism of acceleration andretardation of collective orientation relaxation of water molecules in aqueous solutions, J. Phys. Chem. B 124,
11730-11737 (2020).
‫ ۻ‬M. Maurya, A. K. Metya, J. K. Singh, and S. Saito, Effects of interfaces on structure and dynamics of water
droplets on a graphene surface: A molecular dynamics study, J. Chem. Phys. 154, 164704 (2021).

- 442 -

㧗⢭ᗘ㟁Ꮚ≧ែ⌮ㄽ࡟ࡼࡿග㟁Ꮚ㐣⛬࡜ゐ፹཯ᛂ࡟㛵ࡍࡿ◊✲
Theoretical studies on the photo-electronic processes and catalytic
reactions using the accurate electronic structure theories‫ۑ‬Ụཎṇ༤ࠊPei Zhaoࠊⓑ⏨ᕝ㈗ྐ
㸦ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࠊศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ㄢ㢟࡛ࡣࠊ㧗⢭ᗘ㟁Ꮚ≧ែ⌮ㄽࢆᇶ┙࡜ࡋ࡚」㞧࣭」ྜ⣔ࡢ໬Ꮫ஦㇟ࢆ◊✲ࡋࠊ᪂ࡋ࠸໬Ꮫᴫᛕࢆ

ᵓ⠏ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋ≉࡟ࠊ㧗⢭ᗘ࡞㟁Ꮚ≧ែ⌮ㄽࢆ㛤Ⓨࡋࠊග≀ᛶ⛉Ꮫࡸ୙ᆒ୍
⣔ゐ፹࡟ࡘ࠸࡚◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋᮏᖺࡣࠊ1) 㔠ᒓࢼࣀࢡࣛࢫࢱ࣮ࡢᏳᐃᛶ࡜࢟ࣛࣝග≀ᛶࡢ㉳※ࠊ2) 䝠䝗䝻䜻䝅䝣䜵䝙䝹䝖䝸䜰䝄䝇䝬䝛䞁䛾ศᏊෆບ㉳䝥䝻䝖䞁⛣ື䛻䜘䜛ᅛ┦஧㔜Ⓨග䛾㉳※ࠊ3) 䝅䜰䝜䝀䞁䛾㟁Ꮚඹ㬆≧ែ䛾᣺ືᵓ㐀䛻㛵䛩䜛⌮ㄽゎᯒࠊ4) 㻼㼐㻙㻭㼡 ྜ㔠ゐ፹䛻䜘䜛䝠䝗䝻䝅䝸䝹໬཯ᛂ䛾 㻼㼐 䝃䜲䝖䛸࿘㎶䝃䜲䝖䛾㔜せᛶࠊ5)㻼㼐㻡㻡 䛚䜘䜃 㻾㼔㻡㻡 䝘䝜⢏Ꮚ䛾㟁Ꮚᵓ㐀䛸䝥䝻䝨䞁㓟໬䛾ゐ፹άᛶ䛾┦㛵ࠊ6) 䝸䞁ಟ㣭 㻯㻴㻭 䝊䜸䝷䜲䝖䛾 㻟㻝㻼㻌 㻺㻹㻾 ໬Ꮫ䝅䝣䝖䛻䜘䜛ᵓ㐀ゎ᫂ࠊ7) 」㞧⣔㘒యゐ፹䛾⌮ㄽゎᯒ䠖䝜䝹䝪䝹䝛䞁䛾❧యຠᯝ䜢฼⏝䛧䛯䝯䝍㑅ᢥⓗ 㻯㻙㻴 άᛶ໬࡟ࡘ࠸࡚◊✲ࢆᐇ᪋ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 09 ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ SAC-CI ἲ࡜ࡑࡢ㛤Ⓨ∧࠾ࡼࡧ CAP/SAC-CI ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋDFT ἲࡸTDDFT ἲࠊCCSD(T)ἲ࡟ࡼࡿィ⟬ࢆᐇ᪋ࡋࡓࠋ୺࡟ OpenMP ࡟ࡼࡿ SMP ୪ิィ⟬ࢆ⾜ࡗࡓࠋ3◊✲┠ⓗࠊෆᐜ

3.1. 㔠ᒓࢼࣀࢡࣛࢫࢱ࣮ࡢᏳᐃᛶ࡜࢟ࣛࣝග≀ᛶࡢ㉳※㔠ᒓࢼࣀ⢏Ꮚࡢ㠀ᑐ⛠ᛶࡣ㸪ᒁᅾ⾲㠃ࣉࣛࢬࣔࣥ࡟ࡼࡿ࢟ࣛࣝග≀ᛶቑᙉ࡞࡝᪂つ࡞ᶵ⬟Ⓨ⌧࡬ࡢᒎ㛤ࡀᮇᚅ࡛ࡁࡿࠋ᭱㏆㸪ᐇ㦂ⓗ࡟୙ᩧ㓄఩Ꮚ࡛ಟ㣭ࡋࡓ㖟ࢼࣀࢡࣛࢫࢱ࣮ࡢ࢚ࢼࣥࢳ࢜㐣๫ㄏᑟࡀᡂຌࡋ㸪࢟ࣛࣝග≀ᛶࡀほࡉࢀࡓࠋࡇࡢගᏛάᛶࡢ㉳※ࢆゎ᫂ࡍࡿࡓࡵ㸪㖟ࢼࣀࢡࣛࢫࢱ࣮ࡢ㟁Ꮚᵓ㐀࡜ගᏛ≀ᛶ࡟ࡘ࠸࡚ᐦᗘỗ㛵ᩘἲ࡟ᇶ࡙ࡃ⌮ㄽ◊✲ࢆᐇ᪋ࡋࡓࠋࡑࡢ⤖ᯝ㸪ࢡࣛࢫࢱ࣮ࡢࢥ࢔ࡀ㉸ཎᏊࡢ㛢Ẇ㟁Ꮚᵓ㐀ࢆ࡜ࡾᏳᐃ࡛࠶ࡿࡇ࡜㸪෇஧Ⰽᛶࡢ㉳※ࡀ㖟ࢼࣀࢡࣛࢫࢱ࣮ࡢ࣊ࣜ࢝ࣝ࡞ᵓ㐀ࡢ㟁Ꮚ≧ែࢆ཯ᫎࡋࡓ㔠ᒓ㸫㓄఩Ꮚ㟁Ⲵ⛣ືບ㉳࡛࠶ࡿࡇ࡜ࢆ⌮ㄽⓗ࡟ゎ᫂ࡋࡓࠋ
3.2. 䝠䝗䝻䜻䝅䝣䜵䝙䝹䝖䝸䜰䝄䝇䝬䝛䞁䛾ศᏊෆບ㉳䝥䝻䝖䞁⛣ື䛻䜘䜛ᅛ┦஧㔜Ⓨග䛾㉳※ศᏊෆ䛻䠏䛴䛾 㻻㻴㻙㻺 ᆺỈ⣲⤖ྜ䜢䜒䛴䝖䝸䝇䠄㻞㻙䝠䝗䝻䜻䝅䝣䜵䝙䝹䠅䝖䝸䜰䝄䝇䝬䝛䞁䠄㻻㻴㻼㼔㼀㻭㻿䠅䛿䠈ᅛ┦䛷஧㔜Ⓨග䜢♧䛩䛜䠈㠀ᴟᛶ⁐ᾮ୰䛷䛿Ⓨග䛧䛺䛔䚹䛣䛾஧㔜Ⓨග䛿ບ㉳≧ែศᏊෆ䝥䝻䝖䞁⛣ື䠄㻱㻿㻵㻼㼀䠅䛻㉳ᅉ䛩䜛䛜䠈ศᏊෆ䛻䠏䛴䛾 㻻㻴㻙㻺 ᆺỈ⣲⤖ྜ䛜䛒䜚䠈䛭䛾ヲ⣽䛿୙᫂䛷䛒䛳䛯䚹㼀㻰㻙㻰㻲㼀 ィ⟬䛻䜘䜛 㻿㻝 ≧ែ䛾᩿⇕䜶䝛䝹䜼䞊᭤㠃䛛䜙䠈㻻㻴㻼㼔㼀㻭㻿 䛷䛿䝖䝸䜶䝜䞊䝹య䠄㻱㻱㻱㻖䠅䊻䝰䝜䜿䝖య䠄㻷㻱㻱㻖䠅䛾 㻱㻿㻵㻼㼀 䛜ᨭ㓄ⓗ䛷䛒䜚䠈ᅛ┦䛾஧㔜Ⓨග䛿䜶䝛䝹䜼䞊㞀ቨ䛾ప䛔 㻱㻱㻱㻖䛚䜘䜃 㻷㻱㻱㻖䛾䠎䛴䛾ᵓ㐀䛛䜙䛾Ⓨග䛷䛒䜛䛣䛸䠈ᾮ┦䛷䛿 㻷㻱㻱㻖≧ែ䛛䜙 㼀㻝㻛㻿㻜 䛾䝫䝔䞁䝅䝱䝹஺ᕪ䜢⤒⏤䛧䛶ᇶᗏ≧ែ䛻㠀᩿⇕⦆࿴䛧䠈஧㔜Ⓨග䛜ᾘኻ䛩䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹- 443 -

3.3. 䝅䜰䝜䝀䞁䛾㟁Ꮚඹ㬆≧ែ䛾᣺ືᵓ㐀䛻㛵䛩䜛⌮ㄽゎᯒඹ㬆≧ែ䛿‽Ᏻᐃ≧ែ䛷䛒䜚䠈㟁Ꮚ≧ែ䛷䛿‽Ᏻᐃ䜰䝙䜸䞁䠈ከ౯䜲䜸䞁䠈ෆẆ䝩䞊䝹≧ែ䛺䛹䛜䛒䜛䚹ᡃ䚻䛿䠈㟁Ꮚඹ㬆≧ែ䛾⌮ㄽ䛸䛧䛶⊂⮬䛾ᑕᙳᆺ 㻯㻭㻼㻛㻿㻭㻯㻙㻯㻵 ἲ䜔 㻭㻯㻯㻯㻌 㻿㻭㻯㻙㻯㻵 ἲ䜢㛤Ⓨ䛧䛯䚹ᮏᖺᗘ䛿䠈䝅䜰䝜䝀䞁䠄㻺㻯㻯㻺䠅䛾㐣Ώⓗ䜰䝙䜸䞁≧ែ䜢䠈㟁Ꮚ䜶䝛䝹䜼䞊ᦆኻศගἲ䠈ṇ๎໬䛥䜜䛯ゎᯒ᥋⥆⌮ㄽ䠈䛚䜘䜃」⣲䝫䝔䞁䝅䝱䝹྾཰ἲ䜢⏝䛔䛶◊✲䛧䛯䚹䠐䛴䛾ඹ㬆≧ែ䠄㻜㻚㻟㻢㻘㻌 㻠㻚㻝㻘㻌 㻡㻚㻟㻘㻌 㻣㻚㻟㻌 㼑㼂㻕䜢ゎᯒ䛧䠈㜈್௜㏆䠄㻜㻚㻟㻢㻌 㼑㼂䠅䛾 㻞䃀㼡 ≧ែ䛾᣺ືᵓ㐀䜢」⣲䝫䝔䞁䝅䝱䝹᭤㠃䛻ᇶ䛵䛔䛶ゎ᫂䛧䛯䚹㻌
3.4. 㻼㼐㻙㻭㼡 ྜ㔠ゐ፹䛻䜘䜛䝠䝗䝻䝅䝸䝹໬཯ᛂ䛾 㻼㼐 䝃䜲䝖䛸࿘㎶䝃䜲䝖䛾㔜せᛶෆ㒊䜰䝹䜻䞁䜔䃐㻘䃑㻙୙㣬࿴䜿䝖䞁䛾䝠䝗䝻䝅䝸䝹໬཯ᛂ䜢㧗ຠ⋡䛷ゐ፹䛩䜛 㻼㼐㻙㻭㼡 ྜ㔠ゐ፹䛜㛤Ⓨ䛥䜜䛯䚹䛭䛣䛷 㻼㼐㻙㻭㼡 ྜ㔠䜽䝷䝇䝍䞊䛸 㻼㼐㻙㻭㼡㻔㻝㻝㻝㻕⾲㠃䛻䛚䛡䜛ෆ㒊䜰䝹䜻䞁䛾䝠䝗䝻䝅䝸䝹໬཯ᛂ䛾཯ᛂᶵᵓ䜢ㄪᰝ䛧䛯䚹཯ᛂ䛿 㻯㼔㼍㼘㼗㻙㻴㼍㼞㼞㼛㼐 ᶵᵓ䛻ᚑ䛖䛣䛸䠈ᚊ㏿ẁ㝵䛿 㻼㼐㻙㻭㼡 ྜ㔠䜽䝷䝇䝍䞊䛷䛿䝠䝗䝻䝯䝍䝹໬䛷䛒䜚䠈㻼㼐㻙㻭㼡㻔㻝㻝㻝㻕⾲㠃䛷䛿㻿㼕㻙㻯 䛾㑏ඖⓗ⬺㞳䛷䛒䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹㻼㼐 䝃䜲䝖䛚䜘䜃࿘㎶䛾 㻼㼐㻙㻭㼡 䝃䜲䝖䛜྾╔䜔άᛶ୰ᚰ䛸䛧䛶㔜せ䛷䛒䜚䠈䛣䜜䛿ᆒ୍⣔ゐ፹䛻䛿䛺䛔୙ᆒ୍⣔ྜ㔠ゐ፹䛾≉ᚩ䛷䛒䜛䛣䛸䜢♧䛧䛯䚹㻌
3.5. 㻼㼐㻡㻡 䛚䜘䜃 㻾㼔㻡㻡 䝘䝜⢏Ꮚ䛾㟁Ꮚᵓ㐀䛸䝥䝻䝨䞁㓟໬䛾ゐ፹άᛶ䛾┦㛵⮬ື㌴᤼䜺䝇ί໬ゐ፹䠄୕ඖゐ፹䠅䛷䛿䠈㻼㼠㻘㻌 㻼㼐 䝘䝜⢏Ꮚ䛜 㻯㻻 䜔Ⅳ໬Ỉ⣲䛾㓟໬䛻᭷ຠ䛷䛒䜚䠈㻾㼔 䝘䝜⢏Ꮚ䛿㻺㻻㼤 䛾㑏ඖ䛻᭷ຠ䛷䛒䜛䚹㻼㼐㻡㻡 䛚䜘䜃 㻾㼔㻡㻡 䝘䝜䜽䝷䝇䝍䞊䛾㟁Ꮚᵓ㐀䛸䝥䝻䝨䞁㓟໬䛾ゐ፹άᛶ䛻䛴䛔䛶ㄪᰝ䛧䠈䝥䝻䝨䞁䛜䜰䜽䝻䝺䜲䞁䛸Ỉ䛻㓟໬䛥䜜䜛཯ᛂᶵᵓ䛜᭷฼䛷䛒䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹⾲㠃㓟⣲䜈䛾Ỉ⣲⛣ື䠈㻻㻴 䛾䝥䝻䝢䝺䞁䜈䛾ᨷᧁ䠈㻯㻴㻻 䛛䜙䛾Ỉ⣲⛣ື䛷㐍⾜䛩䜛䛣䛸䠈㻼㼐 䛸 㻾㼔 䜽䝷䝇䝍䞊䛾཯ᛂᛶ䛾㐪䛔䛜 㻹㻙㻻㻴 ⤖ྜ䛾ᙉ䛥䛸┦㛵䛩䜛䛣䛸䠈䛥䜙䛻 㻹 䛾 㼐㻙䝞䞁䝗䝖䝑䝥䛾఩⨨䛸┦㛵䛩䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹㻌
3.6. 䝸䞁ಟ㣭 㻯㻴㻭 䝊䜸䝷䜲䝖䛾 㻟㻝㻼㻌㻺㻹㻾 ໬Ꮫ䝅䝣䝖䛻䜘䜛ᵓ㐀ゎ᫂䝸䞁ಟ㣭䛧䛯䝊䜸䝷䜲䝖㻔㻼㻙㻯㻴㻭㻕䛿䠈Ỉ⇕ฎ⌮䛻ᑐ䛧䛶 㻺㻻 䛾 㻺㻴㻟 㑅ᢥⓗ㑏ඖ཯ᛂ䛾⪏ஂᛶ䛜㧗䛔䚹䛣䛾 㻼㻙㻯㻴㻭䛾Ỉ⇕⪏ஂᛶ䛻䛴䛔䛶 㻟㻝㻼㻌 㻹㻭㻿㻌㻺㻹㻾 䛚䜘䜃⌮ㄽィ⟬䛻䜘䜚ゎᯒ䛧䛯䚹Ỉ⇕ฎ⌮୰䛾 㻼㻙㻯㻴㻭 䛾 㻟㻝㻼㻌㻺㻹㻾 ໬Ꮫ䝅䝣䝖䛿㻙㻞㻣ࠥ㻙㻠㻞㼜㼜㼙 䛾⠊ᅖ䛷ኚ໬䛩䜛䛜䠈䛣䜜䛜Ỉ⇕ฎ⌮䛻䜘䜛䝸䞁✀䛾ᵓ㐀ኚ໬䛸┦㛵䛩䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹⌮ㄽィ⟬䛻䜘䛳䛶䝣䝺䞊䝮䝽䞊䜽ෆእ䛾䝸䞁✀䛾 㻟㻝㻼㻌㻺㻹㻾 ໬Ꮫ䝅䝣䝖䜢ィ⟬䛧䠈Ỉ⇕ฎ⌮ึᮇ䛾㻙㻠㻞㼜㼜㼙 䛾䝢䞊䜽ቑ኱䛿䝣䝺䞊䝮ෆ䛾䝅䝸䝁䜰䝹䝭䝜䝸䞁㓟ሷ㻔㻿㻭㻼㻻㻕✀䛾⏕ᡂ䛻㉳ᅉ䛧䠈Ỉ⇕ฎ⌮ᚋᮇ䛾㻙㻞㻥㼜㼜㼙 䛾䝢䞊䜽ቑ኱䛿䝣䝺䞊䝮ศゎᚋ䛾⦰ྜ䝸䞁㓟ሷ䜎䛯䛿䜰䝹䝭䝜䝸䞁㓟ሷ✀䛷䛒䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹㻌
3.7. 」㞧⣔㘒యゐ፹䛾⌮ㄽゎᯒ䠖䝜䝹䝪䝹䝛䞁䛾❧యຠᯝ䜢฼⏝䛧䛯䝯䝍㑅ᢥⓗ 㻯㻙㻴 άᛶ໬㻯㻙㻴 ⤖ྜάᛶ໬䛿䠈㻯㻙㻴 ⤖ྜ䜢 㻯㻙㻯 ⤖ྜ䜔 㻯㻙㼄 ⤖ྜ䛻ኚ᥮䛩䜛㔜せ䛺ྜᡂἲ䛷䛒䜚䠈ᵝ䚻䛺᪉ἲ䛜㛤Ⓨ䛥䜜䛶䛝䛯䚹䛣䜜䜎䛷㑄⛣㔠ᒓ㘒యゐ፹䛻䜘䜛䜸䝹䝖㻘㻌 䝟䝷 㻯㻙㻴 ⤖ྜάᛶ໬䛿ከ䛟㛤Ⓨ䛥䜜䛶䛝䛯䛜䠈䝯䝍㑅ᢥⓗ 㻯㻙㻴 άᛶ໬䛿㝈ᐃ䛥䜜䛶䛔䛯䚹᭱㏆䠈㼅㼡 䜙䛿 㻯㼍㼠㼑㼘㼘㼍㼚㼕 ཯ᛂ䜢ཧ⪃䛻䛧䛶䠈㻼㼐㻔㻵㻵㻕㘒య䛜䝜䝹䝪䝹䝛䞁䛸䝢䝸䝆䞁㦵᱁䜢᭷䛩䜛㓄఩Ꮚ䛻䜘䜚䠈䜸䝹䝖㑅ᢥⓗ䛺཯ᛂ䜢䝯䝍㑅ᢥⓗ䛺཯ᛂ䛻ኚ᥮䛷䛝䜛䛣䛸䜢ぢฟ䛧䛯䚹ᮏ◊✲䛷䛿䠈㻰㻲㼀 ィ⟬䛻䜘䛳䛶䠈䝯䝍㑅ᢥⓗ 㻯㻙㻴 ⤖ྜάᛶ໬䛾䝯䜹䝙䝈䝮䜢ゎ᫂䛧䛯䚹㻼㼐㻔㻵㻵㻕䛚䜘䜃 㻼㼐㻔㻵㼂㻕䜢⤒⏤䛩䜛ᵝ䚻䛺཯ᛂ⤒㊰䜢᳨ド䛧䠈䛣䛾䝯䝍㑅ᢥⓗ䛺 㻯㻙㻴 ⤖ྜάᛶ໬䛜䠈୺䛻䝜䝹䝪䝹䝛䞁䛾❧యຠᯝ䛻䜘䛳䛶ไᚚ䛥䜜䛶䛔䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹㻌

4

Ⓨ⾲ᐇ⦼

1) մM. Ehara and T. Shiraogawa, "Theoretical Design of Photofunctional Molecular Aggregates for Optical Properties:
An Inverse Design Approach," Japan-Norway Bilateral Symposium from Fundamental Chemistry to Porous Materials:- 444 -

Theory and Experiment, Okazaki (zoom), Japan, August 20-21, 2020.
2) մỤཎṇ༤, “୙ᆒ୍⣔ゐ፹ࡢᵓ㐀࡜ᶵ⬟࡟㛵ࡍࡿ⌮ㄽ◊✲”, ➨ 126 ᅇゐ፹ウㄽ఍ࠕࢥࣥࣆ࣮ࣗࢱ࣮ࡢ฼⏝ࠖ(≉ูㅮ₇), 㟼ᒸ(Zoom), 9 ᭶ 16-18 ᪥, 2020.

5

ฟ∧ᐇ⦼

1) մN. Takagi, M. Ehara, S. Sakaki, "Theoretical Study of NO Dissociative Adsorption onto 3d Metal Particle M55 (M =Fe, Co, Ni, and Cu): Relation between the Reactivity and Position of Metal Element in the Periodic Table", ACS Omega
6, 4888-4898 (2021).
2) մA. Takamatsu, K. Tamai, S. Hosokawa, T. Tanaka, M. Ehara, R. Fukuda, "Oxidation and Storage Mechanisms for
Nitrogen Oxides on Variously Terminated (001) Surfaces of SrFeOíį and Sr3Fe2Oíį Perovskites", ACS Appl. Mater.
Interface 13, 7216–7226 (2021).
3) M. Li, Y. Zhao, K. Yuan, Y. Han, J. Zhang, Y. Wu, M. Ehara, S. Nagase, X. Zhao, "Lithium-Bromine Exchange Reaction
on C60: First Theoretical Proposal of Stable Singlet Fullerene Carbene without Heteroatom", Org. Chem. Frontier 6, 15511562 (2021).
4) M. Ogura, Y. Shimada, T. Ohnishi, N. Nakazawa, Y. Kubota, T. Yokoi, M. Ehara, K. Shimizu, N. Tsunoji, "AFX Zeolitefor Use as a Support of NH3-SCR Catalyst Mining through AICE Joint Research Project of Industries-AcademiaAcademia", Catalysts, 11, 163-1-13 (2021).
5) P. Zhao, B. Boekfa, K. Shimizu, M. Ogura, M. Ehara, "Selective Catalytic Reduction of NO with NH3 over CuExchanged CHA, GME, and AFX Zeolites: A DFT Study", Catal. Sci. Tech. 11, 1780-1790 (2021).
6) մS. Xu, M. Li, G. Pei, P. Zhao, X. Zhao, G. Wu, C. Kong, Z. Yang, M. Ehara, T. Yang, "Stabilities, Electronic Structures,and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)2TMO and their One-Dimensional Sandwich
Molecular Wires (Cp = C5H5, C5(CH3)H4, C5(CH3)5; TM = Cr, Mo, W)", J. Phys. Chem. A,125, 721-730 (2021).
7) H. Yonezawa, T. Shiraogawa, M. Han, S. Tashiro, M. Ehara, M. Shionoya, "Mechanistic Studies on Photoinduced
Catalytic Olefin Migration Reactions at the Pd(II) Centers of a Porous Crystal, Metal-Macrocycle Framework", Chem.
Asian J. 16, 202-206 (2021).
8) մP. Zhao, M. Ehara, A. Satsuma, S. Sakaki, "Theoretical Insight into Oxidation Catalysis of Chromite Spinel MCr2O4(M=Mg, Co, Cu, and Zn): Volcano Plot for Oxygen-vacancy Formation and Catalytic Activity", J. Catal. 393, 30-41(2021).
9) մS. Kinoshita, Y. Harabuchi, Y. Inokuchi, S. Maeda, M. Ehara, K. Yamazaki, T. Ebata, "Substitution Effect on the
1RQUDGLDWLYH 'HFD\ DQG WUDQV ĺ FLV 3KRWRLVRPHUL]DWLRQ URXWH$ *XLGHOLQH WR 'HYHORS (IILFLHQW &LQQDPDWH %DVHG
Sunscreens", Phys. Chem. Chem. Phys. 23, 834-845 (2020).
10) Y. Pathak, K.S. Juneja, G. Varma, M. Ehara, U. Deva Priyakumar, "Deep Learning Enabled Inorganic Material
Generator (DING)", Phys. Chem. Chem. Phys. 22, 26935-26943 (2020).
11) մG. Pei, P. Zhao, S. Xu, X. Zhao, C. Kong, Z. Yang, M. Ehara, T. Yang, "Stabilities, Electronic Structures and Bonding
Properties of Iron Complexes (E1E2)Fe(CO)2(CNArTripp2)2 (E1E2=BF, CO, N2, CN-, or NO+)", ChemistryOpen 9, 11951201 (2020).
12 51DJ5ýXUtN07DUDQD03ROiãHN0(KDUD76RPPHUIHOG-)HGRU5HVRQDQW6WDWHVLQ&\DQRJHQ1&&1
Phys. Chem. Chem. Phys. 22, 23141-23147 (2020).
13) Y.-X. Zhao, K. Yuan, Y.-B. Han, M.-Y. Li, M. Ehara, X. Zhao, "Theoretical Insight into Thermodynamically Optimal
U@C84: Three-Electron Transfer Rather Than Four-Electron Transfer", Inorg. Chem. 59, 12650-12658 (2020).
14) M.-Y. Li, Y.-X. Zhao, Y.-B. Han, K. Yuan, K.-N. Zhang, Y.-Q. Chen, M. Ehara, S. Nagase, X. Zhao, "CovalentInteractions Depended on the Distances between Metals and Fullerenes for Thermodynamically Stable M@C78 (M = La,
Ce, and Sm)", Inorg. Chem. Frontier, 7, 2538-2547 (2020).
15) R. N. Dhital, K. Nomura, Y. Sato, S. Haesuwannakij, M. Ehara, H. Sakurai, "Pt-Pd Nanoalloy for the Unprecedented
Activation of Carbon-Fluorine Bond at Low Temperature", Bull. Chem. Soc. Jpn. 93, 1180-1185 (2020).
16) մT. Shiraogawa, M. Ehara, "Theoretical Design of Photofunctional Molecular Aggregates for Optical Properties: An
Inverse Design Approach", J. Phys. Chem. C 124, 13329-13337 (2020).
17) H. Yoshida, J. Kumar, M. Ehara, Y. Okajima, F. Asanoma, T. Kawai, T. Nakashima, "Impact of Enantiomeric Ligand
Composition on the Photophysical Properties of Chiral Ag29 Nanoclusters", Bull. Chem. Soc. Jpn. 93, 834-840 (2020).
18) մB. Zhu, M. Ehara, S. Sakaki, "Propene Oxidation Catalysis and Electronic Structure of M55 Particle (M= Pd or Rh):
Differences and Similarities between Pd55 and Rh55", Phys. Chem. Chem. Phys. 22, 11783-11796 (2020).
19) մQ. M. Phung, Y. Komori, T. Yanai, T. Sommerfeld, M. Ehara, "Combination of a Voronoi-type Complex Absorbing- 445 -

Potential with the XMS-CASPT2 Method and Pilot Applications", J. Chem. Theory Comput.16, 2606-2616 (2020).
20) M. Promkatkaew, S. Suramitr, T. Karpkird, M. Ehara, S. Hannongbua, "DFT/TD-DFT Investigation on the
Photoinduced Electron Transfer of Diruthenium and Viologen Complexes", J. Lumin. 222, 117121-1-9 (2020).
21) M.-Y. Li, Z.-B. Gao, Y.-B. Han, Y.-X. Zhao, K. Yuan, S. Nagase, M. Ehara, X. Zhao, "Potential Molecular
Semiconductor Devices: Cyclo-Cn (n = 10 and 14) with Higher Stabilities and Aromaticities than Acknowledged CycloC18", Phys. Chem. Chem. Phys. 22, 4823-4831 (2020).
22) մT. Sadhukhan, A. Junkaew, P. Zhao, H. Miura, T. Shishido, M. Ehara, "Importance of the Pd and Surrounding Site
in Hydrosilylation of Internal Alkynes by Palladium-Gold Alloy Catalyst", Organometallics, 39, 528-537 (2020).
23) մS. Sartyoungkul, M. Ehara, H. Sakurai, "Time-Dependent Density Functional Theory Investigation of Excited State
Intramolecular Proton Transfer in Tris(2-hydroxyphenyl)triazasumanene", J. Phys. Chem. A, 124, 1227-1234 (2020).
24) H. Yoshida, M. Ehara, U. Deva Priyakumar, T. Kawai, T. Nakashima, "Enantioseparation and Chiral Induction in Ag29
Nanoclusters with Intrinsic Chirality", Chem. Sci. 11, 2394-2400 (2020).
25) S. Hu, P. Zhao, W. Shen, M. Ehara, Y. Xie, T. Akasaka, X. Lu, "Crystallographic Characterization of Er2C2@C80-88:
Cluster Stretching with Cage Elongation", Inorg. Chem. 59, 1940-1946 (2020).

- 446 -

ࢱࣥࣃࢡ㉁จ㞟ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ
Molecular simulation of protein aggregation‫ۑ‬ዟᮧஂኈ㸪ఀ⸨ᬡ㸪㇂ᮏ຾୍㸪ᒣෆோႛ㸪ᐑ⃝࿴ஂ㸪⚟ཎ኱㍤㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗ㸪ෆᐜ
ࢱࣥࣃࢡ㉁ࡣ㏻ᖖ㸪⏕యෆ࡛ࡑࢀࡒࢀࡀṇࡋࡃᢡࡾࡓࡓࡲࢀ㸪ࡑࡢᶵ⬟ࢆ⥔ᣢࡋ࡚࠸ࡿ㸬ࡋ࠿ࡋ㸪⪁໬࡞࡝ࡢ⌮⏤࡟ࡼࡾࡑࡢ⃰ᗘࡀ㧗ࡃ࡞ࡿ࡜จ㞟ࡋ㸪࢜ࣜࢦ࣐࣮ࡸ࢔࣑ࣟ࢖ࢻ⥺⥔ࢆᙧᡂࡍࡿ㸬࢜ࣜࢦ࣐࣮ࡣ⌫≧㸪࢔࣑ࣟ࢖ࢻ⥺⥔ࡣ⥺⥔≧࡟จ㞟ࡋ࡚࡛ࡁࡓ≀㉁࡛࠶ࡿ㸬ࡇࢀࡽࡢࢱࣥࣃࢡ㉁ࡢจ㞟యࡣ⣙  ✀㢮ࡢࣄࢺࡢ⚄⤒ኚᛶ⑌ᝈ࡜㛵㐃ࡋ࡚࠸ࡿࠋ౛࠼ࡤ㸪࢔ࣝࢶࣁ࢖࣐࣮⑓ࡣ࢔࣑ࣟ࢖ࢻ ȕ㸦$ȕ㸧࣌ࣉࢳࢻࡢจ㞟యࡀཎᅉ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ$ȕ ࣌ࣉࢳࢻࡀ࢔ࣝࢶࣁ࢖࣐࣮⑓ࢆᘬࡁ㉳ࡇࡍᶵᵓࢆゎ᫂ࡍࡿࡓࡵ㸪ᡃࠎࡣࡇࢀࡲ࡛࡟࠸ࡃࡘ
࠿ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࡁࡓࠋලయⓗ࡟ࡣ $ȕ ࣌ࣉࢳࢻࡢࣔࣀ࣐࣮ࠊࢲ࢖࣐࣮ࠊ࢜ࣜࢦ࣐࣮ࠊ࢔࣑ࣟ
࢖ࢻ⥺⥔ࡸࡑࡢ◚ቯ࡟㛵ࡍࡿศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࡁࡓࠋ௒ᖺᗘࡣࠊ㉥እ⥺࣮ࣞࢨ࣮࡟ࡼࡿ$ȕ ࢔࣑ࣟ࢖ࢻ⥺⥔ࡢ◚ቯ࠾ࡼࡧ࣏ࣜࣇ࢙ࣀ࣮ࣝ࡟ࡼࡿ $ȕ ࣇࣛࢢ࣓ࣥࢺࡢจ㞟㜼ᐖ࡟ࡘ࠸࡚◊✲ࡋࡓࠋ㉥እ⥺࣮ࣞࢨ࣮࡟ࡼࡿ࢔࣑ࣟ࢖ࢻ⥺⥔◚ቯࡢ㠀ᖹ⾮ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
࢔࣑ࣟ࢖ࢻ⥺⥔ࡣ㉥እ⥺࣮ࣞࢨ࣮ࢆ↷ᑕࡍࡿࡇ࡜࡟ࡼࡾ◚ቯࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡇࢀࡲ࡛ࡣ࣮ࣞ

ࢨ࣮↷ᑕ࡟ࡼࡾ࢔࣑ࣟ࢖ࢻ⥺⥔ࡀ◚ቯࡉࢀࡿ࣓࢝ࢽࢬ࣒ࡣ௨ୗࡢࡼ࠺࡟⪃࠼ࡽࢀ࡚ࡁࡓࠋ࢔࣑ࣟ࢖
ࢻ⥺⥔ࡢ୺㙐ࡣ C=O ࡜ N̽H ࡢ㛫࡛ศᏊ㛫Ỉ⣲⤖ྜࢆసࡿࡇ࡜࡛ࠊศᏊ㛫 ȕ ࢩ࣮ࢺᵓ㐀ࢆᙧᡂࡋ࡚
࠸ࡿࠋࡇࡢ C=O ࡢఙ⦰᣺ືࡢ࿘ᮇ࡜୍⮴ࡍࡿ࿘ᮇࡢ㉥እ⥺࣮ࣞࢨ࣮ࢆ↷ᑕࡍࡿ࡜ C=O ࡢఙ⦰᣺ື
ࡀቑᖜࡉࢀࠊỈ⣲⤖ྜࡀ◚ቯࡉࢀࡿࡇ࡜࡛⤖ᯝ࡜ࡋ࡚ศᏊ㛫 ȕ ࢩ࣮ࢺᵓ㐀ࡶ◚ቯࡉࢀࡿ࡜⪃࠼ࡽࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊ᭱㏆ࡢᐇ㦂࡛஝⇱ࡋࡓ࢔࣑ࣟ࢖ࢻ⥺⥔ࡣ࣮ࣞࢨ࣮ࢆ↷ᑕࡋ࡚ࡶ◚ቯࡉࢀࡎࠊỈศࢆྵࢇ࡛࠸࡞࠸࡜◚ቯࡉࢀ࡞࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢᐇ㦂஦ᐇࡣỈศᏊࡀ࢔࣑ࣟ࢖ࢻ⥺⥔ࡢ◚ቯ࡟Ỵᐃⓗ࡟㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࡇ࡜ࢆព࿡ࡋ࡚࠸ࡿࠋࡇࡢỈศᏊࡢᙺ๭ࢆゎ᫂ࡍࡿࡓࡵࠊᡃࠎ
ࡣ㉥እ⥺࣮ࣞࢨ࣮ࢆ↷ᑕࡋ࡚ Aȕ ࡢ࢔࣑ࣟ࢖ࢻ⥺⥔ࢆ◚ቯࡍࡿ㠀ᖹ⾮ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᅗ 1

Aȕ ࣌ࣉࢳࢻࡢ㛫ࡢỈ⣲⤖ྜࡢ◚ቯ㐣⛬ࢆ♧ࡍࢫࢼࢵࣉࢩࣙࢵࢺࠋ(a) ࣮ࣞࢨ࣮↷ᑕ๓࡟ࡣ Aȕ ࣌ࣉࢳࢻ㛫ࡢỈ⣲⤖ྜࡀᙧᡂࡉࢀ࡚࠸ࡿࠋ(b) ࣮ࣞࢨ࣮ࡀ↷ᑕࡉࢀࡿ࡜Ỉ⣲⤖ྜࡢ኱㒊ศࡀ◚ቯࡉࢀࡿࠋ(c) ศᏊ㛫Ỉ⣲⤖ྜࡀ◚ቯࡉࢀࡓ㝿࡟ࡑࡢ㝽㛫࡟അ↛ỈศᏊࡀධࡾ㎸ࡴ࡜㸦Ⅼ⥺࡛ᅖࡲࢀࡓ㡿ᇦ㸧Aȕ ࣌ࣉࢳࢻ㛫ࡢỈ⣲⤖ྜࡢ෌ᙧᡂࡀ㜼ᐖࡉࢀࡿࠋ

- 447 -

ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊḟࡢࡼ࠺࡟ỈศᏊࡀࢱࣥࣃࢡ㉁จ㞟యࢆ◚ቯࡍࡿ᪂ࡓ࡞࣓࢝ࢽࢬ࣒ࢆⓎぢࡋࡓࠋࡲࡎ࢔࣑ࣟ࢖ࢻ⥺⥔୰ࡢ C=O ࡜ N̽H ࡀᙧᡂࡍࡿศᏊ㛫Ỉ⣲⤖ྜ㸦ᅗ 1(a)㸧ࡣࠊ࣮ࣞࢨ࣮ࣃࣝ
ࢫࡀ↷ᑕࡉࢀࡿࡓࡧ࡟ษ᩿ࡉࢀࡿ㸦ᅗ 1(b)㸧
ࠋࡋ࠿ࡋࠊࡇࢀࡽࡢ⤖ྜࡣከࡃࡢሙྜࡑࡢ↷ᑕᚋ࡟⮬↛࡟෌ᙧᡂࡉࢀࡿࠋࡔࡀࠊC=O ࡜ N̽H ࡢ㛫࡟ࡓࡲࡓࡲỈศᏊࡀධࡾ㎸ࡴ࡜Ỉ⣲⤖ྜࡢ෌ᙧᡂࡀ㜼ᐖࡉࢀ࡚ࡋࡲ࠺㸦ᅗ 1(c)㸧
ࠋつ๎ⓗ࡟୪ࢇ࡛࠸ࡿỈ⣲⤖ྜ࡟࡜ࡗ࡚ࡑࡢࡼ࠺࡞ሙᡤࡣḞ㝗࡜࡞ࡾࠊࡑࡇ࠿ࡽศᏊ㛫 ȕ ࢩ࣮ࢺࡢ඲࡚ࡢỈ⣲⤖ྜࡀษ᩿ࡉࢀࡿࠋࡇࡢࡼ࠺࡟࣮ࣞࢨ࣮↷ᑕ࡟ࡼࡿ࢔࣑ࣟ࢖
ࢻ⥺⥔ࡢ◚ቯ࡟࠾ࡅࡿỈศᏊࡢᙺ๭ࢆึࡵ࡚ゎ᫂ࡋࡓࠋ
ࢱࣥࣃࢡ㉁ࡢᵓ㐀ࢆỈศᏊࡀ◚ቯࡍࡿ౛࡜ࡋ࡚ᅽຊኚᛶࡸ㉸㡢Ἴ࡟ࡼࡿࡶࡢࡀࡇࢀࡲ࡛࡟▱ࡽࢀ࡚࠸ࡓࡀࠊࡇࢀࡽࡢ࣓࢝ࢽࢬ࣒࡛ࡣỈศᏊࡀ✚ᴟⓗ࡟ࢱࣥࣃࢡ㉁ࡢỈ⣲⤖ྜࢆ◚ቯࡋ࡚࠸ࡿࠋࡇ
ࢀ࡟ᑐࡋࠊ௒ᅇⓎぢࡋࡓ࣓࢝ࢽࢬ࣒࡛ࡣ࢔࣑ࣟ࢖ࢻ⥺⥔ࡢศᏊ㛫Ỉ⣲⤖ྜࡀ◚ቯࡉࢀࡓ㝿ࠊࡑࡢ㝽㛫࡟ࡓࡲࡓࡲỈศᏊࡀධࡾ㎸ࡴ࡜࢔࣑ࣟ࢖ࢻ⥺⥔ࡀ◚ቯࡉࢀ࡚ࡋࡲ࠺࡜࠸࠺Ⅼ࡛ࠊࡇࢀࡲ࡛▱ࡽࢀ࡚࠸ࡓỈศᏊࡢᶵ⬟࡜ࡣ඲ࡃ␗࡞ࡿࡶࡢ࡛࠶ࡿࠋ
ࡉࡽ࡟ࠊ࣮ࣞࢨ࣮࡛࢔࣑ࣟ࢖ࢻ⥺⥔ࢆ◚ቯࡍࡿ࡜ Į ࣊ࣜࢵࢡࢫᵓ㐀ࡀከࡃᙧᡂࡉࢀࡿࡇ࡜ࡶⓎぢࡋࡓࠋࡑࡢ⌮⏤ࢆ✺ࡁṆࡵࡿࡓࡵࠊĮ ࣊ࣜࢵࢡࢫᵓ㐀ࠊศᏊ㛫 ȕ ࢩ࣮ࢺᵓ㐀ࠊࣛࣥࢲ࣒ࢥ࢖ࣝᵓ㐀ࢆྲྀࡗ࡚࠸ࡿ࡜ࡁࡢ C=O ఙ⦰᣺ືࡢඹ᣺࿘Ἴᩘࢆィ⟬ࡋࡓࠋࡑࡢ⤖ᯝࠊĮ ࣊ࣜࢵࢡࢫᵓ㐀ࡢඹ㬆࿘ἼᩘࡣศᏊ㛫 ȕ ࢩ࣮ࢺᵓ㐀ࡢࡶࡢ࡜␗࡞ࡿࡓࡵࠊศᏊ㛫 ȕ ࢩ࣮ࢺᵓ㐀ࡢඹ㬆࿘Ἴᩘ࡟ྜࢃࡏࡓ࣮ࣞ
ࢨ࣮ࡢᙳ㡪ࢆཷࡅ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡑࡢࡓࡵศᏊ㛫 ȕ ࢩ࣮ࢺᵓ㐀ࡀ◚ቯࡉࢀࡿ௦ࢃࡾ࡟ Į ࣊ࣜࢵࢡࢫᵓ㐀ࡀቑຍࡍࡿࡇ࡜ࢆ✺ࡁṆࡵࡓࠋĮ ࣊ࣜࢵࢡࢫᵓ㐀ࡣจ㞟ࡋ࡟ࡃ࠸ࡓࡵࠊ࢔࣑ࣟ࢖ࢻ࣮ࢩ
ࢫᝈ⪅࡟↷ᑕࡍࡿ࡜ࠊจ㞟ࡋࡓࢱࣥࣃࢡ㉁ࢆゎ㞳ࡉࡏࠊయእ࡟᤼ฟࡉࢀࡸࡍࡃ࡛ࡁࡿ࡜ᮇᚅࡉࢀࡿࠋ
ᑗ᮶࢔࣑ࣟ࢖ࢻ࣮ࢩࢫࡢ἞⒪࡟㉥እ⥺࣮ࣞࢨ࣮ࢆ฼⏝ࡍࡿ◊✲ࡀ㐍ࡵࡽࢀ࡚࠸ࡿࡀࠊᮏ◊✲ࡣࡑࡢࡓࡵࡢ⌮ㄽⓗ࡞᰿ᣐ࡜࡞ࡿࡶࡢ࡛࠶ࡿࠋ

$ȕ ࣇࣛࢢ࣓ࣥࢺ࡜࣏ࣜࣇ࢙ࣀ࣮ࣝࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ$ȕ ± ࣌ࣉࢳࢻ࡜࣏ࣜࣇ࢙ࣀ࣮ࣝࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡶ⾜ࡗࡓࠋ࣏ࣜࣇ࢙ࣀ࣮ࣝ࡟

ࡣ $ȕ ࣌ࣉࢳࢻࡢจ㞟ࢆ㜼ᐖࡍࡿຠᯝࡀ࠶ࡿࡇ࡜ࡀศ࠿ࡗ࡚࠾ࡾ㸪࢔ࣝࢶࣁ࢖࣐࣮⑓࡟ᑐࡍࡿ⸆๣
ೃ⿵ศᏊ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿ㸬࣏ࣜࣇ࢙ࣀ࣮ࣝ࡟ࡣ࠸ࡃࡘࡶ✀㢮ࡀ࠶ࡿࡀ㸪᭱㏆ࡢᐇ㦂࡟ࡼࡿ࡜$ȕ ࡢจ㞟ࡍࡿຠᯝࡀ㧗࠸࣏ࣜࣇ࢙ࣀ࣮ࣝ࡜ࡋ࡚࣑ࣜࢭࢳࣥ㸦0\U㸧ࡸࣟࢫ࣐ࣜࣥ㓟㸦5$㸧ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ
ࡇࢀࡽࡢ໬ྜ≀ࡀ$ȕ ࡢจ㞟ࢆ㜼ᐖࡍࡿᶵᵓࡣⰋࡃศ
࠿ࡗ࡚࠸࡞࠸ࠋ
ࡑࡇ࡛ᡃࠎࡣ$ȕ ± ࣌ࣉࢳࢻ࡜ࡇࢀࡽࡢ࣏ࣜ
ࣇ࢙ࣀ࣮ࣝࢆྵࡴ
⣔ࡢࣞࣉࣜ࢝⨨᥮ศᏊືຊᏛࢩ࣑ࣗ ᅗ 2 D  ࣞࣉࣜ࢝஺᥮ἲࡢᴫᛕᅗࠋ E  ࣞࣉࣜ࢝⨨᥮ἲࡢᴫᛕᅗࠋࣞࣉࣜ࢝஺᥮ἲ࡛
࣮ࣞࢩࣙࣥࢆ⾜ࡗࡣ  ࡘࡢࣞࣉࣜ࢝ࡢ㛫࡛ ᗘࢆ஺᥮ࡍࡿࡀࠊࣞࣉࣜ࢝⨨᥮ἲ࡛ࡣ  ࡘ௨ୖࡢࣞࣉ
ࣜ࢝ࡢ㛫࡛ ᗘࢆධࢀ᭰࠼ࡿࠋ

- 448 -

ࡓࠋࣞࣉࣜ࢝⨨᥮ἲࡣ➹⪅ࡽࡀ㛤Ⓨࡋࡓᣑᙇ࢔ࣥࢧࣥࣈࣝἲࡢ୍ࡘ࡛㸪ࣞࣉࣜ࢝஺᥮ἲࡢᨵⰋ∧࡛࠶ࡿ㸬ࡇࢀࡽࡢ᪉ἲ࡛ࡣ⣔ࡢࢥࣆ࣮㸦ࡇࢀࢆࣞࣉࣜ࢝࡜࿧ࡪ㸧ࢆ࠸ࡃࡘ࠿⏝ពࡋ㸪ࡑࢀࡒࢀࡢࣞࣉ
ࣜ࢝࡟␗࡞ࡿ ᗘࢆ๭ࡾᙜ࡚ࡿ㸬ࣞࣉࣜ࢝஺᥮ἲ࡛ࡣᅗ  D ࡢࡼ࠺࡟ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ㏵୰࡟ ࡘࡢࣞࣉࣜ࢝ࡢ㛫࡛ ᗘࢆ஺᥮ࡍࡿヨ⾜ࢆ⾜࠺㸬ࡇࡢヨ⾜ࡢ㝿࡟ࣔࣥࢸ࢝ࣝࣟἲࡢ୍ࡘ࡛࠶ࡿ࣓ࢺ
࣏ࣟࣜࢫἲ࡟ࡼࡾ஺᥮ࡍࡿ࠿ྰ࠿ࢆุᐃࡍࡿ㸬୍᪉㸪ࣞࣉࣜ࢝⨨᥮ἲ࡛ࡣᅗ  E ࡢࡼ࠺࡟  ࡘ௨ୖࡢࣞࣉࣜ࢝ࡢ㛫࡛ᗘࢆධࢀ᭰࠼ࡿ㸦⨨᥮ࡍࡿ㸧㸬ࡇࡢ㝿㸪ẚ㍑ⓗ᭱㏆㛤Ⓨࡉࢀ᭱ࡶຠ⋡ࡢⰋ࠸ࣔࣥࢸ࢝ࣝࣟἲ࡛࠶ࡿㄶゼ࣭⸨ᇽἲࢆ⏝࠸ࡿ㸬ࡇࡢ᪉ἲࢆ⏝࠸ࡿࡇ࡜࡛⏕యศᏊࡢᵓ㐀࡟㛵ࡋ࡚⤫ィⓗ࡟ࡼࡾಙ㢗ᛶࡢ㧗࠸ࢹ࣮ࢱࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡇࡢ᪉ἲࢆ౑ࡗ࡚ $ȕ ± ࣌ࣉࢳࢻ  ᮏ࡜࣏ࣜࣇ࢙ࣀ࣮ࣝ  ศᏊࢆྵࡴ⣔ࡢ඲ཎᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࡇࡇ࡛ࡣࠊ ✀㢮ࡢ࣏ࣜࣇ࢙ࣀ࣮ࣝ㸪0\U ࡜ 5$ ࢆ⏝࠸㸪ࡇࢀࡽࡢ࣏ࣜࣇ࢙ࣀ࣮ࣝࡀ $ȕ ± ࣌ࣉࢳࢻ࡜࡝ࡢࡼ࠺࡟
⤖ྜࡍࡿ࠿ほᐹࡋࡓࠋྛ⣔ࡣ $ȕ ± ࣌ࣉࢳࢻ  ᮏ࡜࣏ࣜࣇ࢙ࣀ࣮ࣝ  ศᏊࠊ࠾ࡼࡧỈศᏊ࠿ࡽ࡞ࡗ࡚࠸ࡿࠋ5$ ࢆྵࡴ⣔࡟ࡘ࠸࡚ࡣ࢝࢘ࣥࢱ࣮࢖࢜ࣥ࡜ࡋ࡚ 1D࢖࢜ࣥࡶຍ࠼ࡓࠋࡇࡇ࡛ࡣᮎ➃ࡢຠᯝࢆῶࡽࡍࡓࡵ࡟ $ȕ ± ࣌ࣉࢳࢻ㹌ᮎ➃࠾ࡼࡧ㹁ᮎ➃ࢆࡑࢀࡒࢀ࢔ࢭࢳࣝᇶ࠾ࡼࡧ㹌࣓ࢳࣝᇶ࡟ࡼࡗ࡚ࣈࣟࢵࢡࡋࡓࠋ
ࡑࡢ⤖ᯝࠊᅗ  ࡢࢫࢼࢵࣉࢩࣙࢵࢺ࡟♧ࡍࡼ࠺࡟ࠊ$ȕ ± ࣌ࣉࢳࢻ࡜࣏ࣜࣇ࢙ࣀ࣮ࣝࡀ⤖ྜࡋࡓᵓ㐀ࡀぢࡽࢀࡓࠋࡇࡇ࡛ $ȕ ± ࣌ࣉࢳࢻ࡜ྛ࣏ࣜࣇ࢙ࣀ࣮ࣝࡢ㛫ࡢᴃ෇ࡣ୧⪅㛫࡟ᙧᡂࡉࢀࡓỈ⣲⤖ྜࢆ♧ࡍࠋ0\U ࢆྵࡴ⣔࡛ࡣᅗ  D㸧ࡢࡼ࠺࡟  ␒┠ࡢࢢࣝࢱ࣑ࣥ㓟㸦*OX㸧ࡢ࢝ࣝ࣎࢟ࢩࣝᇶ㸦±&22㸧ࡀ 0\U ࡢࣄࢻࣟ࢟ࢩᇶ㸦±2+㸧࡜ࡼࡃỈ⣲⤖ྜࢆᙧᡂࡋ࡚࠸ࡓࠋ5$ ࢆྵࡴ⣔࡛ࡣᅗ  E㸧ࡢࡼ࠺࡟ *OX ࡢ࢝ࣝ࣎࢟ࢩࣝᇶࡀ 5$ ࡢࣄࢻࣟ࢟ࢩᇶ࡜ࠊࡲࡓࠊ ␒┠ࡢࣜࢪࣥ
㸦/\V㸧ࡢ࢔࣑ࣥᇶ㸦±1+㸧ࡀ 5$ ࡢ࢝ࣝ࣎࢟ࢩࣝᇶ࡜Ỉ⣲⤖ྜࢆࡼࡃᙧᡂࡋ࡚࠸ࡓࠋ
ࡇࢀࡽࡢ࢔࣑ࣀ㓟ṧᇶࡀ $ȕ ± ࣌ࣉࢳࢻ࡜ࢥࣥࢱࢡࢺࡋ࡚࠸ࡿ☜⋡ࢆ⤫ィⓗ࡟ィ⟬ࡋࡓࠋ0\Uࡢ⣔࡛ࡣ ࡢ☜⋡࡛ *OX ࡜ࢥࣥࢱࢡࢺࡋ࡚࠸ࡓࠋࡋ࠿ࡋ㸪$ȕ ± ࣌ࣉࢳࢻࡢ௚ࡢṧᇶࡣ 0\U࡜ࡣ࡯࡜ࢇ࡝ࢥࣥࢱࢡࢺࡋ࡚࠸࡞࠿ࡗࡓࠋ୍᪉ࠊ5$ ࡢ⣔࡛ࡣ *OX ࡜ 㸣ࠊ/\V ࡜ 㸣ࡢ☜⋡࡛ࢥࣥࢱࢡࢺࡋ࡚࠸ࡓࠋࡑࡢ௚ࡢṧᇶ࡛ࡣ࡯࡜ࢇ࡝ 5$ ࡜ࢥࣥࢱࢡࢺࡋ࡚࠸࡞࠸ࠋ$ȕ ± ࣌ࣉࢳࢻࡣจ㞟ࡍࡿ㝿࡟ *OX ࡢ࢝ࣝ࣎࢟ࢩࣝᇶ࡜ /\V ࡢ࢔࣑ࣀᇶ࡜ࡢ㛫ࡢ㟼㟁ᘬຊ࡟ࡼࡾ཯ᖹ⾜ ȕ ࢩ࣮ࢺࢆᙧᡂࡍࡿࠋࡋࡓࡀࡗ࡚ࠊ*OX ࡸ /\V ࡢഃ㙐࡟ 0\U ࡸ 5$ ࡀ⤖ྜࡍࡿ࡜ $ȕ ± ࣌ࣉࢳࢻࡢจ㞟ࡣᢚไࡉࢀࡿࡢ࡛࠶ࡿࠋ

ᅗ 3 (a) Aȕ(16-22)࣌ࣉࢳࢻ࡜࣑ࣜࢭࢳࣥࡢ⣔࠾ࡼࡧ (b) Aȕ(16-22)࣌ࣉࢳࢻ࡜ࣟࢫ࣐ࣜࣥ㓟ࡢ⣔࡟࠾ࡅࡿ඾
ᆺⓗ࡞ࢫࢼࢵࣉࢩࣙࢵࢺࠋAȕ(16-22)࣌ࣉࢳࢻ࡜ྛ࣏ࣜࣇ࢙ࣀ࣮ࣝࡢ㛫࡟࠶ࡿᴃ෇ࡣ୧⪅㛫࡟ᙧᡂࡉࢀ
ࡓỈ⣲⤖ྜࢆព࿡ࡍࡿࠋ

- 449 -

Ⓨ⾲㸪ฟ∧ᐇ⦼

‫ۻ‬+2NXPXUD6*,WRK.1DNDPXUDDQG7.DZDVDNL³5ROHRIZDWHUPROHFXOHVLQWKHODVHULQGXFHGGLVUXSWLRQRIDP\ORLG ILEULOV REVHUYHG E\ QRQHTXLOLEULXP PROHFXODU G\QDPLFV VLPXODWLRQV´ - 3K\V &KHP % 125  ±‫ۻ‬0<DPDXFKLDQG+2NXPXUD³'LPHUL]DWLRQRIĮV\QXFOHLQIUDJPHQWVVWXGLHGE\LVRWKHUPDOLVREDULFUHSOLFDSHUPXWDWLRQPROHFXODUG\QDPLFVVLPXODWLRQ´-&KHP,QI0RGHO61  ±
‫ۻ‬70L]XNDPL6)XUX]DZD6*,WRK66HJDZD7,NXUD.,KDUD+2NXPXUD+5RGHUDQG.0DNL
³(QHUJHWLFVDQGNLQHWLFVRIVXEVWUDWHDQDORJFRXSOHGVWDSK\ORFRFFDOQXFOHDVHIROGLQJUHYHDOHGE\DVWDWLVWLFDOPHFKDQLFDODSSURDFK´3URF1DWO$FDG6FL86$117  7+'1JX\HQ6*,WRK+2NXPXUDDQG07RPLQDJD³6WUXFWXUDOEDVLVIRUSURPLVFXRXVDFWLRQRIPRQRWHUSHQHVRQ753FKDQQHOV´&RPPXQ%LRO 4   SDJHV -.DPPDUDEXWU30DKDODSEXWU+2NXPXUD3:ROVFKDQQDQG75XQJURWPRQJNRO³6WUXFWXUDOG\QDPLFVDQG
VXVFHSWLELOLW\RIDQWL+,9GUXJVDJDLQVW+%9UHYHUVHWUDQVFULSWDVH´-%LRPRO6WUXFW'\Q39  ±
.8FKLGD7.LWD0+DWWD6*,WRK+2NXPXUD07RPLQDJDDQG-<DPD]DNL³,QYROYHPHQWRISRUHKHOL[LQ
YROWDJHGHSHQGHQWLQDFWLYDWLRQRI7530FKDQQHO´+HOL\RQ7  H SDJHV //H1JX\HQ1JRF6*,WRK36RPSRUQSLVXWDQG+2NXPXUD³5HSOLFDSHUPXWDWLRQPROHFXODUG\QDPLFVVLPXODWLRQVRIDQDP\ORLGȕ ± SHSWLGHDQGSRO\SKHQROV´&KHP3K\V/HWW758   SDJHV - 450 -

 













Molecular simulations for exploring conformational spaces
occupied by multi-domain proteinscharacterized by structural flexibility
Ŀ ïtŒx ¾Ŷ¾ģÀġħÚŷ
1 ġħĝĜ Ė (Tr`Jŕ(»)Ńè([hBrŘĴ;enV[hBrTr`Jŕ$"þĺ" :(ĐÒ)¾([hBr¥ŏĜ'Ř¡:$'79ĖďÀĜ&þĺ>ěå" :$# 9þĺěē'ũ")[
hBrť(ĞÇŞĸº¡:7 &¼ņý&MrbFhsOkrº¢>**  ûŗº¢)[hBr> &ůµŝř¡(ĻĘÍ'Å?
# :$'79®ĺ$&" :5($ÖÂ;:ûŗº¢$þĺěēŘŦ:ŋĲ&hH]Rg)vì# :"Š¾asgċćçz6
NMR ąĬ>ųĮÄ¾ûŗň÷$ĪŉĭģÀ>ĳ2¯=:$'79enV[hBrTr`Jŕ(UB\fWJ&ĩ ûŗº¢(ų¡>E\PDXAJQ(ŇČ8ňì¾(¡Ĝûŗº¢$þĺěē$(ŦŘ>ì
8':$)Ė²¾ģÀ':şń&ŎŰ# :   }ÌÍ)Đ'ùûŗ>ß enV[hBrTr`Jŕ(Ł# :Ü 'ğĝ:Ù);1#Ü '"¦¾¾¡ÀOfjosOkr>ŀ$#ûŗUB\fJQ$þĺ(ŘŦ'"tÂ(ĠŅ>Ñ"té#(7 &@dpsV#)¼ņý& 4 Āûŗº¢1#±4ûŗUB\fJQ>Á')á ;" & $Š¾asgċćçz&%(ÃŴĜ&ł8ì8$&"" :1Ü )ü&¾$(Ğ|ė'7
"(þĺ>ěē" :ŉĭmSsQ(ı(4Ğ|ė¾$(ŘŦ1#>ª9Û $#" & ċćx' "þĺ:Ü (ä>āá :4')Ü $(Ğ|ė¾>±4"79 Ē7ûŗĨť>ãú:Óń :
 enV[hBrTr`Jŕ$"(Ü (þĺ)Ė 'ĲĽ6CBnQ&%(ęďũ';8>âŧ:7 'ĚOQXg>ĆÔ¢:
$# :Ü '7:Ěþĺě¡;:ũ')Ü¦7,EbDJTs
¾$(Ğ|ėÓńv®ÿ# 9Ü¦>ŌőÕ·EbDJTs¾- 451 -

$Ĵ¯:ůµ(đ×'8(#©í;" :5($Ĺ 8;:
(ŋĲ&hH]Rg)ì8$&" & Ü )Ü¦6EbDJTs¾$(Ğ|ė'"[hBr(ĞÇŞĸº¢:$Ġ8;" :$8Ü¦Ĵ¯(ÐŮÜ ¾(ùûŗ>Ŗ"ś'ĸ:~¾$(Ğ|ėŝ(MrbFhsOkr'@pQXmWJ'º¢>58®ĺÔĹ 8;:(þû')¾>Ų:įš(¡Ĝûŗ5ĈŦ=" :®ĺÔ : õġħ#)Ü $Ğ|ė¾$(Ń¯ (¾¡ÀOfjosOkr>
Ãê(MrbFhsOkrĨť>ãú:¾¡ÀOfjosOkr'7"Ü¦$EbDJTs¾$(Ń¯ ÏØ' Ü ¾(ûŗº¢>á :$>Ŋ2Ü ¾(Ü¦Ōő8EbDJTsþĺěē'ļ:¾þ
û(ŋĲ>ì8':$>ĝà2 ġħéąŉĭéą Ũ'ă¾>Şĸĕ¹x'Ü¦7,EbDJTs¾$(Ń¯ >ÏØ
Ü >Şĸ"¾¡ÀOfjosOkr>ŀ ( 4 Āûŗ(¡×>ŇÆ(ġħ#) 10 u¦¾ĥÍ(¾İ(OfjosOkr>Ãŀ
;1# 3 eBJpĤ'7-¦¾¾¡ÀOfjosOkr>ŀ"5Š¾asgċćçz(ÃŴYsT>ē:'ļ" & #79Ţî
ť'ĉ:OfjosOkr>ŀ Ü (MrbFhsOkrĨť>¤'ãú
:$>Ŗ"Ü (ûŗº¢>ŏ/ Ü ) Fc ůµ(įš(ûŗ»üÔ>ò" :įšûŗ'¿ Fc (MrbFhsOkrĨť(Ś >ì8':4'èĦű(ę&:KlBM
bFsg>ò:Ü '"¾¡ÀOfjosOkr>Ãê8'¾¡ÀOfjosOkr'7"Ñ8;MrbFhsOkr@rNrcn>Š¾asgċćçz6 NMR (YsT'¶! "ÃŴĜ'ł;'79Ü¦6EbDJTs¾$(Ń¯>āĢ'á :$>Ŋ2

ÏØ'

Ü

¾(ûŗº¢(ä (ġħ#)ı 10 u¦¾8ûØ;:ă¾>±3Ü (İ(¾¡ÀOfjosOkr>ŀ&8'Ü $EbDJTs¾(Ń¯ 'Çœ>ÞÎ¾¡ÀOfjosOkr) AMBER dpKlg`WLsP7, GLYCAM06 ¸>ė "Ãŀ- 452 -

3 ġħØø ŁĜ&Ü # :ĚKpcmr GŶIgGŷ( Fc ůµ')tÇ( N ´įšĴ¯" :(įš'ğĝ"įš(ûŗ_mEsOkr$ Fc (MrbF
hsOkrĨť(ĞŦŦ>ì8':4įš>±4 Fc (¾¡ÀO
fjosOkr>ÃêĴðûŗ>¶'įšûŗ>æº Fc > in silico#iYmrK"óûŗ$"ă¾>Ŭ='±?¦¾OfjosOk
r>eBJpĤQLsn#ÃêFc (MrbFhsOkrĨť>ãúFc(yń&įš)ŭŜôĪ(IlJZsQĂ¶$bMsQĂ¶(òč'7:_
mEsOkr>ò: 2 õš N ´įš# :;8(įš>±3 Fc (¾¡ÀOfjosOkr$ NMR ŉĊ(YsT'¶! "IlJZsQĂ¶(ŧ§
Fc (MrbFhsOkrĨť'¨0 ø>ŏú(ĴøIlJZsQĂ¶>ŧ§:$#Fc ¾(įš-Tr`Jŕť(Ğ|ė^WZqsJ
º¡;'" Fc ( 4 Āûŗ5º¢:$ì8$&(7& Fc ( 4 Āûŗº¢)IgG $EbDJTs¾$(Ğ|ė'ÐŮ>w :5($ĹÆ;:8' ¾¡ÀOfjosOkr#Ñ8;ûŗ@rNrcn(x'Ū;Õ·>ō2ň4(ĔŐĜ@dpsVą(Ťě'5ª9ĳ?4 ěŁÃķ1){Â
1. Saeko Yanaka, Rina Yogo, Hirokazu Yagi, and Koichi Kato, “Impacts of the N-glycan
variation of antibodies on their dynamic structures of functional relevance”, ī 58 ³ëõĖďďĔÀÌ 2020 Ì 9 ñ 18 ëŶGrlBrŤŷŹ3S-4-4.
2. Œx¾ďĔİľÀŝ½Ŕ«Ŕ , “Ü ( 3 Āûŗ$Ğ|ė(UB\fJQ>ňì:éą(Ťě$Ü (ŵþĺ¢.(ÉŤ”, ëõľÀ ī
141 Ì 2021 Ì 3 ñ 27 ëGrlBrŤ ŹS06-2.

- 453 -

5 ĎÃķ1){Â
1. Tokio Watanabe, Hirokazu Yagi, Saeko Yanaka, Takumi Yamaguchi, and Koichi Kato,“Comprehensive characterization of oligosaccharide conformational ensembles with
conformer classification by free-energy landscape via reproductive kernel Hilbert
space”, Phys. Chem. Chem. Phys. in press (2021)
2. Tatsuya Suzuki, Saeko Yanaka, Tokio Watanabe, Genwei Yan, Tadashi Satoh,

Hirokazu Yagi, Takumi Yamaguchi, and Koichi Kato, “Remodeling of theoligosaccharide conformational space in the prebound state to improve lectin-binding
affinity”, Biochemistry, 59, 3180-3185 (2020).
3. Œx¾, Ŀït, “Ńū&įš(MrbFhsOkrĨť(ãú$æºŉĭ$ÃŴ(ĵ¯'7:@dpsV”, ¢ÀŸ75, 30-71 (2020).
4. ĿïtŸÊ¬ÝÃ, “įš(¡Ĝûŗň÷”, įšĖďÀŶ£Ë ŸĿ+<ŸţöĄĶŷŸ°­È¼ÀĎŸpp.109-110 (2020).
5. Saeko Yanaka, Rina Yogo, and Koichi Kato, “Biophysical characterization of dynamic
structures of immunoglobulin G”, Biophys. Rev., 12, 637–645 (2020).

- 454 -

ศᏊືຊᏛィ⟬࡜㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿᾮయࡢศᏊ㛫┦஫స⏝ࡢ◊✲
Molecular interactions in liquid phase studied by molecular dynamics
simulations and quantum chemical calculations‫ۑ‬㛗ᆏ ᑗᡂ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗᡃࠎࡣᾮయ୰ࡢศᏊ㛫┦஫స⏝ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊศᏊ◊ UVSOR-III ࡟࠾࠸࡚ᵝࠎ࡞⁐ᾮヨᩱࡢ㌾ X⥺྾཰ศගᐃࢆ⾜ࡗ࡚ࡁࡓࠋࢫ࣌ࢡࢺࣝࡢ໬ᏛࢩࣇࢺࡣศᏊ㛫┦஫స⏝࡟⏤᮶ࡍࡿࡓࡵࠊ⁐ᾮࡢศᏊືຊ

Ꮫ(MD)ィ⟬࡜㔞Ꮚ໬Ꮫ࡟ᇶ࡙ࡃෆẆບ㉳ィ⟬ࢆ⾜࠸ࠊᐇ㦂⤖ᯝ࡜ẚ㍑ࡍࡿࡇ࡜࡛ࠊࡑࡢᒁᡤᵓ㐀ࢆ᫂ࡽ࠿࡟
ࡍࡿࡇ࡜ࢆᮏ◊✲ࡢ┠ⓗ࡜ࡍࡿࠋᮏᖺᗘࡣ࢚ࢱࣀ࣮ࣝỈ⁐ᾮࡢศᏊ㛫┦஫స⏝ࡢ⃰ᗘ౫Ꮡᛶࢆㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲMD ィ⟬ࡣ GROMACS 5.1.4 ࢆ⏝࠸࡚⾜ࡗࡓࠋ࢚ࢱࣀ࣮ࣝศᏊࡢ࣏ࢸࣥࢩࣕࣝ࡟ࡣ OPLSAA ࢆ⏝࠸࡚ࠊỈࡢ࣏ࢸࣥࢩࣕࣝ࡟ࡣ TIP-5P ࢆ⏝࠸ࡓࠋศᏊ㓄⨨ࡣ 1 ps ࡈ࡜࡟཰㞟ࡍࡿࡢࢆ 100 ns ࡢ㛫⾜ࡗࡓࠋMD ィ⟬୰ࡢศᏊ㓄⨨࠿ࡽ⮬సࡢゎᯒࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ࠊ࢚ࢱࣀ࣮ࣝ࡜Ỉࡢ㛫ࡢືᚄศᕸ㛵ᩘ(RDF)ࢆồࡵࡓࠋ

3◊✲ᡂᯝ␗࡞ࡿࣔࣝẚ⋡ࡢ࢚ࢱࣀ࣮ࣝỈ⁐ᾮࡢ MD ィ⟬ࢆ⾜ࡗࡓࠋࡑࡇ࠿ࡽࠊ࢚ࢱࣀ࣮ࣝศᏊࡢ࢚ࢳࣝᇶྠኈࠊ࢚

ࢳࣝᇶ࡜Ỉࡢ㛫࡞࡝ࡢ RDF ࡢ⃰ᗘ౫Ꮡᛶࢆồࡵࡓࠋ᭦࡟ࠊRDF ゎᯒ࠿ࡽᚓࡽࢀࡓࣔࢹࣝᵓ㐀࡟࠾ࡅࡿෆẆບ㉳ࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࡓࠋ⌧ᅾࠊ㌾ X ⥺྾཰ศගᐇ㦂࡛ᚓࡽࢀࡓࢫ࣌ࢡࢺࣝኚ໬࡜ィ⟬⤖ᯝࢆẚ㍑ࡍࡿࡇ࡜࡛ࠊ࢚ࢱࣀ࣮ࣝỈ⁐ᾮ୰ࡢศᏊ㛫┦஫స⏝ࡢ⃰ᗘ౫Ꮡᛶ࡟ࡘ࠸࡚ヲ⣽࡟ㄪ࡭࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] ‫“ ۻ‬Molecular Interactions in Liquids Probed by Soft X-ray Absorption Spectroscopy in Transmission Mode”, M.
Nagasaka, Conference on Laser and Synchrotron Radiation Combination Experiment 2020 (LSC 2020), OPTICS &PHOTONICS International Congress 2020, Online Conference, 2020/4/23. (ᣍᚅㅮ₇)[2] ‫͆ ۻ‬ᨺᑕගࢆά⏝ࡋࡓ⁐ᾮࡢ㌾X⥺྾཰ศගἲࡢ㛤Ⓨ࡜ᛂ⏝͇, 㛗ᆏᑗᡂ, Ⲉᇛ኱Ꮫ ௧࿴2ᖺᗘ➨1ᅇ㔞Ꮚ⥺⛉Ꮫࢭ࣑ࢼ࣮, ࢜ࣥࣛ࢖ࣥ఍㆟, 2020/7/30. (ᣍᚅㅮ₇)[3] ‫͆ ۻ‬ᾮయࡢ㌾X⥺྾཰ศගἲࡢࣂ࢖࢜◊✲࡬ࡢᒎᮃ͇, 㛗ᆏᑗᡂ, 㟁ẼᏛ఍ ග࣭㔞Ꮚࢹࣂ࢖ࢫ◊✲఍ࠕ་⒪࣭ࣂ࢖࢜◊✲࡟᭷ຠ࡞࢖ࣥࢱ࣮ࣇ࢙࣮ࢫ࡜㔞Ꮚࣅ࣮࣒ᛂ⏝ࡢᮍ᮶ࠖ, ࢜ࣥࣛ࢖ࣥ఍㆟, 2020/12/8. (ᣍᚅㅮ₇)[4] ‫͆ ۻ‬㌾X⥺྾཰ศගἲ࡟ࡼࡿ⁐ᾮࡢ໬Ꮫ⌧㇟ࡢゎ͇᫂, 㛗ᆏᑗᡂ, ➨34ᅇ᪥ᮏᨺᑕගᏛ఍ᖺ఍, ࢜ࣥࣛ࢖ࣥ఍㆟, 2021/1/9. (ᣍᚅㅮ₇)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] ‫“ ۻ‬⢭ᐦཌࡉไᚚ࡟ࡼࡿᾮయࡢ㌾X⥺㏱㐣྾཰ศගᐃ”, 㛗ᆏᑗᡂ, ᑠᮡಙ༤, ᪥ᮏ≀⌮Ꮫ఍ㄅ 75(8),496-503 (2020).

- 455 -

*)'(#%&,!

          


;

1

+"$! 

# :'; *  $ /= 5 "  (+ >102?

 

<7 !6

02.ă§1[yhPĻ²Fă§TV_r/Bh{^,*½9/Ąè.ă§āķFă9*

B [yhPĻ²1HqeŅń/Ã 7-%Ĝ0?.ÿÉ@ĥĉċ/ÏA%%8AþĆċ.}ëĕçŀFÁË*êĤFĉā B Ì0ďēQv{k+1 ĕçŀÁË=êĤĉā/Ō Bè.ĴFĕ*.@[yhPĻ²FTV_p_I]P/İĘê~+`SJyŘ$C@·ō/-0?
/ B0·ő/?Aĵ6B,Hkx{\/?AďēF·Ù*B C8+0ďē/*êĤF2,8!ģÊ"! ÏA%%909/Ýł %ĕçŀFµ/Yx@`SJy B,/?A
à90ĕçŀF`SJy B%;0ĂĶ,ÎĪ0ŊĉFĩ(% $0Ğä Ö¤ B»Í?3ŏ»ÍĎĄ/Ō Bňçŀv{vFĉĮ $C@0v{vFĄB,+ »Ízŏ»ÍĎĄÖ¤*°ûçŀF´¶

B?.[yhPĻçŀĳİ¡ĂFçę% ċ/1 0ňçŀv{vFù% ?/ĳİ%çŀ0śëçŀ=v{k0ŉFð; ĳİ«FÓ ňçŀFçę B $*çę%ňçŀF´¶

B?/ňçŀŖHqeŅńŗFĳİ B 0, »Íċ/1ĳİ«+ð¶%śëçŀ=v{kF´¶

B?. ŏ»Íċ/1ĈïÈĎĄė+ŜëçŀF´¶

B?. HqeŅńFĳİ B 0ĳİ¡ĂFĄB,+ C8+/ lu]PV?3 β VatybØ@.Bè.aoxU{FÐ)[yhPĻçŀ/)* ¡²wmv0Ě¿+`SJy B,/Ë*% Ħ¦ö,/ 0?/*ĳİC% ¼[yhPĻ1ĥûą0[yhPĻ,1Ć«Ś Ý<Œü´¶ÈFĒ¿1 129.8¼[yhPĻ (a) ü®È/BħÈVnPav0®

(b) Ý<Œü´¶ÈFĒ®È÷¼[yhPĻ0çŀ Ő?3~@Į%çŀ xJTyí¬ļħ JZxJTyí¬iyPħ guyí¬ğħ+īC*B

- 456 -

.A Śřř +<®È.Œü´¶ÈFß*%Ŗ«Śaŗ .# ¼[yhPĻ1æ;*Œü´¶ÈFĒ 0&D
C8+0[yhPĻ0ÏAć9ďē@, [yhPĻÏAć:%;/1, ĈïÈHqeŅí¬ĈïÈĎĄ/?(*[yhPĻŃ/Ŏ8A, $0ňUQZ{hWv0?/¸/h]NyQB,ņĭ+B,ģ@C*% ·ō, ~Ĳ0ĳİ¡ĂFĄ*ĳİC% ¼[yhPĻ/<, ŏ»ÍĎĄ/?B´¶0Ğä,*, ĈïÈí¬ň/?B¸.h]NyQĳİC*%$0|Ø+, ĳİ¡Ă/Ą%ňçŀv{v1, ĈïÈňh]NyQ,?A<»Íňçŀ0ņĭÈFĒ¨*%áďē+1 C8+/ĳİ% ¼[yhPĻ0', Ý<Œü´¶ÈŖ®È÷¿ŚŜř ŗFĒ¼[yhPĻFĄ*Ŗ«Śbŗ, $0[yhPĻŃ0ĈïÈňh]NyQF­%,/, [yhPĻ0ÏAć9Ĥ=´¶È-0?/®EB0FİĘê,·ő Ø+ĵ6B,/?A¼[yhP

Ļ0´¶È0Ľú1[yhPĻŃ0ĈïÈh]NyQ/?B0 $C,< »Íňçŀ/?B0
C@FÛ@/ B,Fčċ,*ďēFĩ(%2

02&93&C8+/ĳİ%¼[yhPĻ0', Ý<Œü´¶ÈFĒ¼[yhPĻFĄ*0[yhPĻŃ0 xJTy(L)?3JZxJTyŖIŗí¬F ?ARJW0ºguyí¬ŖVŗ/ġÔ B
,/?A ĈïÈh]NyQF­%,0´¶È0® F ħÈFĄ%·ő/?Aĵ6%
xJTy,JZxJTyŚří¬F£guy/ġÔ%Śř0®ĆFĬ C@0ü´¶ÈFø¶%,D ®Ć Bí¬,/´¶È0A¤Ć.B,E(%Ŗ« 2ŗ $+ í¬F®

«ś ®Ćí¬,0´¶È0®

(a)xJTyí¬ (L) ?3JZxJTyí¬ (I) 0ġ (b) guyí

¬ (V) /ġÔ%,0ü´¶È0® Tm Ŕ+Ē%0®Ć0MuUcv0 ¼[yhPĻü®ÈÜĠ- 457 -

Ć%,0´¶È0® Fð;*BĭªFÒB%;/ İĘêFĄ* ®ĆÂ0LdvO{® ,ĈïÈh]NyQ>BG&,0Ñé/.AB,ÇECB®ĆÂ0çŀ/BĔô0¯0®
F Rosetta kxQtrFĄ*İĘ ´¶È0® Ŗ®È÷¿0® ŗ,0ĎŌFĵ6% 8% £0í¬®Ć0çŀ/*-0?.ĎĄF*B0FİĘ ĎĄ,´¶È0® ,0Ď
ŌFĵ6% C@0İĘ1*İĘêXy[{FĄ*ĩEC%3 02%
 8! ®ĆÂ0LdvO{® F Rosetta FĄ*İĘ ´¶È0® Ŗ®È÷¿ Tm 0® ŗ,0ĎŌFĵ6% ĎŌ1.(%Ŗ«Ŝaŗ ë/ ĈïÈh]NyQ>BG&,0Ñé/.AB,
ÇECB®ĆÂ0çŀ/BĔô0¯0® F Rosetta FĄ*İĘ ´¶È0® ,0ĎŌ
Fĵ6% C<8%ĎŌ1.(%Ŗ«Ŝbŗ $+ ë/ £0í¬®Ć0çŀ/*0?.ĎĄF*B0FİĘ ĎĄ,´¶È0® ,0ĎŌFĵ6*9%,D ń/ñ(*Łí¬,Ŀí¬0Ø,ĎĄ*Bfj0?.ĈïÈí¬Ŗ«ś «Ŝc 0ļ=MwyUŗ´¶È/¯ĸĀ*B,Û@/.(%







●



оϬ͘ϭϬ



䠎ḟᵓ㐀㛫┦஫స⏝ᩘ


●







●

оϬ͘ϭϱ

●

●





●

●

ZŽƐĞƩĂ空洞スコアZŽƐĞƩĂエネルギー変化 ''

●




●



●






●

●

●


●

●





оϬ͘Ϯϱ

●






●

●
●







оϬ͘ϮϬ

●



оϬ͘ϯϬ
●



оϲ

оϰ


' оϮ«Ŝ è.Ñé,ü´¶È®

Ĕô0¯0®



оϲ

оϰ


' 

оϮ

,0ĎŌ (a) ®ĆÂ0LdvO{®
















㐲䛔

㏆䛔























(b) ®ĆÂ0çŀ/B(c) ń/ñ(*Ł 2 ëçŀ,Ŀśëçŀ,0ĎĄ0Õ í¬0ħ1«ś0`{[,¹Æ B ļ=MwyU+Ē í¬ ń/ñ(*Łí¬,Ŀí¬0Ø,ĎĄ
Bfjí¬ @/ C@ 10 0xJTy JZxJTy*Fguy/ġÔ% [yhPĻŃ07,GŖ88 ŕŗguy@.B ¼[yhPĻ VAL88 FĬ ÈĻFĵ6%,D ĈïÈh]NyQ¯
±EC*B/<E@! 100 ~0´¶ÈFĒ åĐîœò/?Bçŀð¶Fĩ(%,D ®Ć,¥è0çŀ5,ÏAć:,Û@/.(% 0,@¼[yhPĻ0Œü´¶È1 ĈïÈí¬0¸.ňh]NyQ,?A:D »Íňçŀ/Ľª*B,Ē¨C%- 458 -

4 ,84  # $ ¢ĺÀ  ;4035%7-323*239)04537)-2*30(6&<()2393()6-+2  !350(32*)5)2')32537)-2'-)2')
,<6-'63*537)-293087-32Ř¾Þì
# $ ¢ĺÀ;4035%7-323*239)04537)-2*30(6&<()2393()6-+2, Ė  ©ÚáăýýĂ³¾TyoU
KrBiomolecular Design to Control their Functions, MytJyŊ   ¾  Þ.
# $ ¢ĺÀ ¤Ăĳİ/?B[yhPĻńĔŋ0ÒĝŝNMR /?Bçŀð¶1$0ĢŇČ ĨĊď
Xqc{ăě NMR ò0ÝĠ ¬đ@³4Ý× NMR įãò çŀįã0ĥ , MytJyŊ
 ¾

Þ.

 [4] ºâĹó±EC%êĤFÅõ"*©ľ²s{[{FHxV_u]PÄ BĖ  ©²s{[{ıĶMytJyŊŘ   ¾5

)4

Þ.

  # $368+--(%%2%&)-23%2(3+%  =)2393()6-+23*%00367)5-''327530-273537%5<13735 %6)&<5)6735-2+0367*82'7-32> &-3;-9(3-,7746(3-35+        
[2] 3+%"%1%1373368+-3&%<%6,-8+-/-8.-:%5%3+%  =3&867*30(-2+3*%
()2393()6-+2)(-()%04537)-2)9)2:-7,13673*7,)'35)187%7)(739%0-2)>     [3]       - 459 -

    







The search for production pathways of interstellar ring molecules)¢ wÝS\bmdTVm[o]n`o*Â|Þ

¼¿¹¸*sÎ¬>D*¦A §u1¤t5P=-O+hn^nDÓÆÎ¬0MÙÀÙBJÒB7

O4?1u0;=-O1*ÖÁÄRIhn_cbkl  1¤t5P:(!&'" +4
PBLN*hn^nK²ËÜ­x¨ÄRp?6:x×xBLN¦AC²°u1³5
PO{È1½5P=-O+
4CL.AÉª-²°§uD*¦,A>±µ¡CJC1¤t5P=-OJCC*ÙÀÙ>

C³ÅÕDÊ2Q0;=-A-C>*9C³ÅÕR7O+

¼¿©*ÐÃ©Ý"$"'!$#$('%%!# Þ R´-=j[WlzJÇ6=    CzÅÕRÑF:+G8D    >ÅÕR6:+¯BÏÛzBº¹6*ÙÀÙC¥r«>J×Ì6.Oz
ReaXSag6:+



¼¿£
   CzÅÕR6*-2<0CÏÛz1}5P:ÝßÞ+pC    EC»y~EDz

ÚA6>×Ì7O+Ù>J×Ì6.O¨Äqvz1-2<0MP=-O1*ÙÀÙ>L2¤t
5P=-OZSnj[WlÝÞ?*fUclj[WlÝ  ÞCÏÛzJ·Í5P:+4PD* RÔ®B    CÙÀÙB/3O³Ø¾CHAM8*Chn^n* C­x¨ÄCYi\bkoB
ÁÄA@C¶!Rqv7OÅÕ Wc

RÏ7OCBnbBANO+DÐÃ"R:ÐÃBL;=%R5MB¤&6**(¸A'B<AO+- 460 -

5P:hn_cbklCzÅÕC.*ÏÛzR½6:+»y~BDzÚA6>×Ì7

O+·$#G:D ¢w-   ±>³,+u1>O0 Zn [t#G:D

A6

- 461 - Ý    Þ)

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ࢖࢜ࣥᾮయࡢ◊✲Molecular Dynamics Study of Ionic Liquids‫ ⏣▼ۑ‬ᖸᇛ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ

ᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊจ⦰⣔࡟࠾ࡅࡿ◊✲ᑐ㇟ࡢ࠺ࡕࠊ≉࡟࢖࢜ࣥᾮయ࡟ࡘ࠸࡚ࡢ⌮ㄽ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋ
ලయⓗ࡟ࡣࠊ୺࡟ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓゎᯒ࡜◊✲ࢆ⥆ࡅ࡚ࡁ࡚࠸ࡿࠋ௒ᖺᗘࡣ௨ୗࡢ㸰ࡘࡢ◊✲┠ⓗ࡟ἢࡗ࡚◊✲ࢆィ⏬࣭㐙⾜ࡋࡓࠋෆᐜ࡟ࡘ࠸࡚௨ୗ࡟ሗ࿌ࡍࡿࠋ
㸦㸯㸧࢖࢜ࣥᾮయࡣ㝧࣭㝜࢖࢜ࣥ࠿ࡽ࡞ࡾࠊᐊ

࡟࠾࠸࡚ᾮయࡢᣲືࢆ♧ࡍࠋ㝧࣭㝜࢖࢜ࣥࡢ⤌ࡳྜࢃࡏ࡟

ࡼࡾᛶ㉁ࡢ␗࡞ࡿ✀㢮ࡢ࢖࢜ࣥᾮయࡀྜᡂ࡛ࡁࡿࡓࡵࠊᵝࠎ࡞⏝㏵࡟㐺ࡋࡓ࢖࢜ࣥᾮయࡢ◊✲ࡀ㐍ࡵࡽࢀ࡚࠸ࡿࠋ㸯ࡘࡢ౛࡜ࡋ࡚ᣲࡆࡽࢀࡿࡢࡀࢭ࣮ࣝࣟࢫ㧗ศᏊࡢࡼ࠺࡞Ỉࡸ᭷ᶵ⁐፹࡟㞴⁐࡞≀㉁࡟ᑐࡋࠊ፹㉁ࢆ
᭰࠼ࡿࡇ࡜࡟ࡼࡗ࡚⁐ゎ཯ᛂ᮲௳ࡢ㣕㌍ⓗ࡞ᨵၿࢆヨࡳࡿ◊✲࡛࠶ࡿࠋࢭ࣮ࣝࣟࢫࡢศゎ཯ᛂࢆ⏝࠸࡚ࢢࣝࢥ࣮ࢫ࡞࡝ࡢⅣ໬Ỉ⣲໬ྜ≀ࢆ‽ഛࡍࡿ㐣⛬ࡣ๓ฎ⌮㐣⛬࡜࿧ࡤࢀ࡚࠸ࡿࠋࡇࡢ㐣⛬ࢆ࠸࠿࡟ຠ⋡ࡼࡃ⾜࠺࠿ࡀࡑࢀ࡟⥆ࡃࣂ࢖࢜⇞ᩱྜᡂ࣭⢭〇࡟⨨࠸࡚㔜せ࡟࡞ࡿࠋࡇࢀࡲ࡛ࡢᐇ㦂◊✲࡟ࡼࡾࠊỈࡸᚑ᮶ࡢ᭷ᶵ⁐፹࡟ẚ࡭࡚࢖࢜ࣥᾮయࡣࢭ࣮ࣝࣟࢫྵ᭷ࡢࣂ࢖࣐࢜ࢫࡢ⁐ゎࢆ㣕㌍ⓗ࡟ಁ㐍ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟ࡉࢀ࡚ࡁ࡚
࠸ࡿࠋࡋ࠿ࡋࠊ࢖࢜ࣥᾮయ࡟ࡼࡿࢭ࣮ࣝࣟࢫࡢ⁐ゎ㐣⛬ࡀ࡝ࡢࡼ࠺࡞࣓࢝ࢽࢬ࣒࡛㉳ࡇࡗ࡚࠸ࡿࡢ࠿ࡣ᫂ࡽ
࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋᚑࡗ࡚ࠊ࢖࢜ࣥᾮయࡢࡼ࠺࡞͆᪂ࡋ࠸ᾮయ͇࡜࿧ࡤࢀࡿ⁐፹࡟ࡘ࠸࡚ࠊᚑ᮶ࡢ௚ࡢ⁐፹࡟㛵ࡍࡿ▱ぢࢆά࠿ࡋࡓୖ࡛⌮ㄽ◊✲ࢆࡋ࡚࠸ࡃࡇ࡜ࡀࠊᐇ㦂࣭⌮ㄽ◊✲཮᪉࡬ࡢ㔜せ࡞ᶫΏࡋ࡜࡞ࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋ᫖ᖺᗘࡢィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡛ࡢィ⟬ᶵ฼⏝࡟ࡼࡿศᏊືຊᏛἲࢆ⏝࠸ࡓ◊✲࠿ࡽࠊ㧗ศᏊࢭ࣮ࣝࣟࢫ㛫࡟ാࡃࢭ࣮ࣝࣟࢫศᏊ㛫ࠊ࠾ࡼࡧศᏊෆỈ⣲⤖ྜࡣỈ୰࡟㍑࡭࡚࢖࢜ࣥᾮయ୰࡛ࡣ㝧࣭㝜࢖࢜ࣥࡢാࡁ࡟ࡼࡗ࡚ᙅࡵࡽࢀࠊࡇࡢࡇ࡜ࡀ࢖࢜ࣥᾮయ୰࡛ࢭ࣮ࣝࣟࢫࡢศゎࡀಁ㐍ࡉࢀࡸࡍ࠸ཎᅉࡢ㸯ࡘ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ㝜࢖࢜ࣥ࡟ࡼࡾಁ㐍ࡉࢀࡿศᏊෆỈ⣲⤖ྜࡢゎ㞳ࡀศᏊ㛫Ỉ⣲⤖ྜࡢゎ㞳ࡼࡾࡶඃඛࡋ࡚࠾ࡇࡿࡇ࡜ࡀィ⟬⤖ᯝࡼࡾ♧ࡉࢀࠊᐇ㦂◊✲࡟ࡼࡿᣦ᦬࡜ࡶ୍⮴ࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋࡲࡓࠊ㝧࢖࢜ࣥࡢᙺ๭࡟ࡘ࠸࡚ࡶࠊゎ㞳ࡋࡓࢭ࣮ࣝࣟࢫࣇ࢓࢖ࣂ࣮ࡢ࿘㎶࡟ศᏊ㛫┦஫స⏝㸦୺࡟ YDQGHU:DDOV┦஫స⏝㸧ࢆ௓ࡋ࡚Ꮡᅾࡋࠊ⁐ゎ㐣⛬࡟ᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ㸦“Theoretical Investigation of
Dissolution and Decomposition Mechanisms of a Cellulose Fiber in Ionic Liquids”, Tateki Ishida, J. Phys. Chem. B
2020, 124, 3090-3102.㸧௒ᖺᗘࡣ◊✲ࢆࡉࡽ࡟㐍ࡵ࡚ࢭ࣮ࣝࣟࢫࡢᣲື࡜࢖࢜ࣥᾮయ࡜ࡢ┦஫స⏝ࢆゎᯒࡋࡓࠋຍ࠼࡚㝜࢖࢜ࣥࡢ✀㢮ࢆኚ࠼ࡓᩘ✀㢮ࡢ࢖࢜ࣥᾮయ࡟ࡘ࠸࡚㧗ศᏊࢭ࣮ࣝࣟࢫࡢ⁐ゎ࣭ศ㞳㐣⛬ࡢ㐪࠸ࢆ◊✲ࡋࠊᗘຠᯝ࡟ࡘ࠸࡚ࡶศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆィ⏬ࡋࠊᐇ⾜ࡋࡓࠋࡇࢀࡽࡢィ⟬⤖ᯝ࠿ࡽࠊࢭ࣮ࣝࣟࢫࡢ⁐ゎ࣭ศ㞳࡟㛵ࡋ࡚཯ᛂᛶࡢ㧗࠸࢖࢜ࣥᾮయࢆ᥈⣴ࡍࡿୖ࡛ࡢ᭱㐺࡞㝧࣭㝜࢖࢜ࣥࡢ⤌ࡳྜࢃࡏࡢᣦᶆࢆィ⟬⤖ᯝ࠿ࡽᢳฟ
ࡍࡿẁ㝵࡟ࡲ࡛◊✲ࢆ㐍ࡵࡿࡇ࡜ࡀ࡛ࡁࡓࠋ
- 462 -㸰 ࢖࢜ࣥᾮయࡣ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢ࣌࢔ࢆኚ࠼ࡿࡇ࡜࡛ከ✀ከᵝ࡞≀ᛶࡸ≀⌮໬Ꮫⓗᣲືࡀほᐹࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ≉࡟  ୡ⣖ึ㢌࠿ࡽከࡃࡢᐇ㦂◊✲࡟ࡼࡿሗ࿌ࡀ⾜ࢃࢀ࡚ࡁࡓࠋࡇࡢࡼ࠺࡞≧ἣࡢࡶ࡜ࠊ⌮ㄽ◊✲ࡢほⅬ࠿ࡽࡣከࡃࡢ࢖࢜ࣥᾮయࡀ♧ࡍ≀ᛶࡸ≀⌮໬Ꮫⓗᣲື࡟ඹ㏻ࡍࡿᛶ㉁ࢆぢฟࡋࠊ⣔⤫ⓗ࡟ゎᯒࡍࡿࡇ࡜ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋ ࢖࢜ࣥᾮయࡢከᵝ࡞≉ᛶࡢ㸯ࡘ࡟⦆࿴㐣⛬ࡸືⓗ୙ᆒ୍ᛶ࡞࡝ࡢືⓗ࡞ᣲືࡀ࠶ࡿࠋࡇࡢᣲື࡟ࡘ࠸࡚ࡣࠊ
㏆ᖺࠊከࡃࡢᐇ㦂ࡸ⌮ㄽ◊✲࡟ࡼࡿ⤖ᯝ࠿ࡽࠊ࢞ࣛࢫ࡞࡝࡟≉᭷ࡢືⓗ୙ᆒ୍ᛶࡀ࢖࢜ࣥᾮయ࡛ࡶ⌧ࢀࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚ࡣ࠸ࡿࡀࠊศᏊࣞ࣋ࣝ࡟࠾ࡅࡿヲ⣽࡟ࡘ࠸࡚ࡣࡲࡔࢃ࠿ࡗ࡚࠸࡞࠸ࠋ᫖ᖺᗘࡣィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬ᶵࢆ฼⏝ࡋࠊศᏊືຊᏛἲࢆ⏝࠸ࡓᩘⓒࢼࣀ⛊࣮࢜ࢲ࣮ࡢ㛗᫬㛫ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ◊✲ࢆ㐍ࡵࡓࠋ◊✲⤖ᯝࡼࡾࠊ࢖࢜ࣥᾮయࡢ㟼ⓗᵓ㐀ࡀ࢖࢜ࣥᾮయࡢ୙ᆒ୍ᛶ࡟ࡼࡗ࡚኱ࡁࡃᙳ㡪ࡉࢀ࡚࠸ࡿ
ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋཎᅉࡢ୍ࡘ࡜ࡋ࡚ࠊ㝧࣭㝜࢖࢜ࣥ⮬㌟ࡢ✵㛫ⓗ࡞ศᕸ࡜୧࢖࢜ࣥࡢ㓄ྥࡀ኱ࡁࡃ㛵ಀࡋ࡚࠸ࡿࡇ࡜ࡀゎࡗࡓࠋࡲࡓࠊືⓗ୙ᆒ୍ᛶࢆᘬࡁ㉳ࡇࡍ㸯ࡘࡢཎᅉ࡜ࡋ࡚ࡢ㝧࣭㝜࢖࢜ࣥ⮬㌟ࡢ㐠ື㸦ศᏊෆ㐠ືࡶྵࡵࡓ㐠ື㸧ࡢኚ໬ࡀ⪃࠼ࡽࢀࠊ࢖࢜ࣥศᏊࡢ༠ྠ㐠ືࡀ኱ࡁࡃ㛵୚ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
௒ᖺᗘࡣࠊ࢖࢜ࣥศᏊ⮬㌟ࡢᵓ㐀ࡢኚ໬ࡀ✵㛫ⓗ୙ᆒ୍ᛶࡢ㉳※࡟㛵ಀࡋ࡚࠾ࡾࠊ㟼ⓗᵓ㐀ࡢヲ⣽࡞ゎᯒࡀືⓗ୙ᆒ୍ᛶࡢ◊✲࡟ྥࡅ࡚ࠊ㠀ᖖ࡟᭷ຠ࡛࠶ࡿࡇ࡜ࢆㄪ࡭ࡿẁ㝵࡟ࡲ࡛ࡉࡽ࡟◊✲ࢆィ⏬࣭㐙⾜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ࢖࢜ࣥᾮయ୰࡛ࡢ㧗ศᏊࢭ࣮ࣝࣟࢫࡢྍ⁐໬࡟㛵ࡍࡿ◊✲࡟࠾࠸࡚ࡣศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ࢖࢜ࣥᾮ
య࡜Ỉ୰࡟࠾ࡅࡿ㧗ศᏊࢭ࣮ࣝࣟࢫࡢศゎ࣭⁐ゎ㐣⛬ࡢゎᯒࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣ࢖࢜ࣥᾮయ࡟ࡣ཯ᛂຠ⋡ࡢࡼ࠸ࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ࢖࣑ࢲࢰ࣒ࣜ࢘࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ㸦>&PLP@>$FHWDWH@㸧࡟ຍ࠼࡚ࠊ㝜࢖࢜ࣥࢆ᭰࠼ࡓ࣓ࢳࣝளࣜࣥ㓟࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయ㸦>&PLP@> &+2

+ 32@㸧࡜ࠊᐊ࡛ࡢ⢓ᛶࡀᑠࡉࡃ

཯ᛂᛶࡢ㧗࠸ูࡢ࢖࢜ࣥᾮయ㸦>&PLP@>+32@㸧ࡢ㸰✀㢮ࢆ㑅ࢇ࡛㧗ศᏊࢭ࣮ࣝࣟࢫࢆ⁐㉁࡜ࡋ࡚ࢩ࣑ࣗࣞ
࣮ࢩࣙࣥࢆᐇ⾜ࡋࡓࠋ࢖࣑ࢲࢰ࣒ࣜ࢘࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ௨እࡢ㸰✀㢮ࡢ࢖࢜ࣥᾮయ࡟㛵ࡋ࡚ࡣຊሙࡢタᐃ㸦≉࡟㝜࢖࢜ࣥࡢྛཎᏊࢧ࢖ࢺୖࡢ㟁Ⲵࡢタᐃ㸧ࡀᚲせ࡟࡞ࡿࠋᚑࡗ࡚ࠊࡇࢀࡽࡢຊሙタᐃࡣࢭ࣮ࣝࣟࢫ
ࡢศゎ࣭⁐ゎࡀ⏕ࡌࡿ࠿࡝࠺࠿ࢆ☜ㄆࡋ࡞ࡀࡽཎᏊࢧ࢖ࢺୖࡢ㟁Ⲵࡢㄪᩚࢆࡋ࡞ࡀࡽ⾜ࡗࡓࠋ࢖࣑ࢲࢰࣜ࢘
࣒࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ࡜࣓ࢳࣝளࣜࣥ㓟࢔ࢽ࢜ࣥྵ᭷࢖࢜ࣥᾮయࡢྛࠎ࡟ࡘ࠸࡚㸯㸮㸮Υࡢᗘୗ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㐙⾜ࡋࡓࠋ㸯㸮ಶࡢࢢࣝࢥ࣮ࢫࢆྵࢇࡔ㧗ศᏊ㙐ࢆከᩘ⏝࠸࡚✚ᒙᵓ㐀࡟ࡋࡓ㧗ศᏊࢭࣝࣟ
࣮ࢫ࡟㛵ࡋ࡚㸰✀㢮ࡢ࢖࢜ࣥᾮయ୰࡛ࡢ⁐ゎ࣭ศゎ㐣⛬ࡢẚ㍑ࢆ⾜ࡗࡓࠋ≉࡟ࢭ࣮ࣝࣟࢫෆࠊཬࡧࢭ࣮ࣝࣟ
ࢫ㛫Ỉ⣲⤖ྜࡢษ᩿㐣⛬ࡀ㝜࢖࢜ࣥࡢ✀㢮ࢆኚ࠼ࡿ㸦ࡇࡢሙྜࡣ࢖࢜ࣥࡢ኱ࡁࡉ㸧ࡇ࡜࡛࡝ࡢࡼ࠺࡟ኚ໬ࡍ
ࡿ࠿ࢆㄪ࡭ࡓࠋࡉࡽ࡟ࢭ࣮ࣝࣟࢫศᏊෆ࣭㛫Ỉ⣲⤖ྜࡢษ᩿࡟కࡗ࡚㝧࣭㝜࢖࢜ࣥࡀ㧗ศᏊࣇ࢓࢖ࣂ࣮ෆ࡬
࡜౵ධࡋ࡚࠸ࡃ㐣⛬ࡀ㸰ࡘࡢ࢖࢜ࣥᾮయ࡛࡝ࡢࡼ࠺࡟␗࡞ࡿࡢ࠿ࢆゎᯒࡋࡓࠋ
୍᪉ࠊ࢖࢜ࣥᾮయࡢືⓗᣲື࡟㛵ࡍࡿ◊✲࡛ࡣ࢖࣑ࢲࢰ࣒ࣜ࢘ᆺࡢ࢖࢜ࣥᾮయ࡟㛵ࡋ࡚࢔ࣝ࢟ࣝ㙐ࡢ㛗ࡉࢆኚ࠼࡚࠸ࡁࠊᩘ✀㢮ࡢ࢔ࢽ࢜ࣥ࡜⤌ࡳྜࢃࡏࡓ⣔࡟ᑐࡋ࡚ᐊ

࡛ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿィ⟬ࢆᐇ⾜ࡋࡓࠋィ⟬⤖ᯝࢆ⏝࠸࡚ D 㝧࢖࢜ࣥศᏊෆࡢ࢔ࣝ࢟ࣝ㙐ࡢ㐠ືࡢᦂࡽࡂࡢ᫬㛫ࢫࢣ࣮ࣝ࡜࢖࢜ࣥᾮయࡢ㟼ⓗ- 463 -

ᵓ㐀࡜✵㛫ⓗ୙ᆒ୍ᛶࡢ┦㛵㛵ಀࡢゎ᫂ࠊ㸦㹠㸧㝧࣭㝜୧࢖࢜ࣥศᏊࡢ㓄ྥࡀ࢖࢜ࣥศᏊࡢ✵㛫ⓗ࡞ศᕸ࡟୚
࠼ࡿᙳ㡪ࡢゎᯒࢆ⾜ࡗࡓࠋ඲࡚ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥィ⟬ࡣศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࣉࣟࢢ࣒ࣛ *520$&6 ࢆ⏝࠸࡚⾜ࡗࡓࠋ3◊✲ᡂᯝ࢖࢜ࣥᾮయ୰࡛ࡢ㧗ศᏊࢭ࣮ࣝࣟࢫࡢྍ⁐໬࡟㛵ࡍࡿ◊✲࡟ࡘ࠸࡚ࡣࠊỈࡸᚑ᮶ࡢ᭷ᶵ⁐፹࡟ẚ࡭࡚࢖࢜ࣥᾮయࡣࢭ࣮ࣝࣟࢫྵ᭷ࡢࣂ࢖࣐࢜ࢫࡢ⁐ゎࢆ㣕㌍ⓗ࡟ಁ㐍ࡍࡿࡇ࡜ࡀࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ◊✲⤖ᯝࡼࡾ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊ࢖࢜ࣥᾮయ࡟ࡼࡿࢭ࣮ࣝࣟࢫࡢ⁐ゎ㐣⛬ࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࡶࠊ㧗ศᏊࢭࣝࣟ
࣮ࢫ㛫ࡢศᏊ㛫Ỉ⣲⤖ྜࡣỈ୰࡟ẚ࡭࡚࢖࢜ࣥᾮయ୰࡛ࡣᙅࡃ࡞ࡿࡇ࡜ࡀ㔞Ꮚ໬Ꮫィ⟬࡜ศᏊືຊᏛࢩ࣑ࣗ
࣮ࣞࢩࣙࣥ࡟᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࡢ⤖ᯝࡣ࢖࢜ࣥᾮయࡀ⏕య㧗ศᏊ୰ࡢỈ⣲⤖ྜษ᩿⬟ຊࡀ㧗࠸ࡇ࡜ࢆ♧ࡍࡶࡢ࡜ࡋ࡚㔜せ࡞ᡂᯝ࡛࠶ࡿࠋࡉࡽ࡟ࠊศᏊෆỈ⣲⤖ྜࡢゎ㞳ࡀศᏊ㛫Ỉ⣲⤖ྜࡢゎ㞳ࡼࡾࡶඃඛࡋ࡚࠾ࡇ
ࡿࡇ࡜ࡀィ⟬⤖ᯝࡼࡾ♧ࡉࢀࠊᐇ㦂◊✲࡟ࡼࡿᣦ᦬࡜ࡶ୍⮴ࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋຍ࠼࡚ࠊࡇࡢศᏊෆỈ⣲⤖ྜࡢゎ㞳ࡣ㝜࢖࢜ࣥ࡟ࡼࡗ࡚ᘬࡁ㉳ࡇࡉࢀ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊィ⟬⤖ᯝࡢヲ⣽࡞ゎᯒ࠿ࡽࠊ㝧࢖࢜ࣥࡢാࡁࡶ᫂ࡽ࠿࡟ࡉࢀࠊ㧗ศᏊ≧ែ࠿ࡽศ㞳ࡋࡓࢭ࣮ࣝࣟࢫ㙐ࡣࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫຊࢆ㏻ࡋ࡚㝧࢖࢜ࣥ࡟ࡼࡗ࡚Ᏻᐃ໬ࡉࢀࠊ࢖࢜ࣥᾮయ୰࡛ࡢ⁐ゎࡀಁ㐍ࡉࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡽࡢ◊✲ᡂᯝࡣᏛ⾡ㄽᩥ࡜ࡋ࡚Ⓨ⾲ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ㸦“Theoretical Investigation of Dissolution and Decomposition
Mechanisms of a Cellulose Fiber in Ionic Liquids”, Tateki Ishida, J. Phys. Chem. B 2020, 124, 3090-3102.㸧௒ᖺᗘࡣࡉࡽ࡟࢖࣑ࢲࢰ࣒ࣜ࢘࢔ࢭࢸ࣮ࢺ࢖࢜ࣥᾮయ㸦>&PLP@>$FHWDWH@㸧࡟ຍ࠼࡚ࠊ㝜࢖࢜ࣥࢆ᭰࠼ࡓ
࣓ࢳࣝளࣜࣥ㓟࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయ㸦>&PLP@> &+2

+ 32@㸧࡜ࠊᐊ࡛ࡢ⢓ᛶࡀᑠࡉࡃ཯ᛂᛶࡢ㧗࠸ูࡢ࢖࢜ࣥᾮయ㸦>&PLP@>+32@㸧ࡢ㸰✀㢮ࢆ⁐፹࡜ࡋ࡚㑅ࢇࡔࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋィ⟬⤖ᯝ࠿ࡽࡣࣜࣥ㓟ࢆྵࡴ࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయࡢ᭷⏝ᛶࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋලయⓗ࡟ࡣࠊ࢔ࢭࢸ࣮ࢺ⣔࢖࢜ࣥ࡟ẚ࡭࡚ࠊࣜࣥ㓟ࢆྵࡴ࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయࡣ㧗ศᏊࢭ࣮ࣝࣟࢫࢆࡼࡾ▷᫬㛫࡛ຠ⋡ࡼࡃศゎ࣭⁐ゎࢆ㐍ࡵࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ࢔ࢭࢸ࣮ࢺ⣔࢖࢜ࣥࢆྵࡴ࢖࢜ࣥᾮయࡣ⇕ⓗᏳᐃᛶ࡟ஈࡋࡃࠊ㧗࡛ࡢ౑⏝࡟ࡣၥ㢟ࡀ࠶ࡿࡇ࡜ࡀᐇ㦂◊✲࠿ࡽࡶᣦ᦬ࡉࢀ࡚࠸ࡿࡀࠊィ⟬⤖ᯝ࠿ࡽࡶ⇕ⓗᏳᐃᛶࡢ࠶ࡿࣜࣥ㓟ྵ᭷࢖࢜ࣥᾮయࡢ᪉ࡀ㧗࡛ࡢࢭ࣮ࣝࣟࢫࡢศゎ࣭⁐ゎ࡟ࡣ㐺ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋຍ࠼࡚ࠊ

ᗘኚ໬࡟ࡼࡿࣜࣥ㓟ྵ᭷࢖࢜ࣥᾮయ୰࡛ࡢศゎ㐣⛬ࡢ㐪࠸ࡢ◊✲ࢆ⌧ᅾ㐍ࡵ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࡀࠊ㏵୰ࡢゎᯒ⤖ᯝ࠿ࡽࡶ㸯㸮㸮Υࡢࡼ࠺࡞㧗࡛ࡣ࡞ࡃࠊ㸶㸮Υࠊࡶࡋࡃࡣ㸳㸮Υࡢᗘୗ࡛ࡶ࢔ࢭࢸ࣮ࢺ⣔࢖࢜ࣥᾮయ

࡟ẚ࡭࡚ຠ⋡ࡼࡃศゎࢆ㐍ࡵࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡿࠋࡇࢀࡽࡢ◊✲ᡂᯝࡣࠊ࢖࢜ࣥᾮయࡢࡼ࠺࡞͆᪂ࡋ࠸
ᾮయ͇࡟㛵ࡋ࡚ᐇ㦂࣭⌮ㄽ◊✲཮᪉࡬ࡢ㔜せ࡞ᶫΏࡋ࡜࡞ࡾ࠺ࡿࠋ௒ᚋࠊ

ᗘኚ໬࡟ࡼࡿࢭ࣮ࣝࣟࢫࡢศゎ㐣⛬ࡢ㐪࠸࡜ࡑࡢ㐣⛬࡟࠾ࡅࡿ㝧࣭㝜࢖࢜ࣥࡢᣲືࡢ㐪࠸ࢆゎᯒࡋ࡚࠸ࡃணᐃ࡛࠶ࡿࠋ
࢖࢜ࣥᾮయࡢ㟼ⓗᵓ㐀࡟㛵ࡍࡿ◊✲࡟࠾࠸࡚ࡣ࢖࢜ࣥศᏊࡢᵓ㐀ࡢศᕸ࡜✵㛫ⓗ࡞࢖࢜ࣥศᏊࡢศᕸࡢ୙
ᆒ୍ᛶࡢ┦㛵࡟㛵ࡋ࡚㔜せ࡞⤖ᯝࡀᚓࡽࢀࡓࠋ◊✲⤖ᯝࡼࡾࠊ࢖࢜ࣥᾮయ୰࡛ࡣ㝧࣭㝜࢖࢜ࣥศᏊࡣ࢖࢜ࣥ
ศᏊࡢᵓ㐀ࡢศᕸ࡟౫Ꮡࡋ࡚✵㛫ⓗ࡟୙ᆒ୍࡟ศᕸࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡉࡽ࡟ࠊ✵㛫ⓗ࡞࢖࢜ࣥࡢศ

- 464 -

ᕸࡣ㝧࣭㝜୧࢖࢜ࣥࡢ㓄ྥࡢ࠸ࡃࡘ࠿ࡢࣃࢱ࣮ࣥࡀせᅉ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋᚓࡽࢀࡓ◊✲⤖ᯝ࠿ࡽ࢖࢜ࣥᾮయࡢ≀⌮ⓗࠊ໬Ꮫⓗᣲື࡟㛵ࡋ࡚ࡉࡽ࡟▱ぢࢆ῝ࡵ࡚࠸ࡃྍ⬟ᛶࡀ㛤࠿ࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

≉࡟࡞ࡋࠋ  5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫“ۻ‬Theoretical Investigation of Dissolution and Decomposition Mechanisms of a Cellulose Fiber in Ionic Liquids”,
Tateki Ishida, J. Phys. Chem. B 2020, 124, 3090-3102.

- 465 -









Ab-initio calculation of magnetism and phonon properties in molecularsystemD ?=O657#P,  F(E1+), O657#P,&I !.O657#P, 1 ,O( :P, I LO(

' O-;6$@KP,  B
G H

P,

O>M+N8J*P,

O657#P

1 5743ÉÜq³cz Ûz '"D1AO§!Ûz<B.7 (ÉÜ h{mÆ*$¹{ ½tÂÕË*¨4MQF!ÉÜq³cz *·cz¾*ÛzD1AO²V[­P¦§¤°* cz *·!cz<B.77CO=N?37 l d¥-<B.7 ­#×*

BM3¿~*&

+*§R*

cz·Ù*µº!+$

UÈ,+  Z(

<B.7­-È%!

ÖÛ Ì Ë*Öcz Ì!cz ·-y x * ´(+*$cz^!ÖÛ^ · czq³'xÏ*\&wr+* 'cz-Ö®Ü *§xÏ-TÎÝµº-Ô%
$D1AO Ù]*­±¿§ÛzD1AO²V[­k"¦Xª¦ÛÅ¤°*¦Xª!Í¼ ÞÒh *£ {ÄG;O
5IM ­-Ô%*!iY# ­-Ô%

2 57%/C9%/ÖÉÜSq³cz Ó!7KEv-­H<MhÓÁs '"Ûz©
Í¼!Viennna Ab-initio Silumation Package (VASP)-­ÈPAW v G;O5IM-­
W²Ù¢Ù! GGA-PBE -­ÉÜcz Ø ²V[­-')¡¶%
vdW-DFT £-­iY *D1AO Í¼&p VASP -d­È {ÄG;O5IM[*% <Q98:=!LAMMPS Molecular Dynamics Simulator '*naczge{Í- 466 -

¼-­=K6/3=L¬

=K6/3=L(Ó

7>:F5J:=-¬oÓ~ VASP -­Ûz©Í¼-È[ÛzD1AO²V[­!Quantum Espresso k" Electron Phonon
Wannier(EPW)-­»Rj«Í¼-È`Y¯~Ð¾ R Au(110)-2x1 bÉÜS cz* bÉÜ!uß¸'ÊÚÓ-%$q³ÓÀÃ¯_0@M2Q Í¼-È|}q³Ó p}-ÈG b'*(NO q³cz *ÑÇf ok !µº4MQF0×o))tNRG FN4K-­

3

57")

a=O@MUSTM'*zI! ¾|}GA*Ó!bridge .=q³ NO HAQcz

NO czbridge-ontop-bridge .=q³=K. Ó s) (*© Ó*$w=dT

ontop q³ NO

cz LA7COm^ÑÇf'¬*u (+*UcO39O7
T 73=MÓ k+*© ÓH<M-[q³.='czÛz©7CO'xh* -»Rj«Í¼'[( u¸'
ontop .= bridge .=NO cz  *~* PDOS !R© y n*2[Bridge .=!O $7CO*
 E,+© k+*Rontop .=
!O j$ up-spin, down-spin

DOS

+ +

n&ÂCQ3-7CO* (+©
~*73=MR© T(+*
CQ3O !bridge .=!B_ e Q %-NO cz 7CO* Ûxpg
3QNOmoe '%E,+* ontop .=!UFq³Ó  (7CO*-($$ q³ 8Å)NO czGA*LA7CO ÑÇf-¬*-¸?*G (&= NO >K PDOS

- 467 -

$|}Ó! STM W ( Ûc-­ bridge .=q³HAQcz-5ontop q³ÓÑu (+*i|}HAQÓ T(+( Ó&ÑÇf zg+*w=d i|}HAQontop Ó=K. ÓT

ontop Ó!ÑÇfm^*UcO39O7 73=MR© y n*3v!CQ3R©

NB.7#Ñk+*

~Sv!<:FÓ  h- ( *%ontop i|}Ó=K. Tk+*

NO cz *PDOS -b u(a),(b),(c)
CQ3&ÂO n* 2[+( »Rj«Í¼¿ ( Au(110)-2x1 bÉÜS cz!COPÑÇf-V



( LA7

q³Ó~NYm* ! $|-q+-))t'*{`H}u 
u ! Au(110)-2x1 bÉÜS cz-

H<Mh OQOv cz

0@M2QeQ-UJx





*73=MÙÍ¼¿* *  Ü±:cM*Ü0:cM*( D/Mi&Ñ+73=MÙ CQ3- ÑÇf-¬*  .+],* y7+*
 !STM g}+UcO39O7
 i|}HAQontop Ó!CQ3R©
NB.7#Ñk+* ~=K. ÓT

ontop Ó!<:FÓk+*-~[ *CQ3<:FÓ!Fano f>
+*ÑÇ©-"c+*ÛcW (±Ö
B_=O@M*Ûc

Pff'¬

*ÑÇ©-"c+*Ûc

X¯+

CQ349 K+<:F*Ü±:Ü0:cM*ÑÇf



*C

9STM W ( =O@MÈ1Ër!3v G fNP ontop b (&=y *%3v!CQ3Sv!<:F ontop b>Kd

zg++!!@{`¿Z9* '«Í¼H /pµº')NO cz 'N5OFM ·jz-;$cz&q³\LA7CO-( *$ LA7CO  cz<
 lDNY*-HP« 6,'¸  ')y cz- 468 - *K6M7CO &× *¿*u (+*4 2A< B |{AR6 K%",p47lxQ_w

F%",, ),ru5   T  [  Z,(,:  1. .2&1.8&2. '.2.8.3 (&0(90&8.32 3+ *0*(86324-3232 (3940.2, .2 0&<*6*) 1&8*6.&07   #&.;&2$"
7<1437.91):&2(*7.2"(&22*)63'*.(637(34<&2    20.2*
 B |{~nhU KI6?`   TZ^~qvM5M}g5   T  [ Z  Z,(, 0S z1\&88-.&7 3-0/*.( "-&2232.,-+.*0) 74.22*1&8.( 78&8* .2 8-* "   759&6*0&88.(*+69786&8*)+*6631&,2*8
Z^hkM5   TtLJ5   T  [  Z,(,:
 0S z1\!.(33-0*&2%&2.("-&2232"4.2)<2&1.(7.2" '.0&<*6'6*&8-.2,/&,31**.7*2'*6,
1&,2*8Z^hkM5   TtLJ5   T  [  Z,(,:
 0S z1\ 3c;%(+-sU6 $,!&jVY8oruw  F
K$,yru5   T  [ Z,(,: &88-.&7 3-0/* 0S z1\ .( "-&2232.,-.*0) "4.2*1&8.( "8&8* .2 8-* "   "59&6*&88.(*69786&8*)*6631&,2*8
Z^hkM5 w  FTcJ5   T [  Z,(,: /m O a] eC 0S z1\Es@ 9yhU_ i@

K$,*#- " Z^hkM5 w  FTcJ5   T [  Z,(,:#3/963"-.13/&;&!.(33-0*&2%&2.(-30&7"-&2232>#-*61&0&2))<2&1.(&04634*68.*73+8-*" '.0&<*6'6*&8-.2,/&,31**.7*2'*6,1&,2*8&440.(&8.3283&6 =?1*6.(&2-<7.(&0"3(.*8<&6(-**8.2,  
&6    320.2*
 . 2"WD=>K <HX  koruZ^hkM5 w  FTcJ
5   T [   Z,(,:

5 0<1H. Koshida, H. Okuyama, S. Hatta, T. Aruga, E. Minamitani, “Effect of local geometry on magnetic property of
nitric oxide on Au(110)-(1x2)”, Phys. Rev.B 103, 155412 (2021)
2Nao H. Shimada, E. Minamitani, S. Watanabe, “Theoretical prediction of superconductivity in monolayer h-BN
doped with alkaline-earth metals (Ca, Sr, Ba)”, J. Phys.: Condens. Matter 32, 435002 (2020)
3K. Iwata, T. Miyamachi, E. Minamitani, F. Komori, “Sensing surface lattice strain with Kondo resonance of single
Co adatom)”, Appl. Phys. Lett. 114, 051604 (2020)
4. K. Miwa, G. C. Schatz, “Quantum electrodynamics description of localized surface plasmons at a metal nanosphere”,
Phys. Rev. A, 103, L041501 (2021)- 469 -

㟁Ꮚ≧ែィ⟬࡟ࡶ࡜࡙ࡃపḟඖ㛤ẆศᏊ⣔≀㉁ࡢᵓ㐀-≀ᛶ┦㛵ࡢゎ᫂
Elucidation of structure-property correlation in low dimensional
open-shell molecular materials based on electronic structure calculation‫ⲡۑ‬ᮏ ဴ㑻ࠊᯇᒸ ுኴࠊᮌᮧ ⯗㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
୙ᑐ㟁Ꮚࡀ஧ḟඖࣁࢽ࣒࢝᱁Ꮚୖ࡟୪ࢇࡔ≀㉁ࡣࠊࡑࡢᗄఱᵓ㐀࡟ᇶ࡙࠸࡚≉␗࡞㟁Ẽ≉ᛶࡸ☢Ẽ≉ᛶࢆ♧ࡍࡇ࡜ࡀ▱ࡽࢀࠊࡲࡓᑗ᮶ࡢ㟁Ꮚࢹࣂ࢖ࢫᛂ⏝࡟ࡘ࡞ࡀࡿ₯ᅾⓗ࡞ྍ⬟ᛶࢆᣢࡘᮦᩱ࡜ࡋ࡚ࠊᇶ♏࠾ࡼࡧᛂ⏝ࡢ୧㠃࠿ࡽ⢭ຊⓗ࡟◊✲ࡀ㐍ࡵࡽࢀ࡚࠸ࡿࠋᡃࠎࡣ㏆ᖺࠊ୕ゅᙧᵓ㐀ࢆᣢࡘⓎගࣛࢪ࢝ࣝ trisPyM ࢆ㛤Ⓨࡋࠊࡇࢀࡀள㖄(II)࢖࢜ࣥࡸ㖡(II)࢖࢜ࣥ࡞࡝ࡢ㔠ᒓ࢖࢜ࣥ࡜ࡢ㘒ᙧᡂ࡟ࡼࡾ஧ḟඖࣁࢽ࣒࢝᱁Ꮚࢆᣢࡘ㓄఩㧗ศᏊ࡜࡞ࡿࡇ࡜ࢆࡳ࠸ࡔࡋ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊࡇࢀࡽࡢ஧ḟඖ㓄఩㧗ศᏊࡢ୰࡛ࡶࠊ≉ᚩⓗ࡞☢Ẽ≉ᛶࢆ♧ࡍ㖡(II)࢖࢜ࣥࢆྵࢇࡔ㓄఩㧗ศᏊ TrisCu㸦ᅗ㸯㸧࡟ࡘ࠸࡚ DFT ἲ࡟ᇶ࡙ࡃ㟁Ꮚ≧ែィ⟬ࢆ⾜࠸ࠊᐇ㦂࡟࡚ほࡉࢀࡓࣂࣝࢡ୕ḟඖ⤖ᬗࡢ☢Ẽ≉ᛶࢆ㟁Ꮚ≧ែࡢほⅬ࠿ࡽ⌮ゎࡍࡿࡇ࡜ࠊ࠾ࡼࡧࣂࣝࢡ୕ḟඖ⤖ᬗ࠿ࡽ༢ᒙ஧ḟඖࢼࣀࢩ࣮ࢺࡀ༢㞳࡛ࡁࡓሙྜ࡟⌧ࢀࡿ࡜ᮇᚅࡉࢀࡿ㟁Ꮚ≧ែࢆண ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬࡟ࡣ Quantum Espresso 6.5 ࢆ౑⏝ࡋࡓࠋ஺᥮࣭┦㛵ỗ㛵ᩘ࡟ࡣ GGA-PBE ࢆࠊᨃ࣏ࢸࣥࢩࣕࣝ࡟ࡣ࢘ࣝࢺࣛࢯࣇࢺᆺࡢ
ࡶࡢࢆࡑࢀࡒࢀ⏝࠸ࡓࠋ┠ⓗ࡜ࡍࡿ୕ḟඖࡲࡓࡣ஧ḟඖ⤖ᬗࡢᵓ㐀᭱㐺໬ࠊࣂࣥࢻᵓ
㐀ィ⟬ࠊ≧ែᐦᗘィ⟬ࠊࢫࣆࣥᐦᗘィ⟬ࠊ࠾ࡼࡧྛࣂࣥࢻࡢ㧗ᑐ⛠Ⅼ࡟࠾ࡅࡿἼື
㛵ᩘィ⟬ࢆ⾜ࡗࡓࠋ࡞࠾ࠊィ⟬࡟࠶ࡓࡾࠊ
⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ◊✲㡿ᇦࡢ༡㇂ⱥ⨾ᅗ 1. ஧ḟඖ㓄఩㧗ศᏊ TrisCu ࡢᵓ㐀෸ᩍᤵ࡟ᵝࠎ࡞ほⅬ࠿ࡽຓゝ࣭ࢧ࣏࣮ࢺࢆ
࠸ࡓࡔ࠸ࡓࠋ

3◊✲ᡂᯝᐇ㦂࡟ࡼࡾᚓࡽࢀࡓ TrisCu ࡢ⤖ᬗᵓ㐀ࢆึᮇᵓ㐀࡜ࡋࠊࣂࣝࢡ୕ḟඖ⤖ᬗࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋᵓ㐀᭱㐺໬ᚋࡢࣂࣝࢡ୕ḟඖ⤖ᬗࡣ㸳ࡘࡢ༙༨᭷ࣂࣥࢻࢆ᭷ࡋ࡚࠸ࡓࠋࢫࣆࣥᐦᗘ࡜ྛࣂࣥࢻ࡟ᑐᛂࡍࡿ≧ែᐦᗘ࠾ࡼࡧἼື㛵ᩘࡢ✵㛫ศᕸ࠿ࡽࠊ⤖ᬗᏛⓗ࡟⊂❧࡞㸱ࡘࡢ㖡(II)࢖࢜ࣥ࠾ࡼࡧ㸰ࡘࡢࣛࢪ࢝ࣝศᏊࡀ㟁Ꮚࢫࣆࣥࢆ᭷ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ☢ᛶࢆᢸ࠺㖡(II)࢖࢜ࣥࡢ༙༨᭷ࣂࣥࢻࡣ d x2-y2 ㌶㐨࡟⏤᮶ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࢀࡽࡢィ⟬⤖ᯝࡣᐇ㦂࡟࡚᫂ࡽ࠿࡟ࡋࡓ☢Ẽ≉ᛶ࠾ࡼࡧ⤖ᬗᵓ㐀࠿ࡽணࡉࢀࡿ㟁Ꮚ≧ែ࡜࠾࠾ࡴ

ࡡ▩┪࡞࠸ࡶࡢ࡛࠶ࡗࡓࠋࣇ࢙࣑ࣝࣞ࣋ࣝ㏆ഐࡢࣛࢪ࢝ࣝศᏊ㌶㐨⏤᮶ࡢࣂࣥࢻࡣẚ㍑ⓗ኱ࡁ࠸ศᩓࢆ♧ࡋࡓ୍᪉ࠊ㖡(II)࢖࢜ࣥࡢ d ㌶㐨⏤᮶ࡢࣂࣥࢻࡣ࡯ࡰᖹᆠ࡛࠶ࡗࡓࠋ

- 470 -

ࡲࡓࠊࣂࣝࢡ୕ḟඖ⤖ᬗ࠿ࡽࡢ๤㞳࡟ࡼࡗ࡚ᚓࡽࢀࡿ࡜ண᝿ࡉࢀࡿ༢ᒙ஧ḟඖࢼࣀࢩ࣮ࢺࡢࣔࢹࣝࢆࣂࣝࢡ୕ḟඖ⤖ᬗෆࡢᵓ㐀ࢆࡶ࡜࡟ᵓ⠏ࡋࠊࡑࡢᵓ㐀᭱㐺໬࠾ࡼࡧ㟁Ꮚ≧ែィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ㸱ࡘࡢ㖡(II)࢖࢜ࣥ࠾ࡼࡧ㸰ࡘࡢࣛࢪ࢝ࣝศᏊ࡟⏤᮶ࡍࡿ㸳ࡘࡢ༙༨᭷ࣂࣥࢻ
ࡀᏑᅾࡍࡿⅬࡣࣂࣝࢡ୕ḟඖ⤖ᬗ࡜ྠࡌ࡛࠶ࡗࡓࡀࠊ୕ᅇᅇ㌿ᑐ⛠ࢆᣢࡘ✵㛫⩌࡟ᒓࡍࡿࣔࢹࣝ࡟࠾࠸࡚ࠊࣇ࢙࣑ࣝࣞ࣋

ᅗ 2. TrisCu ༢ᒙࡢ᭱㐺໬ᵓ㐀࠾ࡼࡧࢫࣆࣥᐦᗘศᕸ

ࣝ㏆ഐ࡟㸰ࡘࡢࢹ࢕ࣛࢵࢡࣂࣥࢻ࡜㸯ࡘࡢࣇࣛࢵࢺࣂࣥࢻࡀ⌧ࢀࡓࠋࡇࢀࡽࡢ࠺
ࡕࠊࡦ࡜ࡘࡢࢹ࢕ࣛࢵࢡࣂࣥࢻࡣࣁࢽ࢝
࣒ࢫࣆࣥ᱁Ꮚࢆᙧᡂࡍࡿࣛࢪ࢝ࣝศᏊࡢ
༙༨᭷㌶㐨⏤᮶ࠊࡶ࠺୍ࡘࡢࢹ࢕ࣛࢵࢡ
ࣂࣥࢻ࠾ࡼࡧࣇࣛࢵࢺࣂࣥࢻࡣ࢝ࢦ࣓ࢫ
ࣆࣥ᱁Ꮚࢆᙧᡂࡍࡿ㖡(II)࢖࢜ࣥࡢ d ㌶㐨⏤᮶࡛࠶ࡿࡇ࡜ࡀ≧ែᐦᗘ࠾ࡼࡧἼື㛵ᩘࡢ✵㛫ศᕸ࠿ࡽ♧၀ࡉࢀࡓࠋࡍ࡞ࢃࡕࠊ
ࡇࡢ≉ᚩⓗ࡞㟁Ꮚ≧ែࡣࣁࢽ࣒࢝-࢝ࢦ࣓ࣁ࢖ࣈࣜࢵࢻࢫࣆࣥᵓ㐀ࢆࡶࡘ஧ḟඖ᱁Ꮚᵓ㐀࡞ࡽ࡛ࡣࡢࡶࡢ࡛࠶ࡿ࡜⪃࠼ࡽ
ࢀࠊTrisCu ࡢ༢ᒙࢼࣀࢩ࣮ࢺࡀ㠀ᖖ࡟⯆࿡῝࠸☢Ẽ࣭㟁Ẽ≉ᛶࢆ♧ࡍྍ⬟ᛶࢆ♧၀ࡋ࡚࠸ࡿࠋ௨ୖࡼࡾࠊDFT ἲ࡟ࡼࡿ⌮ㄽィ⟬ࡣࣛࢪ࢝ࣝࡢ㟁Ꮚ≧ែࢆ⌮ゎ࣭ணࡍࡿࡓࡵࡢຠᯝⓗ࡞ᡭἲ࡛࠶ࡿ࡜⪃࠼

Γ

Μ

Γ

ᅗ 2. TrisCu ༢ᒙࡢࣂࣥࢻᵓ㐀㸦spin-downࠊࣇ࢙࣑ࣝࣞ࣋ࣝ㏆

ࡽࢀࡿࠋ

4

Κ

ഐࢆᣑ኱㸧

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ࡇࡇ࡛ᚓࡽࢀࡓᡂᯝࡣࠊ௒ᚋࠊ᪥ᮏ໬Ꮫ఍ᖺ఍ࠊ㘒య໬Ꮫ఍ウㄽ఍ࠊICCC, ACCC ࡞࡝ࡢᅜෆእࡢᏛ఍࡟

࡚Ⓨ⾲ࡍࡿணᐃ࡛࠶ࡿࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

ࡇࡇ࡛ᚓࡽࢀࡓᡂᯝࡣࠊ௒ᚋࠊ◊✲ㄽᩥ࡟ࡲ࡜ࡵ࡚Ⓨ⾲ࡍࡿணᐃ࡛࠶ࡿࠋ

- 471 -኱つᶍ GW/BSE ἲ࡟ࡼࡿ㠀ࣇ࣮ࣛࣞࣥ㟁Ꮚ࢔ࢡࢭࣉࢱ࣮ኴ㝧㟁ụࡢ   ⏺㠃㟁Ⲵ⛣ື≧ែࡢゎᯒInvestigations of interfacial charge-transfer states in non-fullerene
acceptor organic solar cells by large-scale GW/BSE method‫ ⏣⸨ۑ‬㈗ᩄ 㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
Internet-of-Thing ᫬௦ࡢࣇࣞ࢟ࢩࣈࣝࢹࣂ࢖ࢫ࡜ࡋ࡚᭷ᶵ༙ᑟయᮦᩱࡀὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋ᭷ᶵ༙ᑟయᮦᩱ

ࡣ஘ࢀࡓศᏊ㞟ྜయ࡛࠶ࡾࠊࡑࡢග㟁Ꮚ≀ᛶࡣ᭷ᶵศᏊࡢᛶ㉁࣭ศᏊ㛫ࡢࣃࢵ࢟ࣥࢢᵓ㐀࣭ᵓ㐀஘ࢀ࡞࡝ࡢ
ᵝࠎ࡞ᅉᏊ࡟౫Ꮡࡍࡿࠋ㟁⏺ຠᯝࢺࣛࣥࢪࢫࢱࡢ㟁Ⲵ㍺㏦ࡸ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢ㟁Ⲵศ㞳࡞࡝ࠊࢹࣂ࢖ࢫ≉ᛶࢆỴࡵ࡚࠸ࡿ⣲㐣⛬ࡣ⏺㠃࡛㉳ࡁࡿࠋࡘࡲࡾࠊࢹࣂ࢖ࢫ≉ᛶணࡢࡓࡵ࡟ࡣ⏺㠃㏆ഐ࡛ࡢ㟁Ꮚ≀ᛶࢆゎᯒࡍࡿᚲせࡀ࠶ࡿࠋᮏ◊✲࡛ࡣ኱つᶍ㟁Ꮚ≧ែ⌮ㄽࡸ㔞ᏊືຊᏛ⌮ㄽࢆ㥑౑ࡋ࡚ࠊ஘ࢀࡓ᭷ᶵ/᭷ᶵ⏺㠃⣔࡟࠾ࡅࡿ㟁Ꮚ≧ែ࣭ග≀ᛶ࣭㟁Ⲵศ㞳࣭㟁Ⲵ෌⤖ྜࢆゎᯒࡋࠊࢹࣂ࢖ࢫᛶ⬟࡜ࡢ㛵ಀࢆ᫂ࡽ࠿࡟ࡍࡿࠋࡉࡽ࡟ࠊ
ࡇࢀࡲ࡛㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓࣇࣛࢢ࣓ࣥࢺศᏊ㌶㐨(FMO)ἲࡢᶵ⬟ᣑᙇࢆࡉࡽ࡟㐍ࡵࡿࡇ࡜࡟ࡼࡾࠊ࢟ࣕࣜ࢔
ࡢ࢚ࢿࣝࢠ࣮‽఩ࡸ㟁Ꮚບ㉳≧ែࢆ㧗⢭ᗘ࡛ィ⟬࡛ࡁࡿᡭἲࢆᥦ᱌ࡍࡿࠋᮏᖺᗘࡣࠊィ⟬ᡭἲࡢ㛤Ⓨ࡜ࡋ࡚
FMO-GW ἲࡢ㧗⢭ᗘ໬ࡸ FMO-GW/BSE ἲࡢ㛤Ⓨࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊᛂ⏝౛࡜ࡋ࡚࣌ࣥࢱࢭࣥ/C60 ⏺㠃ࡸ㠀ࣇ࣮ࣛࣞࣥኴ㝧㟁ụ⏺㠃ࡢ㟁Ⲵ⛣ື≧ែࢆゎᯒࡋࡓ౛ࡶሗ࿌ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲࣉࣟࢢ࣒ࣛࡣ GAUSSIAN, ABINIT-MP,TINKER ࢆ⏝࠸ࡓࠋGaussian ࡛ࡣᏙ❧୍ศᏊࡢᵓ㐀᭱㐺໬࣭ບ㉳≧ែィ⟬ࢆ⾜࠺ࠋABINIT-MP ࡣᙜࢢ࣮ࣝࣉ࡛㛤Ⓨࢆ㐍ࡵ࡚࠸ࡿࣉࣟࢢ࣒࡛ࣛ࠶ࡾࠊFMO ἲ࡟ࡼࡿ኱つᶍ㟁Ꮚ≧ែィ⟬ࢆ⾜࠺ࠋ⏺㠃ᵓ㐀సᡂ࡞࡝ࡣ TINKER ࢆ౑ࡗ࡚‽ഛࡍࡿࠋ3◊✲ᡂᯝ
A. FMO-GW ࡢ㧗⢭ᗘ໬ࢆ┠ᣦࡋࡓศᴟ㛵ᩘࡢ⢭ᗘࡢᨵၿᡃࠎࡀ㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓ FMO-GW ἲࡣḟࡢ㏆ఝ࡟ᇶ࡙࠸࡚࠸ࡿ㸸(a)඲⣔ࡢศᴟ㛵ᩘ࡟ᑐࡍࡿࣇࣛࢢ࣓ࣥ

ࢺศ๭㏆ఝࠊ(b)ࣇࣛࢢ࣓ࣥࢺෆ┦㛵ࢆ GW ࡛ࣞ࣋ࣝࠊ࿘ᅖࡢࣇࣛࢢ࣓ࣥࢺࡢㄏ㉳ศᴟࢆ Coulomb-hole plus
screened exchange (COHSEX)࡛ࣞ࣋ࣝᢅ࠺ǼCOHSEX ㏆ఝࠋࡇࢀࡲ࡛ࡣ඲⣔ࡢศᴟ㛵ᩘࢆࣇࣛࢢ࣓ࣥࢺࣔࣀ࣐
࣮㌶㐨࠿ࡽ㏆ఝࡋ࡚࠸ࡓࡀࠊࣇࣛࢢ࣓ࣥࢺࢲ࢖࣐࣮㌶㐨ࡢ⿵ṇࡶຍ࠼ࡿࡇ࡜࡟ࡼࡾ⣔⤫ⓗ࡟ศᴟ㛵ᩘࡢ⢭ᗘࢆᨵၿ࡛ࡁࡿࡇ࡜ࢆ♧ࡋࡓࠋᚑ᮶ࡢࣇࣛࢢ࣓ࣥࢺࣔࣀ࣐࣮㌶㐨࠿ࡽ㏆ఝࡋࡓ⤖ᯝ࡛ࡣࠊㄏ㉳ศᴟຠᯝࢆ༑ศ
࡟⪃៖࡛ࡁ࡞࠸ሙྜࡀ࠶ࡾࠊලయⓗ࡟ࡣ highest occupied molecular orbital-lowest unoccupied molecular orbital(HOMO-LUMO) gap renormalization ࡸບ㉳Ꮚ᮰⦡࢚ࢿࣝࢠ࣮ࡢ㐽ⶸຠᯝࢆ༑ศ࡟グ㏙࡛ࡁ࡞࠸ሙྜࡀ࠶ࡿࡇ
࡜ࡀࢃ࠿ࡗ࡚ࡁࡓࠋ୍᪉ࠊࣇࣛࢢ࣓ࣥࢺࢲ࢖࣐࣮㌶㐨࡟ࡼࡿ⿵ṇࢆຍ࠼ࡿࡇ࡜࡟ࡼࡾࠊศᴟ㛵ᩘࢆṇ☜࡟ホ౯ࡋࡓሙྜࡢ⤖ᯝࢆ⢭ᗘࡼࡃ෌⌧࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

- 472 -

B. ኱つᶍ⣔ࡢບ㉳≧ែィ⟬ࡢࡓࡵࡢ FMO-GW/BSE ἲࡢ㛤ⓎFMO ἲࠊexciton modelࠊGW/BSE ࢆ⤌ࡳྜࢃࡏࡓ኱つᶍ⣔ࡢບ㉳≧ែィ⟬ࡢ㛤Ⓨࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣࠊศᏊෆບ㉳≧ែࡸศᏊ㛫㟁Ⲵ⛣ືບ㉳≧ែࢆ⾲ࡍࣇࣛࢢ࣓ࣥࢺ configuration state functions (CSFs)ࢆᇶᗏ࡜ࡋ
࡚ࠊ඲⣔ࡢບ㉳≧ែࣁ࣑ࣝࢺࢽ࢔ࣥࢆᵓ⠏ࡍࡿࡇ࡜࡟ࡼࡾࠊศᏊ㞟ྜయࡢ㠀ᒁᡤⓗ࡞ບ㉳≧ែ㸦ࣇࣞࣥࢣࣝ
ບ㉳Ꮚࠊ࣡ࢽ࢚--ࣔࢵࢺບ㉳Ꮚ≧ែ࡞࡝㸧ࡢィ⟬ࡀྍ⬟࡜࡞ࡿࠋࡇࢀࡲ࡛ᡃࠎࡣ configuration interaction single(CIS)࡟ᇶ࡙࠸ࡓ኱つᶍ⣔ࡢບ㉳≧ែィ⟬ἲࢆᥦ᱌ࡋ࡚࠸ࡓࡀࠊᮏ◊✲࡛ࡣ CIS ࣞ࣋ࣝࡢ⌮ㄽࢆ GW/BSE ࣞ࣋ࣝ࡟ᣑᙇࡋࡓࠋTamm-Dancoff ㏆ఝࢆ⏝࠸ࡿ࡜ࠊCIS ࡢບ㉳≧ែࣁ࣑ࣝࢺࢽ࢔ࣥࡢ Hartree-Fock ㌶㐨࢚ࢿࣝࢠ࣮ࢆ GW ‽⢏Ꮚ࢚ࢿࣝࢠ࣮࡟ࠊ㟁Ꮚ-ṇᏍࡢ஺᥮㡯ࢆ㐽ⶸ஺᥮㡯࡟⨨ࡁ᥮࠼ࡿࡇ࡜࡟ࡼࡾᐇ⿦ࡍࡿࡇ࡜ࡀ࡛ࡁ
ࡿࠋࡇࡇ࡛ࠊ඲⣔ࡢศᴟ㛵ᩘ࠿ࡽ㐽ⶸࢡ࣮ࣟࣥຊࢆィ⟬ࡍࡿࡓࡵࠊ㟁Ꮚ-ṇᏍᙧᡂ࡟క࠺ㄏ㉳ศᴟຠᯝࢆ㐺ษ࡟⪃៖ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
㛤Ⓨࡋࡓᡭἲࡢ⢭ᗘࢆ᳨ドࡍࡿࡓࡵ࡟ࠊ᭷ᶵศᏊࢡࣛࢫࢱ࣮ࡢ࣋ࣥࢳ࣐࣮ࢡィ⟬ࢆ⾜ࡗࡓࠋ࣋ࣥࢳ࣐࣮ࢡ
ィ⟬࡜ࡋ࡚⏝࠸ࡓᵓ㐀࡜⤖ᯝࢆ♧ࡍࠋConventional GW/BSE ࡜ FMO-GW/BSE ࡛ィ⟬ࡋࡓບ㉳࢚ࢿࣝࢠ࣮ࢆ➨N ບ㉳≧ែ( N:ศᏊᩘ)ࡲ࡛ẚ㍑ࡋࡓࠋFMO-GW/BSE ࡢ⤖ᯝ࡛ࡣࠊconventional GW/BSE ࡢ⤖ᯝࢆᩘ༑ meV ⛬ᗘࡢ⢭ᗘ࡛෌⌧࡛ࡁ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋィ⟬⢭ᗘࡢᐃ㔞ᛶ࡜࠸࠺Ⅼ࡛ࡣᨵၿࡢవᆅࡀ࠶ࡿࡶࡢࡢࠊᐇ⏝ⓗ࡟ࡣ༑ศ࡞⢭ᗘ࡛࠶ࡿ࡜⪃࠼࡚࠸ࡿࠋᮏ◊✲࡟ࡼࡾࠊGW/BSE ἲࢆ኱つᶍ⣔ࡢບ㉳≧ែィ⟬࡟ᛂ⏝ࡍࡿࡓࡵࡢ‽ഛࡀᩚࡗࡓ࡜࠸࠼ࡿࠋ

ᅗ㸸࣋ࣥࢳ࣐࣮ࢡィ⟬࡟⏝࠸ࡓᵓ㐀ࠋ(a)ࢡ࣐ࣜࣥ 4 㔞యࠊ(b)ࢼࣇࢱࣞࣥ 7 㔞యࠋ⾲: ࣋ࣥࢳ࣐࣮ࢡࡢ⤖ᯝࠋConventional GW/BSE(GW/BSE)࡜ࠊFMO-GW/BSE (FMO)ࡢບ㉳࢚ࢿࣝࢠ࣮ࡢẚ㍑ࠋ࢚ࢿࣝࢠ࣮ࡢ༢఩ࡣ eVࠋ

C. ⏺㠃 CT ≧ែ࡜⏺㠃㓄ྥࡢ㛵ಀ
㛤Ⓨࡋࡓ FMO-GW ἲࢆ࣌ࣥࢱࢭࣥ/C60 ⏺㠃ࡢ㟁Ⲵ⛣ື≧ែࡢゎᯒ࡟ᛂ⏝ࡋࡓࠋࢻࢼ࣮/࢔ࢡࢭࣉࢱ࣮⏺㠃- 473 -

࡛ᙧᡂࡉࢀࡿ㟁Ⲵ⛣ື≧ែࡣࠊ㟁Ⲵศ㞳࣭㟁Ⲵ෌⤖ྜࡢ୰㛫≧ែ࡛࠶ࡾࠊࡉࡽ࡟ࡑࡢ࢚ࢿࣝࢠ࣮ࡀ㛤ᨺ㟁ᅽ್࡜ࡶ┦㛵ࡍࡿࡇ࡜࠿ࡽࠊኴ㝧㟁ụࡢ࢚ࢿࣝࢠ࣮ኚ᥮㐣⛬࡟࠾࠸࡚᰿ᖿⓗ࡞ᙺ๭ࢆᢸ࠺ࠋᮏ◊✲࡛ࡣࠊedge-on
㓄ྥ࡜ face-on 㓄ྥࡢ࣌ࣥࢱࢭࣥ(PEN)/C60 ⏺㠃ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊ⏺㠃㟁Ⲵ⛣ື≧ែࡀ⏺㠃㓄ྥ࡟࡝ࡢࡼ࠺࡟౫Ꮡࡍࡿ࠿ࢆㄪ࡭ࡓࠋ≉࡟ศᴟຠᯝ࡜㟁Ⲵࡢ㠀ᒁᅾ໬ຠᯝ࡜࠸࠺ほⅬ࠿ࡽ㟁Ꮚ≧ែࡢẚ㍑ࢆ⾜ࡗࡓࠋ‽⢏Ꮚ࢚ࢿࣝࢠ࣮ࡢィ⟬ࡣ FMO-GW@B3LYP/6-31G*࡛⾜࠸ࠊ඲⣔ࡢບ㉳≧ែࡢィ⟬ࡣ FMO-GW/BSE ࡛⾜ࡗࡓࠋィ⟬ࡋࡓᵓ㐀࡜ CT ≧ែࡢ྾཰ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋedge-on 㓄ྥ࡜ face-on 㓄ྥࡢ྾཰ࢫ࣌ࢡࢺࣝࡢࣆ࣮
ࢡࡣࡑࢀࡒࢀ 0.98eV ࡜ 1.33eV ࡜ぢ✚ࡶࢀࡿࠋLin ࡽ࡟ࡼࡿእ㒊㔞Ꮚ཰⋡(EQE)ᐃ࡟ࡼࡿ࡜(Lin et al., Appl.

Phys. Lett. 112 (2018) 213302)ࠊPEN/C60 ⏺㠃ࡢ CT ≧ែࡢ࢚ࢿࣝࢠ࣮ࡀ 0.98-1.09 eV ⛬ᗘ࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᐇ㦂࡛ࡣ edge-on 㓄ྥࡀ୺せ࡛࠶ࡿࡢ࡛ࠊᮏィ⟬ࡢ edge-on 㓄ྥࡢィ⟬⤖ᯝࡀᐇ㦂ࡢ EQE ࢫ࣌ࢡࢺࣝࢆࡼࡃ෌⌧ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡲࡓࠊ8:1 PEN:C60 ࢆ ITO ᇶᯈୖ࡟సᡂࡋࡓሙྜࡢࡳ CT ࡢ࢚ࢿࣝࢠ࣮
ࡀ 1.38eV ࡜࡞ࡿࠋᐇ㦂࡛ࡣ⏺㠃ᵓ㐀ࡢヲ⣽ࡣࢃ࠿ࡗ࡚࠸࡞࠸ࡀࠊୖグࡢᵓ㐀࡛ࡣ face-on 㓄ྥࡀ୺࡟࡞ࡗ࡚
࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋJo ࡽ࡟ࡼࡿࢹࣂ࢖ࢫ≉ᛶホ౯࡟ࡼࡿ࡜ࠊPEN/C60 ࡢ edge-on 㓄ྥ࡜ face-on 㓄ྥࡢ㛤ᨺ㟁ᅽ್ࡣࡑࢀࡒࢀ 0.39V ࡜ 0.62V ࡛࠶ࡿ㸦Jo et al., ACS Nano, 9 (2015) 8206.㸧
ࠋࡇࡢᕪࡣᮏ◊✲ࡢ edge-on 㓄ྥ࡜face-on 㓄ྥࡢ࢚ࢿࣝࢠ࣮ᕪ(0.35eV)ࡼࡾࡶᑠࡉ࠸ࡀࠊࡇࢀࡣ face-on 㓄ྥ࡛ࡣ㟁Ⲵ෌⤖ྜ࡟ࡼࡿ㟁ᅽࣟࢫࡀ኱
ࡁ࠸ࡓࡵࠊCT ≧ែࡢ࢚ࢿࣝࢠ࣮ᕪࡼࡾࡶ㛤ᨺ㟁ᅽ್ࡢᕪࡀᑠࡉࡃ࡞ࡗ࡚࠸ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ

(a)edge-on 㓄ྥ࡜(b)face-on 㓄ྥࡢ࣌ࣥࢱࢭࣥ/C60 ⏺㠃ᵓ㐀ࠋ(c)(d)ࡑࢀࡒࢀࡢ CT ≧ែࡢ྾཰ࢫ࣌ࢡ
ࢺࣝࠋ㉥ࡀ㟁Ⲵࡢ㠀ᒁᅾ໬ࢆධࢀࡓሙྜ࡛ࠊ⥳ࡣᒁᅾ໬ CT ≧ែࡢ⤖ᯝࠋD. 㠀ࣇ࣮ࣛࣞࣥ⣔ኴ㝧㟁ụࡢ CT ≧ែ ㏆ᖺࠊࣇ࣮ࣛࣞࣥ௨እࡢศᏊࢆኴ㝧㟁ụࡢ㟁Ꮚ࢔ࢡࢭࣉࢱ࣮࡜ࡋ࡚⏝࠸ࡿヨࡳࡀ㐍ࡵࡽࢀ࡚࠾ࡾࠊ࢚ࢿࣝ
ࢠ࣮ኚ᥮ຠ⋡ࡣ 17%ࢆ㉸࠼࡚࠸ࡿࠋࡋ࠿ࡋࠊ࡝ࡢࡼ࠺࡟㧗ຠ⋡࡞ග㟁ኚ᥮ࡀ㐩ᡂࡉࢀ࡚࠸ࡿ࠿࡟ࡘ࠸࡚ࡣࠊ
᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣ PEN/C60 ⏺㠃࡜ PEN/C8-PTCDI ⏺㠃ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊ㠀ࣇ࣮ࣛࣞࣥ⣔ኴ㝧㟁ụ࡟≉᭷ࡢ㟁Ⲵ⛣ື≧ែࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ᣦࡍࠋ⌧ᅾࡲ࡛ࡣ FMO-GW/BSE ࡟ࡼࡿண- 474 -

ഛⓗ࡞ィ⟬⤖ᯝࡀᚓࡽࢀ࡚࠾ࡾࠊ(a)C8-PTCDI ࡛ࡣගບ㉳ࡋࡓ㟁Ꮚࡀᣑࡀࡾࡸࡍ࠸ࠊ(b)PEN/C60 ⣔࡛ࡣບ㉳࢚ࢿࣝࢠ࣮ࡀቑ኱ࡍࡿ࡟ᚑ࠸ບ㉳Ꮚ᮰⦡࢚ࢿࣝࢠ࣮ࡀᑠࡉࡃ࡞ࡿࡀࠊPEN/C8-PTCDI ⣔࡛ࡣບ㉳Ꮚ᮰⦡࢚ࢿ
ࣝࢠ࣮ࡣບ㉳࢚ࢿࣝࢠ࣮࡟࠶ࡲࡾ౫Ꮡࡋ࡞࠸ࠊ࡞࡝ࡢ⤖ᯝࡀᚓࡽࢀ࡚࠸ࡿࠋ௒ᚋࡣ㟁Ⲵ⛣ື≧ែࡢᒁᅾᛶ/㠀ᒁᅾᛶࡸ㟁Ⲵ෌⤖ྜ࡟ࡘ࠸࡚ࡢゎᯒࡶ㐍ࡵ࡚࠸ࡃணᐃ࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
⸨⏣ ㈗ᩄ, ͇ ࣇࣛࢢ࣓ࣥࢺศ๭ᆺ GW/BSE ἲࡢ㛤Ⓨ࡜ᛂ⏝͇,ィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔࣒

㸦PCoMS㸧ࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍ 2020, ࢜ࣥࣛ࢖ࣥ, 2021 ᖺ 2
᭶ 15 ᪥

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
Takatoshi Fujita, Yoshifumi Noguchi, Takeo Hoshi, Revisiting the Charge-Transfer States at Pentacene/C60

Interfaces with the GW/Bethe–Salpeter Equation Approach”, Materials, vol. 13, p. 2728. (2021).
Takatoshi Fujita, (Masahiro Hiramoto and Seiichiro Izasa, Eds.), “First-Principles Investigations of Electronically
Excited States in Organic Semiconductors”, In “Organic Solar Cells”, Springer Nature, (2021).
Takatoshi Fujita and Takeo Hoshi, (Yuji Mochizuki, Shigenori Tanaka, and Kaori Fukuzawa, Eds.), “FMO-based
excited state dynamics in molecular aggregates”, In “Recent Advances of the fragment molecular orbital method”,
Springer Nature, Singapore, (2021).

- 475 -



Structures and Properties of Molecular Nanocarbons
¬ «ºÞi»ß

1

»¾¸·g#²±¿±Ã%¸,Ä)¸ `¹a!°µ¦Ö2+fi

2DQX?7Vfi`Ç1."sÂÓÁ,z¼¯"Á2Ê 0
]w#DFT2´

7ZPYEHOVD"$)6GV9Z2ÎÀ0©2Ù¶



2

»¾©ÎÀ©
ÎÀ#eGaussian 162b´Ê B3LYP/6-31G(d)2´

¦Ö!

3

¦Ö×m2Ê.1

lÎÀ2Ê ¦Ö2¨»¾¤
7ZPYEHASZL(CNT)"Øi¦Öi

07ZPYEHOVD(CNB)#"±f$)CYMWZDCNTs&"´"rÈ.Ôª¸2Ü*0Ô";VZM#4ZRA54yCNB?;=;yCNB2s1."º"CNB_~!
+CNT"j©2}0-/ÌÝ
NU@Y¦Ö2+CNB#"^Ëc¦Ö2+CNB2ÐÎ0rÈ

/"-

0

¡Ù"CNB"¦Ö·°ª¸10$3¿±ms¯"srÈ2Í½+0
*!#$)6GV9ZÞSEß"ÎÀk

0$3iÞ>:XITK5FWYß!

#p®i2´©[É·!´.1

SEd¶³0|sabhomodesmoticq

0¢©#Ò"

n–2

n–3

Bn

/CNB!#×´armchaircarbon nanotubes#2016![n]<Z8SWY"SEÀh©!JYD2CNB"SEÀh©0Åwi£©2{v"©#­Û!

n–2

CNB"Æ/Õo`2p®!homodesmoticAnDn0 "©"§´#ni!¥Ï1

¦Ö

0CNB!"©×´0



n–3

n–3

q)
.

Cn

En

.°!NU@Y#(\ ("Åw©"NU@Yu CNB&"×´2Ñ'x#CNB AnÞn = 4-16ß
-%BnÞn = 4-14ß"Æ/Õo`
0{v1/"e6GV9Z2n–2"ÚMXBD+"

0i£Ã¤Þn = 3-6ßt1!<- 476 -

" P"Þn = 7-16ß+An"MXBD#Ô9Å-[F[Bn"MXBD# <|s9Å .~102:!;)""MXBD#"Åwi£©Bn!×´

01#An#< 0!1$e!KTBD$"!

­ÛÞnß!

¦Ö!/$)30Bn#<.E.10"-+.3±"!&<!"CNB¦Ö°!NU@YØi¦Ö2u CNB¦Ö2×´<!0*!#.©"-G(I""CNBÞn = 10-14ß2×´

0

R2J¨0*!Åwi£¢"homodesmoticq2@)s (Bn!homodesmoticq2×´[4]NU@YØ`"OY

Y²2NÞretro-benzannulationß

Bn2ONU@YCNB Fn!},Fn"³6#EKWYK5EYDWY2­$)p®i´ÎÀ2!Fn!Åwi£2×´n"Ú"$)6GV9Z2

4*"Ã¤SE(Fn)#265.9·n–1 kcal mol–1S Q¨1'!Bn .Fn&"a³6Fn"SE"2"d2s NU@
CNB Bn"SE24*.1SE

Y2uÞBnß"d#85.9ÞnT4ß90.1ÞnT5ß99.1
ÞnT6ßkcal mol–1

" LUB

n–2

©#[5]NU@Y2u CNB!+×´BnWYK5EYDWY2´!×L"EKÊ

SE(Fn): 265.9·n–1 kcal·mol–1+

2n0!Cn .

Gn&"},#x!;-Fn+

0CNB Gn#[5]NU@Yu CNB Cn!
0ONU@Y¦Ö

n–2

2n

b



0³6ÞÆ/Õo`n!11
U32 kcal mol–1ßSEÞGnßdÞ336.1·n–1 kcal
–1

mol ß

n–3

.Cn"SEd20

+01©#=o)·

Gn
n–3

q!-

Cn
+

ONU@Y>CNB!},0NU@Yu

4n

CNB![É·!×´0ASE(Gn): 336.1·n–1 kcal·mol–1+
4nM!NU@Y¦Ö2+CNB2Ñ'NU@Y¦Ö2*CNB"

benzannulation#ONU@Y¦Ö"CNB!},

- 477 -

retro-CNB"^ËCNB"DnEn2ÐÎDn,En"-

CNB211

0ONU@Y>CNBa

0Hn,In!},0*!#)· C–CÃsq,OYB²q×´02Íh

n–3

n–3

x!;-!OY[ghi]UWY

Dn

–

+

ÞbpSE=0ß
[5]NU@YÞSE=14.5 kcal mol
1ßHnÞSE=588.5·n–1 kcal mol–1ß2´

Hn

SE(Hn): 588.5·n–1 kcal·mol–1
+

2n

2n

Dn"homodesmoticq$t1!

[5]helicene
SE: 14.5 kcal·mol–1

bp–1bp[4]NU@YÞSET7.6 kcal mol ßIn
Þ643.2·n–1 kcal mol–1ß2´SEÞEnß"Jb£!CNB#CNT"#¦Ö2Ë
$e!B²iD1

0*[6]_"NU@Y¦Ö#5?K

0*CNB!#u(1!]w"En§´· ©n–3
In–1
SE(In): 643.2·n kcal·mol–1++

LUB©#¢"©

"Û82H '"rÈ
´rÈ

n–3

"-

CNB¦Ö!×



2n

2n

bp

4

[4]helicene
SE: 7.6 kcal·mol–1¶Ëh7%C(# Double-helix supramolecular nanofibers assembled from negatively curved nanographenes
Kenta Kato,† Kiyofumi Takaba,† Saori Maki-Yonekura,† Nobuhiko Mitoma, Yusuke Nakanishi, Taishi
Nishihara, Taito Hatakeyama, Takuma Kawada, Yuh Hijikata, Jenny Pirillo, Lawrence T. Scott, Koji
Yonekura,* Yasutomo Segawa,* and Kenichiro Itami* († equal contribution)
J. Am. Chem. Soc. 2021, 143, 5465-5469. DOI: 10.1021/jacs.1c00863
 Synthesis of a zigzag carbon nanobelt
Kwang Yin Cheung, Kosuke Watanabe, Yasutomo Segawa,* and Kenichiro Itami*
Nature Chem. 2021, 13, 255-259. DOI: 10.1038/s41557-020-00627-5.
 A theoretical study on the strain energy of helicene-containing carbon nanobelts
Kosuke Watanabe, Yasutomo Segawa,* and Kenichiro Itami*
Chem. Commun. 2020, 56, 15044-15047. DOI: 10.1039/D0CC06373H
 Creation of negatively curved polyaromatics enabled by annulative coupling that forms an eight-memberedring
Satoshi Matsubara, Yoshito Koga, Yasutomo Segawa, Kei Murakami,* and Kenichiro Itami*Nat. Catal. 2020, 3, 710–718. DOI: 10.1038/s41929-020-0487-0
 A Nonalternant Aromatic Belt: Methylene-Bridged [6]Cycloparaphenylene Synthesized from Pillar[6]arene
Yuanming Li, Yasutomo Segawa, Akiko Yagi, and Kenichiro Itami*
J. Am. Chem. Soc. 2020, 142, 12850–12856
 Synthesis of Cycloiptycenes from Carbon Nanobelt
Hiroki Shudo, Motonobu Kuwayama, Yasutomo Segawa,* and Kenichiro Itami*
Chem. Sci. 2020, 11, 6775-6779.

- 478 -

㑄⛣㔠ᒓ㘒యゐ፹ࢆ⏝࠸ࡿ᭷ᶵ཯ᛂࡢ཯ᛂᶵᵓ◊✲
̿ᮌ㉁ࣂ࢖࣐࢜ࢫ㓟໬ศゎ≀ࡢගᶵ⬟≀㉁࡬ࡢᛂ⏝Theoretical Study on Transition-Metal-Catalyzed Organic Reactions-Lignin Valorization to Photoemissive Materials˕߶୫ ޭʤ෾ࢢՌָ‫ॶڂݜ‬ʥɾࢃຌ ಲ࢞ʤ‫౐ښ‬୉ָԿָ‫ॶڂݜ‬ʥɾֿଞ ‫ښ‬Ҳ࿢ʤ஦෨୉
ָ޽ָ෨ʥɾঘࡖ ༑ଢɾұ෨ քࢦɾؔੋ ை೯ʤ੫Ԯ୉ָ޽ָ෨ʥ
̏ɿ‫ڂݜ‬໪ద໨࣯஦Ͷ༁ 30%‫؜‬ΉΗΖϓΥόʖϩ੓߶෾ࢢͲ͍ΖϨήωϱͺɾ୦ϛϨϜʖԿͶΓͮͱ༹ʓ͵๗ߵଔ੓෾
ࢢ͗ಚΔΗΖͪΌɾ࠸ਫ਼Ն೵͵Կָࣁ‫غͱ͢ͳݱ‬ଶ͠Ηͱ͏Ζɽ‫ࡑݳ‬ΉͲͶϨήωϱ͖Δଡ༹͵ଡ‫ׯ‬೵‫خ‬੓ϓΥόʖϩ͗ಚΔΗΖ͞ͳ͗ๅࠄ͠Ηͱ͏Ζ͗ɾࣰࡏͶཤ‫͠༽׈‬Ηͱ͏ΖϨήωϱ༟པ͹๗ߵଔ੓Կ߻෼ͺߵྋΏৱ඾శՅ෼ͳ͢ͱ༽౏ཱི֮͠ΗͪήΠ΢Παʖϩ͕Γ;ώωϨϱͶ‫ݸ‬ఈ͠Ηͱ͏Ζɽͨ͹ͪΌɾϨήωϱ१‫ݱࣁ؂‬Կ͹ͪΌͶͺɾ߶ްི͵੠ື෾մൕԢ͹֋൅͹Ί͵ΔͥɾಚΔΗΖϓΥόʖϩྪ͹༽౏֋൅Ν੷‫ۅ‬దͶߨ͏ɾ༙‫ ؽ‬E L Ώҫ༂඾౵͹߶෉ՅՃ஍ ͵‫ؽ‬೵੓෾ࢢ΃͹ఴ֋‫ڂ ݜ‬Νߨ͵͑චགྷ͍͗Ζɽըʓ͹‫ڂݜ‬ήϩʖϕͲͺɾ໨ฆ஦ϨήωϱΝ௜ં෾մͤΖ͞ͳͶΓͮͱଡ‫ׯ‬೵‫خ‬੓ϓΥόʖϩΝਫ਼ࢊͤΖ
ৰഖൕԢ͹֋൅͕Γ;ಚΔΗΖϓΥόʖϩྪ͹‫ؽ‬೵੓ࡒྋ΃͹ఴ֋Ͷ‫ͤؖ‬Ζ‫ܧ‬౹ద͵‫ڂݜ‬Νߨ͵ͮͱͪ͘ɽ
ͨ͹݃Վɾᅗ 1 Ͷ༹ࣖͤͶ໨࣯Ϩήωϱ͹࢐Կ෾մͶΓͮͱζίφϱ෨ҒΝ༙ͤΖϓΥόʖϩྪͲ͍Ζ
Hibbert ketone [1]Ν༫͓Ζ৿घ๑͕Γ; Hibbert ketone Ν‫ݬ‬ྋͳͤΖ൅ޭ੓ϓΥόʖϩʷϖτϫ๗ߵଔԿ߻෼
ʤPHʥ͹֋൅Ͷ੔ޯͪ͢[2][3]ɽຌ‫Ͳڂݜ‬ͺɾరৰഖͶΓΖ໨࣯Ϩήωϱ෾մ͹ൕԢ‫ߑؽ‬մ໎͕Γ;൅ޭ੓ PH͹൅ޭ‫ߑؽ‬͹մ໎Ν໪దͳ͢ͱ DFT ‫ࢋܯ‬ͶΓΖཀྵ࿨‫ڂݜ‬Νߨ͵ͮͪɽຌๅࠄॽͲͺ PH ྪ൅ޭ‫ߑؽ‬Ͷ‫ͤؖ‬Ζ‫ڂݜ‬੔Վ͹ΊΝ‫ͪ͢ࡎى‬ɽ

ᅗ 1. ᮌ⢊୰ࣜࢢࢽࣥࡢ㓟໬ศゎ࡟ࡼࡿ௚ᐁ⬟ᇶᛶࣇ࢙ࣀ࣮ࣝ⏕⏘࡜Ⓨගᛶࣇ࢙ࣀ࣮ࣝ࢟ࣀࣥ one-pot ྜᡂ̐ɿ‫ڂݜ‬๏๑ɾ‫ࢋܯ‬๏๑ᡃࠎࡀ Hibbert ࢣࢺࣥ࠿ࡽྜᡂࡋࡓⓎගᛶ PH 㢮ࡢ UV-vis ࠾ࡼࡧ⺯ගࢫ࣌ࢡࢺࣝࢆ

ᐃࡋࡓ࡜ࡇࢁ㸪㠀ᖖ࡟኱ࡁ࡞ࢫࢺ࣮ࢡࢫࢩࣇࢺࢆ♧ࡋ㸪⨨᥮ᇶࡢ㟁Ꮚ౪୚/ồᘬᛶ࡟ࡼࡗ࡚Ⓨග㣗ࡀ㟷㹼ᶳⰍࡲ࡛኱ࡁࡃ␗࡞ࡿ
࡜࠸࠺≉ᚩࢆ♧ࡋࡓ㸦ᅗ 2㸧ࠋศᏊෆ࡟ᙉ࠸㟁Ꮚ౪୚ᛶࢆ♧ࡍࣇ࢙ࣀ࣮ࣝᇶ࡜㟁Ꮚཷᐜᛶࡢ㧗࠸࣊ࢸࣟⰾ㤶᪘ࡀඹᏑࡍࡿࢻ
ࢼ࣮࢔ࢡࢭࣉࢱ࣮ᵓ㐀࠿ࡽ㸪ศᏊෆ㟁Ꮚ⛣ື࡟ᇶ࡙ࡃ㟁Ⲵศ㞳≧ែ࠿ࡽࡢ⦆࿴࡟ࡼࡿⓎගᶵᵓࡀ⪃࠼ࡽࢀࡓࠋࡑࡇ࡛㸪⨨᥮ᇶ R ࡜࣊ࢸࣟⰾ㤶᪘㒊ศࡀ␗࡞ࡿྛ✀ PH 㢮࡟ࡘ࠸࡚㸪TDDFT ィ⟬ࢆ⾜࠸㸪୍㟁Ꮚບ㉳㐣⛬࡟࠾ࡅࡿ㟁Ꮚ≧ែ㸪࢚ࢿࣝࢠ࣮㸪ศᏊᵓ㐀࡟ࡘ࠸࡚ヲ⣽࡞᳨ウࢆ⾜ࡗࡓࠋ᭱Ᏻᐃᵓ㐀ࢆᑟฟࡍࡿࡓࡵ࡟㸪ྛ PH ศᏊࡢ༢⤖ᬗ X ⥺ᵓ㐀ゎᯒ࠿ࡽᚓࡽࢀ  ᅗ 2. PH ࡢ⺯ග㸦Oex = 280 nm, toluene㸧- 479 -

ࡓཎᏊᗙᶆࢆึᮇᵓ㐀࡜ࡋ࡚ B3LYP/6-31G*ࣞ࣋ࣝィ⟬࡛ᵓ㐀᭱㐺໬ࢆ⾜࠸㸪ࡉࡽ࡟ GRRM ィ⟬࡟ࡼࡗ࡚ࣇ
࢙ࣀ࣮ࣝ㸫࣊ࢸࣟⰾ㤶⎔࠾ࡼࡧྛ⨨᥮ᇶࡢ᭱Ᏻᐃ㓄ᗙࢆồࡵࡓࠋᚓࡽࢀࡓ᭱Ᏻᐃ㓄ᗙ࡟ࡘ࠸࡚ࣇ࢙ࣀ࣮ࣝ㸫࣊ࢸࣟⰾ㤶⎔ࡢ஧㠃ゅࢆ 10rẖ࡟ኚ໬ࡉࡏ࡞ࡀࡽ ບ ㉳ ≧ ែ ⦆ ࿴ ᮲ ௳ ࡛ TD-DFT 㸦 LC-BLYP/631G*㸧ィ⟬ࢆ⾜ࡗ୍࡚㟁Ꮚບ㉳≧ែࡢᵓ㐀࣭࢚ࢿࣝࢠ࣮࣭㑄⛣࣮࣓ࣔࣥࢺࢆᑟฟࡋࡓࠋ௦⾲౛࡜ࡋ࡚㸪ᮏ◊✲࡛ᚓࡽࢀࡓ PH 㢮୰࡛⺯ග㔞Ꮚ཰⋡ࡀ᭱ࡶ㧗࠿ࡗࡓ Phenol-Pyrazine(CN)2 ศᏊࡢィ⟬⤖ᯝ࡟ࡘ࠸࡚ᅗ 3 ࡟ࡣ♧ࡋࡓࠋᮏィ⟬࡛ࡣ㛗㊥㞳┦஫స⏝ࢆ⪃៖ࡋࡓ LC-BOP㸪CAM-B3LYP ࡀ UVvis ࢫ࣌ࢡࢺࣝࡢᐇ

್࡜Ⰻ࠸୍⮴ࢆ♧ࡍ྾཰Ἴ㛗㸦࢚ࢿࣝࢠ࣮㸧ࢆ୚࠼ࡓࡀ㸪㛗㊥㞳⿵ṇࢆ⪃៖ࡋ࡞࠸ B3LYP ࡸ BOP ỗ㛵ᩘࢆ⏝࠸ࡓሙྜࡣᐇ
್࡜኱ࡁࡃ␗࡞ࡿ⤖ᯝࡀᚓࡽࢀࡓࠋ    

ᅗ 3. ࣇ࢙ࣀ࣮ࣝ-ࣆࣛࢪࣥ஧㠃ゅ࡜ບ㉳࢚ࢿࣝࢠ࣮┦㛵̑ɿ‫ڂݜ‬੔Վ
Phenol-Pyrazine(CN)2 ศᏊࡢ TD-DFT ィ⟬ࡢ⤖ᯝ࠿ࡽ㸪஧㠃ゅȟࡀ 2.6rࡢ㝿࡟᭱ࡶᏳᐃ࡞ບ㉳≧ែࢆ୚࠼㸪ࡑࡢ㝿࡟ HOMOЍLUMO ࠾ࡼࡧ HOMOЍLUMO+1 ࡟࠾࠸࡚኱ࡁ࡞㑄⛣࣮࣓ࣔࣥࢺࢆ୚࠼ࡿࡇ࡜ࡀ᫂ࡽ
࠿࡜࡞ࡗࡓ㸦ᅗ 4㸧ࠋࡑࢀࡒࢀࡢ㟁Ꮚ㌶㐨࠾ࡼࡧᇶᗏ≧ែ㸫ບ㉳≧ែࡢ㟁Ꮚᐦᗘᕪศᕸ࠿ࡽ㸪ࣇ࢙ࣀ࣮ࣝ㸫ࣆࣛࢪࣥ⎔ࡀ⤖ྜࡋࡓศᏊ඲య
࡟ศᕸࡍࡿ LUMOЍHOMO ࡬ࡢ⦆࿴࡟ࡼࡿ LE Ⓨග㐣⛬࡜ࣇ࢙ࣀ࣮ࣝ࠿ࡽࣆࣛࢪࣥ⎔࡬ࡢ㟁Ⲵ⛣ືບ㉳ࢆ⤒⏤ࡍࡿ ICT Ⓨග⤒㊰ࡀΰྜࡋࡓ≧ែ࡛࠶ࡿࡇ࡜ࡀศ
࠿ࡗࡓࠋᑦ㸪኱ࡁ࡞ࢫࢺ࣮ࢡࢫ
ࢩࣇࢺ࠿ࡽࣇ࢙ࣀ࣮ࣝ࡜ࣆࣛࢪ
ࣥ⎔ࡀࡡࡌࢀࡓ≧ែ࠿ࡽࡢⓎග⤒㊰ࡀᏑᅾࡍࡿ࡜᥎ᐹࡉࢀࡿ
ࡀ㸪ヲ⣽ࡣィ⟬㏵୰࡛࠶ࡿࠋ  ᅗ 4. ࣇ࢙ࣀ࣮ࣝࣆࣛࢪࣥࡢ LE ࠾ࡼࡧ ICT Ⓨග⤒㊰̒ɿ൅නࣰ੹
[1] ೖຌԿָճ୊ 101 ॡ‫ل‬೧ճɾA15-3pm-01ɾΨϱϧ΢ϱɾ2021 ೧ 3 ݆ 21 ೖ̓ɿड़൝ࣰ੹Ήͪͺ༩ఈ
RSC Advances Ͷ౦ߚ༩ఈࢂߡช‫ݛ‬[1] Brickman, L.; Pyle, J. J.; Hawkins, W. L.; Hibbert, H. J. Am. Chem. Soc. 1940, 62, 986.
[2] ోวཾ࢚ɾ஦ଞਜ਼࣑ɾ߶୫ޭɾঋࢃ༒ɾෳీ࣑݊ɾಝ֋ 2017-145244.
[3] ోวཾ࢚ɾ஦ଞਜ਼࣑ɾ߶୫ޭɾұ࡜ঋ߄ɾϓϧϱοΥηΩ ϒϱοΥϧɾෳీ࣑݊ɾಝ֋ 20207244.

- 480 -

ᚤᑠ⟶ࡢࢩ࣮࣒㡿ᇦ࡟࠾ࡅࡿᵓ㐀㞟ᅋࡢศᏊືຊᏛィ⟬ゎᯒ
Molecular dynamics simulation for seam region of microtubule
‫ۑ‬ᱵ⃝

1

බ஧ࠊᒣཱྀ

ᗣኴࠊ➉ෆ

ᕊ㸦ಙᕞ኱Ꮫ㎰Ꮫ㒊㸧◊✲┠ⓗᚤᑠ⟶ࡣ⣽⬊࡟࡜ࡗ࡚Ḟ࠿ࡍࡇ࡜ࡢ࡛ࡁ࡞࠸⣽⬊㦵᱁࡛࠶ࡿࠋ

ᚤᑠ⟶ࡢᏳᐃᛶࡣ⣽⬊ศ⿣ࠊ⚄⤒⣽⬊ࡢ≀㉁㍺㏦࡞࡝࡟῝ࡃ㛵ࢃࡗ࡚࠸ࡿࠋᮏ◊✲ࡢ┠ⓗࡣࠊᚤᑠ⟶ࡢᏳᐃᛶ࡟㛵ࢃࡿ㸱ࡘࡢせ⣲㸦ࢾࢡࣞ࢜ࢳࢻ≧ែࠊኳ↛ኚᛶ㡿ᇦ࠾ࡼࡧࢩ࣮࣒㡿ᇦ㸧࡟╔┠ࡋࠊࡑࢀࡽࡢ㛵㐃ᛶࢆ❧యᵓ㐀㞟ᅋ࠿ࡽゎࡁ᫂࠿ࡍࡇ࡜࡛
࠶ࡿ㸦ᅗ㸯㸧ࠋᚤᑠ⟶ࡣ෇⟄≧ࡢ㔜ྜయ࡛࠶ࡾࠊȘ࠾ࡼࡧșࢳ࣮ࣗࣈࣜࣥ࠿
ࡽ࡞ࡿ࣊ࢸࣟ஧㔞యࡀ㔜ྜࡋ࡚ᙧᡂࡉࢀࡿࠋᚤᑠ⟶ࡢ㔜ྜഃ㸦㸩➃㸧࡟ࡣࠊșࢳ࣮ࣗࣈࣜࣥ࡟ GTP ࡀ⤖ྜࡋ࡚࠸ࡿ࣊ࢸࣟ஧㔞య
㸦GTP ⤖ྜᆺ㸧ࡀ⤖ྜࡋ࡚ࡃࡿࠋ㔜ྜᚋ࡟ࡣࠊᚤᑠ⟶ෆ࡛ GTPࡢຍỈศゎࡀ⏕ࡌࠊGDP ࡜࡞ࡿࠋ㸩➃ࡢ཯ᑐഃ࡟࠾࠸࡚ࠊGDP⤖ྜᆺࡢ࣊ࢸࣟ஧㔞యࡀ⬺㔜ྜࡍࡿࠋࡘࡲࡾࠊᚤᑠ⟶ࡢ⬺㔜ྜഃ㸦㸫➃㸧࡜㸩➃࡟࠾࠸࡚ࠊࢳ࣮ࣗࣈࣜࣥࡣ
␗࡞ࡿࢾࢡࣞ࢜ࢳࢻ≧ែ࡜ࡋ࡚Ꮡᅾࡋ࡚࠾ࡾࠊᚤᑠ⟶ࡢ㔜ྜ࣭⬺㔜ྜࡢࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࢃࡗ࡚࠸ࡿࠋ
ࢳ࣮ࣗࣈࣜࣥࡢ࢔࣑ࣀ㓟㓄ิࡢ C ᮎ➃ഃ࡟ࡣࢢࣝࢱ࣑ࣥ㓟ṧᇶ࡟ᐩࡴ㡿ᇦ㸦E-hook ࡸ C ᮎ➃ࢸ࢖ࣝ(C-Terminal-Tail: CTT) 㡿ᇦ࡜࿧ࡤࢀࡿ㸧ࡀᏑᅾࡍࡿࠋ
Șࢳ࣮ࣗࣈࣜࣥ࠾ࡼࡧșࢳ࣮ࣗࣈࣜࣥࡢࡑࢀࡒࢀ࡟ CTT㡿ᇦࡀ࠶ࡾࠊșࢳ࣮ࣗࣈࣜࣥࡢ CTT 㡿ᇦ㸦șCTT㸧ࡣȘࢳ࣮ࣗࣈࣜࣥࡢ CTT 㡿ᇦ㸦ȘCTT㸧ࡼࡾࡶ㛗࠸ࠋȘ
CTT ࠾ࡼࡧșCTT ࡣኳ↛ኚᛶ㡿ᇦ࡛࠶ࡾࠊ୙つ๎࡞❧యᵓ㐀㞟ᅋࢆᙧᡂࡋ࡚࠸ࡿࠋCTT 㡿ᇦࡣ୍ᐃࡢ❧యᵓ㐀ࢆᙧᡂࡋ࡞࠸࡟ࡶ㛵ࢃࡽࡎࠊṇᖖ࡞෇⟄ᵓ㐀ࡢᙧᡂࡸ㔜ྜ࣭⬺㔜ྜࢲ࢖ࢼ࣑ࢡࢫ࡟Ḟ࠿ࡍࡇ࡜ࡢ࡛ࡁ࡞࠸
ᙺ๭ࢆᢸࡗ࡚࠸ࡿࠋຍ࠼࡚ࠊᚤᑠ⟶࡜⤖ྜࡋࠊ≀㉁㍺㏦㸦౛࠼ࡤࠊ࢟ࢿࢩࣥ㸧ࡸᚤᑠ⟶ࡢᏳᐃ໬㸦౛࠼ࡤࠊࢱ࢘⺮ⓑ㉁㸧࡟㛵㐃ࡍࡿ⺮ⓑ㉁࡜ࡢ⤖ྜ࡟ CTT 㡿ᇦࡣ㛵୚ࡋ࡚࠸ࡿࠋ
ᚤᑠ⟶ࡢᵓ㐀Ᏻᐃᛶ࡟ࡣࠊ෇⟄ᵓ㐀ࡢ͆⥅ࡂ┠͇㡿ᇦ㸦ࢩ࣮࣒㡿ᇦ㸧ࡢᏳᐃᛶࡀ኱஦࡛࠶ࡿࠋࢩ࣮࣒㡿ᇦࡢᔂቯࡣ⬺㔜ྜࡢ㛤ጞ࡟ࡘ࡞ࡀࡗ࡚࠸ࡿࠋࢩ࣮࣒㡿ᇦ࡟࠾࠸࡚ࠊ㞄ࡾྜ࠺ࢳ࣮ࣗࣈࣜࣥ࣊ࢸࣟ஧㔞యࡣ௚࡜ࡣ␗࡞ࡿ⏺㠃ࢆᙧᡂࡋ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࢩ࣮࣒㡿ᇦ࡟࠾ࡅࡿ࣊ࢸࣟ஧㔞యࡢ CTT 㡿ᇦࡀ࡝ࡢࡼ࠺࡟✵㛫ⓗ࡟ศᕸࡋ࡚࠸ࡿ࠿ࡣ᫂ࡽ࠿࡛ࡣ࡞࠸ࠋ
௨ୖࡢࡼ࠺࡟ࠊ
ᚤᑠ⟶ࡢᏳᐃᛶ࡟ࡣࢾࢡࣞ࢜ࢳࢻ≧ែ࠾ࡼࡧ CTT 㡿ᇦࠊࢩ࣮࣒㡿ᇦࡢᵓ㐀ࡀ㛵ࢃࡗ࡚࠸ࡿࠋ
ࡋ࠿ࡋࠊࡑࢀࡽ㸱ࡘࡢせ⣲ࡑࢀࡒࢀࡢ㔜せᛶࡣ▱ࡽࢀ࡚࠸ࡿࡶࡢࡢࠊせ⣲㛫ࡢ㛵㐃ᛶࡣゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋ
CTT 㡿ᇦࡣ㞄ࡾྜ࠺࣊ࢸࣟ஧㔞యࡢ⏺㠃௜㏆࡟఩⨨ࡋ࡚࠸ࡿࠋࡲࡓࠊCTT 㡿ᇦࡢ㈇㟁Ⲵࡣࢾࢡࣞ࢜ࢳࢻ≧ែ࡟ࡼࡗ࡚㟼㟁ⓗ࡟ᛂ⟅ࡍࡿྍ⬟ᛶࡀ࠶ࡿࠋࡇࢀࡲ࡛㸱ࡘࡢせ⣲㛫ࡢ㛵㐃ᛶ࡟╔┠ࡉࢀ࡞࠿ࡗࡓ⌮⏤࡜ࡋ࡚ࠊ
CTT 㡿ᇦࡀኳ↛ኚᛶ㡿ᇦ࡛࠶ࡾࠊᵓ㐀ⓗ≉ᚩࢆᤊ࠼࡟ࡃ࠸ࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ࠊᡃࠎࡣศᏊィ⟬ࢆᚤᑠ⟶ࡢࢩ࣮࣒㡿ᇦࣔࢹࣝ࡟ࡘ࠸࡚㐺⏝ࡋࠊ㸱ࡘࡢせ⣲㛫ࢆ❧యᵓ㐀㞟ᅋ࠿ࡽゎࡁ᫂࠿ࡍࡇ࡜࡟ࡋࡓࠋ

- 481 -

2◊✲᪉ἲࠊィ⟬᪉ἲᚤᑠ⟶ࢩ࣮࣒㡿ᇦࡢศᏊࣔࢹࣝࢆ GTP ᆺ࠾ࡼࡧ GDP ᆺࡢᚤᑠ⟶ᵓ㐀㸦ࡑࢀࡒࢀࠊProtein Data Bank ID:3J6E ࠾ࡼࡧ 3J6F㸧࠿ࡽసᡂࡋࡓࠋィ⟬⣔࡟ࡣࠊࢳ࣮ࣗࣈࣜࣥ࣊ࢸࣟ஧㔞యࢆ㸷ࡘ㓄⨨ࡋࡓࠋࡲࡓࠊ࠶ࡽࢃ࡟
ỈศᏊ࠾ࡼࡧ࢖࢜ࣥࢆ㓄⨨ࡋࡓࠋCTT 㡿ᇦࡢึᮇᵓ㐀ࡣ Modeller ࢆ⏝࠸࡚ࣔࢹࣜࣥࢢࡋࡓ㸦ᅗ㸰㸧ࠋࡘࡲࡾࠊ඲ཎᏊࣔࢹࣝ࡟ࡼࡿᚤᑠ⟶ࢩ࣮࣒㡿ᇦࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋࡓࠋィ⟬⣔ෆࡢཎᏊᩘࡣ 100୓ಶࢆ㉸࠼ࡿ኱ࡁࡉ࡜࡞ࡗࡓࠋึᮇᵓ㐀ࡢᙳ㡪ࢆ᤼㝖ࡍࡿࡓࡵࠊCTT 㡿ᇦ࡟ࡢࡳࢩ࣑࣮ࣗࣞࢸࢵࢻ࢔ࢽ࣮ࣜ
ࣥࢢἲࢆ⏝࠸ࡓࠋࢩ࣑࣮ࣗࣞࢸࢵࢻ࢔ࢽ࣮ࣜࣥࢢ࡟࠾ࡅࡿ
⛊ (ns)࠿ࡅ࡚㝆ᗘタᐃࡣࠊ800 K ࠿ࡽጞࡵ࡚ 300 K ࡲ࡛ 10 ࢼࣀ

ࡉࡏࠊCTT 㡿ᇦ௨እࡣ 300 K ࡜ࡋࡓࠋࡑࡢᚋࠊ300 K ࡟࠾ࡅࡿ 500 ns ࡢᵓ㐀ࢧࣥࣉࣜࣥࢢ

ࢆᐇ᪋ࡋࡓࠋࢩ࣑࣮ࣗࣞࢸࢵࢻ࢔ࢽ࣮ࣜࣥࢢ࠾ࡼࡧᵓ㐀ࢧࣥࣉࣜࣥࢢࢆ GTP ᆺ࠾ࡼࡧ GDP ᆺࡑࢀࡒࢀ࡟ᑐ
ࡋ࡚ 12 ᮏࡎࡘᐇ⾜ࡋࡓࠋィ⟬࡟౑⏝ࡋࡓࣉࣟࢢ࣒ࣛ࡟ࡣ Amber ࢆ⏝࠸ࡓࠋࢩ࣑࣮ࣗࣞࢸࢵࢻ࢔ࢽ࣮ࣜࣥࢢࡣᙜ◊✲ᐊ㸦ಙᕞ኱Ꮫ㎰Ꮫ㒊ᶵ⬟ศᏊタィᏛ◊✲ᐊ㸧ࡢィ⟬ᶵ࡟࡚ᐇ᪋ࡋࡓࠋᅗ㸱࡟ࢩ࣑࣮ࣗࣞࢸࢵࢻ࢔ࢽ࣮ࣜࣥࢢᚋࡢ௦⾲ᵓ㐀ࢆ♧ࡍࠋࡑࡢᚋࡢᵓ㐀ࢧࣥࣉࣜࣥࢢࡣ㈗◊✲ᡤ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧ࡢ GPU ᦚ㍕ࢡࣛࢫࢱ࣐ࢩࣥࢆ฼⏝ࡍࡿࡇ࡜࡛ࠊᐇ᪋ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋィ⟬࡟せࡋࡓ᫬㛫ࡣࠊ1GPU ࠾ࡼࡧ 1CPU ࡢࣜࢯ࣮ࢫࢆ౑⏝ࡋࠊGTP ᆺࢩ࣮࣒㡿ᇦࣔࢹࣝ࡟࡚ 6 ns/dayࠊGDP ᆺࢩ࣮࣒㡿ᇦࣔࢹ࡛ࣝࡣ 8 ns/day ࠿࠿ࡗࡓࠋࡲࡓࠊࡍ࡭࡚ࡢィ⟬ࢹ࣮ࢱࡣ 1.8
TB ࡢᐜ㔞࡜࡞ࡗࡓࠋ10 ns ࡈ࡜࡟ィ⟬ࢹ࣮ࢱࢆ༊ษࡾࠊࢹ࣮ࢱ⛣⾜ࡣࢿࢵࢺ࣮࣡ࢡ㸦scp ࢥ࣐ࣥࢻ㸧ࢆ௓ࡋ࡚࠾ࡇ࡞ࡗࡓࠋ
ᵓ㐀ࢧࣥࣉࣜࣥࢢ࠿ࡽᚓࡽࢀࡓ 300 K ᖹ⾮≧ែࡢᵓ㐀ࢫࢼࢵࣉࢩࣙࢵࢺࢆ⏝࠸࡚ࠊGTP ᆺ࠾ࡼࡧ GDP ᆺࢩ࣮࣒㡿ᇦ࡟࠾ࡅࡿ࣊ࢸࣟ஧㔞యᵓ㐀ࡢヲ⣽ࠊࡉࡽ࡟ࡣ CTT ᵓ㐀ศᕸࢆゎᯒࡋ࡚࠸ࡿࠋ

- 482 -

3◊✲ᡂᯝᵓ㐀ࢧࣥࣉࣜࣥࢢ࡟࠾ࡅࡿ᭱⤊ᵓ㐀ࢆᅗ㸲࡟♧ࡍࠋࡇࡇ࡛ࡣࠊ౽ᐅୖࠊᅗ୰ࡢ࣊ࢸࣟ஧㔞యࢆᕥୗ࠿ࡽ㡰␒࡟␒ྕ௜ࡅࡍࡿࠋGTP ᆺ࠾ࡼࡧ GDP ᆺࡢ࡝ࡕࡽ࡟࠾࠸࡚ࡶࠊࢩ࣮࣒㡿ᇦୗഃ࡟఩⨨ࡍࡿ㸯␒㸪㸰␒㸪㸱␒࣊ࢸࣟ஧㔞యࡣᵓ㐀ࡺࡽࡂࡀ኱ࡁ࠸ࠋ≉࡟㸩➃ഃ࡟఩⨨ࡍࡿ㸱␒࣊ࢸࣟ஧㔞యࡣ኱ࡁࡃᦂࡽ࠸࡛࠸ࡿࠋ㸱␒࣊ࢸࣟ஧㔞యࡢᦂࡽࡄ᪉ྥ࡟ࡘ࠸࡚ࠊGDP ᆺ࡜ GTP ᆺ࡛㐪࠸ࡀぢཷࡅࡽࢀࡿࠋGDP ᆺࡢ᪉ࡀ๤ࡀࢀࡿ᪉ྥ
ࡢᦂࡽࡂࡀ኱ࡁ࠸ࡼ࠺࡟ぢ࠼ࡿࠋ
ࡲࡓࠊCTT 㡿ᇦࡢᵓ㐀ศᕸ࡟╔┠ࡍࡿ࡜ࠊ㸴␒࠾ࡼࡧ㸷␒ࡢ࣊ࢸࣟ஧㔞య࡟࠾࠸࡚⯆࿡῝࠸ࠋGDP ᆺࡢࡑࢀࡽࡢșCTT 㡿ᇦࡣ㸩➃ഃ࡟࡞ࡧ࠸ࡓࡼ࠺࡟ศᕸࡋ࡚࠸ࡿࠋGDP ᆺࡣࠊGTP ᆺ࡟ẚ࡭࡚ࠊࢾࢡࣞ࢜ࢳࢻ࡜
CTT 㡿ᇦ࡜ࡢ㛫࡟㟼㟁ⓗ࡞཯Ⓨࡀᙅ࠸ࡓࡵ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊCTT 㡿ᇦࡀ㸩➃ഃ࡟ศᕸࡋ࡚࠸ࡿࡇ࡜ࡀࠊ
GDP ᆺ࡟㔜ྜࡀ㉳ࡇࡾ࡟ࡃ࠸ศᏊᵓ㐀ⓗ࡞ゎ㔘࡟ࡘ࡞ࡀࡿ࠿ࡶࡋࢀ࡞࠸ࠋ
⌧ᅾࠊᵓ㐀ࢫࢼࢵࣉࢩࣙࢵࢺ࠿ࡽ CTT 㡿ᇦࡢ✵㛫ศᕸࢆゎᯒ୰࡛࠶ࡿࠋࡲࡓࠊୖグࡢᵓ㐀ᦂࡽࡂ࠾ࡼࡧ࣊
ࢸࣟ஧㔞యࡢ఩⨨≉␗ᛶ࡟ࡘ࠸࡚ࠊᐃ㔞ⓗ࡞ゎᯒࢆᐇ᪋ࡋ࡚࠸ࡿࠋ௒ᅇࡢࢩ࣮࣒㡿ᇦࢆྵࡴᚤᑠ⟶ࣔࢹࣝ࡜ࡇࢀࡲ࡛࡟ᡃࠎࡀゎᯒࡋ࡚ࡁࡓࢩ࣮࣒㡿ᇦࢆྵࡲ࡞࠸ᚤᑠ⟶ࣔࢹࣝࢆẚ㍑ࡍࡿࡇ࡜࡛ࠊᚤᑠ⟶ࡢᙧᡂ࠾ࡼࡧ
Ᏻᐃᛶ࡟㛵ࢃࡿ㸱ࡘࡢせ⣲ࡢ㛵㐃ᛶࢆ♧ࡋ࡚࠸ࡁࡓ࠸ࠋ

- 483 -

4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᮏ◊✲࠿ࡽᚓࡽࢀࡓᡂᯝࡣࠊ᪥ᮏ⏕≀≀⌮Ꮫ఍➨㸳㸷ᅇᖺ఍㸦࢜ࣥࣛ࢖࣭ࣥ2021 ᖺ 11 ᭶㸧࡟࡚Ⓨ⾲ணᐃ࡛࠶ࡿࠋࡲࡓࠊࡇࢀࡲ࡛ࡢ◊✲ᡂᯝࢆࡲ࡜ࡵࠊ⏕య㐠ື◊✲ྜྠ⌜఍㆟㸦2022 ᖺ 1 ᭶㸧ࡢⓎ⾲ࢆ⪃࠼࡚࠸ࡿࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ࡇࢀࡲ࡛࡟ࠊࢳ࣮ࣗࣈࣜࣥ࣊ࢸࣟ஧㔞యࡢࡳ࡟࠾ࡅࡿィ⟬⤖ᯝ࠾ࡼࡧࢩ࣮࣒㡿ᇦࢆྵࡲ࡞࠸ᚤᑠ⟶ࣔࢹࣝࡢ◊✲ࢹ࣮ࢱࡀ࠶ࡿࠋࡑࢀࡽ࡜௒ᅇᚓࡽࢀࡓ◊✲ᡂᯝࢆࡲ࡜ࡵࠊᑓ㛛Ꮫ⾡㞧ㄅ࡬ࡢᢞ✏ணᐃ࡛࠶ࡿࠋ

- 484 -

῝ᒙᏛ⩦࡟ࡼࡿࣄࢺࡢ▱ぬ࢔ࣝࢦࣜࢬ࣒ࡢ᥈ồ
Exploring Human Perception Algorithms with Deep Learning‫ۑ‬Ώ㎶ ⱥ἞㸦ᇶ♏⏕≀Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
ࣄࢺࡢ⬻ࢆᶍࡋࡓࢹ࢕࣮ࣉࢽ࣮ࣗࣛࣝࢿࢵࢺࢆᵓ⠏ࡋࠊࣄࢺࡢ▱ぬ࡜ẚ㍑ࡍࡿࡇ࡜࡟
ࡼࡗ࡚ࠊࣄࢺࡢどぬ࣓ ࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡟ࡋࡼ࠺࡜ࡋ࡚࠸ࡿࠋලయⓗ࡟ࡣࠊࢹ࢕࣮ࣉ
ࢽ࣮ࣗࣛࣝࢿࢵࢺ࡟ࡣ኱⬻⓶㉁ࡢ⌮ㄽࣔࢹ࡛ࣝ࠶ࡿண ➢ྕ໬ㄝࢆ⤌ࡳ㎸ࡳࠊࡇࡢࢿ
ࢵࢺ࣮࣡ࢡࢆேど⥺ࡢື⏬࡛Ꮫ⩦ࡋࠊேࡢ㘒ぬ⌧㇟ࢆ෌⌧࡛ࡁࡿ࠿࡝࠺࠿ࢆ᳨ドࡋ࡚࠸ࡿࠋࡍ࡛࡟⺬ࡢᅇ㌿㘒どࡢ͆▱ぬ͇ࢆ෌⌧࡛ࡁ࡚࠸ࡿ㸦Watanabe et al., Front. Psychol.,
15 March 2018㸧ࠋᮏᖺᗘࡣࠊࢿࢵࢺ࣮࣡ࢡࢆᣑᙇࡋࠊࢭࣝࣇ࢔ࢸࣥࢩࣙࣥࡢᶵᵓ ࢆ⤌ࡳ㎸ࡴࡇ࡜ࠊࡉࡽ࡟ࡣ࣮࢝ࣛ᝟ሗ RGB ࢆᣑᙇࡉࡏࡓᏛ⩦ࢆ࠾ࡇ࡞࠸⢭ᗘࡢྥୖࢆ≺࠺ࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ౑⏝ࡋࡓࢹ࢕࣮ࣉࢽ࣮ࣗࣛࣝࢿࢵࢺࡣࠊୗグ࡛බ㛤ࡋࡓࡶࡢࢆᣑᙇࡋࡓࠋ
https://github.com/eijwat/Predictive_Coding_Deep_Neural_Networksࡇࡢࢥ࣮ࢻࢆ࣮࣋ࢫ࡟ࢭࣝࣇ࢔ࢸࣥࢩࣙࣥࢿࢵࢺ࣮࣡ࢡࠊ࣮࢝ࣛ⏬ീᣑᙇࢿࢵࢺ࣮࣡ࢡࡶస〇ࡋ࡚Ꮫ⩦ࢆ⾜࠸ࠊண ⏬ീ࡜ࡋ࡚ࡢ㘒ど࢖࣓࣮ࢪࢆᚓࡓࠋ
ᮏࣉࣟࢢ࣒ࣛࡣ GPU ࡟ࡼࡗ࡚㧗㏿࡟✌ാࡍࡿࡓࡵࠊࣛ࣎࡟タ⨨ࡋࡓ࣮ࣟ࢝ࣝࡢ GPU ࢧ࣮ࣂ࣮ࠊཬࡧィ⟬ᶵࢭࣥࢱ࣮ࡢ GPU ࢧ࣮ࣂ࣮ࢆ฼⏝ࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝࢭࣝࣇ࢔ࢸࣥࢩࣙࣥࡢ⏬ീ⏕ᡂ࡟ࡘ࠸࡚ࡣᚲࡎࡋࡶⰋዲ࡞⤖ᯝࢆᚓࡿࡇ࡜ࡣ࡞࠿ࡗࡓࠋ
ཎᅉ࡟ࡘ࠸࡚ࡣㄪᰝ୰࡛࠶ࡿࠋ࣮࢝ࣛ᝟ሗ RGB ࢆᣑᙇࡉࡏࡓᏛ⩦࡟ࡘ࠸࡚ࡢ⤖ᯝࡣⰋዲ࡛ࠊ㘒ど෌⌧ࡢ⢭ᗘࡀ᱁ẁ࡟ୖࡀࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
➨ 30 ᅇ᪥ᮏ⚄⤒ᅇ㊰Ꮫ఍඲ᅜ኱఍㸦㸰㸮㸰㸮㸧ண ➢ྕ໬ㄝ࡟ࡼࡗ࡚෌⌧ࡉࢀࡿࣇࣞ࢖ࢨ࣮࣭࢘࢕ࣝࢥࢵࢡࢫ㘒どᑠᯘử㍜ࠊΏ㎶ⱥ἞‫ۻ‬Ⓨ⾲ணᐃ㸰௳㸦Neurlips 2021, ⚄⤒⛉ᏛᏛ఍㸰㸮㸰㸯ࠊ⚄⤒ᅇ㊰Ꮫ఍㸰㸮㸰㸯㸧5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬ㄽᩥ‽ഛ୰㸱௳

- 485 -

4

 MRI 







Functional and structural analysis of four dimensional MRI of the brain.
 !

"

#

1 
®ĈĪMRI(Ü¾]įÎZÀ)'Ëoĥ&4 ½[ÕòÎZ6D4'ËòÖĎkòwjRÖĎCÔĎSáÖĎúĨáãěÕĀb Õò¹ē}ä`ħ©mpàĈĪČõ©òÁh} `'ø &#ò¹ēò¼ñÙLĔĠĀ²¼ñÕ "¹ēÕëq=6?B-§'×Õ% &ý¤§Ą WðmåÝÝêÑð #oĥ&ç 6000 s 4 ½[Õò MRI ÎZ6D4'ËÖĎH¹ēěÕÎZāÆ'§2020 °6D4¦ĖË& quality check |Ç'!_Ā²'ĕ òÖĎ'òÖĎkòwjRÖĎCÔĎSáÖĎúĨáãěÕÎZāÆ'§2020 GăěÕòāÆ "ò¼ñÎZ'ËÁh·`'§=6@¬Ėi'§%]üdą¥ÀË'ÿĚ
·Ă

2 

Ĳ½[ MRI ÎZ #|³ÖĎH¹ēSáòÖĎkòúĨáòwCòÈúĨ«ÊěÕò¹ē} ` FreeSurfer v6.0.0" v7.0.1 (http://surfer.nmr.mgh.harvard.edu/)'ĳ½[¢£ĉ MRI ÎZ #ÔĎîí¯ěÕ¢£8><D4 ` FSL v5.0.11 (https://fsl.fmrib.ox.ac.uk/fsl/fslwiki/)'Ë `,>14D/15;"%Jai"$gÊi'x3 ½[Õ MRI ¹ēÎZĀ²ġ  y^ 12 §Ąoĥ&Wð 1506 sìqĉÓ 696 sn¸ģ 211 sóĝÓ1:,7>;ģ 126 sÒģ 398 sā 2937 s'ċěÕ¢£8><D4
% Fractional anisotropy(FA) "¢£T¤(MD, RD, AD)'òÔĎîí¯ĄĠĩ{ò
µSÃīNĩ{%ĩ{SáÖĎkÖĎúĨáã'ä`&Ā²!yĢÕòÎ
ZėQ 9A0*,7% ENIGMAİEnhancing Neuro Imaging Genetics through Meta-AnalysisĴIÏ 70'ď%-@D9 lc%þº6D4oĥzòÎZ-ėQĠĔĀ²Ûâ.B3D/(;Ĵ
http://enigma.ini.usc.edu/ongoing/enigma-schizophrenia-working-group/ı Schizophrenia -@D9"%9A7.
D@Ç¡§

3 
ěÕòÎZĀ²āäß Ûâ2B4D §\ûĬðěÕ6D4İÖĎH¹ēSáÖĎ¹ēSáÖĎk "¢£8><D4Dıä`'ø &#'!ÑÉÐÕÑ]Ēò¹ē "¢£8><D4Di'r ùĦĆ}tåÝÑĠĔėQV­ò¹ēĠĔ ùĦĆ}t- 486 -

4 

 ±®èFÂWEęÞ¿ĤuĐđ´®ÄčMEĭÌØĜĊï¶ôĜÌÍö÷®ïªĮ~U¨ĭ»eæÅĘvK»®O ìqĉÓðWûĬð

%¢£5B3@ÎZ'ËòÔĎé¹ēćÚ¼ñćÚ¼ñģfY©ğĠĔİ2020.6.23-7.3ıNPBPPP 2020 qrPİ+B>)BĞXı

5 



 Koshiyama D, Fukunaga M, Okada N, Morita K, Nemoto K, Usui K, Yamamori H,Yasuda Y, Fujimoto M, Kudo N,
Azechi H, Watanabe Y, Hashimoto N, Narita H,Kusumi I, Ohi K, Shimada T, Kataoka Y, Yamamoto M, Ozaki N,
Okada G, Okamoto Y,Harada K, Matsuo K, Yamasue H, Abe O, Hashimoto R, Takahashi T, Hori T, NakatakiM,
Onitsuka T, Holleran L, Jahanshad N, van Erp TGM, Turner J, Donohoe G,Thompson PM, Kasai K, Hashimoto R;
COCORO. White matter microstructuralalterations across four major psychiatric disorders: mega-analysis study in
2937individuals. Mol Psychiatry. 25:883-895 2020 doi:10.1038/s41380-019-0553-7.
 Koshiyama D, Fukunaga M, Okada N, Morita K, Nemoto K, Yamashita F, YamamoriH, Yasuda Y, Matsumoto J,
Fujimoto M, Kudo N, Azechi H, Watanabe Y, Kasai K,Hashimoto R. Association between the superior
longitudinal fasciculus andperceptual organization and working memory: A diffusion tensor imaging
study.Neurosci Lett. 738:135349 2020 doi: 10.1016/j.neulet.2020.135349.
 Ikegame T, Bundo M, Okada N, Murata Y, Koike S, Sugawara H, Saito T, Ikeda M,Owada K, Fukunaga M,
Yamashita F, Koshiyama D, Natsubori T, Iwashiro N, Asai T,Yoshikawa A, Nishimura F, Kawamura Y, Ishigooka J,
Kakiuchi C, Sasaki T, Abe O,Hashimoto R, Iwata N, Yamasue H, Kato T, Kasai K, Iwamoto K. Promoter
Activity-Based Case-Control Association Study on SLC6A4 Highlighting Hypermethylation andAltered
Amygdala Volume in Male Patients With Schizophrenia. Schizophr Bull. 46:1577-1586 2020 doi:
10.1093/schbul/sbaa075.
 Sønderby IE, van der Meer D, Moreau C, Kaufmann T, Walters GB, Ellegaard M,Abdellaoui A, Ames D, Amunts
K, Andersson M, Armstrong NJ, Bernard M, BlackburnNB, Blangero J, Boomsma DI, Brodaty H, Brouwer RM,
Bülow R, Bøen R, Cahn W,Calhoun VD, Caspers S, Ching CRK, Cichon S, Ciufolini S, Crespo-Facorro B,Curran
JE, Dale AM, Dalvie S, Dazzan P, de Geus EJC, de Zubicaray GI, de ZwarteSMC, Desrivieres S, Doherty JL,
Donohoe G, Draganski B, Ehrlich S, Eising E,Espeseth T, Fejgin K, Fisher SE, Fladby T, Frei O, Frouin V,
Fukunaga M, GareauT, Ge T, Glahn DC, Grabe HJ, Groenewold NA, Gústafsson Ó, Haavik J, Haberg AK,Hall J,
Hashimoto R, Hehir-Kwa JY, Hibar DP, Hillegers MHJ, Hoffmann P, HolleranL, Holmes AJ, Homuth G, Hottenga
JJ, Hulshoff Pol HE, Ikeda M, …, Sachdev PS, Sando SB, Schofield PR, SchorkAJ, Schumann G, Shin J,
Shumskaya E, Silva AI, Sisodiya SM, Steen VM, Stein DJ,Strike LT, Suzuki IK, Tamnes CK, Teumer A,
Thalamuthu A, Tordesillas-GutiérrezD, Uhlmann A, Ulfarsson MO, van 't Ent D, van den Bree MBM,
Vanderhaeghen P,Vassos E, Wen W, Wittfeld K, Wright MJ, Agartz I, Djurovic S, Westlye LT,Stefansson H,
Stefansson K, Jacquemont S, Thompson PM, Andreassen OA; ENIGMA-CNVworking group. 1q21.1 distal copy
number variants are associated with cerebraland cognitive alterations in humans. Transl Psychiatry. 11:182 2021
doi: 10.1038/s41398-021-01213-0.

- 487 -

◊✲ㄢ㢟ྡ㸸ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ⬻ᶵ⬟⏬ീゎᯒ
Project Title: Neuroimaging data analysis using machine learningࠐ㏆ῧ῟୍, Quang Trung Pham㸦⏕⌮Ꮫ◊✲ᡤࠊ⏕యᶵ⬟᝟ሗゎᯒᐊ㸧1◊✲┠ⓗࠊෆᐜ
⏕≀ࡢ⾜ືࡣ୺ほⓗ౯್࡟ࡼࡗ࡚つᐃࡉࢀ࡚࠸ࡿࠋእ⏺ࡢ᝟ሗࡣឤぬჾࢆ௓ࡋ࡚ᤊ࠼ࡽࢀࠊ⬻ෆ࡛ᢳ㇟ⓗ౯್᝟ሗ࡟ኚ᥮ࡉࢀࡓᚋࠊ౯್࡟ᇶ࡙ࡃពᛮỴᐃࢆ⤒࡚㐺ษ࡞⾜ືࡀ㑅ᢥࡉࢀࡿࠋࣄࢺࢆᑐ㇟࡜ࡋࡓᶵ⬟ⓗ
MRI ◊✲࡟ࡼࡾࠊ๓㢌║❐㔝ࡸഃᆘ᰾ࠊ⥺᮲యࡀ౯್ฎ⌮࡟㛵ࢃࡿࡇ࡜ࡀ᫂ࡽ࠿࡟ࡉࢀ࡚࠸ࡿࡀࠊឤぬ᝟ሗ࠿ࡽ࡝ࡢࡼ࠺࡞㐣⛬ࢆ⤒࡚౯್ࡢ᝟ሗࡀ⏕ࡌࡿ࠿ࡣ᫂ࡽ࠿࡟ࡉࢀ࡚࠸࡞࠸ࠋどぬ᝟ሗ࠿ࡽ࢝ࢸࢦࣜ᝟ሗ࡬ࡢ
ኚ᥮ࡀ㝵ᒙⓗ࡟⾜ࢃࢀࡿࡇ࡜࠿ࡽࠊどぬ᝟ሗ࠿ࡽ౯್᝟ሗ࡬ࡢኚ᥮ࡶྠᵝࡢ㝵ᒙⓗฎ⌮ࢆཷࡅ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿࠋᮏ◊✲ィ⏬࡟࠾࠸࡚ࡣࠊ౯್ฎ⌮㡿ᇦ࡜ࡋ࡚᪤࡟ྠᐃࡉࢀ࡚࠸ࡿ㡿ᇦ㛫࡛౯್ࡢ᝟ሗ⾲⌧ᵓ㐀ࢆẚ㍑ࡍࡿࡢࡳ࡛࡞ࡃࠊᮍ▱ࡢ౯್ฎ⌮㡿ᇦࢆࣔࢹࣝࡢ᝟ሗᵓ
㐀࡜ࡢᑐᛂ࠿ࡽ᫂ࡽ࠿࡟ࡍࡿࠋලయⓗ࡟ࡣࠊ῝ᒙᏛ⩦࡟ࡼࡾከᒙࢽ࣮ࣗࣛࣝࢿࢵࢺ
࣮࣡ࢡ࡟⏬ീ᝟ሗ࡜౯್ࡢᑐᛂࢆᏛ⩦ࡉࡏࠊᵓ⠏ࡉࢀࡓ㝵ᒙᵓ㐀࠿ࡽ⬻ෆࡢ౯್᝟
ሗࡢ㝵ᒙᵓ㐀ࢆ᥎ࡋࠊ⩻ࡗ࡚ࠊ⬻ෆࡢ㝵ᒙᵓ㐀࠿ࡽከᒙࢽ࣮ࣗࣛࣝࢿࢵࢺࡢタィࢆ⾜࠺㸦ᅗ㸯ࠊ┦஫ཧ↷࢔ࣉ࣮ࣟࢳ㸧ࠋࡇࡢᡭ㡰ࢆ཯᚟ⓗ࡟⾜࠺ࡇ࡜࡛ࠊどぬ᝟ሗ࠿ࡽ౯್᝟ሗ࡬ࡢኚ᥮࡟㛵ࢃࡿᮍ▱ࡢ⚄⤒ᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿ࡜ྠ᫬࡟ࠊどぬ᝟ሗ࠿ࡽ౯್᝟ሗࢆᢳฟࡍࡿேᕤ▱⬟ࢆ㛤Ⓨࡍࡿࠋே㛫ࡢ౯್ホ౯ࡢ⚄⤒ᇶ┙ࢆᶍᅗ㸯㸸┦஫ཧ↷࢔ࣉࡋࡓேᕤ▱⬟ࢆ⏘ᴗᛂ⏝ࡍࡿࡇ࡜࡛ࠊ┤᥋ⓗ࡟♫఍࡟㈉⊩ࡍࡿ࡜࡜ࡶ࡟ࠊឤぬ᝟࣮ࣟࢳࡢᴫ␎ᅗ

ሗ࠿ࡽ౯್᝟ሗ࡬ࡢኚ᥮㐣⛬ࢆ᫂ࡽ࠿࡟ࡋࠊ౯್ࡢࠕ๓㥑యࠖ࡟┦ᙜࡍࡿ⬻ෆ⾲㇟ࢆⓎぢࡍࡿࡇ࡜࡛ࠊ౯್ุ᩿◊✲ࡢ᪂ࡋ࠸ྂ඾࡜࡞ࡿࡼ࠺࡞◊✲ࢆ┠ᣦࡍࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲ィ⏬࡟࠾࠸࡚ࡣࠊᮍࡔ᫂ࡽ࠿࡟ࡉࢀ࡚࠸࡞࠸ࠊ౯್ኚ᥮ฎ⌮ࡢ⚄⤒ᶵᵓࡢᵓ㐀ࢆ᥈ࡿࡓࡵ࡟ࠊࢽࣗ

࣮ࣛࣝࢿࢵࢺ࣮࣡ࢡࣔࢹࣝࢆ฼⏝ࡍࡿࠋලయⓗ࡟ࡣ⨾⾡ရ࣮࢜ࢡࢩࣙࣥࡢࢹ࣮ࢱ࣮࣋ࢫ࠿ࡽྲྀᚓࡋࡓ኱㔞ࡢྲྀᘬ⤖ᯝ࡜⏬ീࡢ᝟ሗࢆ⏝࠸࡚ࠊேᕤ▱⬟࡟⏬ീ࡜౯᱁ࡢ㛵ಀࢆᏛ⩦ࡉࡏࠊどぬ㸫౯್ኚ᥮ࡢᩘ⌮ࣔࢹࣝࢆసᡂࡋࡓࠋḟ࡟ࠊ⤒῭άືࢆᶍࡋࡓ࣮࢜ࢡࢩࣙࣥㄢ㢟࡟࠾࠸࡚ࠊ⿕㦂⪅ࡀධᮐ౯᱁ࢆỴࡵࡿ㝿ࡢ⬻άືࢆᶵ⬟ⓗ MRI ࡟ࡼࡗ࡚ィࡋࡓࠋసᡂࡋࡓேᕤ▱⬟࡟ᶵ⬟ⓗ MRI ᐇ㦂࡛⏝࠸ࡓどぬ่⃭㸦⨾⾡ရ⏬ീ㸧ࢆධຊࡋࠊྛ㝵ᒙ࡟࠾࠸࡚ࡇࢀࡽࡢ่⃭ࡀ࡝ࡢࡼ࠺࡟⾲⌧ࡉࢀࡿ࠿ࢆ᥎ᐃࡋࡓࠋࡉࡽ࡟ࠊࡇࢀࡽࡢどぬ่⃭㛫ࡢ㢮ఝᗘࢆྛ㝵ᒙ࡛ィ⟬ࡋࠊࡇࢀ࡜⬻άືࡢ✵㛫ⓗࣃࢱ࣮ࣥࡢ㢮ఝᗘ࡜ࡢᑐᛂࢆㄪ࡭ࡓࠋ⬻άືࡢ㢮ఝᗘࡣࠊ⬻ෆࡢྛ㡿ᇦ࡛ಶู࡟ồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࡢ࡛ࠊ⏦ㄳ⪅ࡀ㛤Ⓨࡋࡓᡭἲ࡛࠶ࡿ⾲㇟㢮ఝᗘศゎ㸦Chikazoe et al.,2014, Nature Neuroscience㸧ࢆ㐺⏝ࡍࡿࡇ࡜࡟ࡼࡾࠊேᕤ▱⬟ࡢྛ㝵ᒙࡀ⬻ෆࡢ࡝ࡢ㡿ᇦ࡟ᑐᛂࡍࡿ࠿ࢆྠᐃ
ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ

3◊✲ᡂᯝᮏ◊✲࡛ࡣࠊឤぬ᝟ሗ࠿ࡽ౯್᝟ሗ࡬ࡢኚ᥮࡟㛵ࢃࡿᮍ▱ࡢ⚄⤒ᇶ┙ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊேᕤ⚄⤒ᅇ㊰ࢆࣔࢹࣝ࡜ࡋ࡚฼⏝ࡋࡓࠋලయⓗ࡟ࡣ⨾⾡ရ࣮࢜ࢡࢩࣙࣥࡢࢹ࣮ࢱ࣮࣋ࢫ࠿ࡽྲྀᚓࡋࡓ 4 ୓௳ࡢྲྀᘬ⤖ᯝ- 488 -

㸦⏬ീ࡜౯᱁ࡢᑐࢹ࣮ࢱ㸧ࢆ⏝࠸࡚ࠊேᕤ⚄⤒ᅇ㊰࡟⏬ീ࡜౯᱁ࡢ㛵ಀࢆᏛ⩦ࡉࡏࠊどぬ㸫౯್ኚ᥮ࡢᩘ⌮ࣔࢹࣝࢆసᡂࡋࡓࠋḟ࡟ࠊ⤒῭άືࢆᶍࡋࡓ࣮࢜ࢡࢩࣙࣥㄢ㢟࡟࠾࠸࡚ࠊ⿕㦂⪅ࡀධᮐ౯᱁ࢆỴࡵࡿ㝿ࡢ⬻άືࢆᶵ⬟ⓗ MRI ࡟ࡼࡗ࡚ィࡋࡓࠋࡉࡽ࡟ࠊసᡂࡋࡓேᕤ⚄⤒ᅇ㊰࡟ᶵ⬟ⓗ MRI ᐇ㦂࡛⏝࠸ࡓどぬ่⃭㸦⨾⾡ရ⏬ീ㸧ࢆධຊࡋࠊྛ㝵ᒙ࡟࠾࠸࡚ࡇࢀࡽࡢ่⃭ࡀ࡝ࡢࡼ࠺࡟⾲⌧ࡉࢀࡿ࠿ࡢ᥎ᐃࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊࡇࢀࡽࡢどぬ่⃭㛫ࡢ㢮ఝᗘࢆྛ㝵ᒙ࡛ィ⟬ࡋࠊࡇࢀ࡜⬻άືࡢ✵㛫ⓗࣃࢱ࣮ࣥࡢ㢮ఝᗘ࡜ࡢᑐᛂࢆㄪ࡭ࡓࠋ
⬻άືࡢ㢮ఝᗘࡣࠊ⬻ෆࡢྛ㡿ᇦ࡛ಶู࡟ồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࡢ࡛ࠊࣜࢵࢪᅇᖐ࡟ࡼࡿ⾲㇟㢮ఝᗘศゎࢆ㐺⏝ࡍࡿࡇ࡜࡟ࡼࡾࠊேᕤ⚄⤒ᅇ㊰ࡢྛ㝵ᒙ࡜ᑐᛂࡍࡿ⬻㡿ᇦࢆྠᐃࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡑࡢ⤖ᯝࠊV1 ࡸ V2࡜࠸ࡗࡓึᮇどぬ㔝ࡣ⏬ീධຊ࡟㏆࠸ேᕤ⚄⤒ᅇ㊰ࡢపḟᒙ࡜ᑐᛂࡍࡿ୍᪉࡛ࠊdefault mode network ࡣ౯್
ฟຊ࡟㏆࠸ேᕤ⚄⤒ᅇ㊰ࡢ㧗ḟᒙ࡜ᑐᛂࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡉࡽ࡟ࠊどぬ᝟ሗ࠿ࡽ౯್᝟ሗ࡟⮳ࡿ㝵ᒙⓗ᝟ሗฎ⌮ᵓ㐀ࡣࠊ㏆ᖺᥦၐࡉࢀ࡚࠸ࡿ⓶㉁ୖࡢᶵ⬟໙㓄㸦Principal Gradient㸧㸦Margulies et al., 2016㸧࡟ἢࡗࡓࡶࡢ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡉࡽ࡟ࠊᮏᖺᗘࡣ AMED ࡢᢏ⾡㛤Ⓨಶูㄢ㢟ࠕ⬻≧ែ᝟ሗ࡜่⃭㛵㐃᝟ሗࡢ⥺ᙧ⤖ྜ࡟ࡼࡿ⬻άືࣔࢹࣜࣥࢢἲࡢ㛤Ⓨࠖ࡟࠾࠸࡚ࠊᏳ㟼᫬ᶵ⬟ⓗ⤖ྜゎᯒ࡟࠾ࡅࡿ᪂つᡭἲࡢ㛤Ⓨ࡟ྲྀࡾ⤌ࢇࡔࠋ⬻㡿ᇦࢆ 360 ࡢᑠ㡿ᇦ࡟ศ๭ᚋࠊ㡿ᇦ㛫ࡢᶵ⬟ⓗ⤖ྜࡢ᥎ᐃࢆࠊᚑ᮶ࡢ┦㛵࡟ᇶ࡙ࡃ᥎ᐃ࡛
ࡣ࡞ࡃࠊࣜࢵࢪᅇᖐ࡟ᇶ࡙ࡃ᥎ᐃ࡟ࡼࡗ࡚⾜ࡗࡓࠋࡇࡢィ⟬ࢆ 300 ேࡢ data ࡟ᑐࡋ࡚⾜ࡗࡓࡓࡵࠊ⭾኱࡞ィ⟬㔞࡜࡞ࡗࡓࡀࠊィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࢆ฼⏝ࡍࡿࡇ࡜࡛▷ᮇ㛫࡛ᐇ⾜࡛ࡁࡓࠋࡇࡢゎᯒ࡟ࡼࡗ࡚࠼ࡽࢀࡓ
㡿ᇦ㛫⤖ྜࡢ⾜ิࢆ⏝࠸࡚ࠊᛶᕪࡢศ㢮ࠊ▱⬟ࡢணࢆ⾜ࡗࡓࠋᛶᕪࡢ᥎ᐃᡂ⦼ࡣࠊᚑ᮶ἲࠊ᪂つᡭἲࠊᚑ᮶ἲ㸩᪂つᡭἲ࡛ࠊࡑࢀࡒࢀࠊ0.9033, 0.8800, 0.9200 ࡛ࠊ᪂つᡭἲ༢⊂࡛ࡣᚑ᮶ᡭἲࡢᡂ⦼ࢆୖᅇࡿࡇ࡜ࡣ࡛
ࡁ࡞࠿ࡗࡓࡀࠊࡇࢀࡽࢆ⤌ࡳྜࢃࡏࡓ࢔ࣥࢧࣥࣈࣝศ㢮ჾࢆసᡂࡍࡿࡇ࡜࡛ࠊศ㢮ᡂ⦼ࢆᨵၿࡍࡿࡇ࡜ࡀ࡛
ࡁࡓࠋࡲࡓࠊ▱⬟ࡢ᥎ᐃ࡟㛵ࡋ࡚ࡶࠊ᥎ᐃ್࡜ᐇ

್ࡢᖹᆒ஧஌ㄗᕪࡀࠊᚑ᮶ἲࠊ᪂つᡭἲࠊᚑ᮶ἲ㸩᪂つᡭἲ࡛ࠊࡑࢀࡒࢀࠊ23.45, 24.25, 22.72 ࡛ࠊࡇࡢሙྜ࡛ࡶࠊᚑ᮶ᡭἲ࡜᪂つᡭἲࢆ⤌ࡳྜࢃࡏࡓ࢔ࣥࢧࣥࣈࣝ
Ꮫ⩦ࡀ㧗࠸ᡂ⦼ࢆ♧ࡋࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ௒ᅇ㛤Ⓨࡋࡓ᪂つᡭἲ࡟ࡼࡗ࡚ࠊᚑ᮶฼⏝ࡉࢀ࡚࠸࡞࠿ࡗࡓ᝟
ሗࢆᢳฟྍ⬟࡛࠶ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋࡉࡽ࡟ࠊࡇࡢᡭἲࢆ⑌ᝈࢹ࣮ࢱࡢᶵ⬟ⓗ⤖ྜゎᯒ࡟฼⏝ࡍࡿࡇ࡜࡛ࠊ⑌ᝈࡢศ㢮ᡂ⦼ࢆྥୖࡉࡏࡽࢀࡿࡇ࡜ࢆᮇᚅࡋ࡚࠸ࡿࠋ

4

Ⓨ⾲ᐇ⦼

‫ۻ‬1.

J. Chikazoe (2020) The role of the default mode network in value estimation: A combinatorial study of fMRI

and deep learning. ➨10ᅇ ᪂₲኱Ꮫ⬻◊✲ᡤ ඹྠ◊✲ᣐⅬᅜ㝿ࢩ࣏ࣥࢪ࣒࢘‫ۻ‬2.

㏆ῧ῟୍ (2020) ⬻࡜ேᕤ⚄⤒ᅇ㊰ࡢᑐ↷࡟ࡼࡾ᫂ࡽ࠿࡟ࡉࢀࡓ౯್᝟ሗฎ⌮୰ᯡ࡜ࡋ࡚ࡢdefault

mode network. ⮬↛⛉Ꮫ◊✲ᶵᵓ ศ㔝⼥ྜᆺඹྠ◊✲஦ᴗ࣮࣡ࢡࢩࣙࢵࣉࠕ㐠ື࣭⾜ື࠿ࡽ⣣ゎࡃ⬻⚄⤒ᅇ㊰Ⓨ㐩࣓࢝ࢽࢬ࣒ࡢ␗ศ㔝⼥ྜ◊✲࡟ࡼࡿゎ᫂ ࠖ5ฟ∧ᐇ⦼ཬࡧணᐃ
(ᐇ⦼)‫''ۻ‬Vision-to-value transformations in artificial network and human brains'', T. Q. Pham, T. Yoshimoto, H.

Niwa, H. K Takahashi, R. Uchiyama, T. Matsui, A. K. Anderson, *N. Sadato, *J. Chikazoe, bioRxiv (2021)㸦ணᐃ㸧‫ "ۻ‬Coexistence of sensory qualities and value representations in human orbitofrontal cortex ", Takaaki
Yoshimoto, Shuntaro Okazaki, Motofumi Sumiya, Haruka K. Takahashi, Eri Nakagawa, Takahiko Koike, Ryo Kitada,
Shiki Okamoto, Masanori Nakata, Toshihiko Yada, Hirotaka Kosaka, Norihiro Sadato, and Junichi Chikazoe‫ "ۻ‬The truth is in the details: whole-brain activity patterns decoded by regional fine-grained activity patterns",
Balbir Singh, Jun-ichiro Hirayama, Koji Jimura, Tetsuya Yamamoto, Norihiro Sadato, Junichi Chikazoe- 489 -

㻞㻚䚷㻞㻜㻞㻜ᖺᗘ㻌ィ⟬≀㉁⛉Ꮫ䝇䝟䝁䞁ඹ⏝஦ᴗ฼⏝ᯟ◊✲ㄢ㢟䛚䜘䜃฼⏝ሗ࿌᭩ᖺᗘࡼࡾࠊᮾ໭኱Ꮫ㔠ᒓᮦᩱ◊✲ᡤࠊᮾி኱Ꮫ≀ᛶ◊✲ᡤࠊ⮬↛⛉Ꮫ◊✲ᶵᵓศᏊ⛉Ꮫ◊✲ᡤ࣭ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢ㸱◊✲ᡤ࡛ࡣࠊᮦᩱ⛉Ꮫࠊ≀ᛶ⛉ᏛࠊศᏊ⛉Ꮫࡢྛศ㔝ࢥ࣑ࣗࢽࢸ࢕࡟࠾ࡅࡿ୪ิィ⟬ࡢ㧗ᗘ໬࡬ࡉࡽ࡞ࡿྲྀࡾ⤌ࡳࢆಁࡍࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚㸱ศ㔝࡟ඹ㏻ᛶࡢ㧗࠸኱つᶍ୪ิィ⟬ࢆᚿྥࡋࡓ኱ᆺࣉࣟࢪ࢙ࢡࢺࢆᨭ᥼ࡋ࡚ࡁࡲࡋࡓࠋࡇࢀࡲ࡛ᨭ᥼ᑐ㇟࡜࡞ࡗࡓࡶࡢ
࡜ࡋ࡚ࠊᩥ⛉┬࣏ࢫࢺࠕிࠖ㔜Ⅼㄢ㢟ࠊྠࡌࡃ࣏ࢫࢺࠕிࠖⴌⱆⓗㄢ㢟ࠊࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࠕᐩᓅࠖᡂᯝ๰ฟຍ㏿ࣉࣟࢢ࣒ࣛ
ㄢ㢟ࠊ-67⛉Ꮫᢏ⾡ேᮦ⫱ᡂࡢࢥࣥࢯ࣮ࢩ࢔࣒ࡢᵓ⠏஦ᴗࠊඖ⣲ᡓ␎ࣉࣟࢪ࢙ࢡࢺ㸺◊✲ᣐⅬᙧᡂᆺ㸼࡞࡝ࡀ࠶ࡾࡲࡍࠋ
ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡛ࡣࠊᘬࡁ⥆ࡁࡇࡢ┠ⓗࢆ㐩ᡂࡍࡿࡓࡵࠊィ⟬㈨※ࡢᥦ౪ࡸィ⟬ᢏ⾡࣭ᡂᯝ࡟㛵ࡍࡿ᝟ሗ஺᥮࡞࡝ࢆ㏻ࡌ࡚ࠊィ⟬≀㉁⛉Ꮫࢆ୺࡞ࢸ࣮࣐࡜ࡍࡿ኱ᆺࣉࣟࢪ࢙ࢡࢺࡢ᥎㐍ࢆᨭ᥼ࡋ࡚࠸ࡁࡲࡍࠋ
ࠉᖺᗘࡼࡾ඲&38㈨※ࡢ㸦ᖺᗘࡼࡾ⛬ᗘ㸧ࢆୖ㝈࡜ࡍࡿࠕィ⟬≀㉁⛉Ꮫࢫࣃࢥࣥඹ⏝஦ᴗ฼⏝ᯟࠖࢆタ⨨ࡋࡲࡋࡓࠋ௨ୗ࡟ࠊᖺᗘ࡟ィ⟬≀㉁⛉Ꮫࢫࣃࢥࣥඹ⏝஦ᴗ◊✲ㄢ㢟࡜ࡋ࡚᥇ᢥࡉࢀࡓ◊✲ㄢ㢟ྡ୍ぴ࡜฼⏝ሗ࿌᭩ࢆᥖ㍕ࡋࡲࡍࠋࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ◊✲ㄢ㢟ྡㄢ㢟㈐௵⪅ྡ

◊✲ᢸᙜ⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧ᡤᒓ

YG㈗㔠ᒓࣇ࣮ࣜࡢỗ⏝ඖ⣲ࢼࣀ
ゐ፹࡟ྥࡅࡓ➨୍ཎ⌮ィ⟬

Ṋḟᚭஓ

Ṋḟᚭஓ


໭኱㝔
⌮

 㸭 



YH

ゐ፹࠾ࡼࡧ㟁ᴟࡢ㟁Ꮚ≧ែࡢࡓࡵࡢ⌮ㄽ◊✲

୰஭ᾈᕭ

୰஭ᾈᕭ


᪩኱
ඛ㐍⌮ᕤ

 㸭 



YG

᪂つከᶵ⬟㟁ゎᾮࡢಖㆤ⭷ᙧᡂᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗゎᯒ

ᒣ⏣῟ኵ

ᒣ⏣῟ኵ


ᮾ኱
ᕤ

 㸭 



YH

⏕యศᏊ࣐ࢩࣥ࡟࠾ࡅࡿ࣐ࣝ
ࢳࢫࢣ࣮ࣝ࡞ᶵ⬟ࢲ࢖ࢼ࣑ࢡ
ࢫࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᒸᓮᆂ୍

ᒸᓮᆂ୍


ศᏊ⛉Ꮫ◊✲ᡤ 㸭 



YF

㧗ᙉᗘࣇ࢙࣒ࢺ⛊ࣃࣝࢫ࡟ࡼ
ࡾᘬࡁ㉳ࡇࡉࢀࡿࢼࣀศᏊࡢ
㟁Ꮚ࣭཯ᛂືຊᏛ࢖࣓࣮ࢪࣥ
ࢢ࡟㛵ࡍࡿືຊᏛ⌮ㄽ

ᒣᓮࠉ㤾

ᒣᓮࠉ㤾


⌮໬Ꮫ◊✲ᡤ 㸭 



YE

┬࢚ࢿࣝࢠ࣮ḟୡ௦༙ᑟయࢹ
ࣂ࢖ࢫ㛤Ⓨࡢࡓࡵࡢ㔞Ꮚㄽ࣐ࣝࢳࢩ࣑࣮ࣗࣞࢩࣙࣥ

ᢲᒣࠉ῟

ᢲᒣࠉ῟


ྡ኱
ᮍ᮶ᮦᩱ࣭
ࢩࢫࢸ࣒◊✲ᡤ 㸭 



ᮡ㔝ࠉಟ


ᮾ኱
≀ᛶ◊✲ᡤ

 㸭 

ᒸᓮࠉ㐍


ᮾ኱㝔
᪂㡿ᇦ๰ᡂ⛉Ꮫ 㸭 

኱㇂ࠉᐇ


⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

ᯇᯘఙᖾ


㜰኱㝔
ᇶ♏ᕤ

YH

YD

ḟୡ௦஧ḟ㟁ụ࣭⇞ᩱ㟁ụ㛤Ⓨ࡟ࡼࡿ(7㠉࿨࡟ྥࡅࡓィ⟬࣭ࢹ࣮ࢱᮦᩱ⛉Ꮫ

㤋ᒣెᑦ

YD

YD

㧗ศᏊඹ㔜ྜయࡢᑠศᏊ྾཰
⬟࡟࠾ࡅࡿ㔜ྜࢺ࣏ࣟࢪ࣮ࡢ
ຠᯝࡢ඲ཎᏊゎᯒᯇᯘఙᖾ

- 490 -

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧 㸭 

 㸭 



㈗㔠ᒓࣇ࣮ࣜࡢỗ⏝ඖ⣲ࢼࣀゐ፹࡟ྥࡅࡓ➨୍ཎ⌮ィ⟬Ab initio study toward abundant element nanocatalysts
with less precious metals‫ۑ‬Ṋḟ ᚭஓ㸪๓⏣ ⌮㸪ᑠᯘ ṇே㸪Lyalin Andrey㸪ᒾబ ㇦㸪㧗 ᩄ㸪ᑠ㔝 ࡺࡾᏊ㸪➉୰ ᑗᩯ㸦໭ᾏ㐨኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜⓑ㔠࡞࡝ࡢ㈗㔠ᒓࡣከࡃࡢ㔜せ࡞ሙ㠃࡛ゐ፹࡜ࡋ࡚⏝࠸ࡽࢀ࡚࠸ࡿࡀࠊ㧗౯࡛࠶ࡿࡇ࡜࡟ຍ࠼࡚⏘ฟᅜࡀ೫ࡗ࡚࠸ࡿࡓࡵࠊᣢ⥆ྍ⬟♫఍ࡢᐇ⌧࡟ྥࡅࡓᏳ౯࡛㇏ᐩ࡟Ꮡᅾࡍࡿඖ⣲࡟ࡼࡿ௦᭰ゐ፹ࡢ㛤Ⓨࡀᙉࡃᮇᚅ
ࡉࢀ࡚࠸ࡿࠋ୙άᛶ࡛࠶ࡿ㇏ᐩ㔠ᒓࡶࠊࢼࣀࢧ࢖ࢬ໬ࡸ࠶ࡿ࠸ࡣගࢆ᥼⏝ࡍࡿࡇ࡜࡛᪂ࡓ࡞ᶵ⬟ࢆⓎ⌧ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ㇏ᐩඖ⣲ࢆࢼࣀࢧ࢖ࢬ໬ࡋࡓࢡࣛࢫࢱ࣮ࡸⷧ⭷ࡢᵓ㐀࣭㟁Ꮚ≧ែ࣭Ᏻᐃᛶࠊ࠾ࡼࡧゐ፹ᶵ⬟࣭㟁ụᛶ⬟ࠊ࠶ࡿ࠸ࡣගࢆ᥼⏝ࡋࡓບ㉳≧ែ࡛ࡢ໬Ꮫ཯ᛂᶵᵓࢆゎ᫂ࡋࠊࡲࡓࡑࡢࡓࡵ
ࡢᇶ┙ᢏ⾡ࡸ⌮ㄽࢆᵓ⠏ࡍࡿࡇ࡜࡟ࡼࡾࠊᏳ౯࡛Ᏻᐃࡋࡓ౪⤥※ࢆᣢࡘỗ⏝ඖ⣲ࢆ฼⏝ࡋࡓࠊ㈗㔠ᒓ௦᭰ゐ፹㛤Ⓨ࡟ྥࡅࡓᇶ♏ⓗ࡞▱ぢ࠾ࡼࡧタィᣦ㔪ࢆ୚࠼ࡿࡇ࡜ࢆ┠ᣦࡍࠋ
௧࿴ 2 ᖺᗘࡣ≉࡟ࠊ(1) Pt ⾲㠃࡟྾╔ࡋࡓ࢔࣮ࣜࣝ࢖ࢯࢩ࢔ࢽࢻศᏊࡢ CN ⤖ྜࡢ⨨᥮ᇶຠᯝࠊ(2) Li-✵Ẽ஧ḟ㟁ụ࡟࠾ࡅࡿ᪩ᮇᨺ㟁⤊Ṇ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ◊✲ࠊ(3)㏆᥋ሙ࣐ࣛࣥࡢࡓࡵࡢ⌮ㄽ㛤Ⓨ࡜ග STM-TERS࡬ࡢᛂ⏝࡞࡝ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ(1)࡛ࡣ㟁Ꮚ≧ែィ⟬࡟ PAW ᆺᨃ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸ࡓࣂࣥࢻィ⟬ࣉࣟࢢ࣒ࣛ VASP ࢆ฼⏝ࡋࡓࠋỗ㛵ᩘ࡟ࡣศᩓຊࢆ⤒㦂ⓗ࡟⿵ṇࡋࡓ PBE-D3 ࢆ⏝࠸ࠊ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ࡣ 600 eV ࡜ࡋࡓࠋ⤖ྜࡢゎᯒ࡟ࡣࠊ
Dinnington ࡜ Schmidt ࡟ࡼࡾ࿘ᮇ⣔࡟ᣑᙇࡉࢀࡓ⮬↛⤖ྜ㌶㐨㸦NBO㸧ἲࢆ฼⏝ࡋࡓࠋ(2)࡛ࡣࠊSIESTA ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ DFT ィ⟬ࢆ⾜ࡗࡓࠋỗ㛵ᩘ࡟ࡣ WC-GGA ࢆࠊ౯㟁Ꮚࡢᇶᗏ㛵ᩘ࡟ࡣ DZP ࢆ⏝࠸ࠊෆẆࡣࣀ࣒ࣝಖᏑᨃ࣏ࢸࣥࢩ࡛ࣕࣝྲྀࡾᢅࡗࡓࠋࡲࡓࠊ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ࡣ 200 Ry ࡜ࡋࡓࠋ(3)࡛ࡣࡲࡎࠊ㏆᥋ሙࢆ཮ᴟᏊሙ࡛㏆ఝࡋ࡚㏆᥋ሙࡀసࡿ㟁ሙᵓ㐀ࢆồࡵࡓࠋᐇ᫬㛫ᐇ✵㛫 TDDFT ィ⟬ࣉࣟࢢ࣒ࣛ Octopus ࡟ከ㔜ᴟ┦஫స⏝ࢆᐇ⿦ࡋ࡚ࠊከ㔜ᴟ┦஫స⏝࡟ࡼࡿ㟁Ꮚບ㉳≧ែࢆィ⟬ࡋࠊࡑࡢㄏ㉳཮ᴟᏊ࣮࣓ࣔࣥࢺࢆᇶ‽ᗙᶆ࡛ᚤศࡍࡿࡇ࡜࡛ࠊ㏆᥋ሙ࣐ࣛࣥࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࡓࠋ

3

◊✲ᡂᯝ

3.1 Pt ⾲㠃࡟྾╔ࡋࡓ࢔࣮ࣜࣝ࢖ࢯࢩ࢔ࢽࢻศᏊࡢ CN ⤖ྜࡢ⨨᥮ᇶຠᯝ㏆࠸ᑗ᮶࡟ᐇ⌧ࡀ┠ᣦࡉࢀ࡚࠸ࡿศᏊࢫࢣ࣮ࣝ㟁Ꮚࢹࣂ࢖ࢫ࡛ࡣࠊ⮬ᕫ⤌⧊໬༢ศᏊ⭷㸦SAM㸧ࡢไᚚࡀ㟁Ꮚ㍺㏦≉ᛶࡸ᥋ゐ᢬ᢠࢆᕥྑࡍࡿ㔜せ࡞せ⣲ᢏ⾡࡜࡞ࡗ࡚࠸ࡿࠋ㨶ᓮࡽࡣࠊࣃࣛ⨨᥮࢔࣮ࣜࣝ࢖ࢯࢩ࢔ࢽ
ࢻ༢ศᏊ⭷ࡢ࿴࿘Ἴ⏕ᡂศගࢫ࣌ࢡࢺࣝࢆィࡋࠊศᏊ࡜㔠ᒓ㸦Au, Ag, Pt, Pd㸧ࡢ⏺㠃ࡢ⤖ྜᛶࢆᐇ㦂ⓗ࡟᫂ࡽ࠿࡟ࡋࡼ࠺࡜ࡋࡓࠋࡋ࠿ࡋࠊ࢖ࢯࢩ࢔ࢽࢻศᏊ࡜㔠ᒓ⾲㠃ࡢ┦஫స⏝ࡢヲ⣽ࡣࠊࡲࡔ᫂☜࡟ࡣ⌮ゎࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊPt ⾲㠃࡟ࣃࣛ⨨᥮࢔࣮ࣜࣝ࢖ࢯࢩ࢔ࢽࢻ X-C6H4-NC ࡀ྾╔ࡋࡓ⣔ࡢ࿘ᮇቃ⏺ DFT- 491 -

ィ⟬ࢆ⣔⤫ⓗ࡟ᐇ⾜ࡋࠊ⾲㠃྾╔ࡸ⨨᥮ᇶຠᯝࡀ NC ⤖ྜࡢᙉࡉ࡟࡝ࡢࡼ࠺࡟ᙳ㡪ࡍࡿ࠿ࢆㄪᰝࡋࡓࠋ
ࡲࡎࠊᏙ❧ศᏊࡢィ⟬ࢆ⾜࠸ࠊNBO ࢆ౑ࡗ࡚ồࡵࡓ N-C ⤖ྜḟᩘࢆ⨨᥮ᇶࡢ Hammett ᐃᩘ ıp ࢆ⏝࠸࡚ᩚ⌮ࡋࡓ⤖ᯝࢆᅗ 1 ࡟♧ࡍࠋıp = 0 ࢆ㡬Ⅼ࡜ࡋࡓⅆᒣᆺࡢࣉࣟࣇ࢓࢖ࣝࢆ♧ࡍࡇ࡜ࡀ☜ㄆ࡛ࡁࡿ
ࡀࠊN-C ࡢఙ⦰᣺ືᩘࢆ⏝࠸࡚ࡶྠᵝࡢ⤖ᯝࡀぢࡽࢀࡿࠋศᏊࡀ Pt(111)⾲㠃࡟྾╔ࡉࢀࡿ࡜ࠊN-C⤖ྜḟᩘࡣ ıp ࡢቑຍ࡟ࡘࢀ࡚༢ㄪ࡟ῶᑡࡍࡿഴྥ
ࡀ࠶ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋࡇࢀࡣࠊ㟁Ꮚ྾ᘬᛶࡢ㧗࠸⨨᥮ᇶ࡟ࡼࡾࠊPt ⾲㠃࠿ࡽ NC ཯⤖ྜᛶ㌶㐨࡬ࡢ㟁Ꮚ⛣ືࡀಁ㐍ࡉࢀࡿࠊ࡜ឤぬⓗ࡟ࡶㄝ࡛᫂ࡁ

ᅗ1. ࣃࣛ⨨᥮࢔࣮ࣜࣝ࢖ࢯࢩ࢔ࢽࢻᏙ❧ศᏊࡢN-C

ࡿࡀࠊศᏊ࡜㔠ᒓ⾲㠃ࡢ㛫ࡢ ı ౪୚ࠊʌ ㏫౪୚ࡢຠ

⤖ྜḟᩘࡢ⨨᥮ᇶ౫Ꮡᛶࠋᯝࢆヲ⣽࡟ㄪᰝࡋࡓࠋPt-C ࡢ⤖ྜᛶ࣭཯⤖ྜᛶ ı㌶㐨ࡢ༨᭷ᩘࢆ ıp ࢆ⏝࠸࡚ᩚ⌮ࡋࡓ⤖ᯝࢆᅗ 2 ࡟ࡋࡵࡍࠋ⤖ྜᛶ㌶㐨ࡢ༨᭷ᩘࡣࠊ⨨᥮ᇶ࡟ࡼࡽࡎ
࡯ࡰ୍ᐃ࡛࠶ࡿࡀࠊ཯⤖ྜᛶ㌶㐨ࡢ༨᭷ᩘࡀ ıp ࡟ᑐࡋ࡚ቑຍഴྥ࡛࠶ࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋࡲࡓࠊ
N-C ⤖ྜࡢ 2 ࡘࡢ ʌ*㌶㐨࡟ࡘ࠸࡚ࡶྠᵝࡢゎᯒࢆ⾜࠸ࠊ࣋ࣥࢮࣥ⎔࡟ᑐࡋ࡚ out-of-plane ࡢ ʌ*㌶㐨ࡢ༨᭷ᩘࡀ኱ࡁࡃኚ໬ࡍࡿࡢ࡟ᑐࡋ࡚ࠊin-plane ࡢ ʌ*㌶㐨ࡢ༨᭷ᩘኚ໬ࡣ࡯࡜ࢇ࡝࡞࠸ࡇ࡜ࡀ᫂ࡽ࠿࡜
࡞ࡗࡓࠋࡇࡢࡼ࠺࡟ࠊ࿘ᮇቃ⏺ NBO ἲࢆ⏝࠸ࡿࡇ
ᅗ2. Pt⾲㠃࡟྾╔ࡋࡓࣃࣛ⨨᥮࢔࣮ࣜࣝ࢖ࢯࢩ࢔ࢽ

࡜࡟ࡼࡾࠊศᏊ࡜⾲㠃ࡢ㛫ࡢ┦஫స⏝ࢆヲ⣽࡟ゎ

ࢻࡢ(a) Pt-C ı⤖ྜᛶ㌶㐨ࠊ(b) Pt-C ı཯⤖ྜᛶ㌶㐨ࡢ᫂ࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ

NBO༨᭷ᩘࡢ⨨᥮ᇶ౫Ꮡᛶࠋ

3.2 Li-✵Ẽ㸦㓟⣲㸧஧ḟ㟁ụ࡟࠾ࡅࡿ᪩ᮇᨺ㟁⤊Ṇ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ◊✲Li-✵Ẽ஧ḟ㟁ụࡣࠊLi ࢖࢜ࣥ㟁ụ࡞࡝࡜ẚ࡭࡚㠀ᖖ࡟㧗࠸⌮ㄽ࢚ࢿࣝࢠ࣮ᐦᗘࢆᣢࡘ
ࡓࡵࠊ┒ࢇ࡟◊✲ࡀ⾜ࢃࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ
ᨺ㟁ࡀ᪩ᮇ࡟⤊஢ࡋ࡚ࡋࡲ࠺ࡓࡵࠊᐇຠⓗ࡞㟁ụᐜ㔞ࡣᑠࡉࡃࠊᮍࡔᐇ⏝໬࡟ࡣ⮳ࡗ࡚࠸࡞࠸ࠋ᪩ᮇ࡟ᨺ㟁ࡀ⤊஢ࡋ࡚ࡋࡲ࠺ཎᅉ࡜ࡋ
࡚ࠊᨺ㟁᫬࡟ Li2O2 ࡀ⏕ᡂࡋ࡚୙ືែ⭷࡜ࡋ࡚ṇᴟ⾲㠃࡟ሁ✚ࡋࠊ㓟⣲ᣑᩓ࡜㟁Ꮚ⛣ືࡀ㜼ᐖࡉࢀࡿࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚ࡁࡓࠋࡋ
࠿ࡋࠊO2 ࡣከᏍ㉁ᵓ㐀ࢆ௓ࡋ࡚㟁ᴟ୰࡟ᣑᩓ
ࡍࡿࡇ࡜ࠊᑟ㟁ᛶࡢప࠸㑄⛣㔠ᒓ㓟໬≀࡛࠶

ᅗ2. (a)ΎίTiO2(101)㠃ཬࡧ(b)㓟⣲Ḟ㝗ࢆ᭷ࡍࡿTiO2(101)ࡗ࡚ࡶ㓟⣲㟁ᴟ࡜ࡋ࡚Ⰻዲ࡞㟁Ẽ໬Ꮫ≉ᛶࢆ⾲㠃࡬ࡢ྾╔ᵓ㐀࡜྾╔࢚ࢿࣝࢠ࣮

- 492 -

♧ࡍࡇ࡜࡞࡝࠿ࡽࠊ௚࡟ࡶ᪩ᮇᨺ㟁⤊Ṇࢆᘬࡁ㉳ࡇࡍ㔜せ࡞せᅉࡀ࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡿࠋࡲࡓࠊึᅇ
࡜ 2 ᅇ┠௨㝆࡛ᨺ㟁᭤⥺ࡀ኱ࡁࡃ␗࡞ࡿࡇ࡜ࡶุ᫂ࡋࡓࠋᮏ◊✲࡛ࡣࠊࣂ࢖ࣥࢲ࣮ࡀ୙せ࡞㓟໬ࢳࢱࣥ㓟⣲㟁ᴟࢆᛕ㢌࡟ࠊTiO2 ⾲㠃࡬ࡢ LiࠊO2ࠊLiO2 ྾╔࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋࣜࢳ࣒࢘ࡢᤄධ࣭⬺㞳࡟కࡗ࡚⾲㠃࡟㓟⣲Ḟ㝗ࡀ⏕ࡌࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࡓࡵࠊ㓟⣲Ḟ㝗ࡀ࠶ࡿሙྜ࡜࡞࠸ሙྜࡢ୧᪉࡟ᑐࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋ
ᅗ 2(a)࡟ LiࠊO2ࠊLiO2 ࡢ TiO2(101)Ύί⾲㠃࡬ࡢ᭱Ᏻᐃ྾╔ᵓ㐀࡜྾╔࢚ࢿࣝࢠ࣮ࢆ♧ࡍࠋLi ࡢ྾╔࢚ࢿࣝࢠ࣮࡟ᑐࡋ࡚ O2 ࡢ྾╔࢚ࢿࣝࢠ࣮ࡣ࠿࡞ࡾᑠࡉ࠸ࠋLiO2 ࡢ྾╔ᵓ㐀ࡣ┤⥺ᙧ࡟㏆ࡃࠊ྾╔࢚ࢿࣝࢠ࣮ࡶ
Li ཎᏊ࡟ẚ࡭ࡿ࡜࠿࡞ࡾᑠࡉ࠸ࠋᅗ 2(b)࡟ࡣࠊ㓟⣲Ḟ㝗ࢆ᭷ࡍࡿ TiO2(101)⾲㠃࡬ࡢ྾╔ᵓ㐀࡜྾╔࢚ࢿࣝࢠ࣮ࢆ♧ࡍࠋLi ࡢ྾╔࢚ࢿࣝࢠ࣮ࡣΎί⾲㠃࡜࡯ࡰኚࢃࡽ࡞࠸ࡀࠊO2 ࡜ LiO2 ࡢ྾╔࢚ࢿࣝࢠ࣮ࡣ኱ᖜ࡟ୖ᪼
ࡋ࡚࠸ࡿࠋࡇࡢࡇ࡜࠿ࡽࠊึᅇᨺ㟁᫬ࡣ O2 ྾╔ࡀ࡯࡜ࢇ࡝㉳ࡇࡽ࡞࠸ࡢ࡟ᑐࡋࠊ2 ᅇ┠௨㝆ࡣ Li ᤄධ࡟కࡗ
࡚⏕ࡌࡓ㓟⣲Ḟ㝗ࡢࡓࡵ࡟ O2ࠊLiO2 ࡢ྾╔ࡀ㉳ࡇࡿࡇ࡜ࡀࠊᨺ㟁᭤⥺ࡢኚ໬ࠊࡦ࠸࡚ࡣ㟁ụࡢ୙ྍ㏫ᐜ㔞ࡢཎᅉ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ

3.3 ㏆᥋ሙ࣐ࣛࣥࡢࡓࡵࡢ⌮ㄽ㛤Ⓨ࡜ග STM-TERS ࡬ࡢᛂ⏝ᒁᅾගࢆ౑࠺㏆᥋ሙ࣐ࣛࣥ㢧ᚤศගἲࡣࠊ༢ศᏊࡢ᣺ື࣮ࣔࢻࡢཎᏊศゎ⬟࡛ࡢྍど໬ࢆᐇ⌧ࡋࡓࠋ㏆᥋ሙศග࡟࠾ࡅࡿ㑅ᢥ๎ࡢゎ᫂࡟ࡣࠊ཮ᴟᏊ㏆ఝࢆ㉸࠼ࡓ⌮ㄽࡀᚲせ࡟࡞ࡿࠋᡃࠎࡣࠊࡇࡢࡼ࠺࡞ᒁᅾࡋࡓ㏆᥋ሙ࡜ศᏊࡢ┦஫స⏝ࢆグ㏙ࡍࡿࡓࡵ࡟ࠊ
ከ㔜ᴟ┦஫స⏝࡟ᇶ࡙ࡁࠊศᏊࡢグ㏙ࢆⅬ཮ᴟᏊ࠿ࡽศᴟሙ࡬࡜᪼⳹ࡍࡿࡇ࡜࡛ࠊග
-ศᏊ┦஫స⏝ࡢ୍⯡໬ࢆ⾜ࡗ࡚ࡁࡓࠋᮏ◊✲࡛ࡣࠊ㏆᥋ሙ࣐ࣛࣥศගࡢࡓࡵࡢ⌮ㄽᡭἲࢆ㛤Ⓨࡋࠊ࣋ࣥࢮࣥࡢඹ㬆/㠀ඹ㬆㏆᥋ሙ࣐ࣛࣥ࡬࡜㐺⏝ࡋࡓࠋ࣋ࣥࢮࣥୖ࡟࠾ࡅࡿ㟁ሙࡢᵝᏊࢆᅗ 3ᕥ࡟♧ࡍࠋศᏊ㠃ୖ࡟࠾࠸࡚ࠊ㟁ሙࡣ෇ᑐ⛠࡞ᨺᑕ≧ࡢศᕸࢆ♧ࡋ࡚࠸ࡿࠋ㠀ඹ㬆᮲௳ୗࡢ㑅ᢥ๎ࡣࠊࡇࡢ㟁ሙศᕸ࡜᣺ື࣮ࣔ
ࢻࡢ✵㛫ᵓ㐀࠿ࡽ⌮ゎ࡛ࡁࡿࠋ୍᪉ࠊඹ㬆᮲௳ୗ࡛ࡣᅗ 3 ྑ࡟♧ࡍࡼ࠺࡟ࠊບ㉳≧ែ࡟ࡼࡗ࡚኱ࡁࡃ㑅ᢥ๎ࡀኚࢃࡾ࠺ࡿࡇ࡜

ᅗ3. (ᕥ)ィ⟬࡟౑⏝ࡋࡓ㏆᥋ሙࡢࣔࢹࣝࠋ(ྑ)␗࡞ࡿ㟁Ꮚ㑄⛣࡟ᑐࡍࡿඹ㬆㏆᥋ሙ࣐ࣛࣥࢫ࣌ࢡࢺࣝ࡜ࡑࡢᡂศࠋ

ࡀ♧ࡉࢀࡓࠋࡲࡓࠊᅗ 3 ᕥ࡟♧ࡍࡼ࠺࡟㟁ሙࡣ➼᪉ⓗ࡛࠶ࡿࡀࠊᗙᶆᚤศࢆィ⟬ࡍࡿ㝿࡟ኚ␗ࡉࡏࡓᵓ㐀࡟࠾࠸࡚ບ㉳ࡉࡏࡿࠋࡇࢀࡣࠊ᣺㟁┦஫స⏝ࡢ⤖ᯝ࡛࠶ࡿ࡜⪃࠼࡚࠸ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

(1) Ṋḟᚭஓࠕ཯ᛂ⤒㊰࡟ᇶ࡙ࡃືຊᏛຠᯝࡢ⪃ᐹ㸸᭤⋡࣭ศᒱ࣭㑄⛣ࠖࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ 2020ࠖ, 2020.9.12, ࢜ࣥࣛ࢖ࣥ; (2) T. Taketsugu “On-the-fly molecular dynamics approach toexcited-state branching reaction” The 6th Quantum Science (QS) symposium - The Main Symposium of ICCMSE2020 -- 493 -

Computational Chemistry and Computational Physics (ICNAAM 2020 Video Conference), 2020.9.17-23, Rhodes
Sheraton, GREECE (online); (3) ᒾబ㇦ࠕ཯ᛂ⤒㊰⮬ື᥈⣴ἲࢆ⏝࠸ࡓࢡࣛࢫࢱ࣮ゐ፹ࡢ⌮ㄽ◊✲ࠖIQCE 㔞Ꮚ໬Ꮫ᥈⣴ㅮ₇఍ 2020ࠕ㔞Ꮚ໬Ꮫ࡛᥈ࡿ໬Ꮫࡢ᭱ඛ➃ࠖ, 2020.11.2, ࢜ࣥࣛ࢖ࣥ; (5) T. Taketsugu, T. Tsutsumi,
and Y. Ono “Visualization of reaction path, global reaction route map, and on-the-fly trajectories” New Horizons in
Scientific Software: from Legacy Codes to Modular Environments (NHISS 2020), 2020.11.23-26, Jeju Island, Korea(online); (6) ᒾబ㇦ࠕ཮ᴟᏊ㏆ఝࢆ㉸࠼ࡓ㏆᥋ሙග࡜ศᏊࡢከ㔜ᴟ┦஫స⏝࡜ບ㉳≧ែไᚚ࡟ྥࡅ࡚ࠖศᏊ◊◊✲఍ࠕࢼࣀ✵㛫࡛ගࡀ⧊ࡾ࡞ࡍศᏊ᧯స࣭໬Ꮫ཯ᛂไᚚࡢ᪂ᒎ㛤ࠖ, 2020.12.5, ࢜ࣥࣛ࢖ࣥ; (7) ᑠᯘṇேࠕ㔞Ꮚ໬Ꮫィ⟬࡜ࢹ࣮ࢱ⛉Ꮫࡢే⏝࡟ࡼࡿゐ፹࣭⾲㠃྾╔⣔ࡢゎᯒ࡜ணࠖィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࣭ࢼࣀࢸࢡࣀ

ࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗྜྠ࣮࣡ࢡࢩࣙࢵࣉ, 2021.1.12-13, ࢜ࣥࣛ࢖ࣥ; (8) ᑠᯘṇேࠕ㔞Ꮚ໬Ꮫィ⟬×࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿゐ፹࣭⾲㠃྾╔⣔ࡢゎᯒࠖᒱ㜧኱Ꮫேᕤ▱⬟ࢭࣥࢱ࣮ㅮ₇఍, 2021.1.22, ࢜ࣥࣛ࢖ࣥ;(9) A. Lyalin and T. Taketsugu “Theoretical Modelling of a Single-Phase Borophene Layer on Metal Support” PCoMSࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍ 2020, 2021.2.16, online; (10) T. Taketsugu“Visualization of reaction path and dynamical trajectory in reduced dimension” 3rd ICReDD International Symposium,
2021.2.22-24, online; (11) ᒾబ㇦ࠕ➨୍ཎ⌮ィ⟬࡟ࡼࡿ㏆᥋ሙ᣺ືศගࠖ᪥ᮏ≀⌮Ꮫ఍➨ 76 ᅇᖺḟ኱఍(2021ᖺ ), 2021.3.12-15, ࢜ࣥࣛ࢖ࣥ; (12) ሐᣅᮁ㸪ᑠ㔝ࡺࡾᏊ㸪Ⲩ஭㎿㸪Ṋḟᚭஓࠕḟඖ⦰⣙཯ᛂ✵㛫࡟࠾ࡅࡿ
on-the-fly ྂ඾㌶㐨ゎᯒࠖจ⦰⣔ࡢ⌮ㄽ໬Ꮫ, 2021.3.26, ࢜ࣥࣛ࢖ࣥ. 㸦௨ୖᣍᚅㅮ₇ࡢ୍㒊ࠊ௚ከᩘ㸧5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1) ‫ۻ‬T. Machida, T. Iwasa, T. Taketsugu, K. Sada, and K. Kokado, Chem. Eur. J. 26, 8028-8034 (2020); (2) ‫ۻ‬J. Li,
M. Gao, S. Tong, C. Luo, H. Zhu, T. Taketsugu, K. Uosaki, and M. Wu, Electrochim. Acta 340, 135977 (2020); (3) ‫ۻ‬
Y. Ootani, A. Satoh, Y. Harabuchi, and T. Taketsugu J. Comput. Chem. 41, 1549-1556 (2020); (4) ‫ۻ‬M. Takenaka, T.
Taketsugu, and T. Iwasa, J. Chem. Phys. 152, 164103 (2020); (5) ‫ۻ‬B. Wang, M. Gao, K. Uosaki, and T. Taketsugu,
Phys. Chem. Chem. Phys. 22, 12200-12208 (2020); (6) ‫ۻ‬M. Kobayashi, M. Harada, H. Takakura, K. Ando, Y. Goto,
T. Tsuneda, M. Ogawa, and T. Taketsugu, ChemPlusChem 85, 1959-1963 (2020); (7) ‫ۻ‬H. Nabata, M. Takagi, K. Saita,
and S. Maeda, RSC Adv. 10, 22156-22163 (2020); (8) ‫ۻ‬T. Tsutsumi, Y. Ono, Z. Arai, and T. Taketsugu, J. Chem.
Theory Comput. 16, 4029-4037 (2020); (9) ‫ۻ‬Y. Kondo, Y. Goto, M. Kobayashi, T. Akama, T. Noro, and T. Taketsugu,
Phys. Chem. Chem. Phys. 22, 27157-27162 (2020); (10) ‫ۻ‬ᑠᯘṇே, ࣐ࢸࣜ࢔ࣝࢫࢸ࣮ࢪ 20, 42-48 (2020); (11)‫ۻ‬S. Ebisawa, T. Tsutsumi, and T. Taketsugu, J. Comput. Chem. 42, 27-39 (2021); (12) ‫ۻ‬M. Takenaka, T. Taketsugu,
and T. Iwasa, J. Chem. Phys. 154, 024104 (2021); (13) ‫ۻ‬Y. Nitta, O. Schalk, H. Igarashi, S. Wada, T. Tsutsumi, K.
Saita, T. Taketsugu, and T. Sekikawa, J. Phys. Chem. Lett. 12, 674-679 (2021); (14) ‫ۻ‬T. Fujimori, M. Kobayashi, andT. Taketsugu, J. Comput. Chem. 40, 620–629 (2021); (15) ‫ۻ‬ᑠᯘṇே㸪⸨᳃ಇ࿴㸪Ṋḟᚭஓ, J. Comput. Chem. Jap.,
in press.

- 494 -

ゐ፹࠾ࡼࡧ㟁ᴟࡢ㟁Ꮚ≧ែࡢࡓࡵࡢ⌮ㄽ◊✲
Theoretical Studies for Electronic Structure of Catalysts and Electrodes‫ۑ‬୰஭ ᾈᕭࠊΎ㔝 ῟ྖࠊ஬༑ᖭ ᗣᘯࠊすᮧ ዲྐࠊᑠ㔝 ⣧୍ࠊ⸨Ἴ ⨾㉳Ⓩࠊᶡぢ ᮃ㒔ࠊᾆ㇂ ᾈ㍤ࠊ㧗ᓥ ༓Ἴࠊ୰ᮧ ᓫ⋪ࠊ⸨௦ ኳ♸ࠊ➉ᮧ ಇ᫭ࠊ⸨⃝ 㑈ࠊᅵᒇ భኴࠊ⏣ᔱ ୍㍤ࠊ㧗᲍ ೔ဢࠊΎỈ ఀ⧊㸦᪩✄⏣኱Ꮫඛ㐍⌮ᕤᏛ◊✲⛉㸧1◊✲┠ⓗᮏ◊✲࡛ࡣࠊゐ፹ཬࡧ஧ḟ㟁ụ࡟࠾ࡅࡿ⣲㐣⛬ࢆ㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙࠸࡚ᢅ࠸ࠊືసᶵᵓࡢᚤどⓗ⌮ゎཬࡧᛶ⬟ྥୖᣦ㔪ࢆᚓࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋලయⓗ࡞ᑐ㇟࡜ࡋ࡚ࠊࢼࢺ࣒ࣜ࢘࢖࢜ࣥ஧ḟ㟁ụ࡟࠾ࡅࡿ࢖࢜ࣥ
ఏᑟࠊ⮬ື㌴᤼࢞ࢫ⏝୕ඖゐ፹ᢸయ⾲㠃࡟࠾ࡅࡿ᭷ᶵ໬Ꮫ✀ᣑᩓࠊཬࡧᢸయࡢ᱁Ꮚ㓟⣲ࡀ㛵୚ࡍࡿ୕ඖゐ፹ୖ NO-CO ཯ᛂࡢ⌮ㄽⓗ᳨ウࢆ⾜ࡗࡓࡢ࡛ࠊࡇࢀࡽ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬࡟࠾࠸࡚ࡣࠊᙜ◊✲ᐊ࡛㛤Ⓨࡋࡓ DCDFTBMD ࣉࣟࢢ࣒ࣛࡢ࡯࠿ࠊ➨୍ཎ⌮ィ⟬ࣃࢵࢣ࣮ࢪ࡛

࠶ࡿ VASPࠊྂ඾ศᏊືຊᏛィ⟬ࣃࢵࢣ࣮ࢪ࡛࠶ࡿ AMBER ࢆ౑⏝ࡋࡓࠋ

3◊✲ᡂᯝ࠙ࢼࢺ࣒ࣜ࢘࢖࢜ࣥ஧ḟ㟁ụ㸦SIB㸧㟁ゎᾮ࡟࠾ࡅࡿ࢖࢜ࣥఏᑟࢩ࣑࣮ࣗࣞࢩࣙࣥࠚ
2019 ᖺࣀ࣮࣋ࣝ໬Ꮫ㈹ࡢཷ㈹ᑐ㇟࡜࡞ࡗࡓࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụ㸦LIB㸧ࡣࠊ㧗㟁ᅽ࣭㧗࢚ࢿࣝࢠ࣮ᐦ

ᗘ࠿ࡘᑠᆺ࣭㍍㔞࡞࡝ࡢ᭷⏝࡞≉ᚩࢆᣢࡘࡓࡵࠊᦠᖏ⏝㟁Ꮚᶵჾࡸ㟁Ẽ⮬ື㌴࡟࠾ࡅࡿ୺せ࡞࢚ࢿࣝࢠ࣮※࡜ࡋ࡚ᗈࡃᐇ⏝໬ࡉࢀ࡚࠸ࡿࠋᕼᑡඖ⣲ࡢࣜࢳ࣒࢘࡟ᇶ࡙ࡃ LIB ࡟௦ࢃࡿḟୡ௦㧗ᛶ⬟㟁ụ࡜ࡋ࡚ࠊ㏆ᖺࢼࢺ࣒ࣜ࢘࢖࢜ࣥ஧ḟ㟁ụ㸦SIB㸧ࡀὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋ≉࡟ࠊ㧗⃰ᗘ᮲௳ୗ࡟࠾࠸࡚㟁ゎ㉁ሷࡸ⁐፹ࡢከᵝ࡞⤌ࡳྜࢃࡏ࡟ࡼࡗ࡚㧗ᛶ⬟࣭㧗ᶵ⬟࡞⃰ཌ㟁ゎᾮࡀ㛤Ⓨࡉࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊᙜ◊✲ᐊ࡛⊂⮬࡟㛤Ⓨࡋࡓ DCDFTBMD ࣉࣟࢢ࣒ࣛ࡟ࡼࡿศ๭⤫἞ᆺᐦᗘỗ㛵ᩘᙉ᮰⦡ศᏊືຊᏛ㸦DC-DFTB-MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ
࡟ࡼࡾࠊ⁐፹ࡸ⃰ᗘࡀ␗࡞ࡿ SIB ⏝⃰ཌ㟁ゎᾮ࡟࠾ࡅࡿ࢖࢜ࣥᣑᩓᶵᵓࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ㧗⃰ᗘ᮲௳㸦~44%㸧࡟࠾࠸࡚ࠊ㟁ゎ㉁ሷ࡟ NaFSA [NaN(SO2F)2−]ࠊ᭷ᶵ⁐፹࡟ Trimethylphosphate (TMP), acetonitrile(AN), tetrahydrofuran (THF), diglyme (DGE) ࡢ 4 ✀㢮ࢆ᥇⏝ࡋࡓࠋNaFSA/TMP ࡛ࡣ 3 ✀㢮ࡢ⃰ᗘ㸦23.8%, 32.6%,
43.5%㸧ࢆ⪃៖ࡋࡓࠋྂ඾ MD ࡟ࡼࡿணഛᖹ⾮໬࠾ࡼࡧ DC-DFTB-MD ࡟ࡼࡿᖹ⾮໬ࢆ⾜ࡗࡓᚋࠊNVE ᮲௳࡛
60 ps ௨ୖࡢ DC-DFTB-MD ィ⟬ࢆᐇ⾜ࡋࡓࠋDC-DFTB-MD ィ⟬࡟ࡣࠊᙜヱࢭࣥࢱ࣮ࡢ ccnn 1 ࣀ࣮ࢻ㸦40 ࢥ࢔㸧ࢆ⏝࠸ࠊ1 ࢫࢸࢵࣉ㸦0.5 fs㸧ࡢィ⟬࡟ᖹᆒ⣙ 2.5 ⛊ࢆせࡋࡓࠋFigure 1a ࡟ྛ㟁ゎᾮ୰࡟࠾ࡅࡿ࢝ࢳ࢜ࣥ
ࡢᖹᆒ஧஌ኚ఩㸦MSD㸧ࢆ♧ࡍࠋࡇࡇ࡛ࠊMSD ࡢഴࡁࡀ⮬ᕫᣑᩓಀᩘ࡟ᑐᛂࡍࡿࠋᮏィ⟬࡟ࡼࡾࠊNaFSA/TMP࡟࠾࠸࡚ሷ⃰ᗘࡀቑຍࡍࡿ࡟ࡘࢀᣑᩓಀᩘࡀῶᑡࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࢀࡣࠊdimethyl ether (DME)⁐፹ࡢ NaFSA 㟁ゎᾮࢆᑐ㇟࡜ࡋࡓ DC-DFTB-MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿඛ⾜◊✲ࡢ⤖ᯝ࡜ྠᵝࡢഴྥ࡛࠶
ࡿࠋ㧗⃰ᗘ᮲௳࡟࠾ࡅࡿ⁐፹౫Ꮡᛶ࡟ࡘ࠸࡚ࡣࠊAN ⁐፹୰࡛ࡢᣑᩓಀᩘࡀ᭱ࡶ኱ࡁࡃ㸦7.62×10−10 m2/s㸧ࠊḟ࠸࡛ DGE ⁐፹୰࡛ࡢᣑᩓಀᩘࡀ኱ࡁ࠿ࡗࡓ㸦3.05×10−10 m2/s㸧ࠋNaFSA/DME ⃰ཌ㟁ゎᾮࢆᑐ㇟࡜ࡋࡓ
DC-DFTB-MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿඛ⾜◊✲࡟ࡼࡗ࡚ࠊ⃰ཌ᮲௳ୗࡢ࢟ࣕࣜ࢔࢖࢜ࣥᣑᩓ㐣⛬࡛ࡣࠊᕼⷧ
᮲௳ୗ࡟࠾࠸࡚ᨭ㓄ⓗ࡞ vehicular ᆺࡢ࢖࢜ࣥᣑᩓᶵᵓ࡟ຍ࠼ࠊ㓄఩Ꮚ஺᥮཯ᛂࡀ࢖࢜ࣥᣑᩓ࡟ᐤ୚ࡋ࡚࠸ࡿ

- 495 -

ࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ㓄఩Ꮚ஺᥮཯ᛂ㏿ᗘࡢ㐜ᘏ᫬㛫౫Ꮡᛶࢆ Figure 1b ࡟♧ࡍࠋࡇࡢ⤖ᯝࡼࡾࠊNaFSA/TMP࡟࠾࠸ ࡚ሷ ⃰ᗘ ࡀቑ ຍࡍ ࡿ࡟ࡘ ࢀ㓄 ఩Ꮚ ஺᥮ ཯ᛂ ㏿ᗘࡀ ቑຍ ࡍࡿ ࡇ࡜ ࡀ᫂ ࡽ࠿࡟ ࡞ࡗ ࡓࠋ ࡇࢀ ࡣࠊ
NaFSA/DME ࡢඛ⾜◊✲ࡢ⤖ᯝ࡜ྠᵝࠊ⃰ཌ᮲௳ୗ࡛ࡣ㓄఩Ꮚ஺᥮ᆺ࢖࢜ࣥᣑᩓࡢᐤ୚ࡀቑຍࡋ࡚࠸ࡿࡇ࡜
ࢆ♧ࡋ࡚࠸ࡿࠋDGE ⁐፹࡜ TMP ⁐፹ࢆẚ㍑ࡍࡿ࡜ࠊ㧗⃰ᗘ᮲௳ୗ㸦~44%㸧࡟࠾࠸࡚㸪DGE ୰࡛ࡢ Na+ࡢ⮬ᕫᣑᩓಀᩘࡣ TMP ࡜ẚ㍑ࡋ࡚~7.7 ಸ኱ࡁ࠸ࠋ୧⪅ࡢ㓄఩Ꮚ஺᥮཯ᛂ㏿ᗘࡣ࡯ࡰྠ⛬ᗘ࡛࠶ࡿࡇ࡜࠿ࡽࠊ⮬ᕫᣑᩓಀᩘࡢ㢧ⴭ࡞ᕪࡣ vehicular ᆺ࢖࢜ࣥᣑᩓࡢᕪ࡟⏤᮶ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋDGE ࡢศᏊ㔞㸦134.17㸧ࡣ TMP
ࡢศᏊ㔞㸦140.08㸧࡜ྠ⛬ᗘ࡛࠶ࡿࡇ࡜࠿ࡽࠊvehicular ᆺ࢖࢜ࣥᣑᩓࡢᐤ୚ࡣ༢⣧࡟⁐፹ศᏊࡢศᏊ㔞࡛Ỵࡲࡿࢃࡅ࡛ࡣ࡞ࡃࠊࡑࡢ௚ࡢ≉ᛶ㸦౛࠼ࡤ࣮࢟ࣞࢺຠᯝ㸧࡟ᙳ㡪ࢆཷࡅࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ

(a)

(b)

Figure 1. (a) Mean square displacements (MSDs) obtained from the DC-DFTB-MD simulations for the NaFSA electrolyte
solutions. (b) Reaction rate for ligand exchange events in cation diffusion processes.

࠙⮬ື㌴᤼࢞ࢫ⏝ Pt/Al2O3 ゐ፹⾲㠃࡟࠾ࡅࡿ᭷ᶵ໬Ꮫ✀ᣑᩓࢲ࢖ࢼ࣑ࢡࢫࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࠚ
ෆ⇞⮬ື㌴᤼࢞ࢫ୰ࡢ୺࡞኱Ẽởᰁ≀㉁࡜ࡋ࡚ࠊ୍㓟໬Ⅳ⣲㸦CO㸧ࠊ❅⣲㓟໬≀㸦NOx㸧ࠊ࠾ࡼࡧ⇞ᩱࡢ⇞࠼ṧࡾ࡛࠶ࡿⅣ໬Ỉ⣲㸦CxHy㸧ࡀ࠶ࡿࠋ୕ඖゐ፹ࡣࠊNOx ࢆ N2 ࡬࡜㑏ඖࡋࡘࡘࠊCO ࡜ CxHy ࢆ CO2 ࡬࡜㓟໬ࡍࡿࡇ࡜࡟ࡼࡾࠊୖグ 3 ✀㢮ࡢ≀㉁ࢆྠ᫬࡟↓ᐖ໬ࡍࡿࠋᐇ⏝ⓗ࡞୕ඖゐ፹ࡣࠊ㈗㔠ᒓ㸦Pt, Pd, Rh㸧ࢆ Al2O3
ୖ࡟ᢸᣢࡋࡓࡶࡢ࡛࠶ࡾࠊAl2O3 ⾲㠃࡟࠾ࡅࡿⅣ⣲㓟⣲໬Ꮫ✀㸦࢝ࣝ࣎ࣥ㓟➼㸧ࡢᣑᩓࡀ཯ᛂ㏿ᗘࢆỴࡍࡿ㔜せ࡞ࢫࢸࢵࣉࡢ୍ࡘ࡛࠶ࡿࡇ࡜ࡀᣦ᦬ࡉࢀࡿࡀࠊࡑࡢᶵᵓࡣ᫂ࡽ࠿࡛࡞࠿ࡗࡓࠋᮏ◊✲࡛ࡣࠊᙜ◊✲ᐊ࡛㛤Ⓨࡋࡓ DCDFTBMD ࣉࣟࢢ࣒ࣛ࡟ࡼࡿ DC-DFTB-MD/metadynamics ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊ(100)-J-Al2O3 ⾲㠃࡟࠾ࡅࡿⅣ⣲㓟⣲໬Ꮫ✀ࡢᣑᩓ㐣⛬࠾ࡼࡧࡑࡢ࢚ࢿࣝࢠ࣮ㄽࢆ᳨ウࡋࡓࠋⅣ⣲㓟⣲໬Ꮫ✀࡜ࡋ࡚ࡣࠊ࢔ࢭ
ࢸ࣮ࢺࠊ࣑࣍ࣝࣝࠊ࠾ࡼࡧ࣓ࢺ࢟ࢩ໬Ꮫ✀ࢆᑐ㇟࡜ࡋࡓࠋ࢔ࢭࢸ࣮ࢺ໬Ꮫ✀࡜࣑࣍ࣝࣝ໬Ꮫ✀ࡣࠊ࢝ࣝ࣎࢟
ࢩࣝᇶࡀ 2 ᮏࡢ O-Al ⤖ྜࢆᙧᡂࡍࡿࡇ࡜࡛໬Ꮫ྾╔ࡍࡿ࡜࠸࠺Ⅼ࡛ࡣඹ㏻ࡍࡿࡀࠊᣑᩓࡢᶵᵓࡣ኱ࡁࡃ␗࡞
ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ࢔ࢭࢸ࣮ࢺࡣ୍᪉ࡢ O-Al ⤖ྜࡀษࢀࡶ࠺୍᪉ࡢ O-Al ⤖ྜࢆ㍈࡟ᅇ㌿ࡍࡿ࡜࠸࠺
ᶵᵓ࡛ࡺࡗࡃࡾ࡜ᣑᩓࡍࡿࡀࠊ࣑࣍ࣝࣝ໬Ꮫ✀ࡣ H ཎᏊࡀ㛵୚ࡍࡿᶵᵓ࡟ࡼࡾ㠀ᖖ࡟㏿ࡃᣑᩓࡍࡿࡇ࡜ࡀࢃ
࠿ࡗࡓࠋ୍᪉ࠊ࣓ࢺ࢟ࢩ໬Ꮫ✀ࡣࣈࣛ࢘ࣥᣑᩓ࡟㏆࠸ᣲືࢆ♧ࡍࡇ࡜ࡀࢃ࠿ࡗࡓ㸦Figure 2㸧
ࠋ- 496 -

Figure 2. Diffusion mechanisms of (a) acetate, (b) formate, and (c) methoxy species.

࠙ᢸయࡢ᱁Ꮚ㓟⣲ࡀ㛵୚ࡍࡿ୕ඖゐ፹ NOCO ཯ᛂࡢ᳨ウࠚ୕ඖゐ፹ࡢᢸయ࡜ࡋ࡚ CeO2 ➼ࢆ⏝࠸ࡿሙྜࠊᢸయࡢ᱁Ꮚ㓟⣲ࡀ㛵୚ࡍࡿ Mars-van Krevelen (M-vK)ᶵᵓ࡛
཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋM-vK ᶵᵓ࡛ࡣࠊᢸయࡢ O ཎᏊࡀ⬺㞳ࡍࡿࡇ࡜࡛㔠ᒓୖࡢ CO ࡀ CO2
࡬࡜㓟໬ࡉࢀࡿࠋࡇࢀ࡟ࡼࡾᢸయ࡟ O Ḟ㝗ࡀ⏕ࡌࡿࡀࠊO2 ࡟ࡼࡿ㓟໬࡛ඖ࡟ᡠࡾࠊゐ፹ࢧ࢖ࢡࣝࡀᡂ❧ࡍࡿࠋ
M-vK ᶵᵓ࡟࠾࠸࡚ࡣࠊ᱁Ꮚ㓟⣲ࡢ⬺㞳⬟ࡀ CO 㓟໬཯ᛂࡢάᛶࢆᕥྑࡍࡿࡀࠊࡇࢀࡣᢸయࡢ✀㢮ࡸᢸᣢ㔠ᒓ✀࡟౫Ꮡࡍࡿࠋࡉࡽ࡟ࠊO Ḟ㝗ࡀ NO 㑏ඖ࡟ᐤ୚ࡍࡿྍ⬟ᛶࡶᣦ᦬ࡉࢀࡿࡀࠊ࣑ࢡࣟ࡞ほⅬ࠿ࡽࡢ᳨ドࡣ࡞ࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊࢫࣛࣈࣔࢹࣝࢆ⏝࠸ࡓᐦᗘỗ㛵ᩘ⌮ㄽ㸦DFT㸧ィ⟬࡟ࡼࡾࠊᢸయࡢ᱁Ꮚ㓟⣲ࡀ㛵୚ࡍࡿ NO-CO ཯ᛂࡢ࢚ࢿࣝࢠ࣮ㄽ࠾ࡼࡧࡑࡢᢸయ࣭ᢸᣢ㔠ᒓ✀౫Ꮡᛶࢆ᳨ウࡋࡓࠋィ⟬ࣉࣟࢢ࣒ࣛ࡜ࡋ࡚
VASP ࢆ౑⏝ࡋࠊᢸᣢ㔠ᒓ࡜ࡋ࡚ Cu, Ru, Rh, Pd, Ir, Pt ࢆࠊᢸయ࡜ࡋ࡚ CeO2, TiO2, ZrO2 ࢆ᳨ウࡋࡓࠋᢸᣢ㔠ᒓ࡜ᢸయ࡜ࡢቃ⏺㒊ศ㸦࣓࣌ࣜࢱ࣮ࢧ࢖ࢺ㸧࡟࠶ࡿ᱁Ꮚ㓟⣲ࡢ⬺㞳࢚ࢿࣝࢠ࣮ィ⟬್ࢆ Table 1 ࡟♧ࡍࠋẚ㍑ࡢ
ࡓࡵࠊ㔠ᒓࢆᢸᣢࡋ࡚࠸࡞࠸ᢸయ⾲㠃࡟࠾ࡅࡿ᱁Ꮚ㓟⣲ࡢ⬺㞳࢚ࢿࣝࢠ࣮ࡶ♧ࡍࠋከࡃࡢ㔠ᒓ✀࡛ࡣᢸᣢ࡟
ࡼࡾ⬺㞳࢚ࢿࣝࢠ࣮ࡀపୗࡋࡓࡇ࡜ࡀࢃ࠿ࡿࠋࡲࡓࠊO Ḟ㝗࡟ࡼࡿ NO ゎ㞳࢚ࢿࣝࢠ࣮ࢆ Table 2 ࡟♧ࡍࠋࢹ࣮ࢱࡢグࡉࢀ࡚࠸࡞࠸⣔࡟ࡘ࠸࡚ࡣࠊゎ㞳๓ࡢ≧ែ࡟࠶ࡓࡿ NO ࡢ྾╔ᵓ㐀ࡀᚓࡽࢀࡎࠊᵓ㐀᭱㐺໬ࡢ㐣⛬࡛ゎ㞳ࡋࡓࠋࡑࡢ௚ࡢ⣔࡟࠾࠸࡚ࡣࠊNO ࡢゎ㞳࢚ࢿࣝࢠ࣮ࡀ඲࡚㈇࡛࠶ࡿࠊࡍ࡞ࢃࡕゎ㞳ࡀⓎ⇕ⓗ࡟㐍⾜ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡋࡓࡀࡗ࡚ࠊO Ḟ㝗ࡀ NO 㑏ඖ཯ᛂ࡟ᐤ୚ࡍࡿࡇ࡜ࢆᨭᣢࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋ

- 497 -

Table 1. Lattice oxygen desorption energies (eV).
Support

None

Ru

Ir

Rh

Pt

Pd

Cu

CeO2

3.15

3.84

3.74

3.55

2.42

2.66

3.11

TiO2

3.91

4.18

3.81

3.69

1.61

2.25

3.30

ZrO2

5.59

4.79

3.29

3.54

2.14

2.72

3.48

Table 2. NO dissociation energies (eV).
Support

Ru

Ir

Rh

Pt

Pd

Cu

CeO2

-2.38

-1.51

-2.43

-1.01

-1.41

-1.89

TiO2

-2.61

-

-

-1.58

-2.02

-1.41

ZrO2

-2.54

-

-

-1.04

-1.41

-0.72

4

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] Ύ㔝῟ྖࠊ͆໬Ꮫ࡟࠾ࡅࡿேᕤ▱⬟ᢏ⾡࡜ࡢ⼥ྜࡢᇶ♏࡜ᐇ㦂࣭ィ⟬໬Ꮫ࡬ࡢᛂ⏝஦౛͇
ࠊゐ፹࢖ࣥࣇ࢛࣐
ࢸ࢕ࢡࢫࢭ࣑ࢼ࣮ࠊ࢜ࣥࣛ࢖ࣥ㛤ദࠊ2020 ᖺ 6 ᭶㸦ᣍᚅㅮ₇㸧
[2] Ύ㔝῟ྖࠊ͆໬Ꮫ◊✲࡜ேᕤ▱⬟ᢏ⾡ࡢ⼥ྜ࡟㛵ࡍࡿᇶ♏࡜ᛂ⏝͇ࠊCMC ࣜࢧ࣮ࢳࢭ࣑ࢼ࣮ࠊ࢜ࣥࣛ࢖ࣥ
㛤ദࠊ2020 ᖺ 8 ᭶㸦ᣍᚅㅮ₇㸧
[3] Junichi Ono, “Microscopic mechanisms of proton transfers in bacteriorhodopsin revealed by quantum molecular
dynamics method based on molecular movies”, ➨ 58 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍ࠊ࢜ࣥࣛ࢖ࣥ㛤ദࠊ2020 ᖺ 9 ᭶㸦ᣍᚅㅮ₇㸧
[4] Hiromi Nakai and Yoshifumi Nishimura, “DCDFTBMD: Divide-and-conquer density functional tight-binding
program for huge-system quantum mechanical molecular dynamics simulations”, New Horizons in Scientific
Software -From Legacy Codes to Modular Environments (NHISS 2020), online, Nov 2020 (invited)[5] ⸨Ἴ⨾㉳Ⓩࠊ
͆㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘࡢ㛤Ⓨࠊ཯ᛂணࠊ཯ᛂ᮲௳᭱㐺໬࡟ᑐࡍࡿ㔞Ꮚ໬Ꮫィ⟬࡜ᶵᲔᏛ⩦ࡢᛂ⏝͇ࠊィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࣭ࢼࣀࢸࢡࣀࣟࢪ࣮ࣉࣛࢵࢺࣇ࢛࣮࣒஦ᴗྜྠ࣮࣡ࢡࢩࣙࢵࣉࠊ࢜ࣥࣛ
࢖ࣥ㛤ദࠊ2021 ᖺ 1 ᭶㸦ᣍᚅㅮ₇㸧㸦௚ࠊᅜෆᏛ఍ 20 ௳㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

★>@0,QDPRUL<,NDEDWD7<RVKLNDZDDQG+1DNDL³8QYHLOLQJFRQWUROOLQJIDFWRUVRIWKH6 
6 PLQLPXP HQHUJ\ FRQLFDO LQWHUVHFWLRQ   $SSOLFDWLRQ WR SHQDOW\ IXQFWLRQ PHWKRG´ J. Chem. Phys. 152 
  SDJHV ★>@0)XMLQDPL5.DJH\DPD-6HLQR<,NDEDWDDQG+1DNDL³2UELWDOIUHHGHQVLW\IXQFWLRQDOWKHRU\FDOFXODWLRQDSSO\LQJ VHPLORFDOPDFKLQHOHDUQHG NLQHWLF HQHUJ\ GHQVLW\ IXQFWLRQDO DQG NLQHWLF SRWHQWLDO´ Chem. Phys. Lett. 748   SDJHV ★>@-2QRDQG+1DNDL³:HLJKWHGKLVWRJUDPDQDO\VLVPHWKRGIRUPXOWLSOHVKRUWWLPHPHWDG\QDPLFVVLPXODWLRQV´
Chem. Phys. Lett.751   SDJHV ‫@>ۻ‬0)XMLQDPL+0DHNDZDUD5,VVKLNL-6HLQR-<DPDJXFKLDQG+1DNDL³6ROYHQW6HOHFWLRQ6FKHPH8VLQJ- 498 -

0DFKLQH/HDUQLQJ%DVHGRQ3K\VLFRFKHPLFDO'HVFULSWLRQRI6ROYHQW0ROHFXOHV$SSOLFDWLRQWR&\FOLF2UJDQRPHWDOOLF
5HDFWLRQ´Bull. Chem. Soc. Jpn.93²  ‫<@>ۻ‬1LVKLPXUDDQG+1DNDL³+LHUDUFKLFDOSDUDOOHOL]DWLRQRIGLYLGHDQGFRQTXHUGHQVLW\IXQFWLRQDOWLJKWELQGLQJ
PROHFXODUG\QDPLFVDQGPHWDG\QDPLFVVLPXODWLRQV´J. Comput. Chem.41²  
 >@ . 7RNR . ,WR + 6DLWR < +RVRQR . 0XUDNDPL 6 0LVDNL 7 +LJR 6 2JR + 7VXQHNL 6 0DHGD .
+DVKLPRWR+1DNDLDQG<6HNLQH³&DWDO\WLF'HK\GURJHQDWLRQRI(WKDQHRYHU'RSHG3HURYVNLWHYLDWKH
0DUVíYDQ.UHYHOHQ0HFKDQLVP´J. Phys. Chem. C124²  
 >@700DLHU<,NDEDWDDQG+1DNDL³5HODWLYLVWLFORFDOK\EULGIXQFWLRQDOVDQGWKHLULPSDFWRQVFRUHRUELWDOHQHUJLHV´ J. Chem. Phys.152   SDJHV ‫@>ۻ‬+8UDWDQLDQG+1DNDL³6LPXODWLQJWKH&RXSOHG6WUXFWXUDO±(OHFWURQLF'\QDPLFVRI3KRWRH[FLWHG/HDG,RGLGH
3HURYVNLWHV´J. Phys. Chem. Lett.11²  ‫ @> ۻ‬+ 8UDWDQL DQG + 1DNDL ³1RQDGLDEDWLF PROHFXODU G\QDPLFV ZLWK GLYLGHDQGFRQTXHU W\SH ODUJHVFDOH
H[FLWHGVWDWHFDOFXODWLRQV´ J. Chem. Phys.152   SDJHV ‫@>ۻ‬7<RVKLNDZD7'RLDQG+1DNDL³)LQLWHWHPSHUDWXUHEDVHGWLPHGHSHQGHQWGHQVLW\IXQFWLRQDOWKHRU\PHWKRGIRUVWDWLFHOHFWURQFRUUHODWLRQV\VWHPV´J. Chem. Phys.152   SDJHV ‫@>ۻ‬-2QR0,PDL<1LVKLPXUDDQG+1DNDL³+\GUR[LGH,RQ&DUULHUIRU3URWRQ3XPSVLQ%DFWHULRUKRGRSVLQ
3ULPDU\3URWRQ7UDQVIHU´J. Phys. Chem. B124²  (Supplementary Journal Cover)‫ < @>ۻ‬,NDEDWD 5 )XMLVDZD - 6HLQR 7 <RVKLNDZD DQG + 1DNDL ³0DFKLQHOHDUQHG HOHFWURQ FRUUHODWLRQ PRGHOEDVHGRQIUR]HQFRUHDSSUR[LPDWLRQ´J. Chem. Phys.153   SDJHV 
 >@ ) :DQJ 6 /DQJIRUG DQG + 1DNDL ³5REXVW GHVLJQ RI 'S$ PRGHO FRPSRXQGV XVLQJ GLJLWDO VWUXFWXUHV IRURUJDQLF'66&DSSOLFDWLRQV´J. Mol. Graph, Model.102   SDJHV ‫ @>ۻ‬+ 8UDWDQL 7 0RULRND 7 <RVKLNDZD DQG + 1DNDL ³)DVW 1RQDGLDEDWLF 0ROHFXODU '\QDPLFV YLD 6SLQ)OLS
7LPH'HSHQGHQW 'HQVLW\)XQFWLRQDO 7LJKW%LQGLQJ $SSURDFK $SSOLFDWLRQ WR 1RQUDGLDWLYH 5HOD[DWLRQ RI
7HWUDSKHQ\OHWK\OHQH ZLWK /RFNHG $URPDWLF 5LQJV´ J. Chem. Theory Comput. 16 ²  (Supplementary Journal Cover)
‫@>ۻ‬$:6DNWL&3&KRX<1LVKLPXUDDQG+1DNDL³,VR[\JHQGLIIXVLRQIDVWHULQEXON&H2RURQ  &H2
VXUIDFH"$WKHRUHWLFDOVWXG\´Chem. Lett.50²  
 >@ . 0XUDNDPL < 0L]XWDQL + 6DPSHL $ ,VKLNDZD < 7DQDND 6 +D\DVKL 6 'RL 7 +LJR + 7VXQHNL +
1DNDLDQG<6HNLQH³7KHRUHWLFDOSUHGLFWLRQE\')7DQGH[SHULPHQWDOREVHUYDWLRQRIKHWHURFDWLRQGRSLQJHIIHFWVRQK\GURJHQ DGVRUSWLRQ DQG PLJUDWLRQ RYHU WKH &H2   VXUIDFH´ Phys. Chem. Chem. Phys. 23 ²  (Journal Cover) >@<7DQDND.0XUDNDPL6'RL.,WR.6DHJXVD<0L]XWDQL6+D\DVKL7+LJR+7VXQHNL+1DNDLDQG
< 6HNLQH ³(IIHFWV RI $VLWH FRPSRVLWLRQ RI SHURYVNLWH 6Uí[%D[=U2  R[LGHV RQ + DWRP DGVRUSWLRQ PLJUDWLRQ DQGUHDFWLRQ´RSC Adv.11²  ‫ @>ۻ‬+ 8UDWDQL 7 <RVKLNDZD DQG + 1DNDL ³7UDMHFWRU\ 6XUIDFH +RSSLQJ $SSURDFK WR &RQGHQVHG3KDVH
1RQUDGLDWLYH 5HOD[DWLRQ '\QDPLFV 8VLQJ 'LYLGHDQG&RQTXHU 6SLQ)OLS 7LPH'HSHQGHQW 'HQVLW\)XQFWLRQDO 7LJKW%LQGLQJ´ J. Chem. Theory Comput.17²  ‫&@>ۻ‬7DNDVKLPD-6HLQRDQG+1DNDL³,PSOHPHQWDWLRQRI3LFWXUH&KDQJH&RUUHFWHG'HQVLW\)XQFWLRQDO7KHRU\%DVHGRQ,QILQLWH2UGHU7ZR&RPSRQHQW0HWKRGWR*$0(663URJUDP´J. Comput. Chem. Jpn.19²  - 499 -᪂つከᶵ⬟㟁ゎᾮࡢಖㆤ⭷ᙧᡂᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗゎᯒTheoretical analysis on protective film formation mechanism of new
multifunctional electrolyte๪㢟 0;HQHࢆ⏝࠸ࡓỈ⣔㟁Ẽ஧㔜ᒙ࢟ࣕࣃࢩࢱࡢᐁ⬟ᇶ౫Ꮡᛶࡢ⌮ㄽⓗゎᯒTheoretical analysis on functional group dependence of aqueous
electric double-layer capacitor using MXene‫ۑ‬ᒣ⏣ ῟ኵࠊ➉୰ つ㞝ࠊᓥ⏣ 㡴㸦ᮾி኱Ꮫ㸧1◊✲┠ⓗỈ⣔㟁ゎᾮࢆ⏝࠸ࡓ㟁Ẽ஧㔜ᒙ࢟ࣕࣃࢩࢱ㸦Ỉ⣔ EDLC㸧ࡣࠊ㧗࠸ධฟຊᐦᗘ࡟ຍ࠼࡚ࠊ୙⇞ᛶࡢỈࢆ౑⏝ࡍࡿࡓࡵࠊᏳ඲㠃࡛ࡶඃࢀࡓ⵳㟁ࢹࣂ࢖ࢫ࡛࠶ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ⣧Ỉࡢ⊃࠸㟁఩❆㸦1.23 V㸧࡟㉳ᅉࡋ࡚࢚ࢿࣝࢠ࣮ᐦᗘࡀప࠸ࡇ࡜ࡀ኱ࡁ࡞ḞⅬ࡛࠶ࡾࠊ࢚ࢿࣝࢠ
࣮ᐦᗘྥୖ࡟ࡣ㟼㟁ᐜ㔞ࡢቑ኱ࡀ୙ྍḞ࡛࠶ࡿࠋᮏ◊✲࡛ࡣỈ⣔ EDLC ࡢ㟁ᴟᮦᩱ࡜ࡋ࡚᭷ᮃ࡞ MXene㸦⤌ᡂᘧ: Mn+1XnTx, M = Ti, Nb, Mo, etc., X = C, Nࠊn = 1, 2, etc.,⾲㠃ᐁ⬟ᇶ Tx: ̽F, ̽Cl, ̽Br, ̽I, etc.㸧㸦ᅗ 1㸧࡟╔┠ࡋࡓࠋ≉࡟ࠊMXeneࡢ⾲㠃ᐁ⬟ᇶ Tx ࡢ㐪࠸ࡀ㟁Ẽ໬Ꮫ≉ᛶ࡟኱ࡁ࡞ᙳ㡪ࢆཬࡰࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊ⾲㠃ᐁ⬟ᇶࢆ㐺ษ࡟ไᚚࡍࡿࡇ࡜࡛
㧗㏿඘ᨺ㟁࡜㧗ᐜ㔞ࢆ୧❧ྍ⬟࡞⵳㟁ࢹࣂ࢖ࢫࡢ㛤Ⓨ࡟⧅ࡀࡿ࡜ᮇᚅࡉࢀࡿࠋࡑࡇ࡛ࠊMXene 㟁ᴟࢆ⏝࠸ࡓỈ⣔ EDLCࡢ㟼㟁ᐜ㔞ࢆቑ኱ࡉࡏࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࠊࡑࡢ⾲㠃ᐁ⬟ᇶ౫

ᅗ 1. MAX ┦㸦Ti3AlC2㸧࡜ MXene㸦Ti3C2Tx㸧ࡢᶍᘧᅗᏑᛶࢆ⌮ㄽⓗ࡟ㄪᰝࡋࡓࠋ

2ィ⟬᪉ἲᮏ◊✲࡛ࡣࠊ௦⾲ⓗ࡞ MXene ࡛࠶ࡿ Ti3C2T2 ࢆࠊ⾲㠃ᐁ⬟ᇶ࡟ 4 ✀㢮ࡢࣁࣟࢤࣥඖ⣲㸦T = FࠊClࠊBrࠊI㸧ࢆ᥇⏝ࡋࠊ༢ᒙࡢ MXene ࡜ 1 M KOTf Ỉ⁐ᾮ࡜ࡢ⏺㠃ࢆᑐ㇟⣔࡜ࡋࡓࠋࡲࡓࠊ㟼㟁ᐜ㔞ࢆồࡵࡿࡓࡵࠊ
ESM-RISM ἲࢆ⏝࠸ࡓࠋᮏᡭἲ࡛ࡣࠊ㟁ᴟࢆᐦᗘỗ㛵ᩘἲ㸦DFT㸧࡟ࡼࡾグ㏙ࡋࠊ㟁ゎᾮࢆྂ඾⁐ᾮㄽࡢ┦஫స⏝Ⅼࣔࢹࣝ㸦RISM㸧࡟ࡼࡾグ㏙ࡍࡿࠋィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣࠊQuantum Espresso ࢆ౑⏝ࡋࡓࠋDFT ィ⟬࡛ࡣࠊ࢘ࣝࢺࣛࢯࣇࢺᨃ࣏ࢸࣥࢩࣕࣝ࡜ PBE ࢆ᥇⏝ࡋࠊᖹ㠃Ἴᇶᗏࡢ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ࢆ 45 Ry ࡜ࡋࡓࠋࡲࡓࠊRISM 㒊ศࡢྂ඾ຊሙࣃ࣓࣮ࣛࢱ࡜ࡋ࡚ࠊH2O ࡟ࡣ TIP5P ࣔࢹࣝࠊK+࡜ OTf-࡟ࡣ OPLS-AA ຊሙࠊMXene࡟ࡣࣘࢽࣂ࣮ࢧࣝຊሙࢆࡑࢀࡒࢀ⏝࠸ࡓࠋRISM ᪉⛬ᘧࡢ┦㛵㛵ᩘࡢ཰᮰᮲௳ࡣ 3.010̽6 Ry ࡜ࡋࡓࠋ3◊✲ᡂᯝ
ᅗ 2a ࡟ ESM-RISM ィ⟬࠿ࡽᚓࡽࢀࡓ㟁ᴟࡢ㟁఩ኚ໬࡜⾲㠃㟁Ⲵᐦᗘࡢ㛵ಀࢆ♧ࡍࠋ࠸ࡎࢀࡢ⾲㠃ᐁ⬟ᇶࢆᣢࡘ MXene 㟁ᴟ࡛ࡶ㟁ᴟ㟁఩࡜⾲㠃㟁Ⲵᐦᗘࡣ⥺ᙧ㛵ಀ࡜࡞ࡿࡓࡵࠊᮏィ⟬ࡢ㟁఩⠊ᅖ࡟࠾࠸࡚㟼㟁ᐜ㔞ࡣ୍ᐃ࡛࠶ࡿࠋࡲࡓࠊ⾲㠃㟁Ⲵᐦᗘ–6.28 ȝC/cm2 ࡟࠾ࡅࡿ㟼㟁ᐜ㔞ࡢ್ࡣ⾲㠃ᐁ⬟ᇶࢆ–Fࠊ–Clࠊ–Brࠊ–I ࡜- 500 -

ࡋࡓሙྜ࡟ࠊ6.65ࠊ8.63ࠊ9.83ࠊ11.73 ȝF/cm2 ࡜࡞ࡾ㸦ᅗ 2b㸧ࠊ⾲㠃ᐁ⬟ᇶ࡜ࡋ࡚ࡼࡾ㧗࿘ᮇࡢࣁࣟࢤࣥඖ⣲ࢆ᥇⏝ࡍࡿ࡯࡝㟼㟁ᐜ㔞ࡀ኱ࡁࡃ࡞ࡿ࡜࠸࠺᫂☜࡞ഴྥࡀᚓࡽࢀࡓࠋ

ᅗ 2. (a) 㟁఩ኚ໬㸦ǻE㸧࡜⾲㠃㟁Ⲵᐦᗘ㸦ıM㸧ࡢ㛵ಀࠊ(b) ༢఩⾲㠃✚ᙜࡓࡾࡢ㟼㟁ᐜ㔞ࡢᐁ⬟ᇶ౫Ꮡᛶḟ࡟ࠊ㟼㟁ᐜ㔞ࡢ⾲㠃ᐁ⬟ᇶ౫Ꮡᛶࡢせᅉࢆ᥈ࡿࡓࡵࠊ
㟁ᴟ/㟁ゎᾮ⏺㠃ࡢ㐣๫㟁Ⲵᐦᗘศᕸࢆゎᯒࡋࡓ㸦ᅗ 3 㸧ࠋ㟁ゎᾮࡢ㐣๫㟁Ⲵࡢศᕸᙧ≧ࡣ⾲㠃ᐁ⬟ᇶࡢඖ⣲✀࡟ᣊࢃࡽࡎ࡯ࡰྠࡌ࡛࠶ࡿࡀࠊศᕸ఩⨨ࡣ⾲㠃ᐁ⬟ᇶࡀ FࠊClࠊ
BrࠊI ࡜㧗࿘ᮇ࡟࡞ࡿ࡟ࡘࢀ࡚ࠊ㐲᪉࡬࡜⛣ືࡍࡿࠋࡇࢀࡣ
ྛ⾲㠃ᐁ⬟ᇶඖ⣲ࡢࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫ༙ᚄࡀ F < Cl < Br
< I ࡛࠶ࡾࠊ㧗࿘ᮇࡢࣁࣟࢤࣥඖ⣲࡯࡝㟁ゎᾮഃࡢ࢖࢜ࣥࡀ
㟁ᴟ⾲㠃࠿ࡽ㐲ࡃ࡬ᢲࡋฟࡉࢀࡿࡓࡵ࡛࠶ࡿࠋ୍᪉ࠊ㟁ᴟࡢ㐣๫㟁Ꮚࡢศᕸᙧ≧ࡣ⾲㠃ᐁ⬟ᇶࡢඖ⣲✀࡟౫Ꮡࡋ࡚኱
ࡁࡃ␗࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡑࡇ࡛ࠊ㟁ᴟ࣭㟁ゎᾮࡢ㐣๫㟁Ⲵࡢᖹᆒ఩⨨ࢆぢ✚ࡶࡾࠊ㟁Ẽ஧㔜ᒙࡢᖜࢆ⟬ฟࡋࡓ࡜ࡇࢁࠊ㧗࿘ᮇࡢࣁࣟࢤࣥඖ⣲࡯࡝㟁Ẽ஧㔜ᒙࡢᖜࡣ⊃ࡃ࡞ࡗࡓ㸦㟁఩ኚ໬ࡀᑠࡉࡃ࡞ࡾࠊ㟼㟁ᐜ㔞ࡀቑ኱㸧ࠋࡇࢀࡣࠊ
㟁ᴟෆࡢ㐣๫㟁Ꮚࡀ㟁ゎᾮࡢ㏆ഐ࡟ࡼࡾከࡃศᕸࡍࡿࡇ࡜
࡟㉳ᅉࡋ࡚࠾ࡾࠊᐁ⬟ᇶࡢඖ⣲✀࡟ᛂࡌࡓ㟁ᴟࡢ㟁Ꮚ≧ែ

ᅗ 3. 㟁ᴟ/㟁ゎᾮ⏺㠃ࡢ㐣๫㟁Ⲵᐦᗘศᕸ
㸦㯮⥺㸸᭱⾲㠃ཎᏊࡢ఩⨨ࠊ㉥⥺㸸㟁ᴟࡢ㟁Ꮚศᕸࡢᖹᆒ఩⨨ࠊ㟷⥺㸸㟁ゎᾮࡢ㟁Ⲵศᕸࡢᖹᆒ఩⨨㸧ࡢ㐪࠸ࡀ㟼㟁ᐜ㔞ࡢ኱ࡁࡉࢆᨭ㓄ࡍࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ
㟁ᴟࢆᖏ㟁ࡉࡏࡿࡇ࡜࡛⵳✚ࡉࢀࡓ㐣๫㟁Ꮚࡣࠊ㟁ゎᾮ୰ࡢ K+࡜ࡢ㟼㟁ⓗ࡞ᘬຊ┦஫స⏝࡟ࡼࡿ㟼㟁ㄏᑟ࡟ࡼࡾ㟁ᴟ⾲㠃࡬࡜⛣ືࡍࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ㟁Ẽ㝜ᛶᗘࡢ㧗࠸ప࿘ᮇࡢࣁࣟࢤࣥඖ⣲࡯࡝⾲㠃ᐁ⬟ᇶࡢ౯ᩘ㸦㈇㟁Ⲵ㸧ࡀ኱ࡁࡃ࡞ࡿࡓࡵࠊ⾲㠃ᐁ⬟ᇶཎᏊ࡜ࡢ㟼㟁ⓗ཯Ⓨ࡟ࡼࡾ㐣๫㟁Ꮚࡢ⾲㠃࡬ࡢ⛣ືࡣ㜼ᐖࡉࢀࡿࠋᚑࡗ࡚ࠊMXene ࡢ⾲㠃ᐁ⬟ᇶཎᏊࡢ౯ᩘࢆᑠࡉࡃࡍࡿࡇ࡜࡛ࠊỈ⣔ EDLC ࡢ㟼㟁ᐜ㔞ࢆቑ኱ࡉࡏࡿࡇ࡜
ࡀྍ⬟ࡔ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
➨ 15 ᅇศᏊ⛉Ꮫウㄽ఍ 2021㸦ணᐃ㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ᰝㄞ௜ࡁḢᩥㄽᩥ࡜ࡋ࡚ฟ∧ணᐃ- 501 -















Simulations of multiscale functional dynamics in biomolecularmachines 

Md Iqbal MahmoodTitouan Jaunet-Lahary

'!

"

&#!

"



(


1

"
ºB3GQ7?#¤dlP=Z h a´&/£Ä-]¿^s-FUZ?O[A[AZI7È#³¹¼ kg ÖÍ|g ÖÍ×Í{p-yÈl/ÉË-%³¹¼VSEVZ8AZI7È#³¹¼]Útd/e³¹¼/{-"*ºB3GQ7?#×?9[WJ;©+©"6[B[­×?9[W<LGHR[FW+P37YR[FW"6[B[ r$}Ù (PWC?9[W)MY@?-"PWC?9[WB3GQ7?/£Ä-' #<ZMVZ8 )PWC?9[WSEW/Ûf-¿ -%ÐªB3GQ7?/<ZMVZ8- /¥jq MD Å¯ *,FUZ?O[A["eoq£"qXNW"£Ä/¨%*,~Á³¹¼{B3GQ7?/Ä-' ±Âp MDÅ¯/½

2

"&#FUZ?O[A[ÜNa+/H+1ZCO[A[)=T4ÒFUZ?O[A[Ý Ø#»È`Ó¼ FUZ?O[A[AZI7È/x'Ê0²"jq MD Å¯/ NAMD ½Na+/H+1ZCO[A[ ÍÐª"Ç³/Ä-'MD FU>57FV/PW;K¢SEWÄ=T4ÒFU
Z?O[A[ =T4Ò"µt"Ç³/Ä-'µt<3F"ÔpÅ¯/ Gaussian ½
³¹¼VSEVZ8AZI7È Pacsin1

Ø#»È`Ó¼]

Pacsin1 /Ñ·²±ÂpSEWMARTINI /¥ MD Å¯/ Gromacs ½¡ AZI7ÈGō SEW/Ï¥ Gō-MARTINI S

EW  Native contact "¸/iÏp/½Pacsin1 "¼]  -Í+btÎ«/Ä

3

"

3-1 Na+/H+1ZCO[A[PaNhaP
kv Ö¢|v Ö¢  -P37Y©"¾ MD FU>57FVÐªI?<ZMVZ8¨§½ÐªI?=T[D2Z8 *-FU>57FV/¥H+µt¢  -PW;K¢SE
W/°"µß"_×¢/uÞ¨#kv Ö¢ * c¢kg:[F Õ-¢-ß¨#kv Ö¢|v Ö¢"_× -¢-"*- 502 -

_×¢ nÍ{p"w®\ÌÎ×ÜMFPTÝ(À¬(-  3-2 =T4ÒFUZ?O[A[X ¶µÍÄ+.=T4ÒFUZ?O[A["|v ÖÍÕzÍ/¥Å¯/½
%=T4Ò36Z µtÕzÍ =T4Ò36Z !.Í/-
/Æ-' ÔpÅ¯/½"µ=T4Ò36Z#_"Í¦-!.
Í/- + + |v ÖÍÕzÍ/..mÍ-P3
7Y©" MD Å¯ *,.+"Í¢×"Ðª/Ã-  "FV[-§o /u3-3 Gō-MARTINI SEW *-¤d¼]" Pacsin1 "Í+ bt
MARTINI SEW#»Èl²"=QTX[= Z( ¥+.-±ÂpSEW-AZ

I7È Ø#ÍN[?"SEW-dF [7SEW´&t¥+. "SEW#Í+ /Î+ - %+.-#dF [7SEW/ Gō SEW· -,&/½
" Gō-MARTINI /¥»È`Ó¼]" Pacsin1"Í+ btÎ«/Ä
Gō SEW" Native contact "F6K./-&-jqÅ¯À+.Í+ / Gō-MARTINI "-   lÄ *+.+ "v~  jqÅ¯"µ/"ÜÞAÝ+»È`Ó¼] Ñ·ß" Pacsin1

g/$ e¥bt- lÜßAÝ
"**tdÍ#µÍ(À+.1\'-µ-                      

4

%$

Þ2Pacsin1 "Í+ ¼]"*td M. I. Mahmood, A. Poma, and K. OkazakiOptimized Go̅-MARTINI coarse-grained force field parameters basedon structural flexibility of F-BAR protein Pacsin1 on lipid membrane  ®   ¤!!£bb   
O?A[#)
 Titouan Jaunet-Lahary and K. OkazakiNew insight into ion transport mechanism of the Na+/H+ antiporter PaNhaP
revealed by transition path shooting and Markov state model  ®   ¤!!£bb    O?A[#)
 K. Okazaki “Curvature induction and sensing of the F-BAR protein Pacsin1 on lipid membranes via molecular
dynamics simulations”, ®   ¤!!£bb    0#)5$

 M. I. Mahmood, A. B. Poma, and K. OkazakiOptimizing GōMARTINI coarsegrained model for F-BAR protein
on lipid membrane”, Front. Mol. Biosci. 8, 619381 (2021)- 503 -

㧗ᙉᗘࣇ࢙࣒ࢺ⛊ࣃࣝࢫ࡟ࡼࡾᘬࡁ㉳ࡇࡉࢀࡿ
ࢼࣀศᏊࡢ㟁Ꮚ࣭཯ᛂືຊᏛ࢖࣓࣮ࢪࣥࢢ࡟㛵ࡍࡿືຊᏛ⌮ㄽ(OHFWURQDQGUHDFWLRQG\QDPLFVWKHRU\RQQDQRPROHFXOHV 
LQGXFHGE\LQWHQVHIHPWRVHFRQGODVHUSXOVHVżᒣᓮ 㤾㸦⌮໬Ꮫ◊✲ᡤ㸧




◊✲┠ⓗ

㏆ᖺࡢ ; ⥺⮬⏤㟁Ꮚ࣮ࣞࢨ࣮㸦;)(/㸧ࡸ㧗ḟ㧗ㄪἼⓎ⏕㸦++*㸧ග※ࡢᛴ㏿࡞㐍Ṍ࡟ࡼࡾ㸪 H9 ௨ୖࡢගᏊ࢚ࢿࣝࢠ࣮ࢆᣢࡘࣇ࢙࣒ࢺ⛊࣭࢔ࢺ⛊㌾ ; ⥺ࣃࣝࢫග※ࡀᐇ⏝໬ࡉࢀ㸪ከཎᏊศᏊࡢ཯ᛂືຊᏛ㏣㊧࡟ά⏝ࡉࢀࡿࡼ࠺࡟࡞ࡗ࡚ࡁࡓ>DF@㸬ࡲࡓ㸪⌧ᅾᘓタ୰ࡢḟୡ௦ᨺᑕග᪋タ 6/,7- ࡛ࡣ ㌾㹖⥺ࢆ⏝࠸ࡓࠕᮦᩱࡢࡑࡢሙ࢖࣓࣮ࢪࣥࢢἲࠖࢆ┠⋢࡜ࡋࡓࣅ࣮࣒ࣛ࢖ࣥᩚഛࡀ㐍ࡵࡽࢀ࡚࠸ࡿ㸬ࡇࢀࡽࡢ◊✲ࡢ኱┠ᶆࡢ୍ࡘࡣ㸪⏕య㛵㐃ศᏊࡸᶵ⬟ᛶᮦᩱࡢ཯ᛂ୰࣭ ືస୰ࡢࢲ࢖ࢼ࣑ࢡࢫࢆ┤᥋࢖࣓࣮ࢪࣥࢢࡍࡿࡇ࡜࡛࠶ࡿ㸬ࡋ࠿ࡋ㸪ࡇࢀࡽࡢ ㌾ ; ⥺ග※ࡣ㧗࠸ගᏊ࢚ࢿࣝࢠ࣮ࢆࡶࡕ㸪ศᏊࡢ࢖࢜ࣥ໬ࡸゎ㞳࡞࡝ࡢ 5DGLDWLRQGDPDJH
ࢆᐜ᫆࡟ᘬࡁ㉳ࡇࡍ>FG@㸬ࡇࡢࡓࡵ㌾ ; ⥺࢖࣓࣮ࢪࣥࢢ࡛ࡣ㸪㌾ ; ⥺↷ᑕ๓࠿ࡽ኱࡞ࡾᑠ࡞ࡾኚ㉁ࡋࡓᮦᩱ
ࡢほᐹࢆవ൤࡞ࡃࡉࢀ࡚࠾ࡾ㸪⌮ㄽ ィ⟬➼ࢆ⏝࠸࡚ኚ㉁ࡢᙳ㡪ࢆ㐺ษ࡟ホ౯ࡍࡿᚲせࡀ࠶ࡿ>HI@㸬 ࡑࡇ࡛➹⪅ࡽࡣ㸪㌾ ; ⥺↷ᑕ࡟ࡼࡿᮦᩱኚᙧࡢືຊᏛࢆ㏣㊧ࡍࡿࡇ࡜ࢆ┠ᣦࡋ࡚㸪   㹖⥺ㄏ㉳ศᏊᵓ㐀ኚᙧࡢึᮇ≧ែ࡜࡞ࡿ  㔜✵Ꮝ≧ែ࡬ࡢ┦ᑐ $XJHU 㑄⛣☜⋡㸦$XJHU ࢫ࣌ࢡࢺࣝ㸧ィ⟬ἲ࡜   ೫ගᖹᆒศᏊ
ᗙᶆ⣔ෆẆග㟁Ꮚゅᗘศᕸ㸦3$0)3$'㸧࡟ࡼࡿศᏊᵓ㐀Ỵᐃἲࢆ㛤Ⓨࡋࡓ㸬◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 2 ✵Ꮝ㓄⨨㛫┦஫స⏝(2h-CI)ἲ࡟ᇶ࡙ࡃ Auger ࢫ࣌ࢡࢺࣝィ⟬; ⥺↷ᑕ࡟ࡼࡾ㉳ࡁࡿ໬Ꮫ཯ᛂࡢጞ≧ែỴᐃ࡟ᚲせ࡞ $XJHU ࢫ࣌ࢡࢺࣝࡢィ⟬ἲࢆ㸪౯㟁Ꮚ㌶㐨࡟  ࡘࡢ✵Ꮝࢆᣢࡘ㟁Ꮚ㓄⨨ࢆࡍ࡭࡚⪃៖ࡋࡓ㓄⨨㛫┦஫స⏝ K&, ἲ >JK@࡟ᇶ࡙࠸࡚ᨵⰋ࣭ᐇ⿦ࡋࡓ㸬K&, ィ⟬࡟ࡣ㔞Ꮚ໬Ꮫィ⟬ࣃࢵࢣ࣮ࢪ 2SHQ0ROFDV>L@ࢆ⏝࠸ࡓ㸬 
3$0)3$'ᮏ◊✲࡛ࡣ&2 ศᏊࡀ ;)(/ ࣏ࣥࣉࣃࣝࢫ࡛ &V ㌶㐨࠿ࡽ࢖࢜ࣥ໬ࡉࢀࡑࡢᚋ࡟㉳ࡁࡿ $XJHU ⦆࿴࡟ࡼࡗ୍࡚㔜㡯 ı ≧ែࡢ &2㸩 ࡀ⏕ᡂࡋ㸪ࣉ࣮ࣟࣈࣃࣝࢫ࡟ࡼࡗ࡚ 2V ㌶㐨࠿ࡽ࢖࢜ࣥ໬ࡉࢀ࡚஧㔜㡯 ıı ≧ែ࡜࡞ࡗࡓ≧ែࢆ௬ᐃࡋ࡚ 3$0)3$' ࡢィ⟬ࢆ⾜ࡗࡓ㸬ࡲࡎ㸪㔞Ꮚ໬Ꮫィ⟬ࣉࣟࢢ࣒ࣛ 02/&$6

>L@࡟ᐇ⿦ࡉࢀ࡚࠸ࡿไ㝈άᛶ✵㛫ࢆ⏝࠸ࡓከཧ↷஧ḟᦤືㄽ 5$637 ࡟ࡼࡗ࡚ศᏊ㌶㐨Ἴື㛵ᩘ࡜㟁Ꮚᐦᗘࢆィ⟬ࡋࡓ 3RLVVRQ ᪉⛬ᘧࢆゎࡃࡇ࡜࡛ࠊከ㔜ᩓ஘ィ⟬࡟ᚲせ࡞ࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࢆᚓࡓ ᚓࡽࢀࡓ㟁Ꮚᐦᗘ࡜ࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࢆ⏝࠸࡚ )XOOSRWHQWLDO ከ㔜ᩓ஘ィ⟬ࣉࣟࢢ࣒ࣛ )306>M@࠾ࡼࡧࢫ࣌ࢡࢺ

- 504 -

ࣝィ⟬ࣉࣟࢢ࣒ࣛ 0V6SHF>N@࡟ࡼࡾ 3$0)3$' ࢆィ⟬ࡋࡓ㸬2 V ග㟁Ꮚࡢ㐠ື࢚ࢿࣝࢠ࣮ࡣ  H9㸪&2⤖ྜ㛗ࡣ ୰ᛶ &2 ศᏊࡢᖹ⾮᰾㛫㊥㞳 c ࠿ࡽ c ࡲ࡛ c ้ࡳ࡛  Ⅼィ⟬ࡋࡓ

2p-2: 40 % of
total intensity◊✲ᡂᯝᮏᡭἲࢆ +2 ཬࡧ &+ ศᏊ࡟㐺⏝ࡋ㸪V ✵Ꮝ≧ែ࠿

Exp

ࡽ GLFDWLRQ ≧ែ࡬ࡢ㌶㐨⦆࿴ࢆ⪃៖ࡍࡿ>F@ࡇ࡜࡛㸪S ㌶
㐨࡟  ࡘ✵Ꮝࢆᣢࡘ RXWHUYDOHQFH S  㡿ᇦࡢ $XJHU ࢫ࣌ࢡࢺࣝࢆᐃ㔞ⓗ࡟෌⌧࡛ࡁࡓ ᅗ 㸧>@㸬 ⌧ᅾ㸪ᮏࣉ2h-CIࣟࢢ࣒ࣛࢆⰾ㤶᪘ศᏊࡢ㹖⥺ㄏ㉳ゎ㞳㐣⛬ࡢጞ≧ែྠᐃ࡬ࡢᛂ⏝ࢆ㐍ࡵ࡚࠸ࡿ>@㸬 ෆẆග㟁Ꮚゅᗘศᕸ㸦0)3$'㸧࡟ࡼࡿ  ཎᏊศᏊࡢ
㹖⥺ㄏ㉳ືຊᏛ
ᮏ◊✲࡛ᚓࡽࢀࡓ 3$0)3$' ᅗ  >@ࡢᚋ᪉ᩓ஘
࡜๓᪉ᩓ஘ࡢẚ Ș 5 ࢆ &2ࡢ⤖ྜ㛗 5 ࡢ㛵ᩘ࡜ࡋ࡚ᅗᅗ 㸸 K&, ἲ࡟ࡼࡗ࡚ィ⟬ࡉࢀࡓ࢚ࢳࣞࣥ
㸦&+㸧ศᏊࡢ $XJHU ࢫ࣌ࢡࢺࣝ㸦㟷㸧࡜ᐇ㦂್㸦⥳㸧ࡢẚ㍑ ࡟♧ࡍ㸬0XIILQ7LQ ㏆ఝ࡟ᇶ࡙ࡃ  ᅇᩓ஘ࡢゎᯒᘧ>@Ș 5 㸻 D FRV N5 F 5E   N㸸ග㟁Ꮚ㐠ື㔞 㸻 H9D ᣺ືᙉᗘ
E ࣂࢵࢡࢢࣛ࢘ࣥࢻF ᣺ື఩┦࡜ࣇ࣏ࣝࢸࣥࢩࣕࣝከ㔜ᩓ஘⌮ㄽ࡛ồࡵࡓ Ș 5 >@ࢆẚ
㍑ࡍࡿࡇ࡜࡟ࡼࡾ㸪Ș 5 ࡣ࠾ࡼࡑ N5 ࡛ῶ⾶᣺ືࡋ࡚࠸ࡿࡇ࡜ࢆぢฟࡋࡓ>@㸬  ᘧ࡜ྂ඾ࢡ࣮ࣟࣥ⇿Ⓨࣔࢹࣝࢆ⤌ࡳྜࢃࡏࡿࡇ࡜࡛㸪;)(/ ࣃࣝࢫ࡟ࡼࡿከ㔜࢖࢜ࣥ໬࡛⏕ᡂࡋࡓ 2 ከ౯࢖࢜ࣥࡢゎ㞳ືຊᏛࢆᢳฟࡍࡿࡇ
࡜࡟ᡂຌࡋࡓ>@㸬ࡲࡓ㸪෇೫ග 0)3$' ࡢゎᯒᘧࢆᑟฟᅗ 㸸ࣇ࣏ࣝࢸࣥࢩࣕࣝከ㔜ᩓ஘⌮ㄽ࡟ᇶ࡙࠸

ࡋ㸪෇೫ග 0)3$' ࠿ࡽ஧ཎᏊศᏊࡢศᏊᵓ㐀ࢆỴᐃ࡛࡚ィ⟬ࡋࡓ &2ࡢ 3$0)3$'ࡁࡿࡇ࡜ࢆ♧ࡋࡓ>@㸬⌧ᅾ㸪ෆẆග㟁Ꮚࡢ࢔ࢺ⛊ 7LPH
GHOD\ ࡢᐃᘧ໬ࢆ㐍ࡵ࡚࠸ࡿ>@㸬ཧ⪃ᩥ⊩>D@2*HVVQHUHWDO $FF&KHP5HV  >E@.=LQ]HQNRHWDO6FLHQFH  >F@1%HUUDK1DW3K\V   
>G@ K. Yamazaki HW DO - &KHP 3K\V     ᅗ 㸸ࣇ࣏ࣝࢸࣥࢩࣕࣝከ㔜ᩓ஘⌮ㄽ࡟ᇶ࡙࠸࡚
ィ⟬ࡋࡓ Ș 5 㸦Ŷ㸧࡟ᑐࡍࡿ  ᅇᩓ஘ࡢゎᯒᘧ >H@.1DVVHWDO 1DW&RPPXQ   ࡢࣇ࢕ࢵࢸ࢕ࣥࢢ ◚⥺ - 505 -

>I@K. YamazakiHWDO-&KHP3K\V  >J@.00LWDQLHWDO-(OHFWURQ6SHFWURVF5HODW3KHQRP  >K@/,QKHVWHUHWDO-3K\V&KHP/HWW  >L@)$TXLODQWHHWDO-&KHP3K\V  >M@.+DWDGDHWDO Phys. Rev. B 76 060102 (2007)[k] D Sébilleau et al., Comput. Phys. Commun. 182 2567 (2011)ฟ∧ᐇ⦼ࡲࡓࡣணᐃ㈐௵ⴭ⪅>@ ‫)ۻ‬2WD.+DWDGD '6HELOOHDX.8HGDDQG.<DPD]DNL ³7KHRU\RQSRODUL]DWLRQDYHUDJHGFRUHOHYHOPROHFXODUIUDPHSKRWRHOHFWURQDQJXODUGLVWULEXWLRQV,,([WUDFWLQJWKH;UD\LQGXFHGIUDJPHQWDWLRQG\QDPLFVRI FDUERQ PRQR[LGH GLFDWLRQ IURP IRUZDUG DQG EDFNZDUG LQWHQVLWLHV´ - 3K\V %   '2,DEFIG  >@ ‫ ) ۻ‬2WD . <DPD]DNL ' 6 . 8HGD DQG . +DWDGD  ³7KHRU\ RI SRODUL]DWLRQDYHUDJHG FRUHOHYHOPROHFXODUIUDPH SKRWRHOHFWURQ DQJXODU GLVWULEXWLRQV , $ )XOOSRWHQWLDO PHWKRG DQG LWV DSSOLFDWLRQ WR
GLVVRFLDWLQJFDUERQPRQR[LGHGLFDWLRQ´-3K\V%'2,DEG  >@ ‫ۻ‬6.LQRVKLWD<+DUDEXFKL<,QRNXFKL60DHGD0(KDUD.<DPD]DNL   DQG  7(EDWD ³6XEVWLWXWLRQHIIHFWRQWKHQRQUDGLDWLYHGHFD\DQGWUDQVĺFLVSKRWRLVRPHUL]DWLRQURXWHDJXLGHOLQHWRGHYHORSHIILFLHQW
FLQQDPDWHEDVHG VXQVFUHHQV´ 3K\V &KHP &KHP 3K\V   '2, '&3'  
2XWHU)URQW&RYHU ཬࡧ 3&&3+27$UWLFOHV ࡟㑅ฟ㸬>@ ,9HOD3HUp])2WD$0KDPGL<7DPXUD-5LVW10HO]HU68HUNHQ*1DOLQ1$QGHUV'<RX0.LUFKHU&-DQNH0:DLW])7ULQWHU5*XLOOHPLQ013LDQFDVWHOOL06LPRQ97'DYLV-%:LOOLDPV5'|UQHU.+DWDGD.<DPD]DNL.)HKUH3K9'HPHNKLQ.8HGD066FK|IIOHUDQG7-DKQNH
³+LJK(QHUJ\0ROHFXODU)UDPH3KRWRHOHFWURQ$QJXODU'LVWULEXWLRQV$0ROHFXODU%RQG/HQJWK5XOHU´3K\V
5HY/HWW6XEPLWWHG DU;LY>SK\VLFVDWRPSK@ >@ *.DVWLUNH)2WD'95H]YDQ066FK|HU0:HOOHU-5LVW5%ROO1$QGHUV70%DXPDQQ6
(FNDUW%(UN$'H)DQLV.)HKUH$*DWWRQ6*UXQGPDQQ3*U\FKWRO$+DUWXQJ0+RIPDQQ0,OFKHQ&-DQNH0.LUFKHU0.XQLWVNL;/L70D]]D10HO]HU-0RQWDQR90XVLF*1DOLQ<
2YFKDUHQNR$3LHU15HQQKDFN'(5LYDV5'|UQHU'5ROOHV$5XGHQNR36FKPLGW-6LHEHUW1
6WUHQJHU'7UDEHUW,9HOD3HUH]5:DJQHU7:HEHU-%:LOOLDPV3=LRONRZVNL/3K+6FKPLGW$&]DVFK<7DPXUD1+DUD.<DPD]DNL.+DWDGD)7ULQWHU  00H\HU.8HGD3K9'HPHNKLQDQG
7-DKQNH³,QYHVWLJDWLQJFKDUJHXSDQGIUDJPHQWDWLRQG\QDPLFVRIR[\JHQPROHFXOHVDIWHULQWHUDFWLRQZLWKVWURQJIUHHHOHFWURQODVHU;UD\SXOVHV´ ᢞ✏‽ഛ୰㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

>@ ‫ۻ‬żኴ⏣ ⷋᏊ࣭'LGLHU6pELOOHDX࣭ᒣᒣᓮ 㤾࣭ୖ⏣ ₩࣭⏿⏣ ᆂ௓ࠕศᏊᵓ㐀ኚ໬ࡢ㧗᫬㛫ศゎ㏣㊧࡟ྥࡅࡓኚ᭦᪉ྥᖹᆒศᏊᗙᶆ⣔ග㟁Ꮚゅᗘศᕸࡢ )XOOSRWHQWLDO ከ㔜ᩓ஘⌮ㄽ࡟ࡼࡿ◊✲ࠖ➨  ᅇ

- 506 -

(;$)6 ウㄽ఍㸦2㸧㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᖺ  ᭶  ᪥㸬ᒣᓮ 㤾࣭ཎῲ ♸࣭๓⏣ ⌮࣭Ụᖭ Ꮥஅ>@ ‫ۻ‬żᮌୗ ┿அ௓࣭ ஭ཱྀ ెဢ ࣭ⓑ⏨ᕝ ㈗ྐ࣭Ụཎ ṇ༤࣭ᒣࠕ㉸㡢㏿ࢪ࢙ࢵࢺ࣮ࣞࢨ࣮ศග࡜㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ᱇⓶㓟ㄏᑟయࡢ㟁Ꮚ≧ែ࡜ WUDQV ĺFLV ග␗ᛶ໬࡟ཬࡰࡍ⨨᥮ᇶຠᯝࡢ◊✲ࠖศᏊ⛉Ꮫ࢜ࣥࣛ࢖ࣥウㄽ఍㸦$㸧㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᖺ  ᭶  ᪥㸬>@ ‫ۻ‬żᒣᓮ 㤾ࠕග໬Ꮫ཯ᛂࡢ㔞Ꮚ໬Ꮫ㸸ྍど࣭⣸እ㡿ᇦ࠿ࡽ ; ⥺㡿ᇦ࡬ࡢᣑᙇࠖィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔࣒㸦3&R06㸧ࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍
㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᖺ  ᭶  ᪥㸬>@ ‫ۻ‬ż.<DPD]DNL . 0LGRULNDZD ³;UD\ LQGXFHG IHPWRVHFRQG LRQL]DWLRQ NLQHWLFV RI WURSRQH &+2  DW
FDUERQ.HGJH´ ➨  ᅇ໬Ꮫ཯ᛂウㄽ఍㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᖺ  ᭶ 㸫 ᪥>@ ‫ۻ‬żᒣᓮ 㤾࣭⥳ᕝ ඞ⨾ࠕ7URSRQH ஧౯࢝ࢳ࢜ࣥ &+2 ࡟࠾ࡅࡿ㹖⥺ㄏ㉳␗ᛶ໬࣭ゎ㞳⤒㊰ࡢࢫࣆࣥ≧ែ౫Ꮡᛶࠖ➨  ᅇศᏊ⛉Ꮫウㄽ఍㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᭶ 㸫 ᪥㸬>@ ż<7DPXUD.<DPD]DNL)2WD.8HGD.+DWDGDࠕ&2 ศᏊࡢ & V ෆẆග࢖࢜ࣥ໬࡟࠾ࡅࡿ࢔ࢺ⛊ග㟁Ꮚ 7LPHGHOD\ ࡬ࡢከ㔜ᩓ஘⌮ㄽࡢᛂ⏝ࠖ➨  ᅇศᏊ⛉Ꮫウㄽ఍㸪ཱྀ㢌Ⓨ⾲㸪࢜ࣥࣛ࢖ࣥ㛤ദ㸪 ᭶ 㸫 ᪥㸬- 507 -

ࠕᐩᓅࠖᡂᯝ๰ฟࣉࣟࢢ࣒ࣛ
ࠕ┬࢚ࢿࣝࢠ࣮ḟୡ௦༙ᑟయࢹࣂ࢖ࢫ㛤Ⓨࡢࡓࡵࡢ㔞Ꮚㄽ࣐ࣝࢳࢩ࣑࣮ࣗࣞࢩࣙࣥࠖ
Quantum-theory-based multiscale simulation for the development of thenext-generation power devices1‫ۑ‬ᢲᒣ ῟ ࠊࣈ࢖ ࢩ࢚࢟࢘ ࣑ 1ࠊ஭ᮏ ᩥ⿱ 1ࠊ㛗ᕝ೺ኴ 1ࠊཎᔱᗤ௓ 1ࠊ⨾㔛ຕኟ༡ 2ࠊᯇୗ㞝୍㑻 3ࠊᐮᕝ⩏⿱ 4ࠊⲡሙᙲ 4ࠊᑠ㔝೔ஓ 5ࠊ᳜ᮏග἞ 5ࠊỤୖ႐ᖾ 6ࠊⓑ▼㈼஧ 1
1ྡྂᒇ኱Ꮫ ᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒◊✲ᡤࠊ2 ኱㜰኱ᏛᕤᏛ◊✲⛉ࠊ3 ᮾிᕤᴗ኱Ꮫ≀㉁᝟ሗ
༟㉺◊✲ဨࠊ4 ஑ᕞ኱Ꮫᛂ⏝ຊᏛ◊✲ᡤࠊ5 ⚄ᡞ኱ᏛᕤᏛ◊✲⛉ࠊ6 ໭ᾏ㐨኱ᏛᕤᏛ◊✲㝔1◊✲┠ⓗ㔞Ꮚㄽ➨୍ཎ⌮≀㉁ィ⟬࡟ࡼࡾࠊ࢔ࣔࣝࣇ࢓ࢫࢤ࣮ࢺ⤯⦕⭷㸭༙ᑟయ࡟௦⾲ࡉࢀࡿࢹࣂ࢖ࢫ⏺㠃ࡢ≉ᛶࢆゎ᫂ࡋࠊࡉࡽ࡟➨୍ཎ⌮ィ⟬࢔ࣉࣜࢣ࣮ࢩࣙࣥ࡜༙ᑟయࢹࣂ࢖ࢫࢩ࣑࣮ࣗࣞࢱ࠾ࡼࡧ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ࣉࣟࢭࢫࢩ࣑࣮ࣗࣞࢱ࡜ࢆ⤫ྜࡋࡓ᪂ࡓ࡞ࢩ࣑࣮ࣗࣞࢩࣙࣥᢏ⾡ࢆ☜❧ࡍࡿࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝ࡜ᐇ㦂⤖ᯝࡢ᳨ド࡟ࡼࡾࠊḟୡ௦┬࢚ࢿࣝࢠ࣮༙ᑟయࢹࣂ࢖ࢫ࡟࠾ࡅࡿ⛉Ꮫ࡜〇㐀ᢏ⾡ࡢⓎᒎ࡟㈨ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚㄽ➨୍ཎ⌮ィ⟬࡟࠾ࡅࡿ୺ࡓࡿᡭἲࡣࠊᐦᗘỗ㛵ᩘ⌮ㄽ㸦DFT: Density Functional Theory㸧࡟ᇶ࡙ࡃ

Kohn-Sham ᪉ ⛬ ᘧ ࢆᐇ✵㛫ࡢ࣓ ࢵࢩࣗୖ࡛ゎ ࡃᐇ✵㛫ᐦ ᗘỗ㛵ᩘἲ㸦 ࢥ࣮ࢻྡ㸻 RSDFT ࠊ Real-Space
Density-Functional Theory㸧࠾ࡼࡧࣛࢢࣛࣥࢪ࢙ᙧᘧࡢ᫬㛫౫Ꮡ᪉⛬ᘧࢆゎࡃᐇ✵㛫 Car-Parrinello ศᏊືຊᏛ
ἲ㸦ࢥ࣮ࢻྡ㸻RS-CPMDࠊReal-Space Car-Parrinello Molecular Dynamics㸧࡛࠶ࡿࠋྠࡌࡃᐇ✵㛫ᡭἲ࡛࠶ࡿ
RSPACE ࢥ࣮ࢻࡶే⏝ࡉࢀࡿࠋࢹࣂ࢖ࢫࢩ࣑࣮ࣗࣞࢩࣙࣥࡣࠊ㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘ㸦NEGF: Non-Equilibrium
Green’s Function㸧ἲ࡟ࡼࡗ࡚ᐇ⾜ࡉࢀࡿࠋNEGF ࢥ࣮ࢻࡣ RSDFT ࢥ࣮ࢻ࡜⤫ྜࡉࢀ࡚࠸ࡿࠋ࠸ࡎࢀࡢࢥ࣮ࢻ
ࡶᮏࢢ࣮ࣝࣉ࡟࠾ࡅࡿ⊂⮬㛤Ⓨࡢࡶࡢ࡛࠶ࡿࠋ

3◊✲ᡂᯝ
GaN-MOVPE ᡂ㛗࡟࠾ࡅࡿ Ga ཎᩱ࢞ࢫࡢẼ┦ศゎ཯ᛂゎ᫂
GaN ࡢ MOVPE (MetalOrganic Vapor Phase Epitaxy) ᡂ㛗࡛ࡣࠊGa ※࡜ࡋ࡚ TMG [Trimethyl Gallium:
Ga(CH3)3)]ࠊN ※࡜ࡋ࡚࢔ࣥࣔࢽ࢔[NH3]ࠊ࢟ࣕࣜ࢔࢞ࢫ࡜ࡋ࡚ H2 ࡜ N2 ࡀ཯ᛂ⅔ෆ࡟ὶධࡋࠊẼ┦࠾ࡼࡧᇶᯈୖ࡛ࡢ⇕ศゎ㸦ᇶᯈ

ᗘ 1300K㸧࡟ࡼࡾࠊGaN ⷧ⭷ࡀᡂ㛗ࡍࡿࠋ㧗ရ㉁ⷧ⭷ࡢ〇㐀ࡢࡓࡵ࡟ࡣࠊᡂ

㛗୰࡜ࡃ࡟Ẽ┦࡛ࡢᐦᗘሙࠊ
㛗ᗘࡀ㧗ᗘሙࢆไᚚࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࡀࠊࡑࡢࡓࡵࡢᐇ㦂୰࡟࠾ࡅࡿほࡣᡂ࡛࠶ࡿࡓࡵᅔ㞴࡛࠶ࡿࠋࡋࡓࡀࡗ࡚ࠊ㧗⢭ᗘࡢಙ㢗࡛ࡁࡿࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊᡂ㛗⿦⨨ෆࡢ≧ἣࢆᢕᥱࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋ௒ᖺᗘࠊTMG ࡢẼ┦୰ࡢ཯ᛂ࡟ࡘ࠸࡚➨୍ཎ⌮ィ⟬࡜཯ᛂ㏿ᗘㄽࢆ⏝࠸࡚ࠊึࡵ࡚ࡑࡢ࣑ࢡࣟ࡞ᶵᵓࢆゎ᫂ࡋࡓࠋලయⓗ࡟ࡣࠊ㔞Ꮚㄽ࡟ᇶ࡙ࡁ⤖ᬗᡂ㛗ᗘ࡛࠶ࡿ 1300K

࡛ࡢྛ໬Ꮫ཯ᛂࡢάᛶ໬ࢠࣈࢫ࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࠊ㑄⛣≧ែ⌮ㄽ࠿ࡽᑟฟࡉࢀࡿ࢔࢖ࣜࣥࢢࡢᘧࢆ⏝࠸
࡚㏿ᗘᐃᩘࢆィ⟬ࡍࡿ࢔ࣉ࣮ࣟࢳࢆ᥇⏝ࡋࡓࠋࡲࡎ TMG ࠿ࡽ࣓ࢳࣝᇶࡀ୍ࡘእࢀࡿ཯ᛂ࡟ࡘ࠸࡚⪃࠼ࡿࠋ⾲ 1 ࡣ௒ᅇࡢィ⟬࡛ồࡵࡓࠊ1300K ࡟࠾ࡅ- 508 -

⾲ 1: DFT ࡛ィ⟬ࡉࢀࡓ 1300K ࡟࠾ࡅࡿάᛶ໬ࢠࣈࢫ࢚ࢿࣝࢠ࣮࡜ᚓࡽࢀࡓ㏿ᗘᐃᩘࡿྛ໬Ꮫ཯ᛂࡢάᛶ໬ࢠࣈࢫ࢚ࢿࣝࢠ࣮ཬࡧࠊ㏿ᗘᐃᩘ࡛࠶ࡿࠋ⾲୰ࡢ Reaction 1 ࡟࠶ࡿࡼ࠺࡟ࠊTMG ࡀ
H2 ࡜཯ᛂࡍࡿ࡜ࡁࡢ 1300K ࡛ࡢάᛶ໬ࢠࣈࢫ࢚ࢿࣝࢠ࣮ࡣ 3.24eV ࡞ࡢ࡟ᑐࡋࠊ᭱ึ࡟ NH3 ࡜཯ᛂࡋ࢔࣑
ࣀᇶࢆᙧᡂᚋ(Reaction2)ࠊࡉࡽ࡟ H2 ࡜཯ᛂࡋ࢔࣑ࣀᇶࢆ⬺㞳ࡍࡿ཯ᛂ(Reaction3)ࡢάᛶ໬ࢠࣈࢫ࢚ࢿࣝࢠ
࣮ࡣࡑࢀࡒࢀ 2.96eVࠊ2.84eV ࡜ᑠࡉࡃ࡞ࡗࡓࠋࡇࡢάᛶ໬ࢠࣈࢫ࢚ࢿࣝࢠ࣮ࡢᕪ࠿ࡽ㏿ᗘᐃᩘࢆィ⟬ࡍࡿ
࡜ࠊH2 ࡜ࡢ㏿ᗘᐃᩘ࡟ẚ࡭ NH3 ࡜ࡢ㏿ᗘᐃᩘࡢ᪉ࡀ⣙ 12 ಸ኱ࡁࡃ࡞ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋ
ࡇࡢࡼ࠺࡟ࡋ࡚ TMG ࠿ࡽ DMG [Dimethyl Gallium: Ga(CH3)2)]ࠊࡉࡽ࡟ࡣ MMG [Monomethyl Gallium:
GaCH3]ࡀ⏕ᡂࡉࢀ࡚࠸ࡃࡀࠊࡑࡢ㝿ࡢ཯ᛂ࡜ࡋ࡚ࡣ⾲ 1 ࡟♧ࡍࡼ࠺࡞ࠊ29 ಶࡢࡶࡢࡀ⪃࠼ࡽࢀࡿࠋDMGNH2࡟ᑐࡋ࡚ࡣ H2, NH3 ࡀ཯ᛂࡍࡿሙྜࠊReaction3ࠊReaction5ࠊReaction6 ࡢ 3 ㏻ࡾࡀ⪃࠼ࡽࢀࡿࠋࡑࡢ⤖ᯝࠊ࣓ࢳࣝᇶࡀእࢀࡿ཯ᛂ(Reaction5ࠊReaction6) ࡼࡾࠊ
H2 ࡟ࡼࡗ࡚࢔࣑ࣀᇶࡀእࢀࡿ཯ᛂ(Reaction3) ࡢ᪉ࡀࠊάᛶ໬ࢠࣈࢫ࢚ࢿࣝࢠ࣮ࡀᑠࡉࡃ཯ᛂ㏿ᗘࡣ㏿࠸ࡇ࡜ࡀࢃ࠿ࡿࠋࡼࡗ࡚ࠊDMGNH2 ࡣ H2 ࡜཯ᛂࡋ
࡚ DMGH ࡟ኚ໬ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࢀࡣࠊ
࢔࣑ࣀᇶࡢ཯ᛂᛶࡀ࣓ࢳࣝᇶࡢ཯ᛂᛶࡼࡾࡶ㧗࠸ࡓࡵࡔ࡜⪃࠼ࡽࢀࡿࠋDMGH ࡢศゎ࡟࠾࠸࡚ࡶࠊ
DMGH ࡀ H2 ࡜཯ᛂࡍࡿ࡜ࡁࡢάᛶ໬ࢠࣈࢫ࢚ࢿࣝ
ࢠ࣮ࡀ 3.19eV(Reaction9) ࡞ࡢ࡟ᑐࡋࠊ᭱ึ࡟ NH3

ᅗ 2: ࣐ࣝࢳࣇ࢕ࢪࢵࢡࢫ⤖ᬗᡂ㛗ࢩ࣑࣮ࣗࣞࢩ
ࣙࣥ࡟ࡼࡗ࡚ᚓࡽࢀࡓ཯ᛂ⅔ෆࡢ TMG㸦ୖ㸧࡜
GaH3㸦ୗ㸧ࡢศᕸࠋ- 509 -

࡜཯ᛂࡋ࢔࣑ࣀᇶࢆᙧᡂᚋࠊH2 ࡜཯ᛂࡋ࢔࣑ࣀᇶࢆ⬺㞳ࡋࡓ᪉ࡀάᛶ໬࢚ࢿࣝࢠ࣮ࡣࡑࢀࡒࢀ 2.94eV(Reaction10)ࠊ2.82eV (Reaction11)࡜ᑠࡉࡃ࡞ࡾࠊ཯ᛂࡀ㏿ࡃ㐍ࡴࡇ࡜ࡀࢃ࠿ࡿࠋྠᵝ࡟ࠊMMGH2 ࡢศゎࡶ
H2 ࡀࡑࡢࡲࡲ཯ᛂࡋ࣓ࢳࣝᇶࡀእࢀࡿ཯ᛂ(Reaction21) ࡼࡾ NH3 ࡜཯ᛂࡋࡓᚋ(Reaction22)ࠊH2 ࡜཯ᛂࡍࡿ(Reaction23) ᪉ࡀࠊศゎࡀ᪩ࡃ㐍ࡴࡇ࡜ࡀࢃ࠿ࡿࠋࡇࡢࡼ࠺࡟⪃࠼ࡿ࡜ TMG ࡣ NH3 ࡜཯ᛂࡋ࢔࣑ࣀᇶ
ࢆᙧᡂࡋࡓᚋࠊH2 ࡜཯ᛂࡋࡑࡢ࢔࣑ࣀᇶࢆ⬺㞳ࡍࡿ㏲ḟ཯ᛂࢆ⧞ࡾ㏉ࡍࡇ࡜࡛ࠊศゎࡀ㐍ࢇ࡛࠸ࡃࡇ࡜ࡀ
ࢃ࠿ࡗࡓࠋࡲࡓࠊGaH (Reaction26) ࡸ GaCH3 (Reaction27) ࡀ⏕ᡂࡉࢀࡿ཯ᛂࡣάᛶ໬ࢠࣈࢫ࢚ࢿࣝࢠ࣮ࡀ
㧗ࡃ࡞ࡿࡓࡵࠊᐇ㝿࡟ࡣ⏕ᡂࡉࢀ࡟ࡃ࠸ศᏊ࡛࠶ࡿ࡜ண᝿ࡉࢀࡿࠋ௨ୖࡲ࡜ࡵࡿ࡜ TMG ࡢศゎ཯ᛂࡣࠊ
NH3ࠊH2 ࡜஺஫࡟཯ᛂࡋ࡞ࡀࡽ࣓ࢳࣝᇶࢆ୍ࡘࡎࡘእࡋ࡚࠸ࡁࠊGaH3 ࡲ࡛ศゎࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ୺
཯ᛂ⤒㊰ࡣ௨ୗࡢࡼ࠺࡟⾲ࡍࡇ࡜ࡀ࡛ࡁࡿࠋ
Ga(CH3)3 ĺ*D &+3)2NH2 ĺ*D &+3)2+ĺ*D&+3HNH2 ĺ*D&+3H2 ĺ*D+2NH2 Ѝ GaH3ࡉࡽ࡟ࠊࡇ࠺ࡋࡓ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡓẼ┦཯ᛂ࡟ᇶ࡙࠸࡚ࠊᒁᡤᖹ⾮ࡢᴫᛕࢆ⏝࠸࡚㔞ᏊຊᏛ࡜ὶయຊᏛࢆࢩ࣮࣒ࣞࢫ࡟⧅࠸ࡔ࣐ࣝࢳࣇ࢕ࢪࢵࢡࢫ⤖ᬗᡂ㛗ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋලయⓗ࡟ࡣ⾲ 3 ࡟⾲ࡉࢀࡓ 29 ಶࡢ໬Ꮫ཯ᛂࢆࡍ࡭࡚ྲྀࡾ㎸ࢇ࡛ࠊ⤖ᬗᡂ㛗ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ
TMG ࡜ GaH3 ࡢศᕸࡀᅗ 2 ࡛࠶ࡿࠋࡇࡢᅗ࠿ࡽࢃ࠿ࡿࡼ࠺࡟ࠊGaH3 ࡢ⃰ᗘࡣᇶᯈ௜㏆࡛ᛴ⃭࡟ቑຍࡋ࡚࠸
ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡉࡽ࡟ࡇࢀ࠿ࡽᡂ㛗㏿ᗘࡢᇶᯈ㠃ෆࡢศᕸࢆồࡵࡓࠋᚓࡽࢀࡓ⤖ᬗᡂ㛗㏿ᗘࡣ⣙ 2ȣm/h࡜࡞ࡾᐇ㦂࡜ࡼ࠸୍⮴ࢆࡳࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ௒ᚋࡣࠊࢹ࣮ࢱྠ໬࡟ࡼࡿᯟ⤌ࡳ࡛㧗⢭ᗘ࡞Ẽ┦཯ᛂࣔࢹࣝࢆᵓ⠏ࡋࠊᩘ್ὶయ㸦CFD㸧ィ⟬࡟ᐇ⿦ࡍࡿணᐃ࡛࠶ࡿࠋ
௨ୖࡢᡂᯝࡣฟ∧ᴗ⦼ࣜࢫࢺ[1]࡟Ⓨ⾲ࡉࢀࡓࠋࢼࣀࢹࣂ࢖ࢫࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⎔ቃᵓ⠏㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲ㸦NEGF ἲ㸧࡟ᇶ࡙ࡃ㔞Ꮚㄽࢹࣂ࢖ࢫࢩ࣑࣮ࣗࣞࢱࢆ⏝࠸࡚ࠊ┬࢚ࢿࣝࢠ࣮ᆺࢼࣀ
࣡࢖ࣖࢺࣛࣥࢪࢫࢱࡸࢼࣀࢩ࣮ࢺࢺࣛࣥࢪࢫࢱ࡞࡝ࡢ
ࢼࣀࢹࣂ࢖ࢫࡢ㛤Ⓨᣦ㔪ࢆ᪩ᮇ࡟ᚓࡿࡓࡵࡢࢹࣂ࢖ࢫ
ࢩ࣑࣮ࣗࣞࢩࣙࣥ⎔ቃࡢᵓ⠏ࢆ㐍ࡵ࡚࠸ࡿࠋ
ᮏᖺᗘࡣࠊࣇ࢛ࣀࣥᩓ஘㐣⛬ࢆ㔞Ꮚㄽࢹࣂ࢖ࢫࢩ࣑
࣮ࣗࣞࢱ࡟ᑟධࡋࡓࠋSi ࡟࠾ࡅࡿ୺せ࡞ࣇ࢛ࣀࣥᩓ஘
㐣⛬ࡣࠊኚᙧ࣏ࢸࣥࢩࣕࣝ⤖ྜ࡟ࡼࡿᩓ஘࡛࠶ࡾࠊᒁ
ᡤⓗ࡞┦஫స⏝࡜ࡋ࡚ྲྀࡾᢅ࠺ࡇ࡜ࡀ࡛ࡁࡿࠋࡑࡇ࡛ࠊ
㟁Ꮚ㸫ࣇ࢛ࣀࣥ┦஫స⏝ࣁ࣑ࣝࢺࢽ࢔ࣥ

H e-ph†³ < <\ dx࡟࠾࠸࡚ࠊࣇ࢛ࣀࣥሙࡢ₇⟬Ꮚ\ ࡢಀᩘ A ࡟ᑐࡋ࡚

ᅗ 3: ┤ᚄ 60 nm㸪ࢤ࣮ࢺ㛗 100 nm ࡢ Si ࢼࣀ࣡࢖ࣖࢺࣛࣥࢪࢫࢱࡢఏ㐩≉ᛶ㸬ᐇ⥺ࡣᙎ㐨㍺㏦᮲௳㸪㛢ࡌࡓ㉥୸ࡣࣇ࢛ࣀࣥᩓ஘
ࢆ⪃៖ࡋࡓሙྜ㸬㛤࠸ࡓ㟷୸ࡣ ᐃ⤖ᯝࢆ♧ࡍ㸬ḟࡢࡼ࠺࡞ᒁᡤ㏆ఝࢆ⾜ࡗࡓࠋ¦ AQ q ( x) AQ q ( y) BQ G ( x  y)qࡉࡽ࡟ࠊ⡆༢໬ࡢࡓࡵ㸪༢୍ࡢࣇ࢛ࣀ࣮ࣥࣔࢻ㸦ගᏛࣇ࢛ࣀ࣮ࣥࣔࢻ㸧ࡢࡳࢆ⪃៖ࡋࡓࠋ௨ୖࡢ⡆༢໬ࢆ⾜࠺࡜ࠊࣇ࢛ࣀࣥᩓ஘ࢆᑟධࡋࡓ㔞Ꮚㄽࢹࣂ࢖ࢫࢩ࣑࣮ࣗࣞࢱࡢ㛤Ⓨ࡟ࡣࠊ༢୍ࡢࣃ࣓࣮ࣛࢱ B ࡢࡳࡀᚲせ࡟࡞ࡿࠋᮏ◊✲࡛ࡣࠊୖグࡢ㟁Ꮚ㸫ࣇ࢛ࣀࣥ┦஫స⏝ࣁ࣑ࣝࢺࢽ࢔ࣥࢆ⏝࠸࡚ࠊஂಖබᘧࢆ⮬ᕫ↓᧐╔࣎ࣝࣥ㏆ఝࡢ⠊ᅖ࡛ィ⟬ࡋ࡚ᚓࡽࢀࡿప㟁⏺⛣ືᗘࡀࠊᐇ

- 510 -

್࡜୍⮴ࡍࡿࡼ࠺ࣃ࣓࣮ࣛࢱࢆỴᐃࡋࡓࠋᅗ

3 ࡣࡇ࠺ࡋࡓᡭ⥆ࡁ࡟ࡼࡾࠊNEGF ࢥ࣮ࢻࢆ⏝࠸࡚ィ⟬ࡋࡓࠊ┤ᚄ 60 nmࠊࢤ࣮ࢺ㛗 100 nm ࡢࢼࣀ࣡࢖
ࣖࢺࣛࣥࢪࢫࢱࡢ㟁ὶ㟁ᅽ≉ᛶ࡛࠶ࡿࠋࣇ࢛ࣀࣥᩓ஘࡟ࡼࡾ࢜ࣥ㟁ὶࡀῶᑡࡋࠊࡑࡢῶᑡ๭ྜࡣ㸪ࢯ࣮ࢫ࣭ࢻࣞ࢖ࣥ㟁ᅽࡀప࠸᪉ࡀ኱ࡁ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝࡣࠊ౫↛࡜ࡋ࡚ᐃ⤖ᯝࢆ኱ࡁࡵ࡟ぢ✚ࡶࡗ࡚࠾ࡾࠊ⏺㠃ࣛࣇࢿࢫ࡞࡝ࡢ௚ࡢᩓ஘㐣⛬ࡢᑟධࠊࢳࣕࢿࣝ㟁Ꮚ≧ែゎᯒᡭἲࡢᨵⰋࠊࣇ࢛ࣀ
ࣥᩓ஘ࣔࢹࣝࡢ⢭ᐦ໬࡞࡝ࡀᚲせ࡛࠶ࡿࠋ௨ୖ 2 ௳௨እ࡟ࡶࠊ⣬㠃ࡢ㒔ྜୖ᭩ࡁࡁࢀ࡞࠸ࡀࠊGaN ࢚ࣆࢱ࢟ࢩࣕࣝ⭷࡬ࡢ࢔ࢡࢭࣉࢱ࣮ᑟධᶵᵓゎ᫂[2] ࠊSiC ࢙࢘ࢵࢺ㓟໬࡟ࡼࡿࢤ࣮ࢺ⤯⦕⭷ᙧᡂᶵᵓゎ᫂[3]ࠊ᣺ືⓎ㟁⣲Ꮚࡢ࣑ࢡࣟ࡞ᶵᵓ[4]ࠊGaN ࢚
ࣆࢱ࢟ࢩࣕࣝ⭷୰࡬ࡢ㓟⣲୙⣧≀ྲྀࡾ㎸ࡳᶵᵓゎ᫂[5]࡞࡝ࡢᡂᯝࡀᚓࡽࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᣍᚅㅮ₇㸦୍㒊㸧
1.

K. Shiraishi, "Atomic and Electronic Structures of Complexes of Screw Dislocations and Mg
Impurities in GaN", International Webinar on Nanotechnology, 2020/10/1, online.

2.

K. Shiraishi, "What are nesesaary for future non-volatile memories?" Webinar on Science,
Engineering and Technology, 2020/11/17, online.

3.

K. M. Bui, Y-I. Matsushita, K. Chokawa, M. Boero, Y. Kangawa, K. Shiraishi, A. Oshiayama,"Structures, electron states and reactions on growing surfaces and at device interfaces of SiC and
GaN", International Symposium on Wide Gap Semiconductor Growth, Process and Device
Simulation 2021, 2021/1/19, online.

4.

N. Mori, H. Tanaka, T. Hoshino, and G. Mil'nikov, "Monte Carlo simulation of two-dimensional
carrier mobility in wide-gap semiconductor devices," International Symposium on Wide Gap

Semiconductor Growth, Process and Device Simulation 2021, January 19-21, 2021, Virtual
Conference
5.

ᐮᕝ⩏⿱ࠊ
ࠕ❅໬≀༙ᑟయᡂ㛗ࣉࣟࢭࢫࡢ⌮ㄽゎᯒ㸸୙⣧≀ΰධᶵᵓࠖ
ࠊ᪥ᮏ≀⌮Ꮫ఍ 2020 ᖺ⛅Ꮨ኱఍ࠊ࢜ࣥࣛ࢖ࣥࠊ2020.09.08-11.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ㸦୍㒊㸧
1.

S. Sakakibara, K. Chokawa, M. Araidai, A. Kusaba, Y. Kangwa and K. SHiraishi, “Theoretical
study on the effect of H2 and NH3 on trimethylgallium decomposition process in GaN MOVPE”
Jpn. J. Appl. Phys. 60, 045507 (2021).

2.

T. Kimura, K. Ohnishi, Y. Amano, N. Fujimoto, M. Araidai, S. Nitta, Y. Honda, H. Amano, Y.
Kangawa, and K. Shiraishi, “Thermodynamic analysis of the gas phase reaction of Mg-doped GaN
growth by HVPE using MgO", Jpn. J. Appl. Phys., 59, 088001 (2020).

3.

T. Shimizu, T. Akiyama, A. Pradipto, K. Nakamura, T. Ito, H. Kageshima, M. Uematsu, and K.
Shiraishi, "Ab Initio Calculations for the Effect of Wet Oxidation Condition on the Reaction
Mechanism at 4H-SiC/SiO2 Interface", Jpn. J. Appl. Phys., 59, SMMD01, 2020/4/28.

4.

T. Nakanishi, T. Miyajima, K. Chokawa, M. Araidai, H. Toshiyoshi, T. Sugiyama, G. Hashiguchi,
and K. Shiraishi, "Negative-charge-storing mechanism of potassium-ion SiO2-based electrets forvibration-powered generators", Appl. Phys. Lett., 117, 193902, 2020/11/10.

5.

D. Yosho, F. Shintaku, Y. Inatomi, Y. Kangawa, J.-I. Iwata, A. Oshiyama, K. Shiraishi, A. Tanaka,
H. Amano, Oxygen Incorporation KLQHWLFVLQ9LFLQDOP ï *DOOLXP1LWULGH*URZWKE\0HWDO̺Organic Vapor Phase Epitaxy, Physica Status Solidi (RRL)–Rapid Research Letters 14 (6),2000142, 2020.

- 511 -

ḟୡ௦஧ḟ㟁ụ࣭⇞ᩱ㟁ụ㛤Ⓨ࡟ࡼࡿ ET 㠉࿨࡟ྥࡅࡓ
ィ⟬࣭ࢹ࣮ࢱᮦᩱ⛉Ꮫ◊✲㸦ᐩᓅ㟁ụㄢ㢟㸧
Computational and Data Science Study for ET Revolution by Development of
Next-Generation Battery and Fuel Cell‫ۑ‬㤋ᒣెᑦ㸦≀ᮦᶵᵓ㸧ࠊᮡ㔝ಟࠊ᫓ᒣ₶ࠊἙὠບࠊ∦ᒸభኴ㸦ᮾ኱≀ᛶ◊㸧ࠊᒸᓮ㐍ࠊỌ஭ဴ㑻ࠊᕊ⃝⠊⾜ࠊ㔠Ꮚᩄᏹࠊ‫‮‬அஓ㸦ᮾ኱㝔᪂㡿ᇦ㸧ࠊ኱㇂ᐇࠊᏳ⸨ᗣఙࠊⴗ
ཎ⪽㸦⏘⥲◊㸧◊✲┠ⓗᐩᓅ㟁ụㄢ㢟ࡣࠊ࢔ࣉࣜࢣ࣮ࢩࣙࣥࢆ㺀ᐩᓅ㺁࠾ࡼࡧ +3&, ࡟࠾࠸࡚ά⏝ࡍࡿࡇ࡜࡛ࠊ஧ḟ㟁ụ࠾ࡼࡧ⇞ᩱ㟁ụࡢᚤどⓗ཯ᛂᶵᵓࢆ⌮ゎ࣭ゎ᫂ࡋࠊ࠿ࡘḟୡ௦㟁ụ㛤Ⓨ࡟ྥࡅࡓࢩ࣑࣮ࣗࣞࢩ࣭ࣙࣥࢹ࣮ࢱᮦᩱ⛉Ꮫᢏ⾡ࡢ♫఍ᐇ⿦ࢆᙉຊ࡟᥎㐍ࡍࡿࡇ࡜࡟ࡼࡾࠊ⇚Ⅿ࡞ᅜ㝿➇தࡢ୰࡛ࡢᡃࡀᅜࡢ᪂つ㟁ụᮦᩱ㛤Ⓨ࣭ᐇ⏝໬࡟㈉⊩ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ⇞ᩱ㟁ụࡢ⬺ⓑ㔠ゐ፹ࡢ◊✲㛤Ⓨ࡛ࡣࠊⓑ㔠௦᭰㟁ᴟᮦᩱ࡜ࡋ࡚㛤Ⓨࡉࢀ࡚࠸ࡿ㓟໬≀࡟ᑐࡋࠊ㓟⣲㑏ඖάᛶࡢྥୖࡢࡓࡵࡢẕ≀㉁࡜ࢻ࣮ࣃࣥࢺࡢᮦᩱ᥈⣴ᣦ㔪ࢆ➨୍ཎ⌮ィ⟬㸦67$7(9$63㸧࡟ᇶ࡙ࡁᥦ♧ࡍࡿࠋࡲࡎࠊ཯ᛂ࢚ࢿࣝࢠ࣮ィ⟬࡟ᇶ࡙ࡃ㓟⣲㑏ඖάᛶࡢண

ᡭἲࢆ☜❧ࡋࠊ㓟໬≀⾲㠃࡟࠾ࡅࡿ㑄⛣㔠ᒓ୙⣧≀࠾ࡼࡧ㓟⣲Ḟ㝗࡜ࡢ㛵㐃ࢆゎ᫂ࡍࡿࠋ⇞ᩱ㟁ụࡢ㟁ゎ㉁⭷࣭ࣉࣟࢺࣥ㍺㏦ࡢ◊✲㛤Ⓨ࡛ࡣࠊ኱つᶍ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦02'</$6㸧࡟ᇶ࡙࠸࡚ࡉࡽ࡟Ⓨᒎࡉࡏࠊ㟁ゎ㉁⭷୰࡟࠾ࡅࡿ㐃㙐ⓗ࡞ࣉࣟࢺࣥ⛣ື཯ᛂ㸦ࢢ࣮ࣟࢱࢫᶵᵓ㸧ࢆྵࡴࣉࣟࢺࣥ㍺㏦ࡢศᏊᶵᵓࡸࠊ㧗ศᏊ┦࡜㟁ゎᾮ┦ࡢ஧┦࠿ࡽ࡞ࡿ」㞧࡛୙ᆒ୍࡞⣔࡛ࡢ㓟⣲ࠊỈ⣲ࡢ㏱㐣⤒㊰ࡶྵࡵࡓ㍺㏦ᶵᵓࢆ㟁ゎ㉁⭷ᵓ㐀࡜ࡢ┦㛵࡟࠾࠸࡚࣑ࢡࣟ࡟ゎ᫂ࡋࠊ᪂つ㟁ゎ㉁⭷ࡢศᏊタィᣦ㔪ࢆᚓࡿࠋ㟁ゎᾮ⣔ḟୡ௦஧ḟ㟁ụࡢ◊✲㛤Ⓨ࡛ࡣࠊ㟁ゎᾮࡢ⏺㠃཯ᛂ࡜࢖࢜ࣥ㍺㏦ࡀ㐃ືࡍࡿၥ㢟࡟ࡘ࠸࡚㟁ᴟ̿㟁ゎᾮ⏺㠃࡟࠾࠸࡚ࣂ࢖࢔ࢫ༳ຍຠᯝ࡜⁐፹ຠᯝࡢ୧⪅ࢆྠ᫬࡟ྲྀࡾධࢀࡿࡇ࡜ࡢ࡛ࡁࡿ (605,60 ἲ࠾ࡼࡧࡑࢀ࡜཯ᛂ⤒㊰⮬ື᥈⣴ἲࢆ⤫ྜࡋࡓィ⟬ᡭἲ࡛ࡢィ⟬⤖ᯝࢆࡶ࡜࡟ࠊࡼࡾ᭷ᮃ࡞᪂つ㟁ゎᾮࡢᣦ㔪⋓ᚓࡸᥦ᱌ࢆ⾜࠺ࠋ

◊✲ᡂᯝ ⇞ᩱ㟁ụࡢ⬺ⓑ㔠ゐ፹⇞ᩱ㟁ụḟୡ௦ᆺ㟁ᴟ㸦=U2㸧ࡢᵓ㐀ཬࡧ㓟⣲㑏ඖ཯ᛂ㸦255㸧άᛶࢆணࡋࠊᚓࡽࢀࡓ▱ぢࢆࡶ࡜࡟௒

ᚋࡢάᛶྥୖࡢࡓࡵࡢ㆟ㄽࢆ㐃ᦠࡍࡿᐇ㦂ᐙ࡜⾜ࡗ࡚࠸ࡃࠋ௧࿴㸰ᖺᗘࡣࡑࡢ‽ഛࡢࡓࡵ࡟ࠊ➨୍ཎ⌮࠿ࡽࡢࣔࣥࢸ࢝ࣝࣟィ⟬࠾ࡼࡧ཯ᛂ⤒㊰᥈⣴ィ⟬ࢆᑟධࡋ࡚ࣉࣟࢲࢡࢺࣛࣥࢆ㛤ጞࡋࡓࠋࣉࣟࢲࢡࢺࣛࣥ࡟࠾࠸࡚ࡣࠊḞ㝗࡜୙⣧≀ࢆᑟධࡋࡓ =U2 ࡢᵝࠎ࡞⾲㠃࡟ᑐࡋ࡚ 255 άᛶࢆㄪ࡭ࡓ⤖ᯝࠊ- 512 -

ᮏ⾲㠃࡛ࡣⓑ㔠ྜ㔠࡞࡝ࡢ㔠ᒓ⾲㠃࡜␗࡞ࡾࠊᵝࠎ࡞άᛶࢆᣢࡘ྾╔ࢧ࢖ࢺࡀᏑᅾࡋࠊࡑࡢ୰࡟ࡣⓑ㔠⾲㠃ࡼࡾάᛶࡢ㧗࠸ࡶࡢࡀྵࡲࢀ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋィ⟬࡟⏝࠸ࡓ⾲㠃ࣔࢹࣝ࡜ࡋ࡚ࠊ⤒㦂ⓗ࡟᝿ᐃࡋࡓࡶ
ࡢ࡟ຍ࠼࡚ࠊ➨୍ཎ⌮࠿ࡽࡢࣔࣥࢸ࢝ࣝࣟィ⟬࠿ࡽồࡵࡓࡶࡢ࡟ᑐࡋ࡚⾜࠸ࠊࡑࡢィ⟬࠿ࡽࡣᵓ㐀࡜άᛶ࡜ࡢ㛵ಀࢆ♧၀ࡍࡿ⤖ᯝࡀᚓࡽࢀࡘࡘ࠶ࡿ㸦ᅗ 㸧ࠋࡇࢀࡽィ⟬⤖ᯝ࡟㛵ࡋ࡚ࡣࠊᐇ㦂ᐙ࡜ඹ᭷ࡋ࡞ࡀࡽᐇ㦂࡬ࡢࣇ࢕࣮ࢻࣂࢵࢡࢆ⾜ࡗࡓࡾࠊᐇ㦂⤖ᯝ࡜ࡢ┦㐪Ⅼ࡟ᇶ࡙ࡁィ⟬᮲௳ࡢᨵၿ࡟⏝࠸ࡓࡾࡋ࡞ࡀࡽ᭷ຠά⏝ࡀ⾜ࢃࢀ࡚࠸ࡿࠋィ⟬ࠊᐇ㦂ࠊ⏘ᴗ⏺ࡢ㐃ᦠ࡟ྥࡅࡓ୍Ṍࡀ㐍ࡵࡽࢀࡓ࡜⪃࠼࡚࠸ࡿࠋ

ᅗ  㓟໬≀㟁ᴟ࡛ࡢ㓟⣲㑏ඖ཯ᛂ⤒㊰ࡢ᥈⣴ィ⟬ ⇞ᩱ㟁ụࡢ㟁ゎ㉁⭷࣭ࣉࣟࢺࣥ㍺㏦⇞ᩱ㟁ụᛶ⬟ࢆỴࡵࡿ㔜せ࡞ᅉᏊࡢࡦ࡜ࡘ࡛࠶ࡿ㧗ศᏊ㟁ゎ㉁⭷୰࡟࠾ࡅࡿࣉࣟࢺࣥ㍺㏦ࠊ࡞ࡽࡧ࡟࢚ࢿ
ࣝࢠ࣮ᦆኻࡢ୺せ࡞ᅉᏊ࡛࠶ࡿỈ⣲࡜㓟⣲ࡢࢡࣟࢫ࣮ࣜࢡࡢไᚚᢏ⾡ࡢ☜❧࡟ྥࡅ࡚ࠊ㟁ゎ㉁⭷୰࡟࠾ࡅࡿ
ࣉࣟࢺࣥࠊ㓟⣲ࠊỈ⣲㍺㏦ࡢศᏊᶵᵓࡢゎ᫂ࡀᚅࡓࢀ࡚࠸ࡿࠋᮏ◊✲࡟࠾࠸࡚ࡣࠊ㟁ゎ㉁⭷ࣂࣝࢡࡸ㟁ᴟ⏺
㠃ࡢࡼ࠺࡞୙ᆒ୍⣔࡟࠾ࡅࡿࡇࢀࡽ≀㉁㍺㏦ࢆ࣑ࢡࣟ࡟グ㏙ࡍࡿࡓࡵ࡟ࠊ㍺㏦ࡉࢀࡿ≀㉁ࡢ఩⨨࡟౫Ꮡࡋࡓ
⮬⏤࢚ࢿࣝࢠ࣮࡜ᣑᩓಀᩘ࠿ࡽ኱ᇦⓗ࡞ᾐ㏱ಀᩘࡸ≀㉁ࡢ⭷୰ࡢ⛣ື⤒㊰➼ࢆホ౯ࡍࡿ᪉ἲㄽ࡟ࡘ࠸᳨࡚ウࢆ㐍ࡵ࡚ࡁࡓ[1]ࠋ௧࿴㸰ᖺᗘࡣࠊࡇࢀࡲ࡛࡟ᵓ⠏ࡋ࡚ࡁࡓ㧗ศᏊ㟁ゎ㉁⭷ࣔࢹࣝࢆ⏝࠸࡚ࠊỈ⣲࡜㓟⣲ࡢẼ┦࠿ࡽ㟁ゎ㉁⭷୰࡬ࡢ⛣⾜ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࢆホ౯ࡋࠊ㧗ᛶ⬟ 02'</$6>@ࢆ⏝࠸࡚఩⨨࡟౫Ꮡࡍࡿᣑᩓಀ
ᩘࡢィ⟬࡟╔ᡭࡋࡓࠋᅗ  ࡣࠊィ⟬࡟⏝࠸ࡓ㟁ゎ㉁⭷㸦ྵỈ⋡ Ȝ 㸧ࡢ㧗ศᏊ┦࡜Ỉ┦ࢆูࠎ࡟♧ࡍࠋᅗ࠿ࡽ᫂ࡽ࠿࡞ࡼ࠺࡟ࠊ
⣔ࡣ」㞧࡟ධࡾ⤌ࢇࡔ aQP ⛬ᗘࡢ୙ᆒ୍ᛶࢆᵓ㐀࡟᭷ࡋ࡚࠾ࡾࠊ㏻ᖖࡢ 0' ィ⟬࡛ࡣ኱ᇦⓗ࡞ᾐ㏱ಀᩘࢆ
ホ౯ࡍࡿࡇ࡜ࡣ୙ྍ⬟࡛࠶ࡿࠋ- 513 -ᅗ  㸦ᕥ㸧㧗ศᏊ㟁ゎ㉁⭷ࡢ㧗ศᏊ┦ 㸦ྑ㸧㧗ศᏊ㟁ゎ㉁⭷ࡢỈ┦ࡇࡢࡓࡵࠊỈ⣲ࠊ㓟⣲ࡢᾐ㏱ಀᩘࡢ᪂つ᪉ἲㄽ࡟ᚲせ࡞఩⨨࡟౫Ꮡࡍࡿ⛣⾜ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࢆồࡵࠊ୍᪉࡛఩⨨࡟౫Ꮡࡍࡿᣑᩓಀᩘࡢホ౯࡟╔ᡭࡋࡓࠋᅗ  ࡣࠊỈ⣲࡜㓟⣲ࡢẼ┦࠿ࡽ㧗ศᏊ㟁ゎ㉁⭷ෆ㒊࡬୕ḟඖⓗ࡟ồࡵࡓ⛣⾜ࡢ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࡢ୍᩿㠃ᅗ࡛࠶ࡿࠋ⮬⏤࢚ࢿࣝࢠ࣮࣐ࢵࣉࡢヲ⣽࡞᳨ウ࠿ࡽࠊỈ⣲ࠊ㓟⣲ࡢ࠸ࡎࢀ࡟࡜ࡗ࡚ࡶ㧗ศᏊ┦࡟Ᏻᐃ㡿ᇦ࡜୙Ᏻᐃ㡿ᇦࡀྠ᫬࡟ከࡃᏑᅾࡋ࡚࠸ࡿ୍᪉ࠊỈ┦ࡣ್࡜ࡋ࡚
ࡣࡑࡢ୰㛫࡛࠶ࡿࡀᆅᙧ࡜ࡋ࡚ࡣᖹᆠ࡛࠶ࡿࠋࡲࡓࠊỈ⣲࡜㓟⣲࡜࡛ࡣࠊ್ࡣ␗࡞ࡿࡀᴫࡡྠᵝ࡞⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆ♧ࡋ࡚࠸ࡿࡇ࡜ࡶ⯆࿡῝࠸ࠋ㧗ศᏊ┦࡜Ỉ┦࡜࡝ࡕࡽࡀ⛣ື⤒㊰࡟࡞ࡿ࠿ࡣᣑᩓಀᩘࡢホ౯ᚋ࡟⾜࠺ணᐃࡢືⓗࣔࣥࢸ࢝ࣝࣟἲࡢᐇ⾜ࡲ࡛ᚅࡓࡡࡤ࡞ࡽ࡞࠸ࡀࠊࡇࢀࡽࡣ㧗ศᏊ㟁ゎ㉁⭷ᵓ㐀ࡢタィ࡟ࡶ㛵ಀࡋࠊ㠀ᖖ࡟⯆࿡῝࠸ࠋᅗ  㸦ᕥ㸧Ỉ⣲ࡢ㟁ゎ㉁⭷୰࡬ࡢ⛣⾜ࡢ⮬⏤࢚ࢿࣝࢠ࣮㸦ྵỈ⋡ Ȝ ༢఩ࡣ N-PRO㸧㸦ྑ㸧㓟⣲ࡢ㟁ゎ㉁⭷୰࡬ࡢ⛣⾜ࡢ⮬⏤࢚ࢿࣝࢠ࣮㸦ྵỈ⋡ Ȝ ༢఩ࡣ N-PRO㸧 㟁ゎᾮ⣔ḟୡ௦஧ḟ㟁ụ௧࿴㸰ᖺᗘࡣࠊ཯ᛂ⤒㊰⮬ື᥈⣴ἲࡢィ⟬࢚ࣥࢪࣥ࡜ࡋ࡚ືసࡍࡿ (605,60 ἲࢆᐇ⿦ࡋࡓ 4XDQWXP
(635(662 ࢥ࣮ࢻࡢ᭱㐺໬ཬࡧ཯ᛂ⤒㊰⮬ື᥈⣴ἲࡢືస☜ㄆࢆ⾜ࡗࡓࠋࡲࡓࠊ᭱㐺໬ࡋࡓࢥ࣮ࢻ࡟ᐇ⿦ࡉ
ࢀ࡚࠸ࡿ (605,60 ἲࡢィ⟬⢭ᗘࡢ☜ㄆ࡜ᐇ㝿ࡢ㟁Ẽ໬Ꮫ⏺㠃࡬ࡢᛂ⏝࡜ࡋ࡚ࠊ$O1D&O DT ⏺㠃࡟࠾ࡅࡿ⭉㣗㟁఩ࡢィ⟬ࢆ⾜ࡗࡓࠋ- 514 -

(605,60 ἲࡢィ⟬⢭ᗘࡢ☜ㄆ࡛ࡣࠊᵝࠎ࡞᫂♧ⓗ⁐፹࿴ᵓ㐀࡟ᑐࡋ࡚ࠊ(605,60 ἲ࡜ᚑ᮶ࡢᬯ㯲ⓗ⁐፹ᶍᆺ࡟ࡼࡗ࡚ồࡵࡓ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࢆㄪ࡭ࡓࠋィ⟬ࡣࠊࣂࣝࢡ⁐ᾮ୰ࡢ &2 ࡢ㑏ඖ཯ᛂࢆᑐ㇟࡟⾜࡞ࡗࡓࠋᬯ㯲ⓗ⁐፹ᶍᆺ࡟ࡼࡿィ⟬࠿ࡽᚓࡽࢀࡓ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࢆࠊ➨୍ཎ⌮ศᏊືຊᏛἲࡢ⤖ᯝ࡜ẚ㍑ࡋࡓࠋࡑࡢ⤖ᯝࠊ(605,60 ἲࡣ⢭ᗘࡼࡃ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀࢃ
࠿ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ⁐ᾮศᏊࡸ࢖࢜ࣥࡢᵓ㐀ࢆ⪃៖ࡍࡿ⌮ㄽ࡛࠶ࡿ (605,60 ἲࡣ⁐፹࿴ᵓ㐀ࢆẚ㍑ⓗ⢭ᗘࡼࡃ෌⌧ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ࢝࢘ࣥࢱ࣮࢖࢜ࣥࡸ➨୍⁐፹࿴ᅪࡢỈศᏊࢆ᫂♧ⓗ࡟㓄⨨ࡋࡓࣔࢹࣝ࡟ᑐࡍࡿィ⟬⤖ᯝࡣ࡝ࡢᬯ㯲ⓗ⁐፹ᶍᆺ࡛ࡶ㠀ᖖ࡟㏆࠸್࡜࡞ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ㐃⥆య㏆ఝࢆ⏝࠸ࡿࢱ࢖ࣉࡢᬯ㯲ⓗ⁐፹ᶍᆺࡣὀ┠ࡍࡿศᏊ࠿ࡽぢࡓ➨୍⁐፹࿴ᅪࡼࡾ㐲ࡃࡢࣂࣝࢡ⁐ᾮࡢຠᯝࢆⰋࡃグ㏙ࡍࡿࣔࢹࣝ࡜࡞ࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋᚑࡗ࡚ࠊ(605,60 ἲࡣ㐃⥆య㏆ఝࢆ⏝࠸ࡿࢱ࢖ࣉࡢᬯ㯲ⓗ⁐፹ᶍᆺ࡜ẚ㍑ࡋ࡚ࠊ➨୍⁐፹࿴ᅪࡢ⁐፹࿴ᵓ㐀ࢆẚ㍑ⓗ⢭ᗘࡼࡃグ㏙ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿ㸦ᅗ 㸧ࠋᅗ  ᵝࠎ࡞ᬯ㯲ⓗ⁐፹࿴ᶍᆺ࡟ࡼࡾィ⟬ࡋࡓ཯ᛂᗙᶆ࡟ἢࡗࡓ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝ

$O1D&O DT ⏺㠃࡟࠾ࡅࡿ⭉㣗㟁఩ࡢィ⟬࡛ࡣࠊ㓟ᛶỈ⁐ᾮ࡜ $O 㟁ᴟ⏺㠃࡟࠾ࡅࡿ⭉㣗཯ᛂࣔࢹࣝࡢᵓ⠏࡜㏿ᗘㄽࢆ࣮࣋ࢫ࡜ࡋࡓ 7DIHO ᘧ࠿ࡽ⭉㣗㟁఩ࢆィ⟬ࡍࡿ᪉ἲࢆᥦ᱌ࡋࡓࠋ⭉㣗཯ᛂ࡛ࡣࠊ୍⯡࡟⪃࠼ࡽࢀࡿ࢔
ࣀ࣮ࢻ཯ᛂ $O V ĺ$O DT H 0 ࡟ຍ࠼࡚ࠊ1D&O Ỉ⁐ᾮ୰ࡢ &Oࡀ $O࡜཯ᛂࡋ࡚㘒యࢆᙧᡂࡍࡿ཯ᛂ࡟ᑐ
ࡋ࡚ࡶ⭉㣗཯ᛂᶍᆺࢆ⪃࠼ࡓࠋḟ࡟ (605,60 ἲ࠿ࡽᚓࡽࢀࡓ⭉㣗཯ᛂ࡟ᑐࡍࡿ࢔ࣀ࣮ࢻ࡜࢝ࢯ࣮ࢻ཯ᛂࡢ
ᖹ⾮㟁఩࠿ࡽࠊ⭉㣗㟁఩ࢆ 7DIHO እᤄἲ࠿ࡽ཯ᛂ㏿ᗘㄽ࡟ᇶ࡙ࡃᙧᘧ࡛ィ⟬ࡍࡿ᪉ἲࢆ⪃࠼ࡓࠋ௨ୖࡢࡼ࠺࡞
ࣔࢹࣝࢆ⏝ពࡋࠊ(605,60 ἲ࠿ࡽ⭉㣗㟁఩ィ⟬ࢆ⾜࠸ࠊᐇ㦂⤖ᯝ࡜ẚ㍑ࡋࡓࠋᚓࡽࢀࡓ⭉㣗㟁఩ࡣ㟁఩ไᚚ࡟ࡼࡗ࡚ $O ⾲㠃ࢆΎί໬ࡋࡓᐇ㦂⤖ᯝ࡜ࢥࣥࢩࢫࢸࣥࢺ࡞⤖ᯝࡀᚓࡽࢀࡓ㸦ᅗ 㸧>@ࠋ- 515 -  ᅗ  $O1D&O DT ⏺㠃࡟࠾ࡅࡿ⭉㣗㟁఩ࡢィ⟬⤖ᯝⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫[ۻ‬1] ᮡ㔝 ಟ, ࠕ⇞ᩱ㟁ụ཯ᛂࡢィ⟬⛉Ꮫ࡜ḟୡ௦ᆺ㟁ᴟࡢᐇ⌧࡟ྥࡅࡓィ⟬ணࠖ, ᪥ᮏ໬Ꮫ఍➨ ᫓Ꮨᖺ఍ ᐩᓅ㟁ụㄢ㢟➨㸯ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧, ࢜ࣥࣛ࢖ࣥ
‫[ۻ‬2] Ọ஭ ဴ㑻, ࠕ㧗ศᏊ㟁ゎ㉁⭷࠾ࡼࡧ⇞ᩱ㟁ụ㟁ᴟ⏺㠃࡟࠾ࡅࡿ≀㉁㍺㏦ᶵᵓゎ᫂࡟ྥࡅࡓศᏊືຊ
Ꮫィ⟬᪂つᡭἲ㛤Ⓨࠖ, ィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔࣒㸦3&R06㸧ࢩ࣏ࣥࢪ࣒࢘, ࢜ࣥࣛ࢖ࣥ
‫[ۻ‬3] ᒸᓮ 㐍, ࠕ⇞ᩱ㟁ụ㧗ศᏊ㟁ゎ㉁⭷ࣂࣝࢡ୰࡟࠾ࡅࡿ≀㉁㍺㏦ࡢศᏊືຊᏛィ⟬࡟ࡼࡿ◊✲ࠖ, ᪥ᮏ໬Ꮫ఍➨  ᫓Ꮨᖺ఍ ᐩᓅ㟁ụㄢ㢟➨㸯ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧, ࢜ࣥࣛ࢖ࣥ
‫[ۻ‬4] Ọ஭ ဴ㑻, ࠕ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘࡢ᪂つホ౯᪉ἲ࡟ᇶ࡙ࡃ୙ᆒ୍⣔࡟࠾ࡅࡿ≀㉁㍺㏦ࠖ, ᪥ᮏ≀⌮Ꮫ఍  ᖺ⛅Ꮨ኱఍, ࢜ࣥࣛ࢖ࣥ
‫[ۻ‬5] ኱㇂ ᐇ, ࠕ㟁Ẽ໬Ꮫ⏺㠃ࢩ࣑࣮ࣗࣞࢩࣙࣥᢏ⾡ࡢ♫఍ᐇ⿦࡜㟁ụᮦᩱ࡬ࡢ㐺⏝ࠖ, ᪥ᮏ໬Ꮫ఍➨ ᫓Ꮨᖺ఍ ᐩᓅ㟁ụㄢ㢟➨㸯ᅇබ㛤ࢩ࣏ࣥࢪ࣒࢘㸦ᡂᯝሗ࿌఍㸧, ࢜ࣥࣛ࢖ࣥ

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ @> ۻ‬7HWVXUR 1DJDL 6KXKHL 7VXUXPDNL 5\R 8UDQR .D]XVKL )XMLPRWR :DWDUX 6KLQRG 6XVXPX 2ND]DNL
³3RVLWLRQGHSHQGHQW GLIIXVLRQ FRQVWDQW RI PROHFXOHV LQ WKH KHWHURJHQHRXV V\VWHPV DV HYDOXDWHG E\ WKH ORFDO
PHDQVTXDUHGGLVSODFHPHQW´-&KHP7KHRU\&RPSXW16í  '2, DFVMFWFF
‫<@>ۻ‬RVKLPLFKL$QGRK6KLQLFKL,FKLNDZD7DWVX\D6DNDVKLWD1RUL\XNL<RVKLL6XVXPX2ND]DNL³$OJRULWKPWRPLQLPL]H03,FRPPXQLFDWLRQVLQWKHSDUDOOHOL]HGIDVWPXOWLSROHPHWKRGFRPELQHGZLWKPROHFXODUG\QDPLFVFDOFXODWLRQV´-&RPSXW&KHP42  '2,MFF
 >@.RLFKL.DQR6DWRVKL+DJLZDUD7DNDKLUR,JDUDVKLDQG0LQRUX2WDQL³6WXG\RQWKHIUHHFRUURVLRQSRWHQWLDODW
DQLQWHUIDFHEHWZHHQDQ$OHOHFWURGHDQGDQDFLGLFDTXHRXV1D&OVROXWLRQ´(OHFWURFKLPL$FWD377
 '2,MHOHFWDFWD
>@ 6KXVXNH .DVDPDWVX 2VDPX 6XJLQR 7DNDIXPL 2JDZD DQG $NLKLGH .XZDEDUD ³'RSDQW DUUDQJHPHQWV LQ
<GRSHG %D=U2 XQGHU SURFHVVLQJ FRQGLWLRQV DQG WKHLU LPSDFW RQ SURWRQ FRQGXFWLRQ D ODUJHVFDOHILUVWSULQFLSOHVWKHUPRG\QDPLFVVWXG\´-0DWHU&KHP$8  '2, GWDK- 516 -









All-Atom Analysis of Small-Molecule Absorption into Copolymers
!"

.

 ,25 6

1

' 8 97:+-*)RO'OQZnZ×¸ÛZnWÑcR¸ v [ ,+p·i'°cx(+WÑcRlÉÖ.b·+ISb·Í¹m*¯#c-²µ ­rÈ Kb·*+ ¸Z×ÖZnÍ(+q¢ÀiÓ }¿+Z×+ËÎq¿gIËÎZn¸YÏ!
¦¼*YkZÐ.q+eaº1<D2HÜΔGÝ(+ÄU }¿+I»ΔG Â
«Zn^]o5?AEH5CG ),+ WÑcR¬ÛZnÍ.
("*B;8:³*Ê |®Í'B;8:°cP´(*:>F6H"WÑcR407ΔG !{Ù)ÅÚÛZnWÑcR +uZnea·ÄU¤ª.¡V`nZn^]o5?AEH5CGÜMDÝ1<D2H½¥ÆÜERÝ¯#c-(+ΔG ÄU.ÛZnWÑcR¬!Ûw_+¾eaZn.¬± Ã.¼
%polyethylene .WÌB;8:Á O§w vinyl acetate,(*&Áy vinyliden
difluorideÁ z acrylamide ,B;8:.d$WÑcR,,|®Í:>F6H( WÑcR407eΔG !sL.qÒ ÄU+

2

+-

$4/

$

|®Í:>F6H( WÑcR407
e!sL.¬± Ã+%ÛZnWÑcRh 1 ¥Í.
 ethylene B;8:=F83Ü³*ÊÕ lÝØ
ethylene B;8:=F83Ü³*ÊÕ mÝ IÔJf

N/+ periodic ÍØethylene =F83

graft

,+ graft Í+periodic Í graft Í:>F6H *sLÃ%M¶.tÇ,,ÍßB;8:  l:m m+ßWÑcRÍ.S\¶ l:m h 1. £©tÇÞ¨WÑcR periodic ÍÈÒ%t~+XR T ethylene  graft Íl, m, n ,,  ethylene B;
vinyl acetate WÑcRjcB;8:  l:m = 8:³*ÊÕØ ethylene B;8:³*ÊÕ
18:1, 8:1, 14:3, 4:3 ,,4 + m  ,)B;8:(+ diblock ³*Ê +

- 517 -

Íperiodic Í(
ZnY`ngraft ÍÛZn@9D.S

Iq+(l, m, n .eGER ΔG .«&+% MD .WÑcR#8¬WÑcRmZn.d/¬,,
¬h 2 (ÛZn¸YÏÍ.QZn %k+D3¬+,,¬ 300 K1 bar M:6 3:.4GG @D(*U
+;B :qlÍ.4GG +%8¬ 8 ¬ ethylene-acrylamide WÑcR¬ 120 ,kWÑcR 60 SªÍÐ´t MD .rh 2. tÇ+WÑcRD3¬

I
:

MD Zn^]o:O&NÍT

(_+TÛ GROMACS .[1]
ER 1<D2H½¥Æ rb ,I»$Ö ,+ ERmod .
[2]

3+-#ethylen-vinylidene difluorideethylene-vinyl acetate(ethylene-acrylamide WÑcR¨t MD

 ER ¯#c-(*ΔG .«&WÑcR   .+B;8:³*ÊÕ'.B;8: ,  ,  W Ñ c R ¨  periodic  Í   Ø







   ÑcR407ΔG !sL.Ã

ethylene B;8:³*ÊÕ m t+ΔG .h 3:

9Ø ethylene B;8vinylidene difluoride (<5  m+vinyl acetate jc mjc 0.2 kcal/mol 6_u   

 -+ΔG  m

fm



,)B;8:" m(+6_(*&uIqJΔG Iq+B;8:³*ÊÕ|®ÍÛZn.
+B;8:)cΔG !sLu









!
!
!
!
!











!
!
!
!
!

 







acrylamide jc m < 10  1 kcal/mol 6_






¥ΔG J&m sL+B;8:8:)c4*(*ΔG  ÜÈÒ%Ý*Á +Ø ethylene B;

!
"!
!
!
!



+WÑcRÍΔG.h+ |®Í:>F6H( W

periodic °c+ graft °c+:>F6H











  

h 3. ethylene-vinylidene difluorideÜJÝethylene-vinyl
acetateÜO7Ý
ethylene-acrylamideÜÝperiodic ÍØ ethylene B;8:³*ÊÕt+ΔG

 Z+

- 518 -     ! "  ! 

 ! 



















 















 


 
















 

  

h 4. ethylene-vinylidene difluorideÜ>Ýethylene-vinyl acetateÜO7Ýethylene-acrylamideÜ-Ý/I l, m,n  periodic Í graft ÍΔG t~^g



3

 

periodic ÍRg/I l, m, n ¯#c- periodic Í graft
kcal/mol *ΔG

periodic Í graft Í:>F6H

9

+ethylene-acrylamide z À),+ mZ   !"ÍΔG h.h 4 ¥M¶ΔG ? 0.2Í(*&u   Z+J."%+et+WÑcRÍgnÑ¿wlW







 









Z

 ,) IqÍ/5ΔG .h+ !"mWÑcR407sLÃ
periodic Í graft Íethylene =F83
Ø ethylene =F83 diblock ³*Ê
  
          


    



h

WÑcR¯|®Í:>F6H+ Z


              !"),+ ):>F6HΔG !sL|®



9 

+jc& periodic Í graft ÍΔG I_ À¯|®ÍsL

graft ÍΔG periodic# 

$n t h 5. ethylene-vinylidene difluorideÜJÝ
ethylene-vinyl

+ ΔG .h 5 ¥,,WÑcR¨ acetateÜO7Ý
ethylene-acrylamideÜÝethylene
/I l, m!,+jcΔG  n  9 B;8:Ø ethylene B;8: diblock ³*Ê

Iq+  Z+"*diblock /5 t+ΔGa periodic ÍXC

°c(+ΔG !sL&u  °c' graft Í"*.-Z"h 4 t~
Hgraft jc:>F6H?.U#&& +Í&/+*I\):>F6H ΔG !
/sL t~+J&># n = 1  periodic Í& graft Í& diblock 
*M¶ΔG I_+diblock Zn407 origomer /\*_o8Z
n#  +407+(eÄUWÑcRD3WÑcR.
_o 'Hu  origomer  diblock  ,+8#  +

- 519 -

JWÑcReat+|®Í:>F6H( WÑcR407 9 Ã,Ám + 3 ¨WÑcRtÍ.cq+Hteº1<
D2H aL+D+` E),WÑcR¸ÄU5?AEH5CGib·]3v¥ ,WÑcR.u  diblock ´Fb·+ 5?AEH5CG(+WÑcReaÄU.(*Q :mÒrI+ .¥1+

4 (30
1) u= Y0,V 0<V IjNP A G:kc#+WÑcR¸eº
1<D2HdOÜ>HÝ[ 34 2 Zn5?AEH5CGÃÆ G0G2020 @ 12 K2) u= Y0,V 0<V IjNP AWÑcRÛZn¸ËÎÄU +ÛZnÍÃÜ>HÝ[ 23 2 Æ_oÃÆ G0G2021 @ 5 K

5%0 )$#'('(-.1,#2+(+!1(&1,#,) 0-+#,,)&.-#)(#(/+#-1) )*)&1'+,-"+).!"')&.&+1('#,,#'.&-#)((-")+1) ,)&.-#)(,3,.'#--1&+"'-&) -0+    %.+-.1,#)'*.-"'   - 520 -

 ࣮ࣘࢨⓎ⾲ㄽᩥ㻌ᙜ䝉䞁䝍䞊䛾฼⏝䛻ᇶ䛵䛔䛶Ⓨ⾲䛥䜜䛯ㄽᩥ䛾䛖䛱ᙜ䝉䞁䝍䞊䛻ูๅ䛜ᥦฟ䛥䜜䛯䜒䛾䜢 㻟㻚㻝㡯䛻ᥖ㍕䛧䜎䛧䛯䚹Ⓨ⾲ᖺᗘ䛿ᚲ䛪䛧䜒 㻞㻜㻞㻜 ᖺᗘ䛻㝈䜙䛪䚸ึ䜑䛶ᥦฟ䛥䜜䛯䜒䛾䛿䛭䛾ᖺᗘ䛾ศ䛸䛧䛶㍕䛫䛶䛒䜚䜎䛩䚹䜎䛯䝥䝻䝆䜵䜽䝖ู䛾ᥦฟ≧ἣ䜢 㻟㻚㻞 㡯䛻ᥖ㍕䛧䜎䛧䛯䚹ᥦฟㄽᩥ䛾⟶⌮䛿䝥䝻䝆䜵䜽䝖༢఩䛷⾜䛳䛶䛔䜛䛯䜑䚸」ᩘ䝥䝻䝆䜵䜽䝖䛻䜎䛯䛜䜛ㄽᩥ䛾ሙྜ䛷䜒䚸᫂☜䛻䝥䝻䝆䜵䜽䝖ྡ䛜ῧ௜䛥䜜䛪䛻ᥦฟ䛥䜜䛯䜒䛾䛿ᥦฟ⪅䛾ᡤᒓ䛩䜛䝥䝻䝆䜵䜽䝖䛾䜏䛾ᡂᯝ䛸ぢ䛺䛥䜜䜎䛩䚹㻌㻌 ࣮ࣘࢨㄽᩥ୍ぴ㻌ᮏᖺᗘᥦฟ䛥䜜䛯ㄽᩥูๅᩘ䛿ィ 㻞㻡㻞 ௳䛷䛩䚹௨ୗ䛻䛭䛾⾲㢟䚸ⴭ⪅ྡ䚸Ⓨ⾲ㄅྡ䜢ᥖ㍕䛧
䜎䛩䚹ᥖ㍕㡰ᗎ䛿ཎ๎䛸䛧䛶ᙜ䝉䞁䝍䞊䜈ᥦฟ䛥䜜䛯㡰䛻㏻䛧␒ྕ䜢௜䛡䜎䛧䛯䚹ㅰ㎡䛾グ㍕䛜䛺䛔ㄽᩥ䛿ῐⰍ䛷⾲♧䛧䜎䛧䛯䚹㻌
1.

"Solving the Schrödinger equation of the hydrogen molecule with the free-complement variational
theory: essentially exact potential curves and vibrational levels of the ground and excited states ofȆV\PPHWU\Yusaku I. Kurokawa, Hiroyuki Nakashima and Hiroshi Nakatsuji
Phys. Chem. Chem. Phys., 22(24), 13489-13497 (2020)

2.

"Solving the Schrödinger equation of atoms and molecules using one- and two-electron integrals
only"
Hiroshi Nakatsuji, Hiroyuki Nakashima and Yusaku I. Kurokawa
Phys. Rev. A, 101(6), 062508 (2020)3.

"Diprotonative stabilization of ring-opened carbocationic intermediates: conversion oftetrahydroisoquinoline to triarylmethanes"
Hiroaki Kurouchi
Chem. Commun., 56(59), 8313-8316 (2020)

4.

"Synthesis of Carbazole-Fused Azaborines via a Pd-Catalyzed C-H Activation-Cyclization
Reaction"
Masakazu Nagata, Taku Oshiro, Yoshiyuki Mizuhata, Norihiro Tokitoh, Takaaki Hosoya,
Shigeyuki Yamada, Tsutomu Konno, Hiroki Fukumoto, Toshio Kubota and Tomohiro AgouBCSJ, , bcsj.20200129 (2020)5.

"⢭ᐦཌ䛥ไᚚ䛻䜘䜛ᾮయ䛾㌾ X ⥺㏱㐣྾཰ศගᐃ"㛗ᆏᑗᡂ and ᑠᮡಙ༤᪥ᮏ≀⌮Ꮫ఍ㄅ, 75(8), 496-503 (2020)
6.

(IIHFW RI )LOP 7KLFNQHVV RQ 6WUXFWXUDO 6WDELOLW\ IRU %$O1 DQG %*D1 $OOR\V %RQGဨ2UGHUInteratomic Potential Calculations"
Yuya Hasegawa, Toru Akiyama, Abdul-Muizz Pradipto, Kohji Nakamura and Tomonori Ito
Phys. Status Solidi B, 257(8), 2000205 (2020)- 521 -

7.

"Learning reaction coordinates via cross-entropy minimization: Application to alanine dipeptide"
Yusuke Mori, Kei-ichi Okazaki, Toshifumi Mori, Kang Kim and Nobuyuki MATUBAYASI
J. Chem. Phys., 153(5), 054115 (2020)

8.

"Molecular size and shape effects: Rotational diffusion and the Stokes-Einstein-Debye relation"
Norikazu Ohtori, Yuta Kondo and Yoshiki Ishii
Journal of Molecular Liquids, 314, 113764 (2020)

9.

"General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in
Organic Synthesis"
Ryosuke Shishido, Minami Uesugi, Rikuro Takahashi, Tsuyoshi Mita, Tatsuo Ishiyama, Koji
Kubota and Hajime Ito
J. Am. Chem. Soc., 142(33), 14125-14133 (2020)

10. "A DFT Study on FeI/FeII/FeIII Mechanism of the Cross-Coupling between Haloalkane and Aryl
Grignard Reagent Catalyzed by Iron-SciOPP Complexes"
Akhilesh Sharma and Masaharu Nakamura
Molecules, 25(16), 3612 (2020)11. "Thermal Molecular Motion Can Amplify Intermolecular Magnetic Interactions"
Yoshiaki Uchida, Go Watanabe, Takuya Akita and Norikazu Nishiyama
J. Phys. Chem. B, 124(28), 6175-6180 (2020)12. "Alkyl-Substituted Selenium-Bridged V-Shaped Organic Semiconductors Exhibiting High Hole
Mobility and Unusual Aggregation Behavior"
Toshihiro Okamoto, Masato Mitani, Craig P. Yu, Chikahiko Mitsui, Masakazu Yamagishi,
Hiroyuki Ishii, Go Watanabe, Shohei Kumagai, Daisuke Hashizume, Shota Tanaka, Masafumi
Yano, Tomokatsu Kushida, Hiroyasu Sato, Kunihisa Sugimoto, Takashi Kato and Jun Takeya
J. Am. Chem. Soc., 142(35), 14974-14984 (2020)13. &U\VWDO VWUXFWXUH FKDUDFWHUL]DWLRQ RI VRPH ʌ-conjugated ionic crystals toward electronic
applications"
Sota Kodama, Shun Aoyama, Yuka Tanaka, Keisuke Ichijo, Tsukasa Yoshida, Ryohei Yamakado
and Shuji Okada
Molecular Crystals and Liquid Crystals, 704(1), 1-9 (2020)
14. 2SWLFDOSURSHUW\FRQWURORIʌ-electronic systems bearing Lewis pairs by ion coordination"
Takahiro Yanbe, Kei Mizuguchi, Ryohei Yamakado and Shuji Okada
Chem. Commun., 56(73), 10654-10657 (2020)15. "Effects of Wet Ambient on Dry Oxidation Processes at 4H-SiC/SiO2 Interface: An Ab Initio
Study"
Tsunashi Shimizu, Toru Akiyama, Kohji Nakamura, Tomonori Ito, Hiroyuki Kageshima, Masashi
Uematsu and Kenji Shiraishi
ECS Trans., 98(3), 37-46 (2020)16. "A Simple Approach to Growth Mode of InN and InGaN Thin Films on GaN(0001) Substrate"
Katsuya Nagai, Toru Akiyama, Kohji Nakamura and Tomonori Ito- 522 -ECS Trans., 98(6), 155-164 (2020)17. "Intermolecular interaction between anthraquinone dyes and TEMPO mediator in dye-sensitized
photocatalytic systems"
Hitoshi Kusama
Journal of Photochemistry and Photobiology, 2, 100003 (2020)18. "Intramolecular Dispersion Attraction in Tetraalkylammonium Cations Revealed by Cryogenic
Ion Mobility Mass Spectrometry"
Keijiro Ohshimo, Ryosuke Sato and Fuminori Misaizu
J. Phys. Chem. A, 124(39), 7999-8004 (2020)19. "Sequential growth of iridium cluster anions based on simple cubic packing"Kiichirou Koyasu, Ryohei Tomihara, Toshiaki Nagata, Jenna W. J. Wu, Motoyoshi Nakano,
Keijiro Ohshimo, Fuminori Misaizu and Tatsuya Tsukuda
Phys. Chem. Chem. Phys., 22(32), 17842-17846 (2020)20. "Hemisphere and Distance-Dependent Steric Analysis of PNN Iron Pincer Complexes Using
SambVca 2.1 and Its Influence on Alkene Hydrosilylation"
Masahiro Kamitani, Kouta Yujiri and Hidetaka Yuge
Organometallics, 39(19), 3535-3539 (2020)21. "Cationic polymerization of vinyl monomers using halogen bonding organocatalysts with varied
activity"
Koji Takagi, Hiroto Murakata, Koji Yamauchi and Kohei Hashimoto
Polym. Chem. (2020), https://doi.org/10.1039/D0PY01207F
22. "Oxophilicity as a Descriptor for NO Cleavage Efficiency over Group IX Metal Clusters"
Masato Yamaguchi, Yufei Zhang, Satoshi Kudoh, Kohei Koyama, Olga V. Lushchikova, Joost M.
Bakker and Fumitaka Mafuné
J. Phys. Chem. Lett., 11(11), 4408-4412 (2020)23. "The charge reduction rate for multiply charged polymer ions via ion–ion recombination at
atmospheric pressure"
Tomoya Tamadate, Hidenori Higashi, Christopher J. Hogan and Takafumi Seto
Phys. Chem. Chem. Phys., 22(43), 25215-25226 (2020)24. "Probing local distortion around structural defects in half-Heusler thermoelectric NiZrSn alloy"
Hidetoshi Miyazaki, Osman Murat Ozkendir, Selen Gunaydin, Kosuke Watanabe, Kazuo Soda
and Yoichi Nishino
Sci Rep, 10(1), 19820 (2020)25. "Conformation of K+(Crown Ether) Complexes Revealed by Ion Mobility–Mass Spectrometry andUltraviolet Spectroscopy"
Sota Tainaka, Tomoyuki Ujihira, Mayuko Kubo, Motoki Kida, Daisuke Shimoyama, Satoru
Muramatsu, Manabu Abe, Takeharu Haino, Takayuki Ebata, Fuminori Misaizu, Keijiro Ohshimo
and Yoshiya Inokuchi
J. Phys. Chem. A, 124(48), 9980-9990 (2020)- 523 -

26. "Robust folding of a de novo designed ideal protein even with most of the core mutated to valine"
Rie Koga, Mami Yamamoto, Takahiro Kosugi, Naohiro Kobayashi, Toshihiko Sugiki, Toshimichi
Fujiwara and Nobuyasu Koga
Proc Natl Acad Sci USA, 117(49), 31149-31156 (2020)27. "Investigation of Intramolecular Proton Transfer in Ionic States of o-Hydroxybenzaldehyde
Derivatives by Using Electron Spin Resonance Spectroscopy and Computational Chemistry"
Yoshikazu Shinde, Shutaro YAMAMOTO, Kazuo Mukai and Shin-ichi Nagaoka
Chem. Lett., 49(11), 1399-1402 (2020)28. "Substitution of O with a Single Au Atom as an Electron Acceptor in Al Oxide Clusters"
Fumitaka Mafuné, Xinan Liu, Yufei Zhang and Satoshi Kudoh
J. Phys. Chem. A, 124(37), 7511-7517 (2020)29. "Protonation structure of the photosynthetic water oxidizing complex in the S0 state as revealed
by normal mode analysis using quantum mechanics/molecular mechanics calculations"
Masao Yamamoto, Shin Nakamura and Takumi Noguchi
Phys. Chem. Chem. Phys., 22(42), 24213-24225 (2020)30. "HOMO–LUMO Energy-*DS 7XQLQJ RI ʌ-Conjugated Zwitterions Composed of ElectronDonating Anion and Electron-Accepting Cation"
Akihiro Shimizu, Yu Ishizaki, Shun Horiuchi, Takashi Hirose, Kenji Matsuda, Hiroyasu Sato and
Jun-ichi Yoshida
J. Org. Chem., 86(1), 770-781 (2021)
31. "Computational discovery of stable phases of graphene and h-BN van der Waals heterostructures
composed of group III–V binary compounds"
Toru Akiyama, Takahiro Kawamura and Tomonori Ito
Appl. Phys. Lett., 118(2), 023101 (2021)
32. "Theoretical insights into the DNA repair function of Arabidopsis thaliana cryptochrome-DASH"
Ryuma Sato, Yoshiharu Mori, Risa Matsui, Noriaki Okimoto, Junpei Yamamoto and Makoto Taiji
BIOPHYSICS, 17, 113-124 (2020)33. "Enhanced DNA repair by DNA photolyase bearing an artificial light-harvesting chromophore"
Yuma Terai, Ryuma Sato, Risa Matsumura, Shigenori Iwai and Junpei Yamamoto
Nucleic Acids Research, 48(18), 10076-10086 (2020)34. "Self-$VVRFLDWLQJ&XUYHGʌ-Electronic Systems with Electron-Donating and Hydrogen-Bonding
Properties"
Yohei Haketa, Mika Miyasue, Yoichi Kobayashi, Ryuma Sato, Yasuteru Shigeta, Nobuhiro
Yasuda, Naoto Tamai and Hiromitsu Maeda
J. Am. Chem. Soc., 142(38), 16420-16428 (2020)35. "Design and mechanical properties of supramolecular polymeric materials based on host–guest
interactions: the relation between relaxation time and fracture energy"
Subaru Konishi, Yu Kashiwagi, Go Watanabe, Motofumi Osaki, Takuya Katashima, Osamu
Urakawa, Tadashi Inoue, Hiroyasu Yamaguchi, Akira Harada and Yoshinori Takashima- 524 -

Polym. Chem., 11(42), 6811-6820 (2020)36. "Conformation-&KDQJHDEOHʌ-Electronic Systems with Metastable Bent-Core Conformations andLiquid-Crystalline-State Electric-Field-Responsive Properties"
Kazuto Nakamura, Shinya Sugiura, Fumito Araoka, Satoshi Aya, Yoichi Takanishi, Go Watanabe,
Ryuma Sato, Yasuteru Shigeta and Hiromitsu Maeda
Org. Lett., 23(2), 305-310 (2021)
37. "Visualizing the helical stacking of octahedral metallomesogens with a chiral core"
Go Watanabe, Hideyo Watanabe, Kota Suzuki, Hidetaka Yuge, Shintaro Yoshida, Takuyoshi
Mandai, Shigetaka Yoneda, Hisako Sato, Mitsuo Hara and Jun Yoshida
Chem. Commun., 56(81), 12134-12137 (2020)38. "Biomolecular Binding at Aqueous Interfaces of Langmuir Monolayers of BioconjugatedAmphiphilic Mesogenic Molecules: A Molecular Dynamics Study"
Go Watanabe, Hiroki Eimura, Nicholas L. Abbott and Takashi Kato
Langmuir, 36(41), 12281-12287 (2020)39. "Activity correlation among singlet-oxygen quenching, free-radical scavenging and excited-state
proton-transfer in hydroxyflavones: Substituent and solvent effects"
Shin-ichi Nagaoka, Yuki Bandoh, Satoki Matsuhiroya, Kazumasa Inoue, Umpei Nagashima andKeishi Ohara
Journal of Photochemistry and Photobiology A: Chemistry, 409, 113122 (2021)
40. "Higher-order structure of polymer melt described by persistent homology"
Yohei Shimizu, Takanori Kurokawa, Hirokazu Arai and Hitoshi Washizu
Sci Rep, 11(1), 2274 (2021)
41. "Enhancement of the carbamate activation rate enabled syntheses of tetracyclic benzolactams: 8oxoberbines and their 5- and 7-membered C-ring homologues"
Hiroaki Kurouchi
Org. Biomol. Chem., 19(3), 653-658 (2020)42. "Photostimulated desorption of OH radicals from amorphous solid water: Evidence for theinteraction of visible light with an OH-ice complex"
A. Miyazaki, N. Watanabe, W. M. C. Sameera, Y. Nakai, M. Tsuge, T. Hama, H. Hidaka and A.
KouchiPhys. Rev. A, 102(5), 052822 (2020)43. "Palladium-Catalyzed Regioselective and Stereospecific Ring-Opening Cross-Coupling of
Aziridines: Experimental and Computational Studies"
Youhei Takeda, W. M. C. Sameera and Satoshi Minakata
Acc. Chem. Res., 53(8), 1686-1702 (2020)44. "CH3O Radical Binding on Hexagonal Water Ice and Amorphous Solid Water"
W. M. C. Sameera, Bethmini Senevirathne, Stefan Andersson, Muhsen Al-lbadi, Hiroshi Hidaka,
Akira Kouchi, Gunnar Nyman and Naoki Watanabe
J. Phys. Chem. A, 125(1), 387-393 (2021)- 525 -

45. "Reaction of NO molecule at 4H-SiC/SiO2 interface: an ab initio study for the effect of NO
annealing after dry oxidation"
Tsunashi Shimizu, Toru Akiyama, Kohji Nakamura, Tomonori Ito, Hiroyuki Kageshima, Masashi
Uematsu and Kenji Shiraishi
Jpn. J. Appl. Phys., 60(SB), SBBD10 (2021)
46. 6\QWKHVLVRI$QWKUDFHQHဨ%DVHG&\FOLFʌဨ&OXVWHUVDQG(OXFLGDWLRQRIWKHLU3URSHUWLHV2ULJLQDWLng
from Congested Aromatic Planes"
Tomohiko Nishiuchi, Kazuki Kisaka and Takashi Kubo
Angew. Chem. Int. Ed., 60(10), 5400-5406 (2021)
47. "Evaluation of Artificial Crystalline Structure from Amylose Analog Polysaccharide without
Hydroxy Groups at C-2 Position"
Takuya Uto, Shota Nakamura, Kazuya Yamamoto and Jun-ichi Kadokawa
Carbohydr. Polym., 240, 116347 (2020)
48. "Non-aqueous, Zwitterionic Solvent as an Alternative for Dimethyl Sulfoxide in the Life Sciences"
Kosuke Kuroda, Tetsuo Komori, Kojiro Ishibashi, Takuya Uto, Isao Kobayashi, Riki Kadokawa,
Yui Kato, Kazuaki Ninomiya, Kenji Takahashi and Eishu Hirata
Commun. Chem., 3(1), 163 (2020)49. "Nanocellulose Enriches Enantiomers in Asymmetric Aldol Reactions"
Naliharifetra Jessica Ranaivoarimanana, Xin Habaki, Takuya Uto, Kyohei Kanomata, Toshifumi
Yui and Takuya Kitaoka
RSC Adv., 10(61), 37064-37071 (2020)
50. "Molecular Dynamics Simulation of Cellulose Synthase Subunit D Octamer with Cellulose Chainsfrom Acetic Acid Bacteria: Insight into Dynamic Behaviors and Thermodynamics on Substrate
Recognition"
Takuya Uto, Yuki Ikeda, Naoki Sunagawa, Kenji Tajima, Min Yao and Toshifumi Yui
J. Chem. Theory Comput., 17(1), 488-496 (2021)
51. "Thermal Molecular Motion Can Amplify Intermolecular Magnetic Interactions"
Yoshiaki Uchida, Go Watanabe, Takuya Akita and Norikazu Nishiyama
J. Phys. Chem. B, 124(28), 6175-6180 (2020)52. "Ion conductive properties in ionic liquid crystalline phases confined in a porous membrane"
Y. Uchida, T. Matsumoto, T. Akita and N. Nishiyama
J. Mater. Chem. C, 3(24), 6144-6147 (2015)
53. "Terminal Fluorinated Nitroxide Radical Liquid Crystalline Compounds"
Takuya Akita, Yoshiaki Uchida and Norikazu Nishiyama
Molecular Crystals and Liquid Crystals, 613(1), 174-180 (2015)
54. "Size Control of Cholesteric Liquid Crystalline Microcapsules"
Yoshiaki Uchida, Yosuke Iwai, Takuya Akita, Kaho Yamamoto and Norikazu Nishiyama
Molecular Crystals and Liquid Crystals, 613(1), 82-87 (2015)
55. "Effects of Linking Group on Liquid Crystallinity of Nitroxide Radical Compounds"- 526 -

Takuya Akita, Yoshiaki Uchida and Norikazu Nishiyama
Chem. Lett., 45(8), 910-912 (2016)56. "Finite-difference time-domain analysis of light propagation in cholesteric liquid crystalline
droplet array"
Kaho Yamamoto, Yosuke Iwai, Yoshiaki Uchida and Norikazu Nishiyama
Jpn. J. Appl. Phys., 55(8), 082001 (2016)
57. "Large negative magneto-LC effects induced by racemic dimerization of liquid crystalline
nitroxide radicals with a terminal cyano group"
Takuya Akita, Daichi Kiyohara, Taira Yamazaki, Yoshiaki Uchida and Norikazu Nishiyama
J. Mater. Chem. C, 5(47), 12457-12465 (2017)58. "Magnetic properties of terminal iodinated nitroxide radical liquid crystals"
Takuya Akita, Taira Yamazaki, Yoshiaki Uchida and Norikazu Nishiyama
Polyhedron, 136, 79-86 (2017)59. "Unique Superparamagnetic-like Behavior Observed in Non-ʌ-delocalized Nitroxide Diradical
Compounds Showing Discotic Liquid Crystalline Phase"
Yusa Takemoto, Elena Zaytseva, Katsuaki Suzuki, Naoki Yoshioka, Yoichi Takanishi, Masahiro
Funahashi, Yoshiaki Uchida, Takuya Akita, Jayeong Park, Shuichi Sato, Simon Clevers, Gérard
Coquerel, Dmitrii G. Mazhukin, Satoshi Shimono, Masahito Sugiyama, Hiroki Takahashi, Jun
Yamauchi and Rui Tamura
Chem. Eur. J., 24(65), 17293-17302 (2018)60. "Alkali and Alkaline Earth Metal Ions Complexes with a Partial Peptide of the Selectivity Filter
in K + Channels Studied by a Cold Ion Trap Infrared Spectroscopy"
5HPLQD 2WVXND .HLVXNH +LUDWD <XWD 6DVDNL -DPHV 0 /LV\ 6KXQဨLFKL ,VKLXFKL DQG 0DVDDNL
Fujii
ChemPhysChem, 21(8), 712-724 (2020)61. "Chiral discrimination betZHHQW\URVLQHDQGȕ-cyclodextrin revealed by cryogenic ion trap infrared
spectroscopy"
Keisuke Hirata, Yuta Mori, Shun-ichi Ishiuchi, Masaaki Fujii and Anne Zehnacker
Phys. Chem. Chem. Phys., 22(43), 24887-24894 (2020)62. "Rethinking Ion Transport by Ionophores: Experimental and Computational Investigation ofSingle Water Hydration in Valinomycin-K+ Complexes"
Eiko Sato, Keisuke Hirata, James M. Lisy, Shun-ichi Ishiuchi and Masaaki Fujii
J. Phys. Chem. Lett., 12(6), 1754-1758 (2021)
63. "Structural elucidation of a methylenation reagent of esters: synthesis and reactivity of a dinuclear
titanium(iii) methylene complex"
Takashi Kurogi, Kaito Kuroki, Shunsuke Moritani and Kazuhiko Takai
Chem. Sci., 12(10), 3509-3515 (2021)
64. "Conductance selectivity of Na+ across the K+ channel via Na+ trapped in a tortuous trajectory"
Kenichiro Mita, Takashi Sumikama, Masayuki Iwamoto, Yuka Matsuki, Kenji Shigemi and- 527 -

Shigetoshi Oiki
Proc Natl Acad Sci USA, 118(12), e2017168118 (2021)
65. 0HWDO&RPSOH[HVRIဨ3RUSK\ULQTXLQRQHV6\VWHPDWic Study of Crystal Structure, Electronic
Structure, and Lewis Acidity".HQဨLFKL<DPDVKLWD'DLVXNH+LUDQRDQG.HQဨLFKL6XJLXUD
Eur. J. Inorg. Chem., 2020(36), 3507-3516 (2020)66. 6\QWKHVLVRI3RUSK\ULQTXLQRQHDQG'RXEO\ဨ)XVHG'LSRUSK\ULQ4XLQRQH7KURXJK2[Ldation of
Diarylporphyrins Using a Hypervalent Iodine Compound".HQဨLFKL<DPDVKLWD'DLVXNH+LUDQR.HLVXNH)XMLPDNLDQG.HQဨLFKL6XJLXUD
Chem. Asian J., 15(19), 3037-3043 (2020)67. "Structure dependency of the reactivity of aromatic hydrocarbons involving the formation ofoxygenated polycyclic aromatic hydrocarbons (OPAHs)"
Megumi Kayanuma, Shunsuke Suzuki, Yoong-Kee Choe and Yukihiro Shimoi
Chemical Physics Letters, 754, 137652 (2020)
68. "A quantum chemical study of excited states and thermally activated delayed fluorescence intetracyanoquinodimethane"
Toshifumi Iimori
Computational and Theoretical Chemistry, 1199, 113211 (2021)
69. "Bright Solvent-Free Luminescent Liquid with Magnetism Composed of a Thiocyanate Complex
of Ce(III)"
Toshifumi Iimori, Hiroto Sugawa and Nobuya Uchida
J. Phys. Chem. B, 124(38), 8317-8322 (2020)70. &DOFXODWLRQVWXG\RQFRPSOH[IRUPDWLRQRIFDWHFKLQVZLWKȕ-cyclodextrin using density function
theory"Hirohito Ikeda, Tomonori Ohata, Miho Yukawa, Hiroyuki Tsutsumi, Masao Fujisawa and
Hatshumi Aki
Journal of Inclusion Phenomena and Macrocyclic Chemistry (2021)
71. "Structure–property relationship in contrasting aggregation-induced enhancement/quenching ofemission in rigid aromatic molecules"
Yosuke Tani and Takuji Ogawa
J. Mater. Chem. C, 9(12), 4281-4288 (2021)
72. "Application of an Augmentation Method to MCR-ALS Analysis for XAFS and Raman Data
Matrices in the Structural Change of Isopolymolybdates"
Morihisa Saeki, Takumi YOMOGIDA, Daiju MATSUMURA, Takumi SAITO, Ryuzo Nakanishi,
Takuya TSUJI and Hironori Ohba
Anal. Sci., 36(11), 1371-1378 (2020)73. 3DOODGLXPဨ&DWDO\]HG5HJLRVHOHFWLYHDQG6WHUHRVSHFLILF5LQJဨ2SHQLQJ6X]XNLဨ0L\DXUD$U\ODWLYH&URVVဨ&RXSOLQJRIဨ$U\OD]HWLGLQHVZLWK$U\OERURQLF$FLGVYouhei Takeda, Kazuya Toyoda, W. M. C. Sameera, Norimitsu Tohnai and Satoshi Minakata- 528 -

Adv. Synth. Catal., , adsc.202100195 (2021)
74. "The well-established relation r0 > re holds always?"
Tsuneo Hirano, Umpei Nagashima and Masaaki Baba
Journal of Molecular Structure, 1229, 128637 (2020)75. "Synthesis, Structure, and &RPSOH[DWLRQ RI DQ 6ဨ6KDSHG 'RXEOH $]DKHOLFHQH ZLWK ,QQHUဨ(GJH
Nitrogen Atoms"
Takahiro Kawashima, Yuki Matsumoto, Takuma Sato, Yoichi M. A. Yamada, Choji Kono,
Akihiro Tsurusaki and Ken Kamikawa
Chem. Eur. J., 26(58), 13170-13176 (2020)76. *ROG , ဨ&DWDO\]HG ,QWUDPROHFXODU+\GURDU\ODWLRQRIRဨ(WK\Q\ODU\OSKRVSKRQLXP6DOW/HDGLQJWR
WKH)RUPDWLRQRI6HYHQဨDQG6L[ဨPHPEHUHG3KRVSKDF\FOHV
Akihiro Tsurusaki, Hiroki Shimatani and Ken Kamikawa
Asian J. Org. Chem., 10(1), 154-159 (2020)
77. "Single-molecule junctions of multinuclear organometallic wires: long-range carrier transport
brought about by metal–metal interaction"
Yuya Tanaka, Yuya Kato, Kaho Sugimoto, Reo Kawano, Tomofumi Tada, Shintaro Fujii, Manabu
Kiguchi and Munetaka Akita
Chem. Sci., 12(12), 4338-4344 (2021)
78. "Dimesitylborylethynylated Arenes: Unique Electronic and Photophysical Properties Caused by(WK\QHGL\O &Ł& 6SDFHUVKentaro Mishiba, Yuya Tanaka and Munetaka Akita
Chem. Eur. J., 27(17), 5432-5438 (2021)
79. "Single-Molecule Junction of a Cationic Rh(III) Polyyne Molecular Wire"
Yuya Tanaka, Kohei Ohmura, Shintaro Fujii, Tomofumi Tada, Manabu Kiguchi and Munetaka
Akita
Inorg. Chem., 59(18), 13254-13261 (2020)80. "Anisotropic Contraction of a Polyaromatic Capsule and Its Cavity-Induced Compression Effect"
Natsuki Kishida, Kyosuke Matsumoto, Yuya Tanaka, Munetaka Akita, Hidehiro Sakurai andMichito Yoshizawa
J. Am. Chem. Soc., , jacs.0c02932 (2020)81. 1ဨ'RSLQJRI3RO\DURPDWLF&DSVXOHV6PDOO&DYLW\0RGLILFDWLRQ/HDGVWR/DUJH&KDQJHLQ+RVW–
Guest Interactions"
Hiroki Dobashi, Lorenzo Catti, Yuya Tanaka, Munetaka Akita and Michito Yoshizawa
Angew. Chem. Int. Ed., 59(29), 11881-11885 (2020)82. "Energy transfer-driven regioselective synthesis of functionalized phenanthridines by visible-light
Ir photocatalysis"
Yuki Matsushita, Rika Ochi, Yuya Tanaka, Takashi Koike and Munetaka Akita
Org. Chem. Front., 7(10), 1243-1248 (2020)83. "Theoretical Study of NO Dissociative Adsorption onto 3d Metal Particles M55 (M = Fe, Co, Ni,- 529 -

and Cu): Relation between the Reactivity and Position of the Metal Element in the Periodic Table"
Nozomi Takagi, Masahiro Ehara and Shigeyoshi Sakaki
ACS Omega, 6(7), 4888-4898 (2021)
84. "Oxidation and Storage Mechanisms for Nitrogen Oxides on Variously Terminated (001) Surfacesof SrFeOíį and Sr3Fe2Oíį Perovskites"
Akihiko Takamatsu, Kazuki Tamai, Saburo Hosokawa, Tsunehiro Tanaka, Masahiro Ehara and
Ryoichi Fukuda
ACS Appl. Mater. Interfaces, 13(6), 7216-7226 (2021)
85. "Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal
Complexes (Cp)2TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C5H5,
C5(CH3)H4, C5(CH3)5; TM = Cr, Mo, W)"
Song Xu, Mengyang Li, Gerui Pei, Pei Zhao, Xintian Zhao, Guanchen Wu, Chuncai Kong,
Zhimao Yang, Masahiro Ehara and Tao Yang
J. Phys. Chem. A, 125(3), 721-730 (2021)
86. 6XEVWLWXWLRQ (IIHFW RQ WKH 1RQUDGLDWLYH 'HFD\ DQG WUDQV ĺ FLV 3KRWRLVRPHUL]DWLRQ URXWH $
Guideline to Develop Efficient Cinnamate Based Sunscreens"
Shin-nosuke Kinoshita, Yu Harabuchi, Yoshiya Inokuchi, Satoshi Maeda, Masahiro Ehara, Kaoru
Yamazaki and Takayuki Ebata
Phys. Chem. Chem. Phys., 23(2), 834-845 (2020)87. "Stabilities,

Electronic

Structures

andBonding

Properties

of

Iron

Complexes(E1E2)Fe(CO)2(CNArTripp2)2 (E1E2=BF, CO, N2, CN-, or NO+)"
Gerui Pei, Pei Zhao, Song Xu, Xintian Zhao, Chuncai Kong, Zhimao Yang, Masahiro Ehara and
Tao Yang
ChemistryOpen, 9(11), 1195-1201 (2020)88. "Theoretical Design of Photofunctional Molecular Aggregates for Optical Properties: An Inverse
Design Approach"Takafumi Shiraogawa and Masahiro Ehara
J. Phys. Chem. C, 124(24), 13329-13337 (2020)89. "Electronic structures and impurity segregation around extended defects in pentacene films: firstprinciples study"
Shunta Watanabe and Takashi Nakayama
Jpn. J. Appl. Phys., 60(SB), SBBG05-1-9 (2021)
90. "Effect of electron transfer on metal-atom penetration into SiO2 in electric field: first-principles
study"
Riki Nagasawa, Takuya Oikawa and Takashi Nakayama
Jpn. J. Appl. Phys., 60(3), 031005-1-8 (2021)
91. "Theoretical Insight into Oxidation Catalysis of Chromite Spinel MCr2O4 (M=Mg, Co, Cu, andZn): Volcano Plot for Oxygen-vacancy Formation and Catalytic Activity"
Peng Zhao, Masahiro Ehara, Atsushi Satsuma and Shigeyoshi Sakaki- 530 -

Journal of Catalysis, 393, 30-41 (2021)
92. "Circularly Polarized Luminescence Liquids Based on Siloxybinaphthyls: Best Binaphthyl
Dihedral Angle in the Excited State"
Kazuto Takaishi, Tomoki Matsumoto, Miyu Kawataka and Tadashi Ema
Angew. Chem. Int. Ed., 60(18), 9968-9972 (2021)
93. "Soft X-ray Absorption Spectroscopy for Observing Element-specific Intermolecular Interaction
in Solution Chemistry"
Masanari Nagasaka and Nobuhiro Kosugi
Chem. Lett., 50(5), 956-964 (2021)
94. "End-functionalization of dithiarubicene: modulation of optoelectronic properties by metalcatalyzed coupling reactions and device application"
Kenji Tsukamoto, Koji Takagi, Keitaro Yamamoto, Yutaka Ie and Takanori Fukushima
J. Mater. Chem. C (2021), https://doi.org/10.1039/D1TC01169C
95. "Highly Modified Lanostane Triterpenes from the Wood-Rot Basidiomycete Ganoderma colossus:
Comparative Chemical Investigations of Natural and Artificially Cultivated Fruiting Bodies andMycelial Cultures"
Masahiko Isaka, Panida Chinthanom, Rattaket Choeyklin, Tuksaporn Thummarukcharoen, Pranee
Rachtawee, Malipan Sappan, Kitlada Srichomthong, Ryoma Fujii, Kyohei Kawashima and Seiji
Mori
J. Nat. Prod., 83(7), 2066-2075 (2020)96. ,ULGLXPဨ&DWDO\]HG(QDQWLRVHOHFWLYH7UDQVIHU+\GURJHQDWLRQRI.HWRQHV&RQWUROOHGE\$OFRKRO+\GURJHQဨ%RQGLQJDQGVSဨ&í+1RQFRYDOHQW,QWHUDFWLRQV
Hiroaki Murayama, Yoshito Heike, Kosuke Higashida, Yohei Shimizu, Nuttapon Yodsin,
Yutthana Wongnongwa, Siriporn Jungsuttiwong, Seiji Mori and Masaya Sawamura
Adv. Synth. Catal., 362(21), 4655-4661 (2020)
97. "Inter- and Intramolecular Cycloaddition Reactions of Ethenetricarboxylates with Styrenes andHalostyrenes"
Shoko Yamazaki, Zhichao Wang, Kentaro Iwata, Khotaro Katayama, Hirotaka Sugiura, Yuji
Mikata, Tsumoru Morimoto and Akiya Ogawa
Synthesis, 53(04), 731-753 (2021)
98. "Conformer Separation of Dibenzo-Crown-Ether Complexes with Na+ and K+ Ions Studied by
Cryogenic Ion Mobility-Mass Spectrometry"
Keijiro Ohshimo, Xi He, Ryosuke Ito and Fuminori Misaizu
J. Phys. Chem. A, 125(17), 3718-3725 (2021)
99. &RPELQHG 0' DQG 4000 ,QYHVWLJDWLRQV RI +\GULGH 5HGXFWLRQ RI Į-Dihydrotestosterone
Catalyzed by HumaQ Į-Hydroxysteroid Dehydrogenase Type 3: Importance of NoncovalentInteractions"
Hiroaki Mitsuizumi and Seiji Mori
J. Phys. Chem. B, , acs.jpcb.1c01751 (2021)- 531 -

100."“Watching” a Molecular Twist in a Protein by Raman Optical Activity"
Junpei Matsuo, Takashi Kikukawa, Tomotsumi Fujisawa, Wouter D. Hoff and Masashi Unno
J. Phys. Chem. Lett., 11(20), 8579-8584 (2020)
101."Structural basis of the protochromic green/red photocycle of the chromatic acclimation sensor
RcaE"
Takayuki Nagae, Masashi Unno, Taiki Koizumi, Yohei Miyanoiri, Tomotsumi Fujisawa, Kento
Masui, Takanari Kamo, Kei Wada, Toshihiko Eki, Yutaka Ito, Yuu Hirose and Masaki Mishima
Proc Natl Acad Sci USA, 118(20), e2024583118 (2021)
102."pH dependence of aqueous oxalic acid observed by X-ray absorption and emission spectroscopy"
Ryosuke Yamamura, Taiga Suenaga, Masaki Oura, Takashi Tokushima and Osamu Takahashi
Chemical Physics Letters, 738, 136895 (2020)
103."Sub-molecular structural relaxation at a physisorbed interface with monolayer organic singlecrystal semiconductors"
Akifumi Yamamura, Hiromasa Fujii, Hirohito Ogasawara, Dennis Nordlund, Osamu Takahashi,
Yuutaro Kishi, Hiroyuki Ishii, Nobuhiko Kobayashi, Naoyuki Niitsu, Balthasar Blülle, Toshihiro
Okamoto, Yusuke Wakabayashi, Shun Watanabe and Jun Takeya
Commun Phys, 3(1), 20 (2020)
104."Site-specificity reduction during Auger decay following Si:2p photoionization in Cl3SiSi(CH3)3
vapor: An interatomic-Coulombic-decay-like process"Shin-ichi Nagaoka, Osamu Takahashi and Yasumasa Hikosaka
Chemical Physics, 534, 110756 (2020)
105."Soft X-UD\$EVRUSWLRQ6SHFWURVFRS\3UREHV2+āāāʌ,QWHUDFWLRQVLQ(SR[\-Based Polymers"
Hiroyuki Yamane, Masaki Oura, Osamu Takahashi, Paul Fons, Pradeep R. Varadwaj, Yukihiro
Shimoi, Masataka Ohkubo, Tetsuya ishikawa, Noriko Yamazaki, Koichi Hasegawa, Kiyoka
Takagi and Takaki Hatsui
J. Phys. Chem. C, 124(17), 9622-9627 (2020)
106."Photoemission from the gas phase using soft x-ray fs pulses: an investigation of the space-charge
effects"
Adriano Verna, Giovanni Stefani, Francesco Offi, Tatsuo Gejo, Yoshihito Tanaka, Kenta Tanaka,
Tatsuru Nishie, Kiyonobu Nagaya, Akinobu Niozu, Ryosuke Yamamura, Taiga Suenaga, Osamu
Takahashi, Hikaru Fujise, Tadashi Togashi, Makina Yabashi and Masaki Oura
New J. Phys., 22(12), 123029 (2020)
107."Backbone-Modified C2-Symmetrical Chiral Bisphosphine TMS-4XLQR[3  $V\PPHWULF
Borylation of Racemic Allyl Electrophiles"
Hiroaki Iwamoto, Yu Ozawa, Yuta Takenouchi, Tsuneo Imamoto and Hajime Ito
J. Am. Chem. Soc., 143(17), 6413-6422 (2021)
108."Photoluminescent properties and molecular structures of dinuclear gold(i) complexes withbridged diphosphine ligands: near-unity phosphorescence from 3XMMCT/3MC"
Masahisa Osawa, Sakie Soma, Mikio Hoshino, Yuya Tanaka and Munetaka Akita- 532 -

Dalton Trans., 49(43), 15204-15212 (2020)109.4XDQWXPFKHPLFDOFalculation studies toward microscopic understanding of retention mechanismof Cs radioisotopes and other alkali metals in lichens"
Hiroya Suno, Masahiko Machida, Terumi Dohi and Yoshihito Ohmura
Sci Rep, 11(1), 8228 (2021)
110."Path Ensembles for Pin1-Catalyzed Cis–Trans Isomerization of a Substrate Calculated by
Weighted Ensemble Simulations"
Kei Moritsugu, Norifumi Yamamoto, Yasushige Yonezawa, Shin-ichi Tate and Hiroshi Fujisaki
J. Chem. Theory Comput., 17(4), 2522-2529 (2021)
111."Dissecting the electric quadrupolar and polarization effects operating in halogen bonding throughelectron density analysis with a focus on bromine"
Kento Saito, Ryoma Izumi and Hajime Torii
J. Chem. Phys., 153(17), 174302 (2020)112."Role of Intermolecular Charge Fluxes in the Hydrogen-Bond-Induced Frequency Shifts of the
OH Stretching Mode of Water"
Hajime Torii and Ryota Ukawa
J. Phys. Chem. B, 125(5), 1468-1475 (2021)
113."Extending correlation functions of molecular dynamics simulation by Kovalenko–Hirata andKobryn–Gusarov–Kovalenko closures for monatomic Lennard-Jones solvent and its application
to a calculation of solvation"
Tatsuhiko Miyata, Shunsuke Nishida and Yu Ogasawara
AIP Advances, 11(2), 025026 (2021)
114."Transferability of Sigma Enlarging Bridge Function for Lennard-Jones Diatomic Solute Using
Monatomic Solvent Correlation Obtained from Molecular Dynamics Simulation"
Tatsuhiko Miyata, Naoya Yabuki and Jackie Leung
Chem. Lett., 49(11), 1372-1375 (2020)
115."Sigma enlarging bridge function for heteronuclear Lennard-Jones diatomic solute solvated in a
Lennard-Jones monatomic solvent in terms of the parameter transferability"
Tatsuhiko Miyata
Chemical Physics Letters, 755, 137777 (2020)
116."Structural characterization of cellulose nanofibers isolated from spent coffee grounds and theircomposite films with poly(vinyl alcohol): a new non-wood source"
Noriko Kanai, Takumi Honda, Naoki Yoshihara, Toshiyuki Oyama, Akira Naito, Kazuyoshi Ueda
and Izuru Kawamura
Cellulose, 27(9), 5017-5028 (0000)
117."Separation of D-amino acid-containing peptide phenylsHSWLQXVLQJƍ-phenyl-ƍ-binaphthyl18-crown-6-ether columns"
Izuru Kawamura, Batsaikhan Mijiddorj, Yohei Kayano, Yuta Matsuo, Yumi Ozawa, Kazuyoshi
Ueda and Hisako Sato

- 533 -

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics, 1868(8), 140429 (0000)
118."Stereochemical Effects on the Self-Assembly of Pyrenylalanine-Phenylalanine Dipeptide"
Batsaikhan Mijiddorj, Hiroki Shirakata, Tetsuya Nakagawa, Kazuyoshi Ueda, Yasushi Yokoyama
and Izuru Kawamura
BCSJ, 93(8), 969-977 (0000)
119."The [Ag25Cu4H8Br6(CCPh)12 33K @ௗௗ$J+ VLOYHU K\GULGH FRUH SURWHFWHG E\[CuAg3(CCPh)3(PPh3)3]+ motifs"
Kaiyu Mikami, Shen Hui, Kazuyuki Kubo, Shoko Kume and Tsutomu Mizuta
Dalton Trans., 50(16), 5659-5665 (2021)
120."Synthesis of silyl formates, formamides, and aldehydes via solvent-free organocatalytichydrosilylation of CO2"
Takumi Murata, Mahoko Hiyoshi, Manussada Ratanasak, Jun-ya Hasegawa and Tadashi Ema
Chem. Commun., 56(43), 5783-5786 (2020)
121."A quantum chemical study of substituent effects on CN bonds in aryl isocyanide molecules
adsorbed on the Pt surface"
Ben Wang, Min Gao, Kohei Uosaki and Tetsuya Taketsugu
Phys. Chem. Chem. Phys., 22(21), 12200-12208 (2020)
122."Electric Field Effect on Graphene/Organic Interface under Bias Voltage"
Kenji Iida
Chem. Lett., 49(10), 1117-1120 (2020)123."Zeolite-supported ultra-small nickel as catalyst for selective oxidation of methane to syngas"
Shuhei Yasuda, Ryota Osuga, Yusuke Kunitake, Kazuya Kato, Atsushi Fukuoka, Hirokazu
Kobayashi, Min Gao, Jun-ya Hasegawa, Ryo Manabe, Hisashi Shima, Susumu Tsutsuminai and
Toshiyuki Yokoi
Commun Chem, 3(1), 129 (2020)124."Extending nudged elastic band method to reaction pathways involving multiple spin states"
Liming Zhao, K-jiro Watanabe, Naoki Nakatani, Akira Nakayama, Xin Xu and Jun-ya Hasegawa
J. Chem. Phys., 153(13), 134114 (2020)
125."Mechanistic Study on Deoxydehydration and Hydrogenation of Methyl Glycosides to Dideoxy
Sugars over a ReOx–Pd/CeO2 Catalyst"
Ji Cao, Masazumi Tamura, Ryu Hosaka, Akira Nakayama, Jun-ya Hasegawa, Yoshinao Nakagawa
and Keiichi Tomishige
ACS Catal., 10(20), 12040-12051 (2020)
126."Catalytic Mechanism of Liquid-Metal Indium for Direct Dehydrogenative Conversion ofMethane to Higher Hydrocarbons"
Yuta Nishikawa, Yuhki Ohtsuka, Hitoshi Ogihara, Rattanawalee Rattanawan, Min Gao, Akira
Nakayama, Jun-ya Hasegawa and Ichiro Yamanaka
ACS Omega, 5(43), 28158-28167 (2020)
127."Chemoselective Transesterification of Methyl (Meth)acrylates Catalyzed by Sodium(I) or- 534 -

Magnesium(II) Aryloxides"-LH4L1J+LUR$ULPD7DNX\D0RFKL]XNL.RKHL7RK.DL0DWVXi, Manussada Ratanasak, Junya Hasegawa, Manabu Hatano and Kazuaki Ishihara
ACS Catal., 11(1), 199-207 (2021)
128."On the Electronic Structure Origin of Mechanochemically Induced Selectivity in Acid-Catalyzed
Chitin Hydrolysis"
Danjo De Chavez, Hirokazu Kobayashi, Atsushi Fukuoka and Jun-ya Hasegawa
J. Phys. Chem. A, 125(1), 187-197 (2021)
129."Mechanistic study of C–+ ERQG DFWLYDWLRQ E\ 2 RQ QHJDWLYHO\ FKDUJHG $X FOXVWHUV Įȕdehydrogenation of 1-methyl-4-piperidone by supported Au catalysts"
Ray Miyazaki, Xiongjie Jin, Daichi Yoshii, Takafumi Yatabe, Tomohiro Yabe, Noritaka Mizuno,
Kazuya Yamaguchi and Jun-ya Hasegawa
Catal. Sci. Technol. (2021), https://doi.org/10.1039/D1CY00178G
130."Design and prediction of high potent ansa-zirconocene catalyst for olefin polymerizations:
FRPELQHG')7FDOFXODWLRQVDQG4635DSSURDFKManussada Ratanasak, Jun-ya Hasegawa and Vudhichai Parasuk
New J. Chem., 45(18), 8248-8257 (2021)
131."A Triad Fluorenone Derivative Bearing Two Imidazole Groups That Switches between Three
States by Base and Acid Stimuli"
Yuting Wang, Nabin Maity, Liming Zhao, Maximilian Krämer, Jun-ya Hasegawa, Yukatsu
Shichibu, Katsuaki Konishi, Xiaoyuan Wang, Zhiyi Song, Masayoshi Bando and Tamaki Nakano
Chem. Lett., , cl.210112 (2021)
132."Synthesis, characterization and biological evaluation of dipicolylamine sulfonamide derivatized
platinum complexes as potential anticancer agents"
Nadini Thushara, Taniya Darshani, Sameera R. Samarakoon, Inoka C. Perera, Frank R. Fronczek,
W. M. C. Sameera and Theshini Perera
RSC Adv., 11(29), 17658-17668 (2021)
133."Theoretical Study on C Adsorbate at Graphene/Cu(111) or h-BN/Cu(111) Interfaces"
Hiroyuki Kageshima, Shengnan Wang and Hiroki Hibino
e-J. Surf. Sci. Nanotechnol., 18, 70-75 (2020)
134."Free energy profile analysis to identify factors activating the aggregation-induced emission of acyanostilbene derivative"
Norifumi Yamamoto
Phys. Chem. Chem. Phys., 23(2), 1317-1324 (2020)135.7DXWRPHULF(IIHFWRI+LVWLGLQHRQȕ-Sheet Formation of Amyloid Beta 1–40: 2D-IR Simulations"
Yeonsig Nam, Mahroof Kalathingal, Shinji Saito and Jin Yong Lee
Biophysical Journal, 119(4), 831-842 (2020)
136."An alternative interpretation of the slow KaiB-KaiC binding of the cyanobacterial clock proteins"
Shin-ichi Koda and Shinji Saito- 535 -

Sci Rep, 10(1), 10439 (2020)
137."Molecular Mechanism of Acceleration and Retardation of Collective Orientation Relaxation of
Water Molecules in Aqueous Solutions"
Norifumi Moritsugu, Takafumi Nara, Shin-ichi Koda, Keisuke Tominaga and Shinji Saito
J. Phys. Chem. B, 124(51), 11730-11737 (2020)
138."Effects of interfaces on structure and dynamics of water droplets on a graphene surface: A
molecular dynamics study"
Manish Maurya, Atanu K. Metya, Jayant K. Singh and Shinji Saito
J. Chem. Phys., 154(16), 164704 (2021)
139.4XDQWXP PHFKDQLFDOPROHFXODU PHFKDQLcal trajectory surface hopping molecular dynamics
simulation by spin-flip time-dependent density functional theory"
Noriyuki Minezawa and Takahito Nakajima
J. Chem. Phys., 152(2), 024119 (2020)
140."Electron dynamics method using a locally projected group diabatic Fock matrix for molecules
and aggregates"
Takehiro Yonehara and Takahito Nakajima
Chem. Phys., 528, 110508 (2020)141."Concerted Mechanism of Water Insertion and O2 Release during the S4 to S0 Transition of the
Oxygen-Evolving Complex in Photosystem II"
Mitsuo Shoji, Hiroshi Isobe, Yasuteru Shigeta, Takahito Nakajima and Kizashi Yamaguchi
J. Phys. Chem. B, 122(25), 6491-6502 (2018)142."Domain-based local pair natural orbital CCSD(T) calculations of fourteen different S2
intermediates for water oxidation in the Kok cycle of OEC of PSII. Re-visit to one LS-two HS
model for the S2 state"
K. Miyagawa, H. Isobe, T. Kawakami, M. Shoji, S. Yamanaka, M. Okumura, T. Nakajima and K.
Yamaguchi
Chem. Phys. Lett., 734, 136731 (2019)143."Domain-based local pair natural orbital CCSD(T) calculations of six different S1 structures ofoxygen evolving complex of photosystem II. Proposal of multi-intermediate models for the S1state"
K. Miyagawa, T. Kawakami, H. Isobe, M. Shoji, S. Yamanaka, K. Nakatani, M. Okumura, T.
Nakajima and K. Yamaguchi
Chem. Phys. Lett., 732, 136660 (2019)144."White matter microstructural alterations across four major psychiatric disorders: mega-analysis
study in 2937 individuals"
Daisuke Koshiyama, Masaki Fukunaga, Naohiro Okada, Kentaro Morita, Kiyotaka Nemoto, Kaori
Usui, Hidenaga Yamamori, Yuka Yasuda, Michiko Fujimoto, Noriko Kudo, Hirotsugu Azechi,
Yoshiyuki Watanabe, Naoki Hashimoto, Hisashi Narita, Ichiro Kusumi, Kazutaka Ohi, Takamitsu
Shimada, Yuzuru Kataoka, Maeri Yamamoto, Norio Ozaki, Go Okada, Yasumasa Okamoto,- 536 -

Kenichiro Harada, Koji Matsuo, Hidenori Yamasue, Osamu Abe, Ryuichiro Hashimoto, Tsutomu
Takahashi, Tomoki Hori, Masahito Nakataki, Toshiaki Onitsuka, Laurena Holleran, Neda
Jahanshad, Theo G. M. van Erp, Jessica Turner, Gary Donohoe, Paul M. Thompson, Kiyoto Kasai
and Ryota Hashimoto
Mol Psychiatry, 25(4), 883-895 (2020)
145."Association between the superior longitudinal fasciculus and perceptual organization andworking memory: A diffusion tensor imaging study"
Daisuke Koshiyama, Masaki Fukunaga, Naohiro Okada, Kentaro Morita, Kiyotaka Nemoto,
Fumio Yamashita, Hidenaga Yamamori, Yuka Yasuda, Junya Matsumoto, Michiko Fujimoto,
Noriko Kudo, Hirotsugu Azechi, Yoshiyuki Watanabe, Kiyoto Kasai and Ryota Hashimoto
Neuroscience Letters, 738, 135349 (2020)
146."1q21.1 distal copy number variants are associated with cerebral and cognitive alterations inhumans"Ida E. Sønderby, Dennis van der Meer, Clara Moreau, Tobias Kaufmann, G. Bragi Walters, Maria
Ellegaard, Abdel Abdellaoui, David Ames, Katrin Amunts, Micael Andersson, Nicola J.
Armstrong, Manon Bernard, Nicholas B. Blackburn, John Blangero, Dorret I. Boomsma, Henry
Brodaty, Rachel M. Brouwer, Robin Bülow, Rune Bøen, Wiepke Cahn, Vince D. Calhoun, Svenja
Caspers, Christopher R. K. Ching, Sven Cichon, Simone Ciufolini, Benedicto Crespo-Facorro,
Joanne E. Curran, Anders M. Dale, Shareefa Dalvie, Paola Dazzan, Eco J. C. de Geus, Greig I. de
Zubicaray, Sonja M. C. de Zwarte, Sylvane Desrivières, Joanne L. Doherty, Gary Donohoe,
Bogdan Draganski, Stefan Ehrlich, Else Eising, Thomas Espeseth, Kim Fejgin, Simon E. Fisher,
Tormod Fladby, Oleksandr Frei, Vincent Frouin, Masaki Fukunaga, Thomas Gareau, Tian Ge,
David C. Glahn, Hans J. Grabe, Nynke A. Groenewold, Ómar Gústafsson, Jan Haavik, Asta K.
Haberg, Jeremy Hall, Ryota Hashimoto, Jayne Y. Hehir-Kwa, Derrek P. Hibar, Manon H. J.
Hillegers, Per Hoffmann, Laurena Holleran, Avram J. Holmes, Georg Homuth, Jouke-Jan
Hottenga, Hilleke E. Hulshoff Pol, Masashi Ikeda, Neda Jahanshad, Christiane Jockwitz, Stefan
Johansson, Erik G. Jönsson, Niklas R. Jørgensen, Masataka Kikuchi, Emma E. M. Knowles,
Kuldeep Kumar, Stephanie Le Hellard, Costin Leu, David E. J. Linden, Jingyu Liu, Arvid
Lundervold, Astri Johansen Lundervold, Anne M. Maillard, Nicholas G. Martin, Sandra MartinBrevet, Karen A. Mather, Samuel R. Mathias, Katie L. McMahon, Allan F. McRae, Sarah E.
Medland, Andreas Meyer-Lindenberg, Torgeir Moberget, Claudia Modenato, Jennifer Monereo
Sánchez, Derek W. Morris, Thomas W. Mühleisen, Robin M. Murray, Jacob Nielsen, Jan E.
Nordvik, Lars Nyberg, Loes M. Olde Loohuis, Roel A. Ophoff, Michael J. Owen, Tomáš Paus,=GHQND 3DXVRYD -XDQ 0 3HUDOWD * %UXFH 3LNH &DUORV 3ULHWR (ULQ % 4XLQODQ &pOLQH 6
Reinbold, Tiago Reis Marques, James J. H. Rucker, Perminder S. Sachdev, Sigrid B. Sando, Peter
R. Schofield, Andrew J. Schork, Gunter Schumann, Jean Shin, Elena Shumskaya, Ana I. Silva,
Sanjay M. Sisodiya, Vidar M. Steen, Dan J. Stein, Lachlan T. Strike, Ikuo K. Suzuki, Christian K.
Tamnes, Alexander Teumer, Anbupalam Thalamuthu, Diana Tordesillas-Gutiérrez, Anne
Uhlmann, Magnus O. Ulfarsson, Dennis van ‘t Ent, Marianne B. M. van den Bree, Pierre- 537 -

Vanderhaeghen, Evangelos Vassos, Wei Wen, Katharina Wittfeld, Margaret J. Wright, Ingrid
Agartz, Srdjan Djurovic, Lars T. Westlye, Hreinn Stefansson, Kari Stefansson, Sébastien
Jacquemont, Paul M. Thompson and Ole A. Andreassen
Transl Psychiatry, 11(1), 182 (2021)
147."Promoter Activity-Based Case-Control Association Study on SLC6A4 Highlighting
Hypermethylation and Altered Amygdala Volume in Male Patients With Schizophrenia"
Tempei Ikegame, Miki Bundo, Naohiro Okada, Yui Murata, Shinsuke Koike, Hiroko Sugawara,
Takeo Saito, Masashi Ikeda, Keiho Owada, Masaki Fukunaga, Fumio Yamashita, Daisuke
Koshiyama, Tatsunobu Natsubori, Norichika Iwashiro, Tatsuro Asai, Akane Yoshikawa,
Fumichika Nishimura, Yoshiya Kawamura, Jun Ishigooka, Chihiro Kakiuchi, Tsukasa Sasaki,
Osamu Abe, Ryota Hashimoto, Nakao Iwata, Hidenori Yamasue, Tadafumi Kato, Kiyoto Kasai
and Kazuya Iwamoto
Schizophr Bull., 46(6), 1577-1586 (2020)
148."Post-lithium-ion batteries: characterization of phosphorous and tin for potassium-ion anodes"
Saeid Arabnejad, Megumi Kojima and Koichi Yamashita
J. Mater. Sci., 56(18), 10926-10937 (2021)
149."A trinuclear chromium(iii) chlorocarbyne"
Takashi Kurogi, Keiichi Irifune, Takahiro Enoki and Kazuhiko Takai
Chem. Commun., 57, 5199-5202 (2021)
150."Dopant arrangements in Y-doped BaZrO3 under processing conditions and their impact on proton
conduction: a large-scale first-principles thermodynamics study"
Shusuke Kasamatsu, Osamu Sugino, Takafumi Ogawa and Akihide KuwabaraJ. Mater. Chem. A, 8(25), 12674-12686 (2020)
151."Position-Dependent Diffusion Constant of Molecules in Heterogeneous Systems as Evaluated by
the Local Mean Squared Displacement"
Tetsuro Nagai, Shuhei Tsurumaki, Ryo Urano, Kazushi Fujimoto, Wataru Shinoda and Susumu
OkazakiJ. Chem. Theory Comput., 16(12), 7239-7254 (2020)
152."Algorithm to minimize MPI communications in the parallelized fast multipole method combinedwith molecular dynamics calculations"<RVKLPLFKL$QGRK6KLQဨLFKL,FKLNDZD7DWVX\D6DNDVKLWD1RUL\XNL<RVKLLDQG6XVXPX2ND]DNL
J Comput Chem, 42(15), 1073-1087 (2021)
153."Study on the free corrosion potential at an interface between an Al electrode and an acidic
aqueous NaCl solution through density functional theory combined with the reference interaction
site model"
Koichi Kano, Satoshi Hagiwara, Takahiro Igarashi and Minoru Otani
Electrochimica Acta, 377, 138121 (2021)
154."Synthesis and Determination of Absolute Configuration of Zealexin A1, a Sesquiterpenoid
Phytoalexin from Zea mays"- 538 -

Arata Yajima, Mikaho Shimura, Tatsuo Saito, Ryo Katsuta, Ken Ishigami, Alisa Huffaker andEric A. Schmelz
Eur. J. Org. Chem., 2021(7), 1174-1178 (2021)
155."Domain-based local pair natural orbital CCSD(T) calculations of strongly correlated electron
systems: Examination of dynamic equilibrium models based on multiple intermediates in S1 stateof photosystem II"
K. Miyagawa, T. Kawakami, Y. Suzuki, H. Isobe, M. Shoji, S. Yamanaka, M. Okumura, T.
Nakajima and K. Yamaguchi
Mol. Phys., 118(12), e1666171 (2020)
156."Identification of hydrogen species on Pt/Al2O3 by in situ inelastic neutron scattering and theirreactivity with ethylene"
Seiji Yamazoe, Akira Yamamoto, Saburo Hosokawa, Ryoichi Fukuda, Kenji Hara, Mitsutaka
Nakamura, Kazuya Kamazawa, Tatsuya Tsukuda, Hisao Yoshida and Tsunehiro Tanaka
Catal. Sci. Technol., 11(1), 116-123 (2020)
157."Oxidation and Storage Mechanisms for Nitrogen Oxides on Variously Terminated (001) Surfaces
RI6U)H2íįDQG6U)H2íį3HURYVNLWHV"
Akihiko Takamatsu, Kazuki Tamai, Saburo Hosokawa, Tsunehiro Tanaka, Masahiro Ehara and
Ryoichi Fukuda
ACS Appl. Mater. Interfaces, 13(6), 7216-7226 (2021)
158."Determining if Reaction Selectivity Can Be Controlled by the H/D Isotope Effect in CH···O
Interactions"
Haruki Funahashi, Masanori Tachikawa and Taro Udagawa
Org. Lett., 22(24), 9439-9443 (2020)
159.3DOODGLXP&RSSHUဨFDWDO\]HG2[LGDWLRQRI$OLSKDWLF7HUPLQDO$ONHQHVWR$OGHK\GHV$VVLVWHGE\Sဨ%HQ]RTXLQRQH
Saki Komori, Yoshiko Yamaguchi, Yuka Murakami, Yasutaka Kataoka and Yasuyuki Ura
ChemCatChem, 12(15), 3946-3955 (2020)
160."Chiral Octapalladium Chains Supported by Enantiopure P-Stereogenic Linear Tetraphosphines,(R,R)- and (S,S)-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2"
Tomoaki Tanase, Kanako Nakamae, Suzui Hayashi, Ayumi Okue, Risa Otaki, Tomoko Nishida,
Yasuyuki Ura, Yasutaka Kitagawa and Takayuki Nakajima
Inorg. Chem., 60(5), 3259-3273 (2021)
161."Tetranuclear Rh4 chains supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm)
capturing H2 to afford Rh4H3 hydride complexes"
Tomoaki Tanase, Yuka Morita, Kazuki Sato, Risa Aoki, Akiko Yoshii, Kanako Nakamae,
Yasuyuki Ura and Takayuki Nakajima
J. Organomet. Chem., 939, 121771 (2021)
162."Tetranuclear zigzag Ag4 and Ag2Pt2 complexes supported by racPh2PCH2P(Ph)CH2P(Ph)CH2PPh2 (rac-dpmppm)"- 539 -

Tomoaki Tanase, Risa Otaki, Kanako Nakamae, Yasuyuki Ura and Takayuki Nakajima
J. Organomet. Chem., 925, 121488 (2020)
163."pSPICA: A Coarse-Grained Force Field for Lipid Membranes Based on a Polar Water Model"
Yusuke Miyazaki, Susumu Okazaki and Wataru Shinoda
J. Chem. Theory Comput., 16(1), 782-793 (2020)
164.(IIHFWRIWKH3DFNLQJ'HQVLW\RQWKH6XUIDFH+\GURSKRELFLW\RIȦ-)XQFWLRQDOL]HG í&)í&+í2&+DQGí2+ 6HOI-Assembled Monolayers: A Molecular Dynamics Study"
Hari O. S. Yadav, An-Tsung Kuo, Shingo Urata and Wataru Shinoda
J. Phys. Chem. C, 124(26), 14237-14244 (2020)
165."Pivotal Role of Interdigitation in Interleaflet Interactions: Implications from Molecular Dynamics
Simulations"
Sangjae Seo, Michio Murata and Wataru Shinoda
J. Phys. Chem. Lett., 11(13), 5171-5176 (2020)
166."Exact long-range Coulombic energy calculation for net charged systems neutralized by uniformly
distributed background charge using fast multipole method and its application to efficient freeenergy calculation"
Ryo Urano, Wataru Shinoda, Noriyuki Yoshii and Susumu Okazaki
J. Chem. Phys., 152(24), 244115 (2020)
167."Conformation and Orientation of Branched Acyl Chains Responsible for the Physical Stability ofDiphytanoylphosphatidylcholine"
Hiroshi Tsuchikawa, Takuya Ono, Masaki Yamagami, Yuichi Umegawa, Wataru Shinoda andMichio Murata
Biochemistry, 59(40), 3929-3938 (2020)
168."Position-Dependent Diffusion Constant of Molecules in Heterogeneous Systems as Evaluated by
the Local Mean Squared Displacement"
Tetsuro Nagai, Shuhei Tsurumaki, Ryo Urano, Kazushi Fujimoto, Wataru Shinoda and Susumu
OkazakiJ. Chem. Theory Comput., 16(12), 7239-7254 (2020)
169."Chain-End Modification: A Starting Point for Controlling Polymer Crystal Nucleation"
Kyle Wm. Hall, Simona Percec, Wataru Shinoda and Michael L. Klein
Macromolecules, 54(4), 1599-1610 (2021)
170."Property Decoupling across the Embryonic Nucleus–Melt Interface during Polymer Crystal
Nucleation"
Kyle Wm. Hall, Simona Percec, Wataru Shinoda and Michael L. Klein
J. Phys. Chem. B, 124(23), 4793-4804 (2020)
171."Molecular simulation of the shape deformation of a polymersome"Kaushik Chakraborty, Wataru Shinoda and Sharon M. Loverde
Soft Matter, 16(13), 3234-3244 (2020)172."Monodisperse Polymer Melts Crystallize via Structurally Polydisperse Nanoscale Clusters:- 540 -

Insights from Polyethylene"
Kyle Wm. Hall, Timothy W. Sirk, Simona Percec, Michael L. Klein and Wataru Shinoda
Polymers, 12(2), 447 (2020)
173."Seipin accumulates and traps diacylglycerols and triglycerides in its ring-like structure"
Valeria Zoni, Rasha Khaddaj, Ivan Lukmantara, Wataru Shinoda, Hongyuan Yang, Roger
Schneiter and Stefano Vanni
Proc Natl Acad Sci USA, 118(10), e2017205118 (2021)
174."Hemimicelle formation of semi-fluorocarbon chains at air–water interface: coarse-grained
molecular dynamics study with an extension of the SPICA force field"
Hari O. S. Yadav, Shogo Harada, An-Tsung Kuo, Shingo Urata and Wataru Shinoda
Molecular Physics, , e1910355 (2021)
175."Analyzing the Role of Surfactants in the Colloidal Stability of Nanoparticles in Oil throughCoarse-Grained Molecular Dynamics Simulations"Mark Z. Griffiths and Wataru Shinoda
J. Phys. Chem. B, , acs.jpcb.1c01148 (2021)
176."Understanding the scaling of boson peak through insensitivity of elastic heterogeneity to bending
rigidity in polymer glasses"
Naoya Tomoshige, Shota Goto, Hideyuki Mizuno, Tatsuya Mori, Kang Kim and Nobuyuki
MATUBAYASIJ. Phys.: Condens. Matter, 33(27), 274002 (2021)
177."Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus-Boron Bonded
Compounds"
Nathan J. O'Brien, Naokazu Kano, Nizam Havare, Ryohei Uematsu, Romain Ramozzi and Keiji
Morokuma
Eur. J. Inorg. Chem., 2020(20), 1995-2003 (2020)
178."Arylation of aryllithiums with S-arylphenothiazinium ions for biaryl synthesis"
Tatsuya Morofuji, Tatsuki Yoshida, Ryosuke Tsutsumi, Masahiro Yamanaka and Naokazu Kano
Chem. Commun., 56(90), 13995-13998 (2020)
179."Terminal-oxidant-free photocatalytic C–H alkylations of heteroarenes with alkylsilicates as alkyl
radical precursors"
Gun Ikarashi, Tatsuya Morofuji and Naokazu Kano
Chem. Commun., 56(69), 10006-10009 (2020)
180."Synthesis, structure and properties of a boron-substituted phosphorane bearing N,O-bidentate
ligands"
Nathan J. O'Brien, Yoichiro Koda, Hiroaki Maeda and Naokazu Kano
Polyhedron, 192, 114841 (2020)
181.3KRWRFDWDO\WLF*LHVHဨ7\SH5HDFWLRQZLWK$ON\OVLOLFDWHV%HDULQJ&2ဨ%LGHQWDWH/LJDQGV
Tatsuya Morofuji, Yu Matsui, Misa Ohno, Gun Ikarashi and Naokazu Kano
Chem. Eur. J., 27(22), 6713-6718 (2021)- 541 -

182."Negatively Curved Nanographene with Heptagonal and [5]Helicene Units"=LMLH4LX6REL$VDNR<XQELQ+X&KHQJ-Wei Ju, Thomas Liu, Loïc Rondin, Dieter Schollmeyer,
Jean-Sébastien Lauret, Klaus Müllen and Akimitsu Narita
J. Am. Chem. Soc., 142(35), 14814-14819 (2020)
183."PyDISH: database and analysis tools for heme porphyrin distortion in heme proteins"
Hiroko X Kondo, Yusuke Kanematsu, Gen Masumoto and Yu Takano
Database, 2020, Baaa066 (2020)184.6SLQဨSURMHFWHG4000)UHH(QHUJ\6LPXODWLRQVIRU2[LGDWLRQ5HDFWLRQRI*XDQLQHLQ%í'1$
by Singlet Oxygen"
Toru Saito and Yu Takano
ChemPhysChem, 22(6), 561-568 (2021)
185."Free-Energy Calculation of Ribonucleic Inosines and Its Application to Nearest-Neighbor
Parameters"
Shun Sakuraba, Junichi Iwakiri, Michiaki Hamada, Tomoshi Kameda, Genichiro Tsuji, Yasuaki
Kimura, Hiroshi Abe and Kiyoshi Asai
J. Chem. Theory Comput., 16(9), 5923-5935 (2020)186."Modeling the SARS-CoV-2 nsp1–5’-UTR complex via extended ensemble simulations"
6KXQ6DNXUDED4LOLQ;LH.RWD.DVDKDUD-XQLFKL,ZDNLULDQG+LGHWRVKL.RQR
bioRxiv (2021), https://doi.org/10.1101/2021.02.24.432807
187."A Molecular Hybrid of an Atomically Precise Silver Nanocluster and Polyoxometalates for H2
Cleavage into Protons and Electrons"
Kentaro Yonesato, Seiji Yamazoe, Daisuke Yokogawa, Kazuya Yamaguchi and Kosuke Suzuki
Angew. Chem. Int. Ed. (2021), https://doi.org/10.1002/anie.202106786
188."An Ultrastable, Small {Ag7}5+ Nanocluster within a Triangular Hollow Polyoxometalate
Framework"
Kentaro Yonesato, Hiroyasu Ito, Daisuke Yokogawa, Kazuya Yamaguchi and Kosuke Suzuki
Angew. Chem. Int. Ed., 59(38), 16361-16365 (2020)
189."Selenacalix[4]selenophene: Synthesis, Structure, and Gel Formation of Cyclic Selenoether ofSelenophene"
Masashi Hasegawa, Shiori Haga, Tohru Nishinaga and Yasuhiro Mazaki
Org. Lett., 22(10), 3755-3758 (2020)
190."A Nonalternant Aromatic Belt: Methylene-Bridged [6]Cycloparaphenylene Synthesized from
Pillar[6]arene"
Yuanming Li, Yasutomo Segawa, Akiko Yagi and Kenichiro Itami
J. Am. Chem. Soc., 142(29), 12850-12856 (2020)191.7ULVNHOLRQဨ6KDSHG ʌဨ/XPLQRSKRUHV %HDULQJ &RXPDULQ 6\QWKHVHV 6Wructures,
Luminescence Properties"
Masafumi Ueda, Mirai Kokubun and Yasuhiro Mazaki
ChemPhotoChem, 4(10), 5159-5167 (2020)- 542 -

and

192."Dancing with Sulfur: Simple Preparation and Properties ofThiacalix[n]thiophene Derivatives"
Masashi Hasegawa
J. Synth. Org. Chem. Jpn., 78(11), 1066-1075 (2020)
193."Circularly Polarized Luminescence of a Stereogenic Curved Paraphenylene Anchoring a Chiral
Binaphthyl in Solution and Solid State"
Kenta Sato, Masashi Hasegawa, Yuki Nojima, Nobuyuki Hara, Tomohiko Nishiuchi, Yoshitane
Imai and Yasuhiro Mazaki
Chem. Eur. J., 27(4), 1323-1329 (2021)
194.5HGXFWLRQRI(WK\Q\OHQHVWR9LQ\OHQHVLQD0DFURF\FOLFʌ-Extended Thiophene Skeleton Under
McMurry Coupling Conditions"
Keigo Shirahata, Masataka Takashika, Kazunori Hirabayashi, Masashi Hasegawa, Hiroyuki Otani,
Keitaro Yamamoto, Yutaka Ie, Toshio Shimizu, Shinobu Aoyagi and Masahiko Iyoda
J. Org. Chem., 86(1), 302-309 (2021)
195.5HYHUVLEOH &RORU DQG 6KDSH &KDQJHV RI 1DQRVWUXFWXUHG )LEHUV RI D 0DFURF\FOLF ʌ-Extended
Thiophene Hexamer Promoted by Adsorption and Desorption of Organic Vapor"
Masahiko Iyoda, Masataka Takashika, Masashi Hasegawa, Hiroyuki Otani, Saori Mizuno,
Kazuhira Miwa, Wakana Kariya, Toshihiro Fujiwara, Hideyuki Shimizu and Shinobu Aoyagi
J. Am. Chem. Soc., 142(32), 13662-13666 (2020)196.6PDOO )LJXUHဨ(LJKW /XPLQRSKRUHV 'RXEOHဨ7ZLVWHG 7HWKHUHG &\FOLF %LQDSKWK\OV %RRVWCircularly Polarized Luminescence"
Yuki Nojima, Masashi Hasegawa, Nobuyuki Hara, Yoshitane Imai and Yasuhiro Mazaki
Chem. Eur. J., 27(19), 5923-5929 (2021)
197."Non-naturally Occurring Regio Isomer of Lysophosphatidylserine Exhibits Potent Agonistic
Activity toward G Protein-Coupled Receptors"
Sho Nakamura, Misa Sayama, Akiharu Uwamizu, Sejin Jung, Masaya Ikubo, Yuko Otani,
Kuniyuki Kano, Jumpei Omi, Asuka Inoue, Junken Aoki and Tomohiko Ohwada
J. Med. Chem., 63(17), 9990-10029 (2020)
198."Molecular Dynamics Simulation Study on Allosteric Regulation of CD44-Hyaluronan Binding
as a Force Sensing Mechanism"
Masami Lintuluoto, Yota Horioka, Saki Hongo, Juha Mikael Lintuluoto and Yoshifumi Fukunishi
ACS Omega, 6(12), 8045-8055 (2021)
199."Low-pressure chemical vapor deposition of Cu on Ru using CuI as precursor"
Taiji Nishikawa, Kensuke Horiuchi, Tatsuya Joutsuka and Satoshi Yamauchi
Journal of Crystal Growth, 549, 125849 (2020)
200."Constrained Density Functional Theory Molecular Dynamics Simulation of Deprotonation in
Aqueous Silicic Acid"
Tatsuya Joutsuka and Koji Ando
J. Phys. Chem. B, 124(38), 8323-8330 (2020)
201."Facet Dependence of Photocatalytic Activity in Anatase TiO2: Combined Experimental and DFT- 543 -

Study"Tatsuya Joutsuka, Hiroto Yoshinari and Satoshi Yamauchi
BCSJ, 94(1), 106-111 (2021)
202."Efficient Free-Energy Calculation of Proton Transfer by Constrained Density Functional Theory
and Geometrically Restrained Molecular Dynamics Simulation"
Tatsuya Joutsuka and Koji Ando
Chem. Lett., , cl.210132 (2021)
203."Theory of polarization-averaged core-level molecular-frame photoelectron angular distributions:
II. Extracting the x-ray-induced fragmentation dynamics of carbon monoxide dication fromforward and backward intensities"
F Ota, K Hatada, D Sébilleau, K Ueda and K Yamazaki
J. Phys. B: At. Mol. Opt. Phys., 54(8), 084001 (2021)
204."Theory of polarization-averaged core-level molecular-frame photoelectron angular distributions:
II. Extracting the x-ray-induced fragmentation dynamics of carbon monoxide dication fromforward and backward intensities"
F Ota, K Hatada, D Sébilleau, K Ueda and K Yamazaki
J. Phys. B: At. Mol. Opt. Phys., 54(8), 084001 (2021)
205."Theory of polarization-averaged core-level molecular-frame photoelectron angular distributions:
I. A full-potential method and its application to dissociating carbon monoxide dication"
F Ota, K Yamazaki, D Sébilleau, K Ueda and K Hatada
J. Phys. B: At. Mol. Opt. Phys., 54(2), 024003 (2021)
206."Theory of polarization-averaged core-level molecular-frame photoelectron angular distributions:
I. A full-potential method and its application to dissociating carbon monoxide dication"
F Ota, K Yamazaki, D Sébilleau, K Ueda and K Hatada
J. Phys. B: At. Mol. Opt. Phys., 54(2), 024003 (2021)
207."Substitution effect on the nonradiative decay and trans ĺ cis photoisomerization route: aguideline to develop efficient cinnamate-based sunscreens"
Shin-nosuke Kinoshita, Yu Harabuchi, Yoshiya Inokuchi, Satoshi Maeda, Masahiro Ehara, Kaoru
Yamazaki and Takayuki Ebata
Phys. Chem. Chem. Phys., 23(2), 834-845 (2020)
208.6XEVWLWXWLRQ HIIHFW RQ WKH QRQUDGLDWLYH GHFD\ DQG WUDQV ĺ FLV SKRWRLVRPHUL]DWLRQ URXWH Dguideline to develop efficient cinnamate-based sunscreens"
Shin-nosuke Kinoshita, Yu Harabuchi, Yoshiya Inokuchi, Satoshi Maeda, Masahiro Ehara, Kaoru
Yamazaki and Takayuki Ebata
Phys. Chem. Chem. Phys., 23(2), 834-845 (2020)
209."Generation and application of Cu-bound alkyl nitrenes for the catalyst-controlled synthesis of
cyclic ȕ-amino acids"
Raj K. Tak, Fuyuki Amemiya, Hidetoshi Noda and Masakatsu Shibasaki
Chem. Sci. (2021), https://doi.org/10.1039/D1SC01419F- 544 -

210."Cu(I)/sucrose-catalyzed hydroxylation of arenes in water: the dual role of sucrose"
Kohei Watanabe, Mio Takagi, Ayako Watanabe, Shigeo Murata and Ryo Takita
Org. Biomol. Chem., 18(39), 7827-7831 (2020)211.+\GURPDJQHVLDWLRQ RI ဨ(Q\QHV E\ 0DJQHVLXP +\GULGH IRU 6\QWKHVLV RI 7ULဨ DQG 7HWUDဨ
substituted Allenes"
Bin Wang, Yihang Li, Jia Hao Pang, Kohei Watanabe, Ryo Takita and Shunsuke Chiba
Angew. Chem. Int. Ed., 60(1), 217-221 (2021)
212.&DWDO\WLFSKRWRR[\JHQDWLRQGHJUDGHVEUDLQ$ȕLQYLYR
Nozomu Nagashima, Shuta Ozawa, Masahiro Furuta, Miku Oi, Yukiko Hori, Taisuke Tomita,
Youhei Sohma and Motomu Kanai
Sci. Adv., 7(13), eabc9750 (2021)
213.2SWLPL]LQJ*ǀ-MARTINI Coarse-Grained Model for F-BAR Protein on Lipid Membrane"
Md. Iqbal Mahmood, Adolfo B. Poma and Kei-ichi Okazaki
Front. Mol. Biosci., 8, 619381 (2021)
214.5RRPဨ7HPSHUDWXUH 3KRVSKRUHVFHQFH (PLWWHUV ([KLELWLQJ 5HG WR 1HDUဨ,QIUDUHd Emission'HULYHG IURP ,QWHUPROHFXODU &KDUJHဨ7UDQVIHU 7ULSOHW 6WDWHV RI 1DSKWKDOHQHGLLPLGHíHalobenzoate Triad Molecules"
Toshikazu Ono, Kazuki Kimura, Megumi Ihara, Yuri Yamanaka, Miori Sasaki, Hirotoshi Moriand Yoshio Hisaeda
Chem. Eur. J., , chem.202100906 (2021)
215."Cyclic Heterometallic Interactions formed from a Flexible Tripeptide Complex Showing
Effective Antiferromagnetic Spin Coupling"
Ryosuke Miyake, Eri Suganuma, Shun Kimura, Hirotoshi Mori, Jun Okabayashi and Tetsuro
Kusamoto
Angew. Chem. Int. Ed., 60(10), 5179-5183 (2021)
216."Functional Group-Directed Photochemical Reactions of Aromatic Alcohols, Amines, and Thiols
Triggered by Excited-State Hydrogen Detachment: Additive-free Oligomerization, Disulfidation,
and C(sp2)–H Carboxylation with CO2"
Kanae Abe, Akinobu Nakada, Takeshi Matsumoto, Daiki Uchijyo, Hirotoshi Mori and Ho-Chol
Chang
J. Org. Chem., 86(1), 959-969 (2021)
217."Theoretical Strategy for Improving CO2 Absorption of Mixed Ionic Liquids Focusing on theAnion Effect: A Comprehensive COSMO-RS Study"
Nahoko Kuroki, Shunta Maruyama and Hirotoshi MoriInd. Eng. Chem. Res., 59(18), 8848-8854 (2020)
218."Theoretical analysis of the binding of a positron and pair-annihilation in fluorinated benzene
molecules"
Kuniaki Ono, Takayuki Oyamada, Yukiumi Kita and Masanori Tachikawa
Eur. Phys. J. D, 74(5), 89 (2020)- 545 -

219."Role of water molecules in the laser-induced disruption of amyloid fibrils observed bynonequilibrium molecular dynamics simulations"
H. Okumura, S. G. Itoh, K. Nakamura and and T. Kawasaki
J. Phys. Chem. B, 125, 4964-4976 (2021)
220.'LPHUL]DWLRQ RI Į-Synuclein Fragments Studied by Isothermal–Isobaric Replica-Permutation
Molecular Dynamics Simulation"
Masataka Yamauchi and Hisashi Okumura
Journal of Chemical Information and Modeling, 61, 1307-1321 (2021)
221."Energetics and kinetics of substrate analog-coupled staphylococcal nuclease folding revealed bya statistical mechanical approach"Takuya Mizukami, Shunta Furuzawa, Satoru G Itoh, Saho Segawa, Teikichi Ikura, Kunio Ihara,
Hisashi Okumura, Heinrich Roder and Kosuke Maki
roceedings of the National Academy of Sciences, 117, 19953-19962 (2020)
222."Protecting group-free method for synthesis of N-glycosyl carbamates and an assessment of theanomeric effect of nitrogen in the carbamate group"
Yoshiyasu Ichikawa, Daisuke Kaneno, Nobuyoshi Saeki, Takahiro Minami, Toshiya Masuda,
Kumi Yoshida, Tadao Kondo and Rika Ochi
Carbohydrate Research, 505, 108280 (2021)
223."኱つᶍ䜹䝂ᆺ䜰䝹䜻䝹㦵᱁ෆ䛻 ʌ 㟁Ꮚ⣔䛜ᯫᶫ䛧䛯䛂ศᏊ䝆䝱䜲䝻䝁䝬䛃䛾ྜᡂᵓ㐀໬Ꮫ"℩㧗㻌 ΅䞉✄ᇉ㻌 భு䞉ᒣཱྀ㻌 ೺ኴ㑻᭷ᶵྜᡂ໬Ꮫ༠఍ㄅ, 77(8), 813-822 (2019)
224."Polarized Fluorescence of a Crystal having Uniaxially Oriented Molecules by a Carbazole-diylbridged Macrocage"
H. Hashimoto, Y. Inagaki, H. Momma, E. Kwon, K. Yamaguchi and and W. Setaka
CrystEngComm, 21, 3910-3914 (2019)
225."Kinetic Stabilization of Carbazole Nitroxides by Inclusion in a Macrocage and Their Electron
Spin Resonance Characterization"
Hikaru Hashimoto, Yusuke Inagaki, Hiroyuki Momma, Eunsang Kwon and Wataru Setaka
J. Org. Chem., 84(18), 11783-11789 (2019)
226."Gear Slippage in Molecular Bevel Gears Bridged with a Group 14 Element"
K. Okamura, Y. Inagaki, H. Momma, E. Kwon and and W. Setaka
J. Org. Chem., 84(18), 14636-14643 (2019)
227."A Furan-2,5-diyl Bridged Macrocage as a Highly Distorted Molecular Gyrotop"
Yusuke Inagaki, Satsuki Ueda, Kentaro Yamaguchi and Wataru Setaka
Chem. Lett., 49(11), 1291-1293 (2020)
228."Molecular Design Principle for Efficient Singlet Fission Based on Diradical Characters andExchange Integrals: Multiple Heteroatom Substitution Effect on Anthracenes"
Takanori Nagami, Kenji Okada, Hajime Miyamoto, Wataru Yoshida, Takayoshi Tonami and
Masayoshi Nakano- 546 -

J. Phys. Chem. C, 124(22), 11800-11809 (2020)
229.8OWUDIDVW ([FLWRQ 6HOIဨ7UDSSLQJ DQG 'HORFDOL]DWLRQ LQ &\FORSDUDSKHQ\OHQHV 7KH 5ROH RI
([FLWHGဨ6WDWH6\PPHWU\LQ(OHFWURQဨ9LEUDWLRQDO&RXSOLQJ
Juno Kim, Ryohei Kishi, Eiichi Kayahara, Woojae Kim, Shigeru Yamago, Masayoshi Nakano andDongho Kim
Angew. Chem. Int. Ed., 59(39), 16989-16996 (2020)
230."Theoretical study on aromatic and open-shell characteristics of carbon nanobelts composed ofindeno[1,2-b]fluorene units: dependence on the number of units and charge states"
Ryohei Kishi, Masaki Yamane, Ryosuke Sugiura, Wataru Yoshida, Yosuke Shimizu andMasayoshi Nakano
RSC Adv., 10(43), 25736-25745 (2020)
231."Late-Stage Modification of Electronic Properties of Antiaromatic and Diradicaloid Indeno[1,2b]fluorene Analogues via Sulfur Oxidation"
Justin J. Dressler, Joshua E. Barker, Lucas J. Karas, Hannah E. Hashimoto, Ryohei Kishi, Lev N.
Zakharov, Samantha N. MacMillan, Carlos J. Gómez-García, Masayoshi Nakano, Judy I. Wu andMichael M. Haley
J. Org. Chem., 85(16), 10846-10857 (2020)
232."Theoretical Molecular Design of Phenanthrenes for Singlet Fission by Diazadibora-Substitution"
Takanori Nagami, Hajime Miyamoto, Wataru Yoshida, Kenji Okada, Takayoshi Tonami and
Masayoshi Nakano
J. Phys. Chem. A, 124(34), 6778-6789 (2020)
233.4XDQWXPGHVLJQIRUVLQJOHW-fission-LQGXFHGQRQOLQHDURSWLFDOV\VWHPV(IIHFWVRIʌ-conjugation
length and molecular packing of butterfly-shaped acenes"
Takayoshi Tonami, Takanori Nagami, Kenji Okada, Wataru Yoshida, Hajime Miyamoto and
Masayoshi Nakano
J. Chem. Phys., 153(8), 084304 (2020)
234."Theoretical Study on Singlet Fission Dynamics in Sumanene-Fused Acene Dimers"
Kenji Okada, Masayoshi Nakano, Hajime Miyamoto, Hironobu Nakazawa, Yuta Uetake andHidehiro Sakurai
J. Phys. Chem. C, 124(36), 19499-19507 (2020)
235."Vibronic coupling density analysis and quantum dynamics simulation for singlet fission inpentacene and its halogenated derivatives"
Takanori Nagami, Takayoshi Tonami, Kenji Okada, Wataru Yoshida, Hajime Miyamoto and
Masayoshi Nakano
J. Chem. Phys., 153(13), 134302 (2020)236."Monoradicals and Diradicals of Dibenzofluoreno[3,2-b]fluorene Isomers: Mechanisms of
Electronic Delocalization"
Hideki Hayashi, Joshua E. Barker, Abel Cárdenas Valdivia, Ryohei Kishi, Samantha N.
MacMillan, Carlos J. Gómez-García, Hidenori Miyauchi, Yosuke Nakamura, Masayoshi Nakano,- 547 -

Shin-ichiro Kato, Michael M. Haley and Juan Casado
J. Am. Chem. Soc., 142(48), 20444-20455 (2020)
237."Theoretical Study on Third-Order Nonlinear Optical Properties for One-Hole-Doped
Diradicaloids"
Wataru Yoshida, Hiroshi Matsui, Hajime Miyamoto, Takayoshi Tonami, Ryota Sugimori, Kyohei
Yoneda, Ryohei Kishi and Masayoshi Nakano
ACS Omega, 6(4), 3046-3059 (2021)
238."Stabilization of Charge-Transfer States in Pentacene Crystals and Its Role in Singlet Fission"
Takanori Nagami, Hajime Miyamoto, Ryota Sakai and Masayoshi Nakano
J. Phys. Chem. C, 125(4), 2264-2275 (2021)
239."Theoretical Study on Singlet Fission in Aromatic Diaza s-Indacene Dimers"
Takanori Nagami, Ryota Sugimori, Ryota Sakai, Kenji Okada and Masayoshi Nakano
J. Phys. Chem. A, 125(16), 3257-3267 (2021)
240.&KDUDFWHUL]DWLRQRI%HQ]R>D@QDSKWKR>ဨI@SHQWDOHQH,QWHUUHODWLRQEHWZHHQ2SHQဨVKHOODQG
$QWLDURPDWLF&KDUDFWHUV*RYHUQHGE\0RGHRIWKH4Xinoidal Subunit and Molecular Symmetry"
Akihito Konishi, Koki Horii, Haruna Iwasa, Yui Okada, Ryohei Kishi, Masayoshi Nakano and
Makoto Yasuda
Chem. Asian J., 16(12), 1553-1561 (2021)
241."Chiral Octapalladium Chains Supported by Enantiopure P-Stereogenic Linear Tetraphosphines,(R,R)- and (S,S)-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2"
Tomoaki Tanase, Kanako Nakamae, Suzui Hayashi, Ayumi Okue, Risa Otaki, Tomoko Nishida,
Yasuyuki Ura, Yasutaka Kitagawa and Takayuki Nakajima
Inorg. Chem., 60(5), 3259-3273 (2021)
242."TheoreticaO 6WXG\ RQ 6LQJOHW )LVVLRQ '\QDPLFV LQ 3HQWDFHQH 5LQJဨ6KDSHG $JJUHJDWH 0RGHOV
with Different Configurations"Hajime Miyamoto and Masayoshi Nakano
ChemPhotoChem, 4(11), 5249-5263 (2020)
243."Transition pathway of hydrogen bond switching in supercooled water analyzed by the Markov
state model"
Takuma Kikutsuji, Kang Kim and Nobuyuki MATUBAYASI
J. Chem. Phys., 154(23), 234501 (2021)
244."Potassium and sodium ion complexes with a partial peptide of the selectivity filter in K+ channels
studied by cold ion trap infrared spectroscopy: the effect of hydration"
Takumi Negoro, Keisuke Hirata, James M. Lisy, Shun-ichi Ishiuchi and Masaaki Fujii
Phys. Chem. Chem. Phys., 23(21), 12045-12050 (2021)
245.5ROHRIEDFNERQHVWUDLQLQGHQRYRGHVLJQRIFRPSOH[ĮȕSURWHLQVWUXFWXUHVNobuyasu Koga, Rie Koga, Gaohua Liu, Javier Castellanos, Gaetano T. Montelione and DavidBaker
Nat Commun, 12(1), 3921 (2021)- 548 -

246."Convenient synthesis of copper(i) halide quasi-one-dimensional coordination polymers: theirstructures and solid-state luminescent properties"
Shingo Masahara, Hiromichi Yokoyama, Yuji Suzaki and Tomohito Ide
Dalton Trans., 50(25), 8889-8898 (2021)
247."Spectroscopic approach for exploring structure and function of photoreceptor proteins"
Masashi Unno, Yuu Hirose, Masaki Mishima, Takashi Kikukawa, Tomotsumi Fujisawa, Tatsuya
Iwata and Jun Tamogami
Biophysics and Physicobiology, 18, 127-130 (2021)
248."Effect of surface structural change on adsorption behavior on InAs wetting layer surface grown
on GaAs(001) substrate"
Toru Akiyama, Kazuhiro Yonemoto, Fumiaki Hishiki and Tomonori Ito
Journal of Crystal Growth, 570, 126233 (2021)
249."Diversity-RULHQWHGV\QWKHVLVRIQDQRJUDSKHQHVHQDEOHGE\GHDURPDWLYHDQQXODWLYHʌ-extension"
Wataru Matsuoka, Hideto Ito, David Sarlah and Kenichiro Itami
Nat. Commun., 12(1), 3940 (2021)
250."Effect of step edges on the adsorption behavior on vicinal AlN(0001) surface during metalorganic vapor phase epitaxy: an ab initio study"
Toru Akiyama, Takumi Ohka, Katsuya Nagai and Tomonori Ito
Journal of Crystal Growth, 571, 126244 (2021)
251."Effective approach for calculating individual energy of step edges on polar AlN(0001) and
GaN(0001) surfaces"
Toru Akiyama, Atsutaka Nakatani, Tsunashi Shimizu, Takumi Ohka and Tomonori Ito
Jpn. J. Appl. Phys., 60(8), 080701 (2021)
252."Molecular insights on confined water in the nanochannels of self-assembled ionic liquid crystal"
Yoshiki Ishii, Nobuyuki MATUBAYASI, Go Watanabe, Takashi Kato and Hitoshi Washizu
Sci. Adv., 7(31), eabf0669 (2021)- 549 -

㻟㻚㻞䚷䝥䝻䝆䜵䜽䝖ูㄽᩥูๅᥦฟ≧ἣ䠄㻞㻜㻞㻝ᖺ㻣᭶㻟㻝᪥⌧ᅾ䠅
ࢥ࣮ࢻ
௦⾲⪅ྡ
࣓ࣥࣂ࣮ᩘ
ㄽᩥᩘ
DD
ᩧ⸨ࠉ┿ྖ


DG
Ụཎࠉṇ༤


DG
ዟᮧࠉஂኈ


DI
ຍ⸨ࠉ᫭୍

DI
㛗ᆏࠉᑗᡂ


DI
ྂ㈡ࠉಙᗣ


DJ
ᑠᯇࠉຬ

DJ
▼⏣ࠉᖸᇛ

DJ
༡㇂ࠉⱥ⨾

DK
ⲡᮏࠉဴ㑻

DK
⸨⏣ࠉ㈗ᩄ

DK
ᖹࠉ⩏㝯

DK
℩ᕝࠉὈ▱

DK
㧗㇂ࠉග

FD
ᾏ㔝ࠉ㞞ྖ


FE
⏣௰ࠉ஧ᮁ

FE
㇂ᮧࠉྜྷ㝯

FE
᪩℩ࠉಟ୍

FF
ᫍ㔝ࠉᛅḟ

FF
㛗㇂ᕝࠉ῟ஓ


FF
ᒸᮏࠉ♸ᖾ

FG
ᴬࠉⱱዲ

FG
୰㔝ࠉ㞞⏤


FH
ᒾ㔝ࠉ⸅

FI
℩Ἴࠉ኱ᅵ

FI
ᒣୗࠉㄔ

FJ
㮚㔝ࠉඃ


FJ
㛵ᒣࠉ⚽㞝

FJ
▼ᕝࠉ᫓ᶞ

FJ
㉥℩ࠉ኱

FK
❧ᕝࠉோ඾


FL
㕥ᮌࠉ⪽


FL
ᩘ⣡ࠉᗈဢ


FL
ᐩỌࠉᆂ௓

FL
ᢲᒣࠉ῟

FN
୰ᮧࠉ༟

FN
୰㎷ࠉ༤


FO
ⲡ㛫ࠉோ


FO
ᾏ⪁ཎࠉᫀᘯ

FO
➉ෆࠉᏕỤ

FP
⏣୰ࠉᡂ඾

FP
Ỉ℩ࠉ㈼ኴ

FP
᳃ࠉᐶᩄ


FQ
᳃⏣ࠉ᫂ᘯ

FQ
㔝ᓮࠉிᏊ

FR
▼⏣ࠉ㇏

FR
ụ⏣ࠉᾈே


FR
ᐑᓮࠉ඘ᙪ

- 550 -

ㄽᩥ␒ྕ























ࢥ࣮ࢻ
FS
FU
FU
FW
FW
FY
FY
FZ
FZ
FZ
F[
F\
F\
F\
F]
GD
GE
GE
GF
GF
GI
GJ
GJ
GK
GK
GL
GM
GM
GN
GS
GT
GV
GX
GX
GZ
G[
HE
HK
HK
HN
HN
HP
HP
HS
HS
HT
HT
HT
HT

௦⾲⪅ྡ
ᶓᒣࠉ኱㍜
ᒾ⏣ࠉᮎᘅ
Ṋḟࠉᚭஓ
ᒣ㛛ࠉⱥ㞝
ୖ⏣ࠉ୍⩏
బ⸨ࠉၨᩥ
㔠㔝ࠉ኱ຓ
㰻⸨ࠉ኱᫂
‫‮‬஭ࠉᩄᩥ
ᒸᓮࠉ㐍
ྜྷ⏣ࠉ೺
ᒾᮏࠉၨ
⛅ὠࠉ㈗ᇛ
ᐑ⏣ࠉ❳ᙪ
ᒣཱྀࠉ඙
㛗㇂ᕝࠉ┿ኈ
ஂ᪂ࠉⲮ୍㑻
ὠ␃ᓮࠉ㝧኱
ᒣ໭ࠉెᏹ
ఀ⸨ࠉ႐ග
ᒣᮏࠉ඾ྐ
୕஭ࠉṇ᫂
ᑎ⏣ࠉᬛᶞ
ᯘࠉ㔜ᙪ
ධబࠉṇᖾ
ᯇᮏࠉṇ࿴
୰ᔱࠉ㝯ே
ᰰ἟ࠉឡ
᳃ḟࠉᆂ
㛗ᒸࠉఙ୍
ຍ⸨ࠉᫀᏊ
⬟Ⓩࠉ㤶
୰ᮧࠉᰤ୍
㧗ᶫࠉಟ
ᒣୗࠉ᫭୍
኱࿴⏣ࠉᬛᙪ
బࠎᮌࠉᓅᙪ
ᕷᶫࠉṇᙪ࿴బ⏣ࠉ⿱᫛
㮚㔝ࠉᬒᏊ
ᮏከࠉ୍ᙪ
㫽ᒃࠉ⫕
⡿⏣ࠉⱱ㝯
୰஭ࠉᾈᕭ
ሷぢࠉ኱㍜
ᯇᮏࠉ୍Ⴙ
୰㔝ࠉᖾྖ
ᕝཱྀࠉ୍᭸
✄ⴥࠉ▱ኈ

࣓ࣥࣂ࣮ᩘ

















































- 551 -

ㄽᩥᩘ

ㄽᩥ␒ྕ



















































ࢥ࣮ࢻ
HV
HW
HX
HY
HZ
H[
H[
H\
H]
H]
ID
IE
IF
IF
IF
IF
IG
IG
IG
IG
IG
IH
IJ
IJ
IJ
IJ
IJ
IJ
IK
IK
IK
IK
IK
IK
IK
IL
IL
IL
IM
IM
IN
IN
IO
IO
IO
IP
IP
IP
IP

௦⾲⪅ྡ
᳃ࠉ⪷἞
ఀ⸨ࠉᙲᾈ
ᑠ㔝ࠉඞᙪ
ᕤ⸨ࠉ⪽
Ἴ⏣ࠉ㞞ᙪ
ⓑ▼ࠉ㈼஧
᳃ୗࠉᚭஓ
㯮ᓮࠉㆡ
໭ᑿࠉᙲᮁ
⛅ᒣࠉ஽
㧘ᶫࠉ༟ஓ
኱ୗࠉ៞ḟ㑻
ࣜࣥࢺࢗࣝ࢜ࢺࠉṇ⨾
ෆ⏣ࠉᖾ᫂
୰㔝ࠉ⩏᫂
㔠ࠉ㗰
ᒣᓮࠉ⚈ᖹ
ᮃ᭶ࠉᘓ∞
Ᏹ⏣ᕝࠉኴ㑻
ᑠᏳࠉ႐୍㑻
ᙳᓥࠉ༤அ
⏣୰ࠉ኱㍜
▼ᒣࠉ㐩ஓ
ᮧᒸࠉᱻ
బ⸨ࠉᚭ
୰ᒣࠉ㝯ྐ
⏿୰ࠉ⨾✑
኱㫽ࠉ⠊࿴
Ḉ஭ࠉⱥ༤
ఀ⸨ࠉⱥே
-XKDV]*HUJHO\
ᱜᗞࠉಇ
㛵ࠉಟᖹ
ྜྷ⏣ࠉ⣧
ᰗ⏣ࠉு
⏣୰ࠉ⿱ஓ
ὸᏊࠉኊ⨾
ᖹ㔝ࠉᜏኵ
ὸᕝࠉ኱ᶞ
ᯇ஭ࠉ஽
ྜྷ⏣ࠉ⣖⏕
๓⏣ࠉ኱ග
ᾆࠉᗣஅ
୕ᶫࠉ஢∞
⏣௦ࠉᇶ៞
Ỉ⏣ࠉຮ
ᒣୗࠉ೺୍
᳃ᮏࠉ῟ᖹ
᏷ᡞࠉ༤⣖

࣓ࣥࣂ࣮ᩘ

















































- 552 -

ㄽᩥᩘ


ㄽᩥ␒ྕ
























































ࢥ࣮ࢻ
IP
IQ
IQ
IQ
IQ
IR
IR
IR
IR
IR
IR
IR
IS
IS
IS
IS
IS
IT
IT
IT
IT
IT
IU
IU
IU
IU
IU
IU
IU
IU
IV
IV
IV
IV
IV
IV
IV
IW
IW
IW
IW
IX
IX
IX
IX
IX
IX
IY
IY

௦⾲⪅ྡ
すෆࠉᬛᙪ
୸ᒣࠉⱱኵ
஭ཱྀࠉెဢ
⚄㇂ࠉᫀᏹ
㔝ཱྀࠉᕦ
ᮧ⏣ࠉ្
⚟⏣ࠉⰋ୍
బ⸨ࠉஂᏊ
ᮾᯘࠉಟᖹ
ᕭୖࠉᖾ୍㑻
኱⃝ࠉṇஂ
኱㔝ࠉ┿ஓ
ᒸࠉ┿ᝆᏊ
ᑠ㛛ࠉ᠇ኴ
Ώ㑔ࠉ⥲୍㑻
㯮ෆࠉᐶ᫂
㣤᳃ࠉಇᩥ
⊁㔝ࠉ┤࿴
஭ᡭࠉᬛோ
ΎỈࠉ❶ᘯ
୕Ꮿࠉு௓
ఀ⸨ࠉ⫕
⠛⏣ࠉᜨᏊ
ᆏᮏࠉ㐨᫛
㯮⏣ࠉ኱♸
๓⏣ࠉ⌮
ఀໃᕝࠉ⨾✑
ᐑᓮࠉ⚽ಇ
㓇ᕳࠉ኱㍜
ᯘࠉ⪽Ꮚ
⁪⏣ࠉⰋ
బ⸨ࠉ❳㤿
ᐑ⏣኱㍜
ᑠỮࠉె♸
℩㧗ࠉ΅
:0&6DPHHUD
୰ᮧࠉಟ୍
㕥ᮌࠉ㈼⣖
ᓥ⏣ࠉ㏱
㕥ᮌࠉ῟ᕧ
㛗ᒸࠉṇᏹ
ᰗ஭ࠉẎ
⛅ᒣࠉⰋ
⏣୰ࠉៅ୍㑻
୰ᮧࠉ᣺୍㑻
ᇛሯࠉ㐩ஓ
㛗⏣ࠉᾈ୍
ỤᕝࠉὈᬸ
ᩧ⸨ࠉ❳⏨

࣓ࣥࣂ࣮ᩘ

















































- 553 -

ㄽᩥᩘ


ㄽᩥ␒ྕ

















































ࢥ࣮ࢻ
IY
IY
IY
IY
IZ
IZ
IZ
IZ
IZ
IZ
IZ
IZ
I[
I[
I[
I[
I[
I[
I\
I\
I\
I\
I\
I\
I\
I\
I]
I]
I]
I]
I]
I]
I]
I]
I]
I]
JD
JD
JD
JD
JD
JD
JD
JD
JD
JD
JE
JE
JE

௦⾲⪅ྡ
ᮧ஭ࠉᚁྐ
㯮ᮌࠉᑲ
ṇ஭ࠉᏹ
⋢⯓ࠉ▱ஓ
ᡭᓥࠉṇ࿃
▼ᶫࠉᏕ❶
ᒸ⏣ࠉὒྐ
す⃝ࠉᏹ᫭
᳜⏣ࠉ୍ṇ
ᑠᮡࠉ೺ᩯ
ኴ⏣ࠉⱥ௓
㉥஭ࠉ࿘ྖ
ᯇ⏣ࠉḠஅ
ዟᮧࠉὈᚿ
࿃㒓ࠉ཭ᏹ
ᱵ᰿ࠉ㍤᮶ே
ᒣᓮࠉ⚈Ꮚ
⏕㉺ࠉᑓ௓
ஂୡࠉಙᙪ
୰ᒣࠉဴ
⠛⏣ࠉ΅
㮖ὠࠉோᚿ
ኳ⬟ࠉ⢭୍㑻
ᖹ⏣ࠉᆂ♸
ᒣ㛛ࠉ㝠ᖹ
ྂᒇࠉ⚽ᓠ
㔝ཱྀࠉ༤ྖ
ᮎᯇࠉᏳ⏤⨾
Ⅳ❤ࠉாྖ
㧗▼ࠉ࿴ே
⟪ᾆࠉ┿⏕
⯪᭥ࠉ୍ṇ
ᒣᓮࠉ㤾
)ORULVYDQ(HUGHQ
୰ᮧࠉᾈ❶
⏣୰ࠉ⚽ᶞ
❧ⰼࠉᏹ
㕥ᮌࠉᗣ௓
ෆᒣࠉὒ௓
/,8ࠉ&$1
ᯇᮏࠉ๛᫛
ᖹᯘࠉ♸௓
㧗ᮌࠉᖾ἞
኱ᕝࠉᑗᚿ
ᮤࠉ⚽ᰤ
ᒣᮏࠉဴஓ
ᇽᮏࠉᝆஓ
ಙ⏣ࠉᑦẎ
ᅵᑕὠࠉᫀஂ

࣓ࣥࣂ࣮ᩘ

















































- 554 -

ㄽᩥᩘ

ㄽᩥ␒ྕ










































ࢥ࣮ࢻ
JE
JE
JE
JE
JE
JE
JE
JF
JF
JF
JF
JF
JF
LD
LD
RD
TF
YD
YD
YD
YE
YF
YG
YG
YH
YH
YH

௦⾲⪅ྡ
᪂ᯘࠉ༟ஓ
἟⏣ࠉ᐀඾
1JX\HQ7KDQK3KXF
すᮏࠉ⬟ᘯ
ᒣཱྀࠉᓧⱥ
ᕝᓮࠉᖹᗣ
ᐑ⏣ࠉ₩ᚿ
⡿ᒣࠉබၨ
ᑠ⃝ࠉᬛᏹ
ぬ▱ࠉுᖹ
ᑠᓥࠉṇᐶ
ୖᆅࠉ㐩▮
஬༑ᔒࠉ᫂๎
⚟Ọࠉ㞞႐
㏆ῧࠉ῟୍
Ώ㎶ࠉⱥ἞
ᱵ⃝ࠉබ஧
኱㇂ࠉᐇ
ᒸᓮࠉ㐍
ᯇᯘࠉఙᖾ
ᢲᒣࠉ῟
ᒣᓮࠉ㤾
Ṋḟࠉᚭஓ
ᒣ⏣ࠉ῟ኵ
ᮡ㔝ࠉಟ
୰஭ࠉᾈᕭ
ᒸᓮࠉᆂ୍

࣓ࣥࣂ࣮ᩘ




























- 555 -

ㄽᩥᩘ

ㄽᩥ␒ྕ

















ࢭࣥࢱ࣮࣏࣮ࣞࢺ 21
2021 ᖺ 9 ᭶Ⓨ⾜(2020 ᖺ 4 ᭶㹼2021 ᖺ 3 ᭶)㸺⦅㞟࣭Ⓨ⾜㸼⮬↛⛉Ꮫ◊✲ᶵᵓ ᒸᓮඹ㏻◊✲᪋タィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮
ࠛ444-8585 ឡ▱┴ᒸᓮᕷ᫂኱ᑎ⏫Ꮠす㒓୰ 38 ␒ᆅ
TEL 0564-55-7462 FAX 0564-55-7025
ᮏ᭩ࡢ୍㒊ࡲࡓࡣ඲㒊ࢆࠊⴭసᶒ⪅ࡢチྍ࡞ࡋ࡟ࠊ」〇ࠊ㌿㍕ࡍࡿࡇ࡜ࢆ⚗Ṇࡋࡲࡍࠋ