II 㒊┠ḟ1 2019 ᖺᗘ◊✲ㄢ㢟࠾ࡼࡧ฼⏝ሗ࿌᭩ ···························································· 11.1 2019 ᖺᗘ◊✲ㄢ㢟୍ぴ࡜฼⏝ሗ࿌᭩ᥦฟ≧ἣ(๭ᙜⅬᩘ 30,000 Ⅼ௨ୗ) ··········· 11.2 2019 ᖺᗘ◊✲ㄢ㢟୍ぴ࡜฼⏝ሗ࿌᭩(๭ᙜⅬᩘ 30,000 Ⅼ㉸)·························· 8
2 2019 ᖺᗘィ⟬≀㉁⛉Ꮫࢫࣃࢥࣥඹ⏝஦ᴗ฼⏝ᯟ◊✲ㄢ㢟࠾ࡼࡧ฼⏝ሗ࿌᭩ ······· 439
3 ࣮ࣘࢨⓎ⾲ㄽᩥ ····················································································· 469
3.1 ࣮ࣘࢨㄽᩥ୍ぴ················································································ 469
3.2 ࣉࣟࢪ࢙ࢡࢺูㄽᩥูๅᥦฟ≧ἣ························································ 507

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ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FD

ศගἲ࡜ศᏊືຊᏛィ⟬㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓ⏕య㛵㐃ศᏊࡢືⓗ
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

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◊✲ᶵᵓ

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㟼ᒸ⌮ᕤ⛉኱⌮ᕤ㛵ᒣ⚽㞝 㸭 

6L+ᇶࢆྵࡴ஧Ỉ⣲⤖ྜࢡࣛࢫࢱ࣮࡟࠾ࡅࡿࢡࣛࢫࢱ࣮ෆ࢖࢜ࣥ
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ᾏ⪁ཎᫀᘯ


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ཎᏊᒙไᚚ࢚ࢵࢳࣥࢢ཯ᛂ㐣⛬࡟㛵ࡍࡿDELQLWLRᐦᗘỗ㛵ᩘ⌮ㄽ◊
✲

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➉ෆᏕỤ
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ศᏊࢡࣛࢫࢱ࣮ࡢ᪂つ㧗ศゎ⬟᣺ືᅇ㌿ศගἲࡢ㛤Ⓨ

ᮾᕤ኱
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Ỉ℩㈼ኴ


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㧗཯ᛂάᛶ㑄⛣㔠ᒓ㘒యࡢᵓ㐀࡜཯ᛂ࡟㛵ࡍࡿ⌮ㄽィ⟬

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▼⏣ࠉ㇏


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⸆≀࡜㣧㣗≀࡟ྵࡲࢀࡿ⏕⌮άᛶ≀㉁࡜ࡢ┦஫స⏝ゎᯒ

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ᬗ㉁᭷ᶵ༙ᑟయᮦᩱࡢจ㞟≧ែ࡟
㛵ࡍࡿィ⟬

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᭷ᶵᮦᩱࢩࢫࢸ࣒

ᶓᒣ኱㍜ 㸭 

ศᏊ㛫┦஫స⏝⌮ㄽ࡜ࡑࡢศᏊࢡ
ࣛࢫࢱ࣮◊✲࡬ࡢᛂ⏝ศᏊ⛉Ꮫ◊✲ᡤᒾ⏣ᮎᘅ 㸭 

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㔠ᒓ㘒య࡟㛵ࡍࡿ⌮ㄽⓗ◊✲- 1 -㸦࣓ࣥࣂ࣮ᩘ㸧

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

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ᚤ⣽ᵓ㐀ࢆㄆ㆑ࡍࡿ㉸ศᏊ」ྜ⣔ࡢᵓ⠏࡜ᵓ㐀ゎᯒ

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DOOKHDGWRWDLO⎔≧SRO\ 
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໬Ꮫ཯ᛂࡢDELQLWLRィ⟬࡟ࡼࡿ◊
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

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ᮾ኱
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ᒣୗ㞝ྐ
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ࢡࣛࢫࢱ࣮」ྜయ࡟ࡼࡿ໬Ꮫ཯ᛂ
ࡢゎ᫂

㇏⏣ᕤᴗ኱
ࢡࣛࢫࢱ࣮◊✲ᐊᕷᶫṇᙪ 㸭 

㑄⛣⣔ิ࢖࢜ࣥࢆྵࡴ໬ྜ≀ࡢ཯ᛂไᚚ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

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࢟ࣛࣝ㉸ศᏊ㞟ྜయࡢ⌮ㄽⓗ᳨ウ'1$࡜㔠ᒓ㘒యࡢ┦஫స⏝

ࢆᇶ┙

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◊✲ㄢ㢟ྡ

ᡤᒓ

HN

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿศᏊ
㞟ྜయࡢ◊✲

ྡྂᒇᩥ⌮኱

HP

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㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧ᮏከ୍ᙪ 㸭 Ᏻ⸨㤶⧊ 㸭 

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᫂ᫍ኱
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ᯇᮏ୍Ⴙ


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⦰ྜከ⎔ⰾ㤶᪘໬ྜ≀࡟ᇶ࡙ࡃ᭷
ᶵⓎගᮦᩱ࠾ࡼࡧ᭷ᶵ༙ᑟయᮦᩱ
ࡢ㛤Ⓨ

ᮾி㎰ᕤ኱㝔ᕤ୰㔝ᖾྖ 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿⅣ⣲ཎᏊࢆ
ྵࡴศᏊࡢ㓟໬㑏ඖ཯ᛂ㐣⛬ࡢゎ
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✄ⴥ▱ኈ


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࣍࢘⣲㘒యࢆ㟁Ꮚ࢔ࢡࢭࣉࢱ࡜ࡍ
ࡿ㧗ᛶ⬟㹬ᆺ༙ᑟయࡢ㛤Ⓨ

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

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➨୍ཎ⌮㔞Ꮚㄽ࡟ࡼࡿḟୡ௦(PHUJLQJ࣓ࣔࣜࡢタィᣦ㔪ࡢ⋓ᚓ

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➨୍ཎ⌮ཬࡧྂ඾ศᏊືຊᏛィ⟬࡟ࡼࡿḟඖࢼࣀ≀㉁ࡢᵓ㐀ᙧᡂࣉࣟࢭࢫ࡜㟁Ꮚ≀ᛶࡢゎ᫂

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ග໬Ꮫ཯ᛂࡢไᚚ࡜ᛂ⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲㔞Ꮚ⛉Ꮫᢏ⾡
◊✲㛤Ⓨᶵᵓ

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⏕యศᏊ࠾ࡼࡧ⁐፹ࡢᵓ㐀ᶵ⬟┦
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ࡀᙧᡂࡍࡿ㟁Ⲵ⛣ື㘒యࡢ≀ᛶホ
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

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㓄఩Ꮚಖㆤ㔠ᒓࢡࣛࢫࢱ࣮ࡢ㟁Ꮚ
≧ែࡢゎ᫂

❧ᩍ኱
⌮

᪂ᇼె⣖


 㸭 

᱁Ꮚࣔࢹࣝࢆ⏝࠸ࡓࢱࣥࣃࢡ㉁ࢺ
࣏ࣟࢪ࣮ࡢ⇕ຊᏛⓗゎᯒ୕㔜኱⥲ྜ᝟ሗฎ⌮
ࢭࣥࢱ࣮

ⓑ஭ఙᐂ


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

㜰኱㝔
⌮

ᒣୗ೺୍


 㸭 

ࢭ࣮ࣝࣟࢫ⤖ᬗ㸦,,,㸧ᵓ㐀┦㌿⛣࡟ࡘ࠸࡚ࡢ኱つᶍ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ᳨ウ㸸㸴఩ࣄࢻࣟ࢟ࢩ࣓ࢳ
ࣝᇶࢥࣥࣇ࢛࣓࣮ࢩࣙࣥ࡜Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࡢᙳ㡪

໭኱㝔
ᕤ

᝴Ⰻ⏣▱ᶞ


 㸭 

ᢠ㔠ᒓ㘒యᢠయࡢศᏊㄆ㆑ᇶ┙ࡢศගᏛ࡟ࡼࡿ⌮ゎ་⸆ᇶ┙࣭೺ᗣ࣭
ᰤ㣴◊✲ᡤ

⛅ⴥᏹᶞ


 㸭 

᣺ື෇஧Ⰽᛶศගἲࡢ㉸ศᏊ࢟ࣛࣜࢸ࢕࡬ࡢᛂ⏝

ឡ፾኱㝔
⌮ᕤ

బ⸨ஂᏊ


 㸭 

㐜ᘏ⺯ගᮦᩱࡢບ㉳≧ែࡢ◊✲

᪥ᮏᕤᴗ኱
ᕤ

኱⃝ṇஂ


 㸭 

ࢩࣜࢥࣥᇶᯈୖࡢ᭷ᶵศᏊ྾╔ᵓ㐀࡜㟁Ꮚ≧ែࡢゎᯒ

ᶓ὾ᅜ኱
⌮ᕤ

኱㔝┿ஓ


 㸭 

ᶵ⬟ᛶᮦᩱ࡟࠾ࡅࡿ≀㉁㍺㏦ཬࡧ
࢖࢜ࣥఏᑟᛶࡢ⪃ᐹ

ᮾ㑥኱
་

ᒸ┿ᝆᏊ


 㸭 

᭷ᶵ༙ᑟయ⵨╔⭷ࡢ⮬Ⓨⓗ㓄ྥศᴟ⌧㇟ࡢゎ᫂

᫂἞኱
⌮ᕤ

㔝ཱྀࠉ⿱


 㸭 

᭷ᶵศᏊࡢගບ㉳≧ែ࡟࠾ࡅࡿᵓ
㐀ኚ໬ࡢ◊✲

໭኱㝔
⌮

ᑠ㛛᠇ኴ


 㸭 

ṍࢇࡔከ⎔ⰾ㤶᪘໬ྜ≀ࡢᵓ㐀࡜
ᛶ㉁

ᮾ㑥኱
⌮

Ώ㑔⥲୍㑻


 㸭 

ගᶵ⬟ᛶศᏊࡢ㟁Ꮚ≧ែ࠾ࡼࡧ᣺
ືࢫ࣌ࢡࢺࣝィ⟬

ᐊ⹒ᕤᴗ኱
ᕤ

㣤᳃ಇᩥ


 㸭 ᪂つ࡞඾ᆺඖ⣲໬ྜ≀ࡢᵓ㐀ࡢ◊
✲

Ꮫ⩦㝔኱
⌮

⊁㔝┤࿴


 㸭 

IO

IO

IO

IP

IQ

IR

IR

IR

IR

IS

IS

IS

IS

IS

IT

- 4 -

㸦࣓ࣥࣂ࣮ᩘ㸧

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

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‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

IT

ྍ㏫࡞཯ᛂ࡟ࡼࡿศᏊ」ྜయᙧᡂ
࡟ᇶ࡙ࡃ᪂つᮦᩱ㛤Ⓨᮾி㧗ᑓ᪂つᶵ⬟ᛶȧඹᙺศᏊࡢྜᡂ࡜≀ᛶ࡟㛵ࡍࡿ◊✲

IT

IT

IU

IV

IV

IV

IV

IX

IX

IX

IY

IY

IY

IY

IZ

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

㜰኱㝔
ᇶ♏ᕤ

ΎỈ❶ᘯ


 㸭 

࢔ࣝ࢝ࣜ㔠ᒓࢆ฼⏝ࡋࡓⅣ⣲ᅛయྜᡂ཯ᛂࡢィ⟬໬Ꮫⓗゎ᫂

໭኱㝔
ᕤ

ᓥ⏣ᩄᏹ


 㸭 

ග࣭☢Ẽ࣭㟁Ẽⓗ≉ᛶࢆ」ྜⓗ࡟♧ࡍ᪂つศᏊᛶ≀㉁ࡢ㛤Ⓨ

኱㜰ᗓ኱㝔
⌮

㓇ᕳ኱㍜


 㸭 

⢾⤖ྜࢱࣥࣃࢡ㉁K*DO࡜ࣇ࢓ࣝ
ࢿࢩࣝᇶ㢮ఝ໬ྜ≀ࡢ┦஫స⏝ゎ
ᯒ

ᮾ໭኱㝔
⸆

ᐑ⏣኱㍜


 㸭 

ȧඹᙺᣑᙇᆺ᭷ᶵ༙ᑟయᮦᩱࡢ㛤Ⓨ࡟㛵ࡍࡿ⌮ㄽィ⟬ᮾி㒔❧⏘ᴗᢏ⾡◊✲ࢭࣥࢱ࣮ᑠỮె♸ 㸭 

࣐ࣝࢳࢫࢣ࣮ࣝᵓ㐀ࢆ᭷ࡍࡿᾮయ
ࡢࢲ࢖ࢼ࣑ࢡࢫ࡜㍺㏦≀ᛶࡢ◊✲

ྡ኱㝔
ᕤ

ᒣཱྀࠉẎ


 㸭 

ࢡࣛࢫ࣮ࣞࢺࣁ࢖ࢻ࣮ࣞࢺࡢࢣ࣮
ࢪᵓ㐀࡟࠾ࡅࡿྛ✀ࢤࢫࢺ࡜࣍ࢫ
ࢺ࡜ࡢ┦஫స⏝ࡢホ౯

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

⚄ࠉ⿱௓


 㸭 

ྡ኱

‫ۑ‬

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‫ۑ‬

஬᰾㕲ࢡࣛࢫࢱ࣮ࡢ㟁Ꮚ≧ែ࡜཯ᛂᛶࡢ⌮ㄽゎᯒࢺࣛࣥࢫࣇ࢛࣮࣐ࢸ࢕ࣈ
⏕࿨ศᏊ◊✲ᡤᰗ஭ࠉẎ 㸭 

ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ㠀ᑐ⛠ࢥ࣐ศᏊࡢ㸱ḟඖᩚิไᚚ

ᮾ໭኱㝔
⌮

኱ᵳᖾ⩏


 㸭 

㑄⛣㔠ᒓࢲ࢖࢝ࣝࢥࢤࢼ࢖ࢻࡢ➨
୍ཎ⌮ィ⟬

㜰኱
⏘ᴗ⛉Ꮫ◊✲ᡤ⏣୰ៅ୍㑻 㸭 

࢝ࢸ࢟ࣥㄏᑟయࡢศᏊෆ࢝ࢵࣉࣜ
ࣥࢢ཯ᛂ࡟ᑐࡍࡿ')7ィ⟬

ᐩᒣ┴኱
ᕤ

༨㒊኱௓


 㸭 

᭷ᶵࢣ࢖⣲ᮦᩱࡢྜᡂ࡜≀ᛶゎ᫂

Ⲉᇛ㧗ᑓ

ỤᕝὈᬸ


 㸭 

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

‫ۑ‬

ィ⟬໬Ꮫⓗ࡞࢔ࣉ࣮ࣟࢳ࡟ᇶ࡙ࡃ᪂つ㏆㉥እⓎග⣲Ꮚࡢ㛤Ⓨ

ྡ኱㝔
⌮

ᮧ஭ᚁྐ


 㸭 

ከ᰾๓࿘ᮇ㑄⛣㔠ᒓ㘒య཯ᛂሙࢆ
⏝࠸ࡓ㔠ᒓ࢔ࣝ࢟ࣜࢹࣥ✀ࡢྜᡂ
࡜཯ᛂ

ᒸᒣ኱㝔
⮬↛⛉Ꮫ

㯮ᮌࠉᑲ


 㸭 

▷ᑑ࿨✀ࡸ⏺㠃໬Ꮫ✀ࡢ᣺ືࢫ࣌
ࢡࢺࣝゎᯒ

⟃Ἴ኱㝔
ᩘ⌮≀㉁

▼ᶫᏕ❶


 㸭 

- 5 -

‫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 

୰ศᏊ་⸆ရࡢ⭷㏱㐣ᛶ࡟ᑐࡍࡿ
ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ

⟃Ἴ኱ィ⟬⛉Ꮫ◊✲
ࢭࣥࢱ࣮

す⃝ᏹ᫭


 㸭 

ࢪࢳ࢔ࢩࢡࣟ࣌ࣥࢸࣥ࢜ࣜࢦ࣐࣮
ࡢ㟁Ꮚ≧ែゎᯒ

㟼ᒸ኱㝔
ᕤ

᳜⏣୍ṇ


 㸭 

㧗࠸཯ⰾ㤶᪘ᛶࢆ♧ࡍQȧ㟁Ꮚ⣔ࡢタィ࡜ᵓ⠏

㤳㒔኱ᮾி
⌮

す㛗ࠉ஽


 㸭 

㔞Ꮚ໬Ꮫ࡜⤫ィຊᏛ࡟ᇶ࡙ࡃ⁐ᾮ୰㔠ᒓ㘒యࡢ⌮ㄽⓗ◊✲

⥲◊኱

ᑠᮡ೺ᩯ


 㸭 

㑄⛣㔠ᒓゐ፹࡜ᇶ㉁࡜ࡢ┦஫స⏝࡟㛵ࡍࡿ⌮ㄽⓗ⪃ᐹ

᪩኱
ඛ㐍⌮ᕤ

ኴ⏣ⱥ௓


 㸭 

ᐦᗘỗ㛵ᩘἲ࡟ࡼࡿࢪ࢔ࢮࣆ
ࣥㄏᑟయࡢᵓ㐀ゎᯒ

ᮾி㒔ᕷ኱
ᕤ

ሷ᭶㞞ኈ


 㸭 

඾ᆺඖ⣲ࡢ≉ᛶࢆά⏝ࡋࡓගᶵ⬟ᛶศᏊࡢ㛤Ⓨ

Ⲉᇛ኱
ᕤ

࿃㒓཭ᏹ


 㸭 

6+ࢻ࣓࢖ࣥࢆ༢≉␗ⓗ࡟άᛶ໬ࡍ
ࡿࣔࢳ࣮ࣇࡢ㛤Ⓨ

ᮾ኱㝔
ᕤ

ᱵ᰿㍤᮶ே


 㸭 

㑄⛣㔠ᒓ㘒యࢆ⏝࠸ࡓ᭷ᶵࣇࢵ⣲໬ྜ≀ࡢ୙άᛶ⤖ྜษ᩿཯ᛂࡢᶵ
ᵓゎ᫂

㜰኱
ᕤ

⏕㉺ᑓ௓


 㸭 

ศᏊࡢᵓ㐀㸪཯ᛂ㸪ᶵ⬟ࡢ⌮ㄽ◊
✲

ᨺ㏦኱

ᶫᮏ೺ᮁ


 㸭 

ȧ㟁Ꮚ㒊఩㐃⤖໬ྜ≀ࡢ኱᣺ᖜࡡ
ࡌࢀ㐠ື࣏ࢸࣥࢩࣕࣝ࡟࠾ࡅࡿᆶ
┤㓄ྥ㞀ቨࡢศගᏛⓗ⢭ᗘ࡜㔞Ꮚ
໬Ꮫィ⟬

᪥኱
ᕤ

ዟᒣඞᙪ


 㸭 

᪂ወపḟඖ㑄⛣㔠ᒓ࢝ࣝࢥࢤࢼ࢖
ࢻࡢ㟁Ꮚ≧ែࡢゎ᫂

㤳㒔኱ᮾி
⌮

୰すຬ௓


 㸭 

6WUXFWXUDODQDO\VLVDQG
HQHUJHWLFSHUVSHFWLYHRI%HQ]RLFDFLGGHULYDWLYHV

8QLYHUVLW\RI
7VXNXED

5XPSD3DO
 㸭 ࣓ࢱࣥ㌿᥮⏝㔠ᒓྵ᭷ࢮ࢜ࣛ࢖ࢺ
ゐ፹ࡢᵓ㐀ゎᯒ࡜཯ᛂᶵᵓゎᯒᮾᕤ኱⛉Ꮫᢏ⾡๰ᡂᶓ஭ಇஅ 㸭 

&1ࡢỌஂ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ෌ホ
౯

ୖᬛ኱
⌮ᕤ

ஂୡಙᙪ


 㸭 

IZ

IZ

IZ

IZ

IZ

IZ

I[

I[

I[

I[

I[

I[

I\

I\

I\

- 6 -

㸦࣓ࣥࣂ࣮ᩘ㸧

‫ۑ‬

‫ۑ‬

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ᡤෆ
ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

DG

1&1ࣆࣥࢧ࣮ᆺ㘒య࡟࠾ࡅࡿ㓄఩Ꮚ஺᥮཯ᛂᕤ⛬࡟㛵ࡍࡿ◊✲⏕࿨࣭㘒యศᏊ⛉Ꮫ

DI

DK

ศᏊືຊᏛィ⟬࡜ඛ➃ⓗィࡿᢠయࡢືⓗᵓ㐀ゎᯒ࡟ࡼᶵ⬟ᛶ㛤ẆศᏊࡢᵓ㐀㸫≀ᛶ̿㟁Ꮚ≧ែ┦㛵ࡢゎ᫂௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧὾ᆏࠉ๛ 㸭 

⏕࿨๰ᡂ᥈✲
ࢭࣥࢱ࣮

㇂୰෪Ꮚ


 㸭 

⏕࿨࣭㘒యศᏊ⛉Ꮫⲡᮏဴ㑻 㸭 

‫ۑ‬

‫ۑ‬

‫ۑ‬

ࠑᇶ♏⏕≀Ꮫࠒ᪋タ฼⏝ $
ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

TE

0'ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓ࢔ࢡࢳࣥ⥺⥔ࡢᏳᐃᛶࡢ◊✲

ᮾᾏᏛ㝔኱
೺ᗣ⚟♴

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧ᑠ⏣ಇ㑻

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧 㸭 
‫ۑ‬ᡤෆࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

RD

῝ᒙ⚄⤒ࢿࢵࢺ࣮࣡ࢡ࡟ࡼࡿ⬻⌮ㄽࡢ᳨ド⚄⤒⏕⌮Ꮫ◊✲ᐊ௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ώ㎶ⱥ἞


Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧 㸭 
‫ۑ‬ࠑ⏕⌮Ꮫࠒ᪋タ฼⏝ $
ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

ND

་ᕤ㐃ᦠ࡟ᇶ࡙࠸ࡓேయෆࡢᅛᾮ
ΰ┦ὶゎᯒ

ᮾᾏ኱
ᕤ

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧㧗ᶫࠉಇⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧 㸭 
‫ۑ‬ᡤෆࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

LD

ࢸࢫࣛ05,ࢆ⏝࠸ࡓࣄࢺ⬻ࢿࢵࢺ࣮࣡ࢡࡢືⓗ࣓࢝ࢽࢬ࣒ࡢゎ᫂

⥲◊኱

- 7 -

௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧୸ᒣಟ⣖Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩ᥦฟ≧ἣ㸦༳ᮍᥦฟ㸧 㸭 
‫ۑ‬㻝㻚㻞㻌㻌㻞㻜㻝㻥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

FE

ศᏊෆ࠾ࡼࡧศᏊ㛫㟁Ꮚ⛣ືࡢศ
Ꮚ㌶㐨ἲ࡟ࡼࡿ◊✲

⚄ዉᕝ኱
⌮

⏣௰஧ᮁ


 㸭 

㧗཯ᛂᛶࡢࢪ࣎ࣛࣥ  ࣭$O࢔ࢽ࣭࢜ࣥ࣊ࢸࣟ࣋ࣥࢮࣥ㢮ࡢᛶ㉁ࡢゎ
᫂

ྡ኱㝔
ᕤ

ᒣୗࠉㄔ


 㸭 

ࣃ࢖ඹᙺ⣔ศᏊ࡟ࡼࡿⓎගᮦᩱࡢ
㛤Ⓨ

໭㔛኱
⌮

㛗㇂ᕝ┿ኈ


 㸭 

จ㞟ㄏ㉳Ⓨග࡟ࡘ࠸࡚ࡢ⌮ㄽⓗ◊
✲

༓ⴥᕤᴗ኱
ᕤ

ᒣᮏ඾ྐ


 㸭 

࣎࢘ࣝᆺඹᙺ໬ྜ≀ࡢ≀ᛶㄪᰝࠊ࠾ࡼࡧ㔠ᒓࢡࣛࢫࢱ࣮ゐ፹ࡢάᛶ
ホ౯◊✲

㜰኱㝔
ᕤ

Ḉ஭ⱥ༤


 㸭 

ከᗙ㓄఩Ꮚ࡛ᵓ㐀つไࡉࢀࡓ㑄⛣㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀㸪㟁Ꮚ≧ែ࠾ࡼࡧ཯ᛂᛶ

ዉⰋዪ኱㝔
⮬↛⛉Ꮫ

ᾆࠉᗣஅ


 㸭 

ȧࢡࣛࢫࢱ࣮ศᏊࡢ㟁Ꮚ≀ᛶࡢゎ
᫂

㜰኱㝔
⌮

すෆᬛᙪ


 㸭 

㉸ཎᏊ౯໬ྜ≀ࡢ㟁Ꮚ࣭ᗄఱᵓ㐀ࡢศගᏛⓗ◊✲

ᗈᓥ኱㝔
⌮

஭ཱྀెဢ


 㸭 

6L11ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ᪘
㑄⛣㔠ᒓ㘒య࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

໭㔛኱
⌮

⚄㇂ᫀᏹ


 㸭 

ࣈࣟࣔࢳ࣮ࣔࣝࣈ࣮ࣝࡢⰍ࡜ᵓ㐀
ࡢ㛵ಀ

ᘯ๓኱
ᩍ⫱

ᓥ⏣ࠉ㏱


 㸭 

㔠ᒓ୰ᚰ࢟ࣛࣜࢸ࢕࣮ࡢ⢭ᐦไᚚ࡜㘒యࡢᛶ㉁ゎ᫂

ᮾ኱㝔
⌮

㛗⏣ᾈ୍


 㸭 

࢖࣑ࢲࢡࣟࣉࣜࢻࡢගศゎ㐣⛬ࡢゎ᫂࡞ࡽࡧ࡟つ๎Ⅳ⣲ゐ፹࡟࠾ࡅ
ࡿ཯ᛂ⌮ゎ

ᮾ໭኱
ከඖ≀㉁⛉Ꮫ◊✲ᡤᒣᮏ㞞⣡ 㸭 

ගㄏ㉳㐣Ώᵓ㐀ኚ໬ࢆ฼⏝ࡋࡓศᏊ㛫཯ᛂ㛤Ⓨ

ᮾ኱㝔
⥲ྜᩥ໬

ṇ஭ࠉᏹ


 㸭 

Ẽ┦ࢼࣀ⢏Ꮚࡢ㍺㏦࡜Ⲵ㟁࡟㛵ࡍࡿศᏊືຊᏛⓗゎᯒ

㔠ἑ኱
⌮

⋢⯓▱ஓ


 㸭 

')7ィ⟬ࢆ⏝࠸ࡓ཯ᛂᶵᵓࡢゎ᫂࡟ࡼࡿ㑅ᢥⓗ᭷ᶵྜᡂ཯ᛂࡢ㛤Ⓨ

ዉⰋᩍ⫱኱
⌮

ᒣᓮ⚈Ꮚ


 㸭 

FI

GD

GI

IK

IO

IP

IQ

IQ

IW

IX

IY

IY

IY

I[

- 8 -

㸦࣓ࣥࣂ࣮ᩘ㸧































᪋タ฼⏝ %௦⾲฼⏝⪅ྡ

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

FE

ศᏊືຊᏛἲ࡟ࡼࡿỈࡢḟඖ࣐ࣛ
࣭ࣥ7+]᣺ືศගィ⟬

ி኱㝔
⌮

㇂ᮧྜྷ㝯


 㸭 ⏕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 

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 

ሙࡢ㔞Ꮚㄽ࡟ᇶ࡙ࡃᒁᡤ≀⌮㔞࡟ࡼࡿ㔞Ꮚ≀ᛶࡢ◊✲

ி኱㝔
ᕤ

℩Ἴ኱ᅵ


 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
⌮

┦⏣⨾◁Ꮚ


 㸭 

㔞Ꮚከᡂศ⣔ศᏊ⌮ㄽࢆ⏝࠸ࡓᶵ⬟ᛶศᏊࡢ⌮ㄽⓗ◊✲ᶓ὾ᕷ኱㝔⏕࿨ࢼࣀࢩࢫࢸ࣒

❧ᕝோ඾ 㸭 

」㞧ศᏊ⣔ࡢ໬Ꮫ཯ᛂࢩ࣑࣮ࣗࣞ
ࢩࣙࣥி኱⚟஭ㅬ୍グᛕ
◊✲ࢭࣥࢱ࣮

㕥ᮌࠉ⪽ 㸭 ᐩỌᆂ௓ 㸭 

FF

FF

FF

FG

FG

FI

FJ

FJ

FK

FL

FL

FL

FN

FN

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

㸦࣓ࣥࣂ࣮ᩘ㸧

























ࢼࣀࣂ࢖࢜≀㉁ࡢ㟁Ꮚ≧ែ࣭ᵓ㐀࣭ᶵ⬟ࡢ┦㛵ྡ኱ᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒
◊✲ᡤ

ᢲᒣࠉ῟


 㸭 ࣁࣟ㓟⬺ࣁࣟࢤࣥ໬㓝⣲࡜ࢩࢫࢸ࢖ࣥྜᡂ㓝⣲ࡢ཯ᛂᶵᵓゎᯒ࡜ࡑࢀ࡟ᇶ࡙࠸ࡓ㧗ᶵ⬟㓝⣲ࡢࢹࢨ࢖ࣥ㛗὾ࣂ࢖࢜኱
ࣂ࢖࢜ࢧ࢖࢚ࣥࢫ

୰ᮧࠉ༟ 㸭 㠉᪂ⓗ㔞Ꮚ⛉Ꮫ࡜኱つᶍࢩ࣑࣮ࣗࣞࢩࣙࣥ⛉Ꮫࡢ๰㐀㔞Ꮚ໬Ꮫ◊✲༠఍
◊✲ᡤ

୰㎷ࠉ༤


 㸭 

- 9 -







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

◊✲ㄢ㢟ྡ

ᡤᒓ

FO

Ⰽ⣲ቑឤ๣ࢆ⏝࠸ࡓㅖㄢ㢟࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

໭ᑿࠉಟ


 㸭 

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

࠾Ⲕ኱㝔
ே㛫ᩥ໬๰ᡂ

᳃ࠉᐶᩄ 㸭 

⁐ᾮ⏺㠃ࡢᵓ㐀࡜ᶵ⬟ࡢィ⟬໬Ꮫ

ᮾ໭኱㝔
⌮

᳃⏣᫂ᘯ


 㸭 

᪘㔠ᒓ࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࡢᶵᵓゎᯒ࡜᭷ᶵࢹࣂ࢖ࢫࢆᣦ
ྥࡋࡓⰾ㤶᪘໬ྜ≀ࡢタィ

ᮾ኱㝔
ᕤ

㔝ᓮிᏊ


 㸭 

ⰾ㤶᪘⁐፹࿴ࢡࣛࢫࢱ࣮ࡢගㄏ㉳⁐፹෌㓄ྥࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࢃࡿ⁐፹࿴ᵓ㐀᥈⣴࠾ࡼࡧ᣺ືࢫ࣌ࢡ
ࢺࣝࡢ㔞Ꮚ໬Ꮫィ⟬࠾ࡼࡧࠊࣇࣛ
ࣅ̺ࣥ㔠ᒓ࢖࢜ࣥ㓄఩㘒యࡢ᣺㟁ࣂࣥࢻࡢ⌮ㄽⓗゎᯒ

࠾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 ศᏊࢼࣀ࣮࢝࣎ࣥࡢᵓ㐀࡜≀ᛶ

ྡ኱㝔
⌮

℩ᕝὈ▱


 㸭 

㔞Ꮚ໬Ꮫ࡜⤫ィຊᏛ࡟ᇶ࡙ࡃ」㞧
໬Ꮫ⣔ࡢ⌮ㄽⓗ◊✲

ி኱㝔
ᕤ

బ⸨ၨᩥ


 㸭 

」⣲⎔ᘧ໬ྜ≀ࡢྜᡂ࠾ࡼࡧ཯ᛂ
ᛶ࡟㛵ࡍࡿ⌮ㄽ◊✲㧗▱኱㝔⥲ྜே㛫⮬↛⛉Ꮫ㔠㔝኱ຓ 㸭 

ࣜࣥ⬡㉁ࣇࣜࢵࣉࢆㄏ㉳ࡍࡿ⭷㈏㏻࣌ࣉࢳࢻࡢィ⟬ศᏊタィ⌮໬Ꮫ◊✲ᡤ

㰻⸨኱᫂ 㸭 

ࢭ࣮ࣝࣟࢫᮦᩱ࠾ࡼࡧ㛵㐃ࢱࣥࣃ
ࢡ㉁ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲ᐑᓮ኱ᕤ‫‮‬஭ᩄᩥ
 㸭 

ศᏊ㞟ᅋ⣔ࡢᵓ㐀ᙧᡂ࡜ᶵ⬟

ྡ኱㝔
ᕤ

ᒸᓮࠉ㐍


 㸭 

ᚨᓥ኱㝔♫఍⏘ᴗ⌮ᕤ

ྜྷ⏣ࠉ೺ 㸭 

FP

FQ

FQ

FR

FU

FW

FW

FY

FY

FY

FZ

FZ

FZ

F[

㉸⮫⏺᮲௳ୗࡢỈ̿᭷ᶵ⁐፹ΰྜ⣔ࡢ୪㐍ࢲ࢖ࢼ࣑ࢡࢫ࡜⁐፹࿴ᵓ㐀㸦࣓ࣥࣂ࣮ᩘ㸧











- 10 -





















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

◊✲ㄢ㢟ྡ

ᡤᒓ

F\

ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ࢞ࣛࢫ≧ែࡢᙎᛶ࡜ረᛶࡢ◊✲

ᮾ኱㝔
⥲ྜᩥ໬

ụ⏣ᫀྖ


 㸭 

2=⌮ㄽ࠿ࡽồࡲࡿ஧ཎᏊศᏊ⁐㉁ࡢ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮⿵ṇ࡟㛵ࡍࡿ◊✲㸸ࢡ࣮ࣟࣥ┦஫స⏝ࢆ⪃
៖ࡍࡿሙྜ

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 

㠀ᖹ㠃ᆺࣃ࢖ඹᙺศᏊࡢᵓ㐀࡜≀
ᛶ

኱㜰ᗓ኱㝔
⌮

ὠ␃ᓮ㝧኱


 㸭 

ࢼࣀ࣮࣭࢝࣎ࣥ࢔࣑ࣀ㓟࣭ࢡࣛࢫࢱ࣮ࡢ཯ᛂືຊᏛࡢ㔞Ꮚ໬Ꮫⓗ◊✲㟁Ẽ㏻ಙ኱㝔
᝟ሗ⌮ᕤ

ᒣ໭ెᏹ


 㸭 

ࢡࣛ࢘ࢹ࢕ࣥࢢศᏊࡢࢡࣛࢫࢱ࣮
ᵓ㐀ࡀ᰾㓟ࡢᏳᐃᛶ࡟୚࠼ࡿᙳ㡪ࡢゎᯒ⏥༡኱ඛ➃⏕࿨ᕤᏛ◊✲ᡤᮡᮏ┤ᕫ 㸭 

࣑࢜ࢩࣥ9,ࡢ㛗㊥㞳ࢫࢸࢵࣉ㐠ືࢆ฼⏝ࡋࡓ㧗ຠ⋡࡞ືస࣓࢝ࢽࢬ
࣒ࡢゎ᫂

ྡྂᒇ኱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


 㸭 

┦㛵㟁Ꮚ⣔ࡢ≉␗࡞≀ᛶ࡟㛵ࡍࡿ
ᩘ್ⓗ◊✲

༓ⴥ኱㝔
⌮

ኴ⏣ᖾ๎


 㸭 

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 

Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧ㞟ྜయࡢ㟁Ꮚ≧ែ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ࢔ࣉ
࣮ࣟࢳ

໭኱㝔
⌮

ຍ⸨ᫀᏊ


 㸭 

⁐፹ຠᯝࢆ⪃៖ࡋࡓᡭἲ࡟ࡼࡿᢠ
యࡢ⢾㙐ㄆ㆑ᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗ
◊✲

໭㔛኱
୍⯡ᩍ⫱

⬟Ⓩࠉ㤶


 㸭 

㌾;⥺ග⛉Ꮫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᗈᓥ኱㝔
⌮

㧗ᶫࠉಟ


 㸭 

F\

F]

GE

GF

GI

GJ

GK

GK

GK

GL

GM

GN

GT

GV

GX

- 11 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































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

◊✲ㄢ㢟ྡ

ᡤᒓ

GZ

໬Ꮫ཯ᛂࡢ㔞Ꮚࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ᮾ኱㝔
ᕤ

ᒣୗ᫭୍


 㸭 

ศᏊ㌶㐨ィ⟬࡟ࡼࡿ᭷ᶵ཯ᛂ࠾ࡼ
ࡧ᭷ᶵศᏊᵓ㐀ࡢタィ࡜ゎᯒ

ᮾ኱㝔
⸆

኱࿴⏣ᬛᙪ


 㸭 

➨୍ཎ⌮ィ⟬ࢆ฼⏝ࡋࡓ᪂つ⸆≀ࡢྜ⌮ⓗタィ㛤Ⓨ❧ᩍ኱⌮

6XQGDUDP$UXOPR]KLUDMDບ㉳≧ែ࡜ࡑࡢ⦆࿴㐣⛬࡟㛵ࡍࡿ
⌮ㄽⓗ◊✲

៞᠕኱
⌮ᕤ

⸭ୗࠉ⪽


 㸭 㑄⛣㔠ᒓ໬ྜ≀ࡢᵓ㐀࣭཯ᛂ࣭ศ
Ꮚ㛫┦஫స⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

࠾Ⲕ኱
ᇶᖿ◊✲㝔

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

໭㔛኱
⌮

⡿⏣ⱱ㝯


 㸭 

ࢼࣀ࣐ࢸࣜ࢔ࣝཬࡧ⏕యศᏊࡢᶵ
⬟࣭≀ᛶ࣭཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽⓗ
◊✲

᪩኱
ඛ㐍⌮ᕤ

୰஭ᾈᕭ


 㸭 

ᾮᬗศᏊࡢ⇕ఏᑟ⋡ࡢศᏊືຊᏛ
ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿண

ᮾᕤ኱
≀㉁⌮ᕤ

ᕝෆࠉ㐍


 㸭 

ࢱࣥࣃࢡ㉁㛫┦஫స⏝ࡢ⢒ど໬ࣔࢹࣝࡢ㛤Ⓨ࡜ᛂ⏝

㔠ἑ኱
⌮ᕤ

ᕝ୍ཱྀ᭸


 㸭 

ゐ፹ࢆ⏝࠸ࡓ໬Ꮫ཯ᛂᶵᵓࡢ⌮ㄽ
ⓗゎ᫂

Ⲉᇛ኱
⌮

᳃ࠉ⪷἞


 㸭 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⟬

㤳㒔኱ᮾி
⌮ᕤ

Ἴ⏣㞞ᙪ


 㸭 

⏕య㉸ศᏊࡢ❧యᵓ㐀ኚ໬࡜ᶵ⬟

ᮾᕤ኱
⏕࿨⌮ᕤ

໭ᑿᙲᮁ


 㸭 

୕㔜኱㝔
ᕤ

⛅ᒣࠉ஽


 㸭 

G[

HE

HJ

HN

HP

HP

HS

HS

HT

HV

HW

HY

HZ

H]

H]

➨୍ཎ⌮ィ⟬ᡭἲ࡟ࡶ࡜࡙ࡃࢼࣀ
ᵓ㐀࠾ࡼࡧཎᏊᒙ≀㉁ࡢᙧᡂ࡜ᶵ
⬟࡟㛵ࡍࡿ◊✲- 12 -

㸦࣓ࣥࣂ࣮ᩘ㸧 㸭 




























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

◊✲ㄢ㢟ྡ

ᡤᒓ

IE

ࢡࣛࢫࢱ࣮࢖࢜ࣥࡢᗄఱᵓ㐀ࠊ཯ᛂᛶ࠾ࡼࡧ⾪✺᩿㠃✚ࡢィ⟬

ᮾ໭኱㝔
⌮

኱ୗ៞ḟ㑻


ࢱࣥࣃࢡ㉁ࡢᵓ㐀࡜ᶵ⬟Ⓨ⌧ࡢ㛵
㐃ᛶ

ி㒔ᗓ኱㝔
⏕࿨⎔ቃ

ࣜࣥࢺࢗࣝ࢜ࢺṇ⨾ືⓗศᏊ㛫┦஫స⏝࡟ὀ┠ࡋࡓᾮᬗࡢᶵ⬟㛤Ⓨ

㜰኱㝔
ᇶ♏ᕤ

ෆ⏣ᖾ᫂


 㸭 

ศᏊᛶᑟ㟁࣭☢ᛶᮦᩱ࡟㛵ࡍࡿ⌮
ㄽⓗ◊✲

ி኱Ꮫ㝔
⌮

୰㔝⩏᫂


 㸭 

࢞ࣛࢫ⣔࡟࠾ࡅࡿ㐜࠸ࢲ࢖ࢼ࣑ࢡ
ࢫࡢ⌮ㄽ࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲

㜰኱㝔
ᇶ♏ᕤ

㔠ࠉ㗰


 㸭 ᭷ᶵศᏊࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿศᏊ
㛫┦஫స⏝ࡢᙺ๭

ᘯ๓኱㝔
⌮ᕤ

ᒣᓮ⚈ᖹ


୙෾ࢱࣥࣃࢡ㉁ࡀị࡟྾╔ࡍࡿศᏊᶵᵓಙᕞ኱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 ୧ぶ፹ᛶศᏊ㞟ྜయ࠿ࡽ࡞ࡿ኱つᶍ୙ᆒ୍⣔୰ࡢ≀㉁㍺㏦ࢩ࣑ࣗ
࣮ࣞࢩࣙࣥࡢᵓ⠏

ྡ኱㝔
ᕤ

ྜྷ஭⠊⾜


 㸭 ࢔ࣝࢥ࣮ࣝ༢ศᏊ⭷Ỉ⏺㠃࡛ࡢᵓ㐀࡜᣺ືࢫ࣌ࢡࢺࣝࡢศᏊືຊᏛ
ࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲

ᐩᒣ኱
⌮ᕤ

▼ᒣ㐩ஓ


 㸭 

᭷ᶵග㉳㟁ຊࢹࣂ࢖ࢫࡢ㟁Ⲵᵓ㐀ゎᯒ࡜ᶵ⬟᥈⣴ࢆ┠ᣦࡋࡓ⌮ㄽ◊
✲

᪥ᮏዪᏊ኱
⌮

ᮧᒸࠉᱻ


 㸭 

᣺㟁┦஫స⏝࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ி኱⚟஭ㅬ୍グᛕ
◊✲ࢭࣥࢱ࣮

బ⸨ࠉᚭ 㸭 

᭷ᶵ⤯⦕ศᏊ⭷୰ࡢ㔠ᒓཎᏊࢡࣛ
ࢫࢱ࣮ࡢືⓗᣲືࡢ◊✲

༓ⴥ኱㝔
⌮

୰ᒣ㝯ྐ


 㸭 

ᕼⷧ⁐ᾮ୰ࡢ⌫≧࠾ࡼࡧᲬ≧ศᏊࡢᅇ㌿ᣑᩓಀᩘ࡜6WRNH(LQVWHLQ
'HE\Hࡢ㛵ಀࡢศᏊㄽⓗ⾲ᘧࡢ☜❧

᪂₲኱
⌮

኱㫽⠊࿴


 㸭 

IF

IF

IF

IF

IG

IG

IG

IG

IG

IJ

IJ

IJ

IJ

IJ

IJ

- 13 -

㸦࣓ࣥࣂ࣮ᩘ㸧 㸭 
 㸭 







 㸭 






















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

◊✲ㄢ㢟ྡ

ᡤᒓ

IK

$3(;཯ᛂ࠾ࡼࡧ$3(;㔜ྜ཯ᛂࡢ཯
ᛂᶵᵓ࡜ࢼࣀ࣮࢝࣎ࣥศᏊࡢᵓ㐀≀ᛶゎ᫂◊✲

ྡ኱㝔
⌮

ఀ⸨ⱥே


 㸭 $FFXUDWHHVWLPDWLRQRI
HOHFWURGHSRWHQWLDORQ7L2
W\SHFDWKRGHV

ᮾᕤ኱㝔
໬Ꮫ

-XKDV]*HUJHO\ 㸭 

࣓ࢰࢫࢣ࣮ࣝࢧ࢖ࢬࢆ᭷ࡍࡿ㔠ᒓ㘒యࡢ㟁Ꮚ≧ែゎᯒᮾᕤ኱໬Ꮫ⏕࿨⛉Ꮫ◊✲ᡤ⏣୰⿱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 

㧗ຠ⋡ኴ㝧㟁ụタィ࡟ྥࡅࡓ᭷ᶵ
↓ᶵ⏺㠃࡟࠾ࡅࡿศᏊᵓ㐀࣭㟁Ꮚ
≧ែࡢゎ᫂

ᮾ኱
ඛ➃⛉Ꮫᢏ⾡
◊✲ࢭࣥࢱ࣮

ᇛ㔝ுኴ 㸭 

㉁㔞ศᯒἲ࡟ࡼࡿ⏕యศᏊࡢࣛࢪ
࢝ࣝศゎ㐣⛬࡟㛵ࡍࡿ◊✲

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

ὸᕝ኱ᶞ


 㸭 

ᶵᲔᏛ⩦࡟ኪ⁐፹࿴ࣔࢹࣝࡢ⢭ᗘྥୖࢆ┠ᣦࡋࡓࢹ࣮ࢱࡢゎᯒ

⟃Ἴ኱㝔
ᩘ⌮≀㉁

ᯇ஭ࠉ஽


 㸭 

」ྜࢼࣀࢡࣛࢫࢱ࣮࣭ศᏊ」ྜయ
ࡢᵓ㐀࠾ࡼࡧ㟁Ꮚ≧ែ࡟㛵ࡍࡿ◊
✲

៞᠕኱
⌮ᕤ

ゅᒣᐶつ


 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 

⏕యศᏊ࡟⤖ྜࡍࡿ୺㙐ಟ㣭ᆺ࣌ࣉࢳࢻࡢྜ⌮ⓗタィ

ᮾ኱㝔
ᕤ

᳃ᮏ῟ᖹ


 㸭 

㑄⛣㔠ᒓࢡࣛࢫࢱ࣮࡜᭷ᶵ໬ྜ≀
ࡢ཯ᛂゎᯒ

ᮾ኱㝔
ᕤ

୸ᒣⱱኵ


 㸭 

㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿගྜᡂỈศゎ཯ᛂࡢศᏊᶵᵓࡢゎ᫂

ྡ኱㝔
⌮

㔝ཱྀࠉᕦ


 㸭 

ࣞࢽ࣒࢘ , ࣇࢱࣟࢩ࢔ࢽࣥ㘒యࡢ㟁Ẽ໬Ꮫⓗ&2㑏ඖ཯ᛂᮾ኱⏕⏘ᢏ⾡◊✲ᡤᮧ⏣ࠉ្ 㸭 

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

IK

IL

IL

IL

IL

IM

IM

IM

IN

IN

IP

IQ

IQ

IR

IR

- 14 -

㸦࣓ࣥࣂ࣮ᩘ㸧

































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

◊✲ㄢ㢟ྡ

ᡤᒓ

IR

ィ⟬໬Ꮫⓗᡭἲࢆ⏝࠸ࡓ᭷ᶵྜᡂ
཯ᛂࡢᶵᵓࠊ᭷ᶵ≀㉁ࡢ≀ᛶゎ᫂

៞᠕኱
⸆

ᮾᯘಟᖹ


 㸭 

㔞Ꮚ໬Ꮫィ⟬࡜ᶵᲔᏛ⩦࡛ᣅࡃゐ፹໬Ꮫ࣭ᮦᩱ⛉Ꮫ

┦ᶍ୰ኸ
໬Ꮫ◊✲ᡤ

ᕭୖᖾ୍㑻


 㸭 

໬Ꮫ཯ᛂືຊᏛ⌮ㄽィ⟬ࢆά⏝ࡋࡓ᭷ᶵ໬Ꮫ཯ᛂࡢ཯ᛂᶵᵓゎᯒ

எ༲◊✲ᡤ

㯮ෆᐶ᫂


 㸭 

᭷ᶵ㔠ᒓ㘒యࢆ⏝࠸ࡓゐ፹࠾ࡼࡧⓎගᛶᮦᩱࡢ⌮ㄽⓗタィ࡜≀ᛶゎ
ᯒ

໭኱㝔
ᕤ

ఀ⸨ࠉ⫕


 㸭 

ࢩࣗ࢘ࢻ࢔ࢬࣜࣥ࡟࠾ࡅࡿᙅ࠸┦஫స⏝ࡢຠᯝⲈᇛ኱㝔⌮ᕤ

7DERURVL$WWLOD 㸭 

0'ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓከ๣᤼ฟࢺࣛࣥࢫ࣏࣮ࢱ࣮」ྜయࡢᇶ
㉁᤼ฟ࣓࢝ࢽࢬ࣒ࡢゎ᫂㸸⬡㉁ศ
Ꮚࡢᙳ㡪ᮾ኱ඛ➃⛉Ꮫᢏ⾡
◊✲ࢭࣥࢱ࣮

⠛⏣ᜨᏊ 㸭 

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

ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜≀⌮໬Ꮫᐃ࡟ࡼࡿᢠయᢠཎ」ྜయࡢ┦஫స⏝ゎᯒ࡜ࡑࡢ≀ᛶᨵኚ

ᮾ኱㝔
ᕤ

㯮⏣኱♸


 㸭 

཯ᛂ⮬ື᥈⣴ἲࡢ㛤Ⓨ࡜ᛂ⏝

໭኱㝔
⌮

๓⏣ࠉ⌮


 㸭 

㑄⛣㔠ᒓ㘒య࡟ࡼࡿᑠศᏊάᛶ໬
ࡢゐ፹཯ᛂ࣓࢝ࢽࢬ࣒ࡢゎ᫂஑኱
,t&1(5ఀໃᕝ⨾✑ 㸭 

ḟୡ௦⇕㟁ኚ᥮ᮦᩱࡢࡓࡵࡢ⇕ఏᑟ⋡ไᚚ࡟㛵ࡍࡿ◊✲

ྡᕤ኱㝔
ᕤ

ᐑᓮ⚽ಇ


 㸭 

ᐇ㦂࡜ィ⟬࡟ࡼࡿ᭷ᶵ཯ᛂᶵᵓゎ
ᯒ

ᮾ኱㝔
⸆

⁪⏣ࠉⰋ


 㸭 

㟷Ⰽගཷᐜయ⺮ⓑ㉁ࡢ'1$ಟ᚟ᶵᵓࡢ⌮ㄽⓗゎᯒ

⌮໬Ꮫ◊✲ᡤ

బ⸨❳㤿 㸭 

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

໭኱
⛉Ꮫ◊✲ᡤ

:0&
6DPHHUD

ከ᰾0Q㘒య࡟ゐ፹ࡉࢀࡿỈศゎࡢ㠀᩿⇕㟁ᏊືຊᏛ࡟ࡼࡿ◊✲ி኱⚟஭ㅬ୍グᛕ
◊✲ࢭࣥࢱ࣮

ᒣᮏ᠇ኴ㑻 㸭 

ศᏊືຊᏛィ⟬࡟ࡼࡿ㧗᥋╔⺮ⓑ㉁ࡢỈ୰᥋╔࣓࢝ࢽࢬ࣒ࡢゎ᫂

ྡ኱㝔
ᕤ

㕥ᮌ῟ᕧ


 㸭 

IR

IS

IT

IT

IU

IU

IU

IU

IU

IU

IV

IV

IV

IW

IW

ప

- 15 -

㸦࣓ࣥࣂ࣮ᩘ㸧


























 㸭 






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

◊✲ㄢ㢟ྡ

ᡤᒓ

IW

&RPSXWDWLRQDOLQQRYDWLRQRI
QDQRFRPSRVLWHPDWHULDOVXVLQJILUVWSULQFLSOHVDQG
PROHFXODUG\QDPLFVVLPXODWLRQV

⏘ᴗᢏ⾡
⥲ྜ◊✲ᡤ

3UDGHHS
9DUDGZDMᑠศᏊࡢኚ᥮཯ᛂࢆᣦྥࡋࡓ㑄⛣㔠ᒓゐ፹ྜᡂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

┦ᶍ୰ኸ
໬Ꮫ◊✲ᡤ

㛗ᒸṇᏹ


 㸭 

ᾮయ୰ࡢ⏕యศᏊࡢᣑᩓಀᩘࡢศ
ᏊືຊᏛィ⟬࡜ࡑࡢᇶᮏࢭࣝࢧ࢖
ࢬ౫Ꮡᛶ

஑኱㝔
⌮

⛅ᒣࠉⰋ


 㸭 

0760''5,60.+ἲࢆᛂ⏝ࡋࡓ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ண ἲࡢ☜❧

❧࿨㤋኱
⏕࿨⛉Ꮫ

ᮡ⏣ᫀᓅ


 㸭 ➨୍ཎ⌮ศᏊືຊᏛἲ࡟ࡼࡿᇶᗏ
≧ែ࠾ࡼࡧບ㉳≧ែࡢ⏕య⣔࡬ࡢᒎ㛤⌮໬Ꮫ◊✲ᡤ

୰ᮧ᣺୍㑻 㸭 

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

Ⲉᇛ኱
ᕤ

ᇛሯ㐩ஓ


 㸭 

࣏ࢫࢺ࣓ࢱࣟࢭࣥゐ፹࡟ࡼࡿ࢜ࣞ
ࣇ࢕ࣥ㔜ྜ཯ᛂ࠾ࡼࡧ㐃㙐⛣ື཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲

ྡ኱㝔
᝟ሗ

୕⃝ዉࠎ


 㸭 

⌮ㄽィ⟬ࢆᇶ┙࡜ࡍࡿ᪂つྜᡂ཯
ᛂࡢ㛤ᣅ

ᮾ㎰኱
⏕࿨⛉Ꮫ

ᩧ⸨❳⏨


 㸭 

⣽⬊ෆ࣓ࢱ࣎ࣛ࢖ࢺ࡟ࡼࡿ㠀≉␗ⓗ┦஫స⏝ࡢศᏊືຊᏛࢩ࣑ࣗ
࣮ࣞࢩࣙࣥ

๓ᶫᕤ⛉኱
⏕࿨᝟ሗ

ඃࠉஎ▼


 㸭 ⣽⬊ෆ࡟࠾ࡅࡿ⺮ⓑ㉁ࡢືⓗᵓ㐀ࡢゎ᫂ࢆ┠ᣦࡋࡓศᏊືຊᏛࢩ
࣑࣮ࣗࣞࢩࣙࣥ

⌮໬Ꮫ◊✲ᡤ

ᯇᓅ኱㍜ 㸭 

ග࣭㟁Ꮚᶵ⬟᭷ᶵศᏊᮦᩱࡢᶵ⬟ゎ᫂࡜ࢹࢨ࢖ࣥࡢࡓࡵࡢィ⟬໬Ꮫࢩ࣑࣮ࣗࣞࢩࣙࣥ

㧗ᗘ᝟ሗ⛉Ꮫᢏ⾡
◊✲ᶵᵓ

Ἑᮾ⏣㐨ኵ


 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 

࣒࣊㍺㏦య࡬ࡢ࣒࣊⤖ྜ㐣⛬ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ

⌮໬Ꮫ◊✲ᡤ

⏣ᮧᗣ୍ 㸭 

㧗ᴟᛶᾮᬗ໬ྜ≀ࡢศᏊືຊᏛࢩ
࣑࣮ࣗࣞࢩࣙࣥ

஑኱ඛᑟ≀㉁໬Ꮫ◊✲ᡤዟᮧὈᚿ 㸭 

IW

IX

IX

IX

IX

IX

IY

IY

IY

IZ

IZ

I[

I[

I[

- 16 -

㸦࣓ࣥࣂ࣮ᩘ㸧 㸭 






























ᡤෆ
௦⾲฼⏝⪅ྡ

Ⅼᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧ࣉࣟࢪ࢙ࢡࢺ
ࢥ࣮ࢻ

◊✲ㄢ㢟ྡ

ᡤᒓ

DD

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

ィ⟬⛉Ꮫ
◊✲ࢭࣥࢱ࣮Ụཎṇ༤ 㸭 

ࢱࣥࣃࢡ㉁จ㞟ࡢศᏊࢩ࣑࣮ࣗࣞ
ࢩࣙࣥ

⏕࿨๰ᡂ
᥈✲ࢭࣥࢱ࣮

ዟᮧஂኈ 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࡟࠾ࡅࡿⰾ㤶᪘Ⅳ໬Ỉ⣲ࡢ⏕ᡂ⤒㊰ࡢゎ᫂࢔ࢫࢺࣟࣂ࢖࢜ࣟࢪ࣮
ࢭࣥࢱ࣮

ᑠᯇࠉຬ


 㸭 

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

⾲㠃྾╔ศᏊࡢ㟁Ꮚཬࡧࣇ࢛ࣀࣥ
≀ᛶ⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ༡㇂ⱥ⨾ 㸭 

7KHRUHWLFDOVWXG\RIPROHFXODUYLEUDWLRQDOSRODULWRQLQWKHXOWUDVWURQJFRXSOLQJUHJLPH⌮ㄽ࣭ィ⟬ศᏊ⛉Ꮫ

DF

DG

DG

DI

DI

DJ

DJ

DJ

DI

㸦࣓ࣥࣂ࣮ᩘ㸧ᩧ⸨┿ྖ 㸭 㣤⏣೺஧ 㸭 

1*8<(17+$1+
3+8&
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௦⾲฼⏝⪅ྡ
㸦࣓ࣥࣂ࣮ᩘ㸧Ⅳ❤ாྖⅬᩘ㸦ᐇ⦼㸭๭ᙜ㸧฼⏝ሗ࿌᭩㸦ᥖ㍕࣮࣌ࢪ㸧 㸭 
ࠑ⏕⌮Ꮫࠒ
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ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ⬻ᶵ⬟⏬ീゎᯒ⏕యᶵ⬟᝟ሗゎᯒᐊ

LD

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)ORRGILOOLQJQHWZRUNV ))1V ࢆ౑ࡗࡓ㟁㢧ࢹ࣮ࢱࢭࢵࢺࡢ⮬ື඲ᵓ㐀ḟඖ෌ᵓ⠏኱⬻⚄⤒ᅇ㊰ㄽ- 18 -

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

❑⏣ⰾஅ 㸭 

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Ў‫܇‬ϋấợỎЎ‫᧓܇‬ᩓ‫܇‬ᆆѣể҄‫ܖ‬Ӓࣖೞನỉᄂᆮᴾᵧᶌᶒᶐᵿᴾ ᴾ ᵿᶌᶂᴾᵧᶌᶒᶃᶐᵋᵫᶍᶊᶃᶁᶓᶊᵿᶐᴾ ᾒᾷᾰ῁ᾶᾴᴾ ᵲᶐᵿᶌᶑᶄᶃᶐᴾᵿᶌᶂᴾᵫᶃᶁᶆᵿᶌᶇᶑᶋᴾᶍᶄᴾ
ᵡᶆᶃᶋᶇᶁᵿᶊᴾ ᵰᶃᵿᶁᶒᶇᶍᶌᴾ ᴾ ᴾ     ‫⏣ۑ‬௰஧ᮁ 㸦⚄ዉᕝ኱Ꮫ ⥲ྜ⌮Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
1.1ࢢࣜࢽ࣮ࣖ཯ᛂࡢ࣓࢝ࢽࢬ࣒

ࡇࢀࡲ࡛㛗ᖺ࠿ࡅ࡚ࠊࢢࣜࢽ࣮ࣖ཯ᛂࡢ࣓࢝ࢽࢬ࣒ࢆ◊✲ࡋ࡚ࠊHolm ࡟ࡼࡾሗ࿌ࡉࢀ
ࡓࠊ࢔ࢭࢺࣥ࡜ ࣋ࣥࢰࣇ࢙ࣀࣥ࡟ᑐࡋ࡚ࠊ40 ✀㢮ࡢࢢࣜࢽ࣮ࣖ཯ᛂࡢ㏿ᗘᐃᩘ࡜㛵㐃࡙ࡅࡿࡼ࠺࡟ࠊάᛶ໬࢚ࢿࣝࢠ࣮ࢆィ⟬ࡍࡿࡇ࡜࡛ࠊ◊✲ࡋࡓࠋ ཯ᛂࡢ࣓࢝ࢽࢬ࣒࡜ࡋ࡚ࠊ
㟁Ꮚᑐ⛣ື࡛࠾ࡇࡿ࣮ࣝࢺ࡜ࠊ୰㛫య࡜ࡋ࡚ࠊ୍㟁Ꮚ⛣ື࡟ࡼࡾࠊ࢔ࢽ࢜ࣥ ࣛࢪ࢝ࣝࡢ
⏕ᡂࢆ⤒࡚࠾ࡇࡿࡶࡢ࡜ࡀ࠶ࡾࠊ࡝࠺࠸࠺᮲௳࡛ࡑࢀࡽࡀ㉳ࡇࡿࡇ࡜ࢆࠊ᫂ࡽ࠿࡟ࡋࡓࠋ   ᭷ᶵ໬Ꮫࡢᩍ⛉᭩࡟ࠊࡼࡃ᭩࠿ࢀ࡚࠸ࡿ࣓࢝ࢽࢬ࣒ࡣࠊࢢࣜࢽ࣮ࣖヨ⸆ RMgX ࠿ࡽࠊ࢔ࣝࢹࣄࢻ࠿ࠊࢣࢺࣥࡢ࢝ࣝ࣎ࢽࣝᇶ࡬ࠊ㟁Ꮚᑐࡢ⛣ືࡀ࠾ࡇࡿࡇ࡜࡛ጞࡲࡿ࡜࠸࠺ࡶࡢ࡛
࠶ࡿࠋࡑࡢ㝿ࠊ࡜ࡃ࡟ Grignard ヨ⸆ࡢ Mg ࠿ࡽࠊ࢝ࣝ࣎ࢽࣝᇶ࡟ࠊ┤᥋࡟㓄఩ࡀ࠾ࡇࡗ
࡚ࠊࡇࡢ⛣ືࢆᐜ᫆࡟ࡍࡿ࡜࠸࠺ࠊConcerted Mechanism ࡶᥦၐࡉࢀ࡚࠸ࡿࠋࡇࢀ࡟ᑐࡋ࡚ࠊ
ࡲࡎࣛࢪ࢝ࣝࡢ⏕ᡂࡀ㔜せ࡛࠶ࡿ࡜࠸࠺ㄝࡀ࠶ࡗ࡚ࠊ࡝࠺࠸࠺᫬࡟ࠊࣛࢪ࢝ࣝ཯ᛂ࡛㐍ࡴࡢ࠿ࠊࡣࡗࡁࡾࡋ࡚࠸࡞࠿ࡗࡓࠋ㛗ᖺ◊✲ࢆ⥆ࡅ࡚ࠊ ࡑࢀࡒࢀࡢ᮲௳ࢆ᫂ࡽ࠿࡟࡛ࡁࡓࠋ㸰 ◊✲᪉ἲࠊィ⟬᪉ἲ ࡍ࡭࡚ࡢィ⟬ࡣࠊG09 ࣉࣟࢢ࣒࡛ࣛ⾜ࡗࡓࠋ 㛢Ẇ⣔ࡢィ⟬࡛ࡣࠊCAM-B3LYP ἲ࡛⾜࠸ࠊ㛤᰾⣔ࡢィ⟬࡛ࡣࠊB3LYP ἲ࡛⾜ࡗࡓࠋ㑄⛣≧ែࡢᵓ㐀࡜࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋ࡚ࠊฟⓎศᏊ࡜ࡢ࢚ࢿࣝࢠ࣮ᕪࢆィ⟬ࡋ࡚ࠊࡇࢀࢆ཯ᛂࡢάᛶ໬࢚ࢿࣝࢠ࣮࡜ࡳ࡞ࡋ࡚ࠊᐇ㦂⤖ᯝ࡜ẚ㍑ࡋࡓࠋᇶᗏ㛵ᩘࡣࠊ6-31+g(d,p) ࡛࠶ࡿࠋ㸱 ◊✲ᡂᯝ
Holm ࡢሗ࿌࡟࠶ࡿࠊ㸰㸮✀㢮ࡢࠊRMgX ࡜ R2Mg ࡜ acetone ࡜ benzophenone ࡜ࠊࡢ཯ᛂ࡟ࡘ࠸࡚ࠊࡍ࡭࡚࡛㸲㸮✀㢮ࡢ཯ᛂࡢ཯ᛂ㏿ᗘࡢᐇ㦂್ࢆࠊሗ࿌ࡋ࡚࠶ࡿࠋィ⟬ࡋࡓάᛶ໬࢚ࢿࣝࢠ್࣮࡜ᐇ㦂್ࢆẚ㍑ࡋ࡚ࠊacetone ࡜ࠊbenzophenone ࡢࡑࢀࡒࢀ࡟ࡘ࠸࡚ࠊᐇ

- 19 -

㦂್࡜ࠊィ⟬್ࡢ㛫࡟ࠊࡼ࠸┦㛵㛵ಀࡀ♧ࡉࢀࡓࠋAcetone ࡢሙྜ࡜ࠊBenzophenone ࡢࡑࢀࡒࢀ࡟ࡘ࠸࡚ࠊ཯ᛂ㏿ᗘ࡜ࠊィ⟬ࡋࡓάᛶ໬࢚ࢿࣝࢠ࣮ࡢ㛫࡟ࡣࠊࡼ࠸┤⥺㛵ಀ ࡀᚓࡽࢀࡓࠋ཯ᛂࡀࣛࢪ࢝ࣝᶵᵓ࡛㐍ࡴࡢࡣࠊ benzophenone ࡜ࡢ཯ᛂࡢሙྜࡔࡅ࡛࠶ࡿࡀࠊࡑࢀ࡟ࡶ ᮲௳ࡀ࠶ࡿࡇ࡜ࡀࠊ᫂ࡽ࠿࡟ࡉࢀࡓࠋHolm ࡢㄽᩥ࡟ࡣࠊ୍ࡘࡢ ࢢࣜࢽ࣮ࣖヨ⸆ RMgX࡟ࡘ࠸࡚ࠊ஧ࡘࡢᩘ್ࡀ࡛࡚࠸ࡿሙྜࡀ࠶ࡿࡀࠊࡇࢀࡣ ࣛࢪ࢝ࣝᶵᵓ࡛㐍ࡴሙྜ࡜ࠊ㟁Ꮚᑐ⛣ື࡛࠾ࡇࡿሙྜࡢ୧᪉ࡀ࠶ࡿࡓࡵ࡛࠶ࡿࠋ
ࣛࢪ࢝ࣝ཯ᛂ࡛ࠊ᪂ࡋ࠸⤖ྜࡀ࡛ࡁࡿࡓࡵ࡟ࡣࠊ཯ᛂࡢ㑄⛣≧ែ࡛ࠊ⤖ྜࡢ࡛ࡁࡿ࡜ࡇ
ࢁ࡛ࠊ୍㔜㡯≧ែ࡟࡞ࡽ࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࠋ᭱ึࡢࣛࢪ࢝ࣝࡣ ୕㔜㡯≧ែ࡛࠶ࡿ࠿ࡽࠊ
㑄⛣≧ែ࡛⣔㛫஺ᕪࡀ㉳ࡇࡿࡇ࡜࡟࡞ࡿࡀࠊࡇࡢࡓࡵ࡟ࡣ࠶ࡿ᮲௳ࡀᚲせ࡟࡞ࡿࠋGrignard཯ᛂࡀࣛࢪ࢝ࣝᶵᵓ࡛㐍ࡴࡓࡵ࡟ࡣࠊ࠸ࢁ࠸ࢁࡢ ᮲௳ࡀ ᩚࡗ࡚࠸࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࡢ
࡛ࠊ௒᪥ࡲ࡛ࡇࢀࡽࡢⅬࡀࠊ῝ࡃ◊✲ࡉࢀ࡚࠸࡞࠿ࡗࡓࠋ≉࡟ R2Mg ࡜ Benzophenone ࡢ཯ᛂࡣ ࣛࢪ࢝ࣝ⤒⏤࡛࠾ࡇࡿࡀࠊ୰㛫యࡀ ୙Ᏻᐃ࡞ࡓࡵ࡟ ◊✲࡟ ᫬㛫ࡀ࠿࠿ࡗࡓࠋ
௒ᅇ Grignard ཯ᛂࡢࣛࢪ࢝ࣝᶵᵓࡀࠊࡼࡃศ࠿ࡗ࡚ࡁࡓࡢ࡛ࠊࡉࡽ࡟࡯࠿ࡢ໬Ꮫ཯ᛂࡢ
ࠕ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࠊゎᯒࢆ㐍ࡵࡿ‽ഛࡀ࡛ࡁࡓࠋ
ࣛࢪ࢝ࣝࢆ⤒⏤ࡍࡿ⤖ྜࡢ⏕ᡂࡣࠊ᭷ᶵ໬Ꮫ࡛ࡶࡗ࡜ࡶ㔜せ࡞཯ᛂࡢ୍ࡘ࡛࠶ࡿ࠿ࡽࠊ
௒ᚋ௚ࡢ཯ᛂ࡛࡝ࡢࡼ࠺࡟࡞ࡗ࡚࠸ࡿࡢ࠿ࠊ᫂ࡽ࠿࡟ࡋ࡚࠸ࡃணᐃ࡛࠶ࡿࠋ
Ⓨ⾲ ฟ∧ணᐃ ⏣௰ࠊ ᯇᮏ  ௒ᖺ୰࡟ㄽᩥᢞ✏ࡢணᐃࠋ- 20 -

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Elucidating properties of reactive diborane(4)s, Al-anion, andheterobenzenes
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- 21 -(kÉÜÖÇ.Ï(B3LYP/def2-SVP LEÔn/K4KÌ Al /A2M 3 (Scheme 2a) Al j{Pvgïaî{R x
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1.

Akiyama, S.; Yamada, K.; Yamashita, M., Angew. Chem. Int. Ed. 2019, 58, 11806-11810.

2.

Ishikawa, Y.; Suzuki, K.; Yamashita, M., Organometallics 2019, 38, 2597-2601.

3.

Kaiya, C.; Suzuki, K.; Yamashita, M., Angew. Chem. Int. Ed. 2019, 58, 7749-7752.

4.

Morisako, S.; Watanabe, S.; Ikemoto, S.; Muratsugu, S.; Tada, M.; Yamashita, M., Angew. Chem. Int. Ed. 2019,58, 15031-15035.

5.

Yagi, A.; Kisu, H.; Yamashita, M., Dalton Trans. 2019, 48, 5496-5499.

6.

Akiyama, S.; Ikemoto, S.; Muratsugu, S.; Tada, M.; Yamashita, M., Organometallics 2020, 39, 500-504.

7.

Kobayashi, A.; Suzuki, K.; Kitamura, R.; Yamashita, M., Organometallics 2020, 39, 383-387.

8.

Kurumada, S.; Takamori, S.; Yamashita, M., Nat. Chem. 2020, 12, 36-39.

9.

Sugita, K.; Nakano, R.; Yamashita, M., Chem. Eur. J. 2020, 26, 2174-2177.

10. Sugita, K.; Yamashita, M., Chem. Eur. J. 2020, 26, 4520-4523.
11.  Kuno,

M.;

Suzuki,K.;

Nakamura,

T.;

Yamashita,

10.1021/acs.organomet.9b00796.

- 22 -

M.,

Organometallics

2020,

39,

doi:

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(1) “Synthesis and Chiroptical Properties of Stereogenic Macrocycles Based on Axially Chiral Binaphtyl” The 18th
International Symposium on Novel Aromatic Compounds (ISNA-18)
(2)”C9G7GA1?Go/,903F:57[n]0HKJÝ!i Î” ZnW´btÁÇS

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 3 R/ÂËã (1)"Synthesis and Chiroptical Properties of Stereogenic Cyclic Dimers Based on 2,2’-Biselenophene and[2.2]Paracyclophane" Org. Biomol. Chem., 2019, 17, 8822-8826. (doi: 10.1039/C9OB01907C)
(2)"Chiroptical Properties of Oligophenylenes Anchoring with Stereogenic [2.2]Paracyclophane" Chem. Lett., 2019,48, 640–643. (doi: 10.1246/cl.190149)
 (3) "Self-assembly of Radially  -Extended Tetrathiafulvalene Tetramers for Visible and Near Infrared
Electrochromic Nanofiber " Bull. Chem. Soc. Jpn., 2020, 93, 154–162. (doi: 10.1246/bcsj.20190283)- 23 -

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1.

 Yamamoto, N., “Free Energy Profile Analysis for the Aggregation-Induced Emission ofDiphenyldibenzofulvene”, J. Phys. Chem. A, doi: 10.1021/acs.jpca.0c03240 (2020)- 25 -

࣎࢘ࣝᆺඹᙺ໬ྜ≀ࡢ≀ᛶㄪᰝࠊ࠾ࡼࡧ㔠ᒓࢡࣛࢫࢱ࣮ゐ፹ࡢάᛶホ౯◊✲Properties of Bowl-shaped aromatic compounds
and studies on the catalytic activity of metal clusters䕿Ḉ஭㻌 ⱥ༤䚸㻿㼕㼠㼍㼚㼍㼚㻌㻿㼍㼞㼠㼥㼛㼡㼚㼓㼗㼡㼘䚸ᮏᶫ㻌 ඃ㤶䚸㼂㼕㼚㼟㼑㼚䚸㻺㼍㼦㼓㼡㼘㻌㻿㼍㼎㼞㼕㼓㼍㼘㼕㼑㼢㼍㻌 㻔኱㜰኱Ꮫ㻕㻌1◊✲┠ⓗࠊෆᐜ
࠾ࢃࢇᆺඹᙺ໬ྜ≀ࠕࣂࢵ࣮࢟࣎࢘ࣝࠖࡣࠊࣇ࣮ࣛࣞࣥࡸࢼࣀࢳ࣮ࣗࣈࡢࣔࢹࣝ໬ྜ≀࡜ࡋ࡚ࡔࡅ࡛࡞ࡃࠊ࠾ࢃࢇᵓ㐀࡟❧⬮ࡋࡓ⊂⮬ࡢᣲືࠊ≀ᛶࢆ♧ࡍࠋ㏆ᖺࠊ⊂⮬ࡢྜᡂἲ࡟ࡼࡾ✀ࠎࡢ⨨᥮ᇶࢆ᭷ࡍࡿ⨨᥮ࢫ࣐ࢿࣥࡢྜᡂࡀྍ⬟࡜࡞ࡾࠊ࠾ࢃࢇᵓ㐀ࠊ࣎࢘ࣝ཯㌿㐠ືࠊ໬Ꮫ཯ᛂᛶ➼࡟ࡘ࠸࡚ࠊᐇ㦂ⓗ࡟⯆࿡῝࠸▱ぢࡀᚓࡽࢀ࡚ࡁ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡇࢀ
ࡽࡢᐇ㦂ⓗ▱ぢ࡟㛵ࡋ࡚ࠊᐇ㦂ⓗ࡞࢔ࣉ࣮ࣟࢳࡢࡳ࡛ࡣ༑ศ࡞⌮ㄽⓗㄝ᫂ࢆ୚࠼ࡿࡇ࡜ࡀ
ᅔ㞴࡛࠶ࡾࠊィ⟬໬Ꮫⓗ࡞࢔ࣉ࣮ࣟࢳ࡟ࡼࡗ࡚ࡑࡢ≀ᛶ࡟⌮ㄽⓗ࡞ㄝ᫂ࢆ୚࠼ࡿࠊ࠶ࡿ࠸ࡣண ࡍࡿࡇ࡜ࡀᚲせ࡜ࡉࢀ࡚࠸ࡿࠋ
୍᪉ࠊࢼࣀࢧ࢖ࢬࡢ㔠ࢡࣛࢫࢱ࣮ࡣࠊࣂࣝࢡ㔠࡛ࡣ♧ࡉ࡞࠸⊂≉࡞ゐ፹άᛶࢆ♧ࡍࠋ≉࡟㧗ศᏊ࡛ಖㆤࡉࢀࡓᨃᆒ୍⣔ࢼࣀࢡࣛࢫࢱ࣮࡟࠾࠸࡚ࡣࠊᐊ ௜㏆࡛ࡢ✜ࡸ࠿࡞᮲௳ୗ
࡟࠾࠸࡚ࡶ✵Ẽ㓟໬཯ᛂ࡞࡝࡟ⴭࡋ࠸ゐ፹άᛶࡀぢࡽࢀࠊࡑࡢ⌮⏤ࡢ୍ࡘ࡜ࡋ࡚཯ᛂ⣔୰࡛ࢡࣛࢫࢱ࣮ࡢᙧ≧ࡀᰂ㌾࡟ኚ໬ࡍࡿࡇ࡜ࡀண ࡉࢀ࡚࠸ࡿࠋ㏆ᖺࡢࢥࣥࣆ࣮ࣗࢱ࣮ࡢ㐍Ṍ࡟ࡼࡾࠊ㔠ᒓࢡࣛࢫࢱ࣮ࢆ┤᥋ࠕศᏊࠖ࡜ࡋ࡚ᢅ࠸ࠊ཯ᛂ⣔࡟࠾ࡅࡿᵓ㐀ኚ໬ࡶࡍ࡭࡚
⪃៖࡟ධࢀࡓィ⟬ࡀྍ⬟࡜࡞ࡗ࡚ࡁࡓࠋᐇ㝿ᡃࠎࡣ᪤࡟ࠊ㔠֚㸮㔞యࡸྜ㔠ࢡࣛࢫࢱ࣮ࡢ
㸯㸱㔞యࠊ㸰㸮㔞యࢆᐇ㝿ࡢࢡࣛࢫࢱ࣮ࢧ࢖ࢬࡶ⪃៖ࡋࡓࣔࢹࣝ࡜ࡋ࡚㑅ࡧࠊᵝࠎ࡞ゐ፹཯ᛂࡢ඲ࣉࣟࢭࢫゎᯒ࡟ᡂຌࡋ࡚࠸ࡿࠋ
௒ᖺᗘࡶ୧ศ㔝࡟㛵ࡋ࡚ィ⟬◊✲ࢆᐇ᪋ࡋࡓࡀࠊ௒ᖺᗘࡣTris(2-hydroxyphenyl)-triazasumanene㸦ᅗ E㸧ࡢ ESIPT-AIEE άᛶ࡟㛵ࡍࡿ⌮ㄽ◊✲࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ‴᭤ඹᙺ໬ྜ≀ࢫ࣐ࢿࣥࡢ࿘⦕࣋ࣥࢮࣥ⎔ࢆࣆࣜࢪࣥ⎔࡛⨨᥮ࡋࡓࢺࣜ࢔ࢨࢫ࣐ࢿࣥࡣࠊ❅⣲ࢻ࣮ࣉຠᯝ࡟ࡼࡾࢫ࣐ࢿࣥ࡜ࡣ኱ࡁࡃ␗࡞ࡿᛶ㉁ࢆ᭷ࡍࡿࠋᡃࠎࡣࢺࣜ࢔ࢨࢫ࣐ࢿࣥ࠾ࡼࡧ
ࡑࡢㄏᑟయࢆྜᡂࡋࠊࡑࡢᛶ㉁ࢆ᫂ࡽ࠿࡟ࡋ࡚ࡁࡓࠋࡑࡢ୰࡛ࠊTris(2-hydroxyphenyl)-triazasumanene  ࡀࠊᅛయ≧ែ࡛ ESIPT(Excited State Intramolecular Proton Transfer)࡟ࡼࡿ
኱ࡁ࡞ࢫࢺ࣮ࢡࢫࢩࣇࢺࢆ⏕ࡌࡿࡇ࡜ࠊࡲࡓࠊࡑࡢⓎගᣲື࡟࠾࠸࡚ AIEE(Aggregation
Induced Emission Enhancement)ࢆ♧ࡍࡇ࡜ࢆぢฟࡋࡓࠋESIPT ࡣࠊບ㉳≧ែࡢ㉸㧗㏿ࣉࣟࢺࣥ⛣ື㸦PT㸧ࣉࣟࢭࢫࢆ௓ࡋ࡚Ⓨ⏕ࡋࠊ኱ࡁ࡞ࢫࢺ࣮ࢡࢫࢩࣇࢺࢆᘬࡁ㉳ࡇࡋࠊከࡃࡢሙ
ྜࢹࣗ࢔࢚࣑ࣝࢵࢩࣙࣥࡀほ ࡉࢀࡿࠋ ࡟ࡣࠊࣇ࢙ࣀ࣮ࣝᛶᐁ⬟ᇶ࡜ࢺࣜ࢔ࢨࢫ࣐ࢿࣥ
㦵᱁ୖࡢࣆࣜࢪࣥ㒊఩ࡀ୕⟠ᡤ࡛ṇᑐࡋ࡚࠾ࡾࠊ᭱኱࡛୕⟠ᡤ ESIPT ࢆᘬࡁ㉳ࡇࡍྍ⬟ᛶࡀ࠶ࡿࠋࡲࡓ୍⯡࡟ࠊࣂࢵ࣮࢟࣎࢘ࣝㄏᑟయࡣࠊᅛయ≧ែ࡟࠾࠸࡚ࠊConcave-Convex ┦஫- 26 -

స⏝࡟ࡼࡾ࣒࢝ࣛ≧✚ᒙᵓ㐀ࢆᙧᡂࡋࠊࡇࡢࡼ࠺࡞ࢫࢱࢵ࢟ࣥࢢᵓ㐀ࡣࠊᅛయⓎග࡟ࡣ୙฼࡜ࡉࢀࠊᐇ㝿ࠊࣂࢵ࣮࢟࣎࢘ࣝㄏᑟయࡣⓎගᛶ⤖ᬗࡣ࡯࡜ࢇ࡝ほ ࡉࢀ࡞࠸ࡇ࡜࠿ࡽࠊ
㸯ࡢᛶ㉁ࡣ≉Ṧ࡛࠶ࡿࠋࡑࡇ࡛ࠊ㸯㸯ࡢ ESIPT-AIEE ᣲື࡟ࡘ࠸࡚ࠊィ⟬⛉Ꮫࢆ⏝࠸᳨࡚ドࡍࡿࡇ࡜࡟ࡋࡓ
2◊✲᪉ἲࠊィ⟬᪉ἲ඲࡚ࡢィ⟬ࡣ GAUSSIAN09 ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚⾜ࡗࡓࠋィ⟬᪉ἲࡣ DFT ἲࢆ⏝࠸ࠊỗ㛵ᩘ࡜ࡋ࡚ B3LYPࠊPBE0ࠊZB97XDࠊLC-ZPBEࠊCAM-B3LYPࠊM06ࠊM06-2xࠊᇶᗏ㛵ᩘ
࡜ࡋ࡚ 6-31G(d)ࠊ6-311+G(d,p)ࢆ⏝࠸࡚ࠊᵓ㐀᭱㐺໬ཬࡧ㑄⛣≧ែࡢィ⟬ࢆ⾜ࡗࡓࠋᵓ㐀᭱㐺໬࡜㑄⛣≧ែࡣ᣺ືゎᯒ࡟ࡼࡾ☜ㄆࡋࡓࠋ
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ࡿࡇ࡜ࠊࡉࡽ࡟ࠊࡑࡢ⤖ᯝࠊ㏻ᖖࡢࢫ࣐ࢿࣥㄏᑟయ࡜ࡣ␗࡞ࡾࠊ࣒࢝ࣛࢼ࣮ࣃࢵ࢟ࣥࢢᵓ
㐀ࡣᙧᡂࡏࡎࠊẚ㍑ⓗ YRLG ࡢከ࠸ᵓ㐀ࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸦ᅗ E㸧ࠋࡇ- 27 -

ࡢᵓ㐀ࡣࠊᅛయⓎගᣲື࡟ࡣ᭷฼࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊESIPT ࡟⏤᮶ࡍࡿ኱ࡁ࡞ࢫ
ࢺ࣮ࢡࢫࢩࣇࢺࡣࠊCH2Cl2 ⁐ᾮ࡛ࡣほ ࡉࢀ࡞࠿ࡗࡓࠊࡘࡲࡾࠊESIPT ࡣᅛయ≧ែ࡟≉᭷࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡿ㸦ᅗ F㸧ࠋᅛయ≧ែ࡜⁐ᾮ≧ែ࡟࠾ࡅࡿ ESIPT ᣲືࡢ㐪࠸ࠊ࠾ࡼࡧヲ⣽࡞࣓࢝ࢽࢬ࣒ࢆㄪ࡭ࡓࠋ
CAM-B3LYP ࡣᐇ㦂⤖ᯝ࡜࠺ࡲࡃ┦㛵ࡋࡓ⤖ᯝࢆᥦ౪ࡋࠊ600 nm ࡛ࡢࢫࢺ࣮ࢡࢩࣇࢺࢩࣇ
ࢺࡀࠊ௵ពࡢࢣࢺ୰㛫య࠿ࡽࡢ⦆࿴࡟ᑐᛂࡋ࡚࠸ࡿࡇ࡜ࢆ☜ㄆࡋࡓ㸦ᅗ Fࠊ㯮࠸⥺㸧ࠋ
ඛ࡟㏙࡭ࡓࡼ࠺࡟ࠊ ࡟ࡣ୕⟠ᡤࡢศᏊෆỈ⣲⤖ྜ㒊఩ࡀ࠶ࡿࡢ࡛ࠊ᭱኱୕⟠ᡤࡢ ESIPTࣉࣟࢭࢫࡀྠ᫬࡟ࠊ࠶ࡿ࠸ࡣูಶ࡟⏕ࡌࡿྍ⬟ᛶࡀ࠶ࡿࠋࡍ࡞ࢃࡕࠊࢣࢺ . ࢚ࣀ࣮ࣝ (ᖹ⾮ᵓ㐀య࡜ࡋ࡚ࠊEEE, KEE, KKE, KKK ࡢྜィ㸲㏻ࡾࡢບ㉳≧ែᵓ㐀యࡀ᝿ᐃࡉࢀࡿࡀࠊ
ィ⟬ࡉࢀࡓᆶ┤ᨺᑕ࢚ࢿࣝࢠ࣮㸦6Ѝ6 ≧ែ㸧ࡣࠊ࠸ࡎࢀࡶ࡯ࡰྠᵝࡢ್ࢆ♧ࡋࡓࡇ࡜࠿
ࡽࠊ㸦c.a. 1.93–2.15 eVࠊ577–643 nm㸧ࠊࡇࡇ࡛ࡣ ȧ ඹᙺࡢᐤ୚ࡣ࡞ࡃࠊ6 ≧ែ࡛ࡢ᩿⇕඲࢚ࢿࣝࢠ࣮ࡣࠊ.((㸦ࣔࣀࢣࢺ㸧ࣇ࢛࣮࣒ࡀ௚ࡢບ㉳ࡉࢀࡓࢣࢺ୰㛫య࡜ẚ㍑ࡋ࡚᭱ࡶᏳ
ᐃ࡛࠶ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿ㸦ᅗ DE㸧ࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ1 ࡟࠾ࡅࡿ PT ࡣࠊࡶࡗ࡜ࡶ࢚
ࢿࣝࢠ࣮ⓗ࡟Ᏻᐃ࡞ EEE* -> KEE*࡛⏕ࡌ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿ㸦ᅗ G㸧ࠋὀ┠࡟್ࡍࡿࡢࡣࠊບ㉳≧ែ PT ࡀࠊࣂࢵ࣮࢟࣎࢘ࣝᵓ㐀ࡢࣇ࢙ࣀ࣮ࣝ⎔࡜ࣆࣜࢪࣥ㒊ศࡢ㛫ࡢ஧
㠃ゅ ȭ ࡛࠶ࡿ 9.66r௜㏆࡛ࢫ࣒࣮ࢬ࡟㐩ᡂࡉࢀࡿࡇ࡜࡛࠶ࡿࠋ
㻌
Fig. 2.D 9HUWLFDOHPLVVLRQHQHUJLHV 6՜6WUDQVLWLRQ E $GLDEDWLFHQHUJLHVRIWKH6 EODFNOLQH DQG6 UHGOLQH VWDWHVF 㻌 7KH
3(6VRIWKHUDGLDWLYHDQGQRQUDGLDWLYHGHFD\SDWKZD\VRI7LQFU\VWDOZKHUHWKHGLKHGUDODQJOHĳZDVIL[HGDWDQG㻌 DOOWKHRWKHUFRRUGLQDWHVZHUHRSWLPL]HGDQGG LQVROXWLRQZKHUH㻌 6DQG7VWDWHVZHUHRSWLPL]HGIRUHDFKVWDWHZLWKRXWUHVWULFWLQJWKHGLKHGUDODQJOH$VWHULVNGHQRWHVWKH6VWDWHLQHDFKVWUXFWXUH(((HQRO.((PRQRNHWR$VWHULVNGHQRWHVWKH6VWDWHLQHDFKVWUXFWXUH㻌ḟ࡟ࠊ ࡢ↓㍽ᑕῶ⾶࡟ࡘ࠸࡚ࠊ6 ≧ែࡢ EEE *࠿ࡽ KEE *࡟ἢࡗࡓ࣏ࢸࣥࢩ࢚ࣕࣝࢿ
ࣝࢠ࣮ࢧ࣮ࣇ࢙ࢫ㸦3(&㸧ࢆ⏝࠸࡚ศᯒࡋࡓࠋ↓㍽ᑕῶ⾶ࡣᅛయ≧ែ࡛ࡣ࡯࡜ࢇ࡝⏕ࡌ࡞࠸ࡀࠊ㠀ᴟᛶ⁐ᾮ㸦ᅗ FG㸧ࠋ⁐ᾮ≧ែ࡛ࡢ㠀ᨺᑕ⤒㊰ࡣࠊȭࡀ r࡟⦆࿴ࡍࡿ T1 / S0 ⤒㊰ࡢ᭱ᑠ࢚ࢿࣝࢠ࣮஺ᕪⅬ㸦MECP㸧࡟ࡼࡗ࡚☜ㄆࡉࢀࡓࠋ ௨ୖࡢࡼ࠺࡟ࠊࢺࣜ࢔ࢨࢫ࣐ࢿࣥㄏᑟయ㸯㸯ࡢ♧ࡍᅛయ≧ែ࡟࠾ࡅࡿ≉␗࡞ ESIPT-AIEE≉ᛶࡣࠊࡑࡢ⤖ᬗᵓ㐀࡟౫Ꮡࡋ࡚࠾ࡾࠊࡲࡓᅛయ≧ែ࡛ᵓ㐀つไࡉࢀࡿࡇ࡜࡟ࡼࡗ࡚⏕ࡌ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡇࡢࡇ࡜ࡣࠊࡇࡢࡼ࠺࡞‴᭤ඹᙺ໬ྜ≀ࡶࠊⓎගᛶ᭷ᶵᮦ
ᩱࡢ㔜せ࡞ࣔࢳ࣮ࣇ࡜ࡋ࡚ᮇᚅ࡛ࡁࡿࡇ࡜ࠊࡲࡓࡑࢀࡣᅛయ≧ែ࡟࠾ࡅࡿࣃࢵ࢟ࣥࢢᵓ㐀ࢆ࠸࠿࡟ࢹࢨ࢖ࣥࡍࡿ࠿࡟࠿࠿ࡗ࡚࠸ࡿࡇ࡜ࢆዴᐇ࡟♧ࡍ⤖ᯝ࡜࡞ࡗࡓࠋ㻌- 28 -

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

䠍䠅䠄୍㒊★䠅 “Understanding the Mechanism of C-F Bond Activation by Pt/Pd Bimetallic Nanoalloy: Interplay ofExperiment and Theory”, Hidehiro Sakurai, The 23rd International Annual Symposium on Computational Scienceand Engineering (ANSCSE23), Chiangmai University, Chiang Mai, Thailand, 2019 ᖺ 6 ᭶.
䠎䠅䠄୍㒊★䠅“Synthesis and Properties of Cup- and Bowl-shaped Cyclic Trilactams and Its Derivatives”, Sitanan
Sartyoungkul, Yumi Yakiyama, Hidehiro Sakurai, The 18th International Symposium of Novel Aromatic
Compounds (ISNA-18), Sapporo, 2019 ᖺ 7 ᭶.
䠏䠅䠄୍㒊★䠅“Synthesis of Sumanenylacene Derivatives”, Sitanan Sartyoungkul, Yumi Yakiyama, Hidehiro Sakurai,
The 18th International Symposium of Novel Aromatic Compounds (ISNA-18), Sapporo, 2019 ᖺ 7 ᭶.
䠐䠅䠄୍㒊★䠅“Synthesis and Properties of Cup- and Bowl-shaped Cyclic Trilactams and Its Derivatives”, Sitanan
Sartyoungkul, Yumi Yakiyama, Hidehiro Sakurai, 27th International Society of Heterocyclic Chemistry Congress(ISCH), Kyoto, 2019 ᖺ 9 ᭶.
䠑䠅䠄୍㒊★䠅 “Understanding the Mechanism of C-F Bond Activation by Pt/Pd Bimetallic Nanoalloy: Interplay ofExperiment and Theory”, Hidehiro Sakurai, NOST-RMIT-RACI Organic and Biomolecular Chemistry Conference,
RMIT, Melbourne, Australia, 2019 ᖺ 11 ᭶.
䠒䠅䠄୍㒊★䠅 “Synthesis, Reactions, and Properties of Oxosumanenes”, Hidehiro Sakurai, p-EJ2019, Guido Mine andCoal Mining Museum, Zabrze, Poland, 2019 ᖺ 11 ᭶.
5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

䠍䠅䠄୍㒊★䠅"Sumanene Hexaester: An Electron Deficient Buckybowl", H. Toda, Y. Uetake, Y. Yakiyama, H.
Nakazawa, T. Kajitani, T. Fukushima, H. Sakurai, Synthesis 2019, 51, 4576-4581.
䠎䠅䠄୍㒊★䠅"Formation of Large Confined Spherical Space with Small Aperture Using Flexible Hexa-substituted
Sumanene", Y. Yakiyama, T. Hasegawa, H. Sakurai, J. Am. Chem. Soc. 2019, 141, 18099-18103.
䠏䠅䠄୍㒊★䠅"The Excimer Formation of Aryl Iodides Chemisorbed on Gold Nanoparticles for Significant Enhancementof the Photoluminescence", P. Maity, K. Sasai, R. N. Dhital, H. Sakai, T. Hasobe, H. Sakurai, J. Phys. Chem. Lett.
2020, 11, 1199-1203.
䠐䠅䠄★䠅"Time-dependent Density Functional Theory Investigation of Excited State Intramolecular Proton Transfer inTris(2-hydroxyphenyl)triazasumanene", S. Sartyoungkul, M. Ehara, H. Sakurai, J. Phys. Chem. A 2020, 124,
1227-1234.
䠑䠅䠄୍㒊★䠅"Synthesis of C70-fragment Buckybowls Having Alkoxy Substituents", Y. Yakiyama, S. Hishikawa, H.
Sakurai, Beilstein J. Org. Chem. 2020, 16, 681-690.

㻌㻌- 29 -

ከᗙ㓄఩Ꮚ࡛ᵓ㐀つไࡉࢀࡓ㑄⛣㔠ᒓࢡࣛࢫࢱ࣮ࡢ
ᵓ㐀㸪㟁Ꮚ≧ែ࠾ࡼࡧ཯ᛂᛶ
Structures, Electronic States, and Reactivity of Transition-Metal Clusters
Structurally Controlled by Multidentate Ligands‫ۑ‬ᾆ ᗣஅࠊ୰ᓥ 㝯⾜ࠊᲴ℩ ▱᫂㸦ዉⰋዪᏊ኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ
Ᏻ౯࡞༝㔠ᒓ࡛࠶ࡿ㖡ࢆ⏝࠸ࡓከ᰾㔠ᒓ࣏ࣜࣄࢻࣜࢻ㘒యࡣỈ⣲ศᏊࡢ྾ⶶࡸ஧㓟໬Ⅳ⣲ࡢ㑏ඖ࡞࡝㸪㈨※࣭࢚ࢿࣝࢠ࣮ࡢຠ⋡ⓗ࡞฼⏝࡟࠾ࡅࡿ㈗㔠ᒓ௦᭰ᮦᩱ࡜ࡋ࡚ඖ⣲ᡓ␎ࡢほⅬ࠿ࡽὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋᮏ◊✲࡛ࡣ㸪ᙜ◊✲ࢢ࣮ࣝࣉ࡛⣔⤫ⓗ࡟ྜᡂࡋࡓከᗙ࣍ࢫࣇ࢕ࣥ㓄఩Ꮚ࡟ᨭᣢࡉࢀࡓ㖡ከ᰾࣏ࣜࣄࢻࣜࢻ㘒య࡟࠾ࡅࡿࣄࢻࣜࢻ㓄఩Ꮚࡢ఩⨨ࢆ⢭ᐦ࡟Ỵᐃࡍࡿ┠ⓗ࡛㸪ࡑࢀࡽࡢ⤖ᬗᵓ㐀ࢆᇶ࡟ DFT ἲࢆ⏝࠸ࡓ㔞Ꮚ໬Ꮫィ⟬ࢆ⾜࠺ࠋ༢⤖ᬗ㹖⥺ᅇᢡἲࡸ NMR ศගἲ➼࡛ࡣࣄࢻࣜࢻࡢṇ☜࡞఩⨨ࡢỴᐃࡣ㞴ࡋࡃ㸪DFT ἲࡀ᭷ຠ࡞
⿵᏶ⓗᡭẁ࡜࡞ࡾᚓࡿࠋᮏ◊✲࡛ࡣ㸪Ph2PCH2P(Ph)CH2PPh2 (dpmp)ཬࡧ meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2(dpmppm) ࢆ ⏝ ࠸ ࡚ ྜ ᡂ ࡋ ࡓ 㖡 6 ᰾ ཬ ࡧ 8 ᰾ 㘒 య 㸪 [Cu6(P-H)5(dpmp)3]+ (1), [Cu8(P-H)6(dpmp)4]2+ (2),[Cu8(P-H)6(meso-dpmppm)2]2+ (3)࡟ࡘ࠸࡚㸪⤖ᬗᵓ㐀ࢆᇶ࡟ࣄࢻࣜࢻ㓄఩Ꮚࡢ఩⨨ࢆ DFT ィ⟬࡟ࡼࡾỴᐃࡋࡓࠋ
2◊✲᪉ἲࠊィ⟬᪉ἲ㘒య 1, 2 ࡢ⤖ᬗᵓ㐀ࡼࡾᑟฟࡋࡓ㘒యᵓ㐀࡟ᑐࡋࣄࢻࣜࢻ㓄఩Ꮚࢆᕪࣇ࣮࢚ࣜྜᡂࡼࡾ᥎ᐃࡉࢀࡿ఩⨨࡟௜ຍࡋࡓࡶࡢࢆึᮇᵓ㐀࡜ࡋ㸪B3LYP/LANL2DZ ࡛ࣄࢻࣜࢻࡢࡳࢆྍືཎᏊ࡜ࡋ࡚ᵓ㐀ࡢ᭱㐺໬ࢆ⾜ࡗࡓ㸦ࣄࢻࣜࢻ௨እࡢཎᏊࡣᅛᐃ㸧ࠋḟ࡟㸪ࡇࡢᡭ⥆ࡁ࡛ᚓࡽࢀࡓ᭱㐺໬ᵓ㐀ࢆึᮇᵓ㐀࡜ࡋ࡚㸪ᇶᗏ㛵ᩘࢆ LANL2DZ(Cu), 6-311+G(d,p) (hydride H), 6-31G(d) (others)࡟ୖࡆ B3LYP ἲ࡟ࡼࡾ඲ཎᏊࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋᚓࡽࢀ
ࡓᵓ㐀࡟ࡘ࠸࡚᣺ືィ⟬㸪NBO ゎᯒ➼ࢆ⾜ࡗࡓࠋィ⟬࡟ࡣ Gaussian 09, Rev. E.01 ࢆ⏝࠸ࡓࠋࡲࡓ㸪㘒య 3 ࡟ࡘ࠸࡚ࡣ㸪ࢡࣛࢫࢱ࣮㦵᱁࠿ࡽண᝿ࡉࢀࡿᗄࡘ࠿ࡢࣄࢻࣜࢻ఩⨨ࢆึᮇᵓ㐀࡜ࡋ࡚㸪ྠᵝࡢィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝDFT ἲ࡟ࡼࡾ㸪㘒య 1, 2, 3 ࡢᵓ㐀ࢆࣄࢻࣜࢻࡢ఩⨨ࢆྵࡵ࡚Ᏻᐃᵓ㐀࡜ࡋ࡚⢭ᗘࡼࡃỴᐃࡍࡿࡇ࡜ࡀ࡛ࡁ㸪ᮏᡭἲࡀ㖡ࣄࢻࣜࢻከ᰾㘒యࡢࣄࢻࣜࢻࡢ఩⨨Ỵᐃ࡜ከ୰ᚰ㟁Ꮚ୙㊊⤖ྜࡢゎ᫂࡟᭷ຠ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡲࡓ㸪㖡ࣄࢻࣜࢻࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜཯ᛂᛶࡢ┦㛵࡟ࡘ࠸࡚ࡢ▱ぢࡶᚓࡽࢀ㸪㠀ᑐ⛠ᆺ㘒య 3 ࡣ CO2 ࡜㏿ࡸ࠿࡟཯ᛂࡋ㸪DBU Ꮡᅾୗ࡛ࢠ㓟ࢆゐ፹ⓗ࡟୚࠼ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬T. Nakajima, K. Nakamae, R. Hatano, K. Imai, M. Harada, Y. Ura, T. Tanase, Dalton Trans, 2019, 48,

12050-12059.
‫ۻ‬K. Nakamae, T. Nakajima, Y. Ura, Y. Kitagawa, T. Tanase, Angew. Chem. Int. Ed., 2020, 59, 2262-2267.

- 30 -

ȧࢡࣛࢫࢱ࣮ศᏊࡢ㟁Ꮚ≀ᛶࡢゎ᫂Investigation of the electronic properties of pi-cluster molecules‫ۑ‬すෆ ᬛᙪࠊஂಖ Ꮥྐࠊ㛗⏫ ఙᏹ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࡟࠾࠸࡚ࡣࠊࣅࣛࢪ࢝ࣝᵓ㐀ࢆ᭷ࡍࡿⅣ໬Ỉ⣲ࡢྛ✀≀ᛶ࠾ࡼࡧ஧㔞໬ᙧᡂ࡟ࡘ࠸࡚㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ࣉࣟࢢ࣒ࣛࡣ Gaussian16 ࢆ౑⏝ࠋᇶᗏ≧ែ࡟࠾ࡅࡿᵓ㐀᭱㐺໬ࡣZB97XD ỗ㛵ᩘࡲࡓࡣ B3LYP-D3ࠊ

ࢫࣆࣥᐦᗘィ⟬ࡣ UBLYP ỗ㛵ᩘࠊගບ㉳≧ែ࡛ࡣ TD ἲࠊB3LYP ỗ㛵ᩘἲࢆ⏝࠸࡚ホ౯ࢆ⾜ࡗࡓࠋᇶᗏ㛵ᩘࡣ࠸ࡎࢀࡶ 6-31G(d,p)ࢆ⏝࠸ࡓࠋ3◊✲ᡂᯝᅗ  D  E ࡟♧ࡋࡓྛ✀ࣅࣛࢪ࢝ࣝࡢᵓ㐀࠾ࡼࡧࢫࣆࣥᐦᗘィ⟬ࡼࡾぢ✚ࡶࡗࡓ (65 ࢫ࣌ࢡࢺࣝࢩ
࣑࣮ࣗࣞࢩࣙࣥࡣᐇ㦂್࡜㠀ᖖ࡟Ⰻ࠸୍⮴ࢆ♧ࡍࡇ࡜ࡀ࡛ࡁࡓࠋࡑࡋ࡚ᅗ  D ࡟࠾ࡅࡿศᏊࡢᵓ㐀ኚ໬ࠊᅗ  E ࡟࠾ࡅࡿ཯ᛂࡢ㝿ࡢ࢚ࢿࣝࢠ࣮ࢲ࢖
ࣖࢢ࣒ࣛࢆぢ✚ࡶࡿࡇ࡜࡟ࡶᡂຌࡋࠊᐇ㝿ࡢ⌧㇟ᅗ  D እ㒊่⃭࡛ኚ໬ࡍࡿࣅࣛࢪ࢝ࣝ
E ஧㠃ᛶࡢ཯ᛂࢆ♧ࡍࣅࣛࢪ࢝ࣝ

ࢆ㠀ᖖ࡟ᩚྜᛶⰋࡃㄝ᫂ࡍࡿࡇ࡜ࡀฟ᮶ࡓࠋ

4

Ⓨ⾲ᐇ⦼

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Yoshiya Inokuchi, J. Phys. Chem. A, 123, 9185–9192, 2019.
 Yoshiya Inokuchi, Takayuki Ebata, and Thomas R. Rizzo, J. Phys. Chem. A, 123, 6781–6786, 2019.
Shin-nosuke Kinoshita, Yoshiya Inokuchi, Yuuki Onitsuka, Hiroshi Kohguchi, Nobuyuki Akai, Takafumi Shiraogawa,
Masahiro Ehara, Kaoru Yamazaki, Yu Harabuchi, Satoshi Maeda, Takayuki Ebata, Phys. Chem. Chem. Phys. 21,
19755–19763, 2019.

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[1] Akiba K.; et al. J. Am. Chem. Soc. 1999, 121, 10644. [2] Inokuchi, Y.; et al. J. Phys. Chem. A 2015, 119, 8512. [3]Pimentel, G. C. J. Chem. Phys. 1951, 19, 446.


- 33 -SiNN ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ 10 ᪘㑄⛣㔠ᒓ㘒య࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Studies on Group 10 Transition Metal Complexes
Bearing SiNN Pincer Ligand‫⚄ۑ‬㇂ ᫀᏹ㸦໭㔛኱Ꮫ ⌮Ꮫ㒊໬Ꮫ⛉㸧1◊✲┠ⓗࠊෆᐜ
ᙜࢢ࣮ࣝࣉ࡛ࡣ SiNN ࣆࣥࢧ࣮㓄఩Ꮚࢆ᭷ࡍࡿ㑄⛣㔠ᒓ㘒య࡟㛵ࡋ࡚ࠊ㘒యࡢᵓ㐀ࠊ⏕ᡂ㐣⛬ࠊ཯ᛂᛶࠊ

཯ᛂᶵᵓࡢゎ᫂࡟↔Ⅼࢆᙜ࡚࡚◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋᮏᖺᗘࡣࠊࡇࢀࡽ㘒యࢆ฼⏝ࡋࡓ᭷ᶵྜᡂ཯ᛂࡢ㛤Ⓨ࡟࠶ࡓࡾࠊᐇ㦂ⓗᡭἲ࡟ࡼࡾᚓࡽࢀࡓᵓ㐀ࣃ࣓࣮ࣛࢱ࡜ Gaussian ࣉࣟࢢ࣒ࣛࢆ฼⏝ࡋࡓ DFT ィ⟬࡟ࡼࡿ᭱㐺໬ᵓ㐀࡜ࡢẚ㍑ࢆ⾜࠺࡜࡜ࡶ࡟ࠊᐇ㦂ⓗᡭἲ࠿ࡽࡢ࢔ࣉ࣮ࣟࢳࡀ㞴ࡋ࠸㘒యࡢᵓ㐀ࠊ཯ᛂᶵᵓࡢゎ᫂ࢆ⾜ࡗࡓ㸦ᅗ 1㸧
ࠋࡲࡓࠊPNN ࡞࡝ࡢ㢮ఝࡢᵓ㐀ࢆ᭷ࡍࡿࣆࣥࢧ࣮㘒య࡟ࡘ࠸࡚ࡶྠᵝࡢ᳨ウࢆ⾜ࡗࡓࠋ≉࡟ࠊ࢔ࣝࢣࣥࡢࣄࢻࣟࢩࣜࣝ໬཯ᛂࠊⰾ㤶᪘໬ྜ≀ࡢ࣍࢘⣲໬཯ᛂ࡞࡝ࠊ㏆ᖺᙜ◊✲ᐊ࠿ࡽሗ࿌ࡋࡓ㑄⛣㔠ᒓゐ፹ࢆ฼⏝ࡋࡓ᭷ᶵྜᡂ཯ᛂ࡟㛵ࡋ࡚㔜Ⅼⓗ࡟ィ⟬໬Ꮫ࡟ࡼࡿᐇ㦂⤖ᯝࡢࢧ࣏࣮ࢺࢆ⾜ࡗࡓࠋࡇࢀࡽ཯ᛂ࡟ࡘ࠸࡚
ࡣࠊ᪤Ꮡࡢゐ፹࡜ẚ㍑ࡋ࡚ᴟࡵ࡚㧗࠸ゐ፹άᛶࢆ♧ࡍࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠾ࡾࠊヲ⣽࡞཯ᛂᶵᵓࡢゎ᫂ࡀᮃࡲࢀࡿࠋࣄࢻࣟࢩࣜࣝ໬཯ᛂࡣࣃࣛࢪ࣒࢘ࠊⓑ㔠࡞࡝ࡢ➨஧ࠊ➨୕㑄⛣⣔ิࡢඖ⣲࡛◊✲ࡀ⾜ࢃࢀ࡚ࡁࡓ
Chalk-Harrod ᶵᵓࡸ Modified Chalk-Harrod ᶵᵓࢆཧ⪃࡜ࡋࡘࡘࠊ➨୍㑄⛣⣔ิࡢ㑄⛣㔠ᒓゐ፹࡟ࡼࡿ཯ᛂᶵ
ᵓࢆ᫂ࡽ࠿࡟ࡍࡿࠋ

ᅗ 1㸬SiNN 㓄఩Ꮚࢆ᭷ࡍࡿ Ni ࠾ࡼࡧ Pd ஧᰾㘒యࡢྜᡂ

2◊✲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࠺ࠋᚓࡽࢀࡓィ⟬⤖ᯝ࡜ᐇ㦂⤖ᯝࢆẚ㍑ࡍࡿࡇ࡜࡛ィ⟬ࡢጇᙜᛶࢆホ౯ࡍࡿ࡜࡜ࡶ࡟ࠊᐇ㦂⤖ᯝ࡜᭱ࡶࡼ࠸୍⮴ࢆ♧ࡋࡓィ⟬ᡭἲࢆ཯ᛂᶵᵓゎᯒ࡟㐺⏝ࡋࡓࠋDFT ィ⟬࡟ࡣ Gaussian ࣉࣟࢢ࣒ࣛ 09 ࠾ࡼࡧ 16 ࢆ⏝࠸ࠊỗ㛵ᩘ࡟ࡣ B3LYP,
B3PW91, M06, M06L ᇶᗏ㛵ᩘ࡟ࡣ㑄⛣㔠ᒓཎᏊ࡟ LanL2DZ ࡶࡋࡃࡣ SDDࠊࡑࡢ௚ࡢཎᏊ࡟ def2-SV(P),
def2-TZVP, 6-311G(d,p) ࢆ⏝࠸࡚ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ⏕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⤒㊰
ࢆ᥎ᐃࡋࡓࠋ

- 34 -

3◊✲ᡂᯝ
SiNN ࠾ࡼࡧ PNN ࣆࣥࢧ࣮㘒యࡢᵓ㐀᭱㐺໬ࢆ✀ࠎࡢỗ㛵ᩘࠊᇶᗏ㛵ᩘࢆ⏝࠸᳨࡚ウࢆ⾜ࡗࡓ࡜ࡇࢁࠊM06/SDD(Fe, Ni, Pd),
6-311G* (others) ࡛ࣞ࣋ࣝィ⟬ࡋࡓ㝿࡟ࠊ༢⤖ᬗ X ⥺ᵓ㐀ゎᯒࡢ⤖ᯝࢆࡼࡃ෌⌧ࡋࡓࠋ
SiNN 㓄఩Ꮚࢆ᭷ࡍࡿ Ni ࠾ࡼࡧ Pd ࡢ஧᰾㘒య࡟ࡘ࠸࡚ࠊ᭱㐺໬ᵓ㐀ࢆᅗ 2 ࡟♧ࡍࠋྛ஧᰾㘒యࡢ⏕ᡂ㐣⛬࡟ࡘ࠸࡚ࡶ཯ᛂᶵᵓゎ

ᅗ 2㸬Ni ஧᰾㘒య㸦ᕥ㸧࠾ࡼࡧ Pd ஧᰾㘒య㸦ྑ㸧ࡢ᭱㐺໬ᵓ㐀ᯒࢆ⾜ࡗࡓࡀࠊࣄࢻࣜࢻ㘒య⏕ᡂᚋࡢ⤒㊰࡟ࡘ࠸࡚ࡢヲ⣽ࡣ᫂ࡽ࠿࡟࡞ࡽ࠿࡞࠿ࡗࡓࠋࡲࡓࠊࣄࢻࣜࢻ㘒యࢆ⣔୰࡛Ⓨ⏕ࡉࡏࡓᚋࠊࢪ࣎ࣟࣥ࡜ࡢ཯ᛂ࡟ࡼࡾ⏕ࡌࡿࢽࢵࢣࣝ࣎ࣜࣝ㘒య࡟ࡘ࠸࡚ࡶィ⟬ࢆ⾜ࡗࡓࠋNBOゎᯒࡢ⤖ᯝ࠿ࡽࠊ㔠ᒓ࠿ࡽ࣍࢘⣲ࡢ✵㌶㐨࡬ࡢ㏫౪୚ࡣ࡯࡜ࢇ࡝ぢࡽࢀࡎࠊ㞄᥋ࡍࡿ㓟⣲ཎᏊୖࡢᏙ❧㟁Ꮚ࠿ࡽࡢ㟁Ꮚ౪୚ࡀࡼࡾᨭ㓄ⓗ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ௨ୖࡢ⤖ᯝࡣ㔠ᒓ㸫࣍࢘⣲㛫⤖ྜࡣከ㔜⤖ྜᛶࢆᖏࡧ࡚࠾ࡽࡎࠊẚ㍑ⓗᐜ᫆࡟㛤⿣ࡍࡿࡇ࡜ࢆ♧၀ࡍࡿࠋࡇࡢࡇ࡜ࡣࠊᮏ࣎ࣜࣝ㘒యࡀ᭷ᶵ໬ྜ≀ࡢ࣍࢘⣲໬཯ᛂ࡟ᑐࡋ࡚ᐊ

࡛ࡶ㧗࠸άᛶࢆ♧ࡋࡓࡇ࡜࡜୍⮴ࡍࡿࠋᅗ 3㸬SiNN 㓄఩Ꮚࢆ᭷ࡍࡿ࣍࢘⣲㘒యࡢྜᡂ⤒㊰᭷ᶵྜᡂ཯ᛂ࡟࠾ࡅࡿ཯ᛂゎᯒ࡟ࡘ࠸࡚ࡣࠊࣄࢻࣟࢩࣜࣝ໬཯ᛂ࡟ࡘ࠸࡚㔜Ⅼⓗ࡟ィ⟬ࢆ⾜ࡗࡓࠋࡇࢀࡲ
࡛ࡢィ⟬࡟ࡼࡾᚓࡽࢀࡓάᛶ✀࠾ࡼࡧ୰㛫యࡢ⇕ຊᏛⓗࣃ࣓࣮ࣛࢱࡢẚ㍑࠿ࡽࠊゐ፹ࢧ࢖ࢡࣝ୰࡟୍㔜㡯ࠊ୕㔜㡯ࠊ஬㔜㡯≧ែࡀΰᅾࡍࡿࢫࣆࣥ㌿⛣ࢆྵࡴᶵᵓ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࢀ࡟ࡼࡾࠊࡇࢀࡲ࡛▱ぢࡢᑡ࡞࠿ࡗࡓ➨୍㑄⛣⣔ิࡢ㑄⛣㔠ᒓࢆ⏝࠸ࡓࣄࢻࣟࢩࣜࣝ໬཯ᛂࡢゐ፹཯ᛂᶵᵓࡀ㒊ศⓗ࡟࡛ࡣ࠶ࡿࡶࡢ
ࡢ᫂ࡽ࠿࡜࡞ࡗࡓࠋᘬࡁ⥆ࡁࠊḟᖺᗘ௨㝆࡛ࡶ⥅⥆ࡋ࡚཯ᛂ⤒㊰ࡢ᥈⣴ࢆᐇ᪋ࡍࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬4-1. ‫‮‬ᑼᾈኴࠊ᪥ୗᬕ㈗ࠊ⚄㇂ᫀᏹࠊᘪ๐⚽㝯ࠊ➨ 9 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ
‫ۻ‬4-2. ᪥ୗᬕ㈗ࠊ‫‮‬ᑼᾈኴࠊ⚄㇂ᫀᏹࠊᘪ๐⚽㝯ࠊ➨ 23 ᅇࢣ࢖⣲໬Ꮫ༠఍ࢩ࣏ࣥࢪ࣒࢘
‫ۻ‬4-3. ⚄㇂ࠊ‫‮‬ᑼᾈኴࠊ᪥ୗᬕ㈗ࠊᘪ๐⚽㝯ࠊ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍‫ۻ‬4-4. Masahiro KamitaniࠊInternational Congress on Pure & Applied Chemistry 2019 Yangon

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
5-1. Kamitani, M.; Kusaka, H.; Yuge, H., Chem. Lett. 2019, 48, 1196.
5-2. Kamitani, M.; Kusaka, H.; Yuge, H., Chem. Lett. 2019, 48, 898. (Open Access)- 35 -

ࣈࣟࣔࢳ࣮ࣔࣝࣈ࣮ࣝࡢⰍ࡜ᵓ㐀ࡢ㛵ಀ
Relation between Color and Structure of Bromothyimol Blue‫ۑ‬ᓥ⏣ ㏱㸦ᘯ๓኱Ꮫᩍ⫱Ꮫ㒊㸧1◊✲┠ⓗࠊෆᐜ
ࣈࣟࣔࢳ࣮ࣔࣝࣈ࣮ࣝࡣ⁐ᾮࡢ pH ኚ໬࡟ᛂࡌ࡚Ⰽኚ໬ࢆࡍࡿࡓࡵࠊ㓟ሷᇶᣦ♧⸆࡜ࡋ࡚ᗈࡃ⏝࠸ࡽࢀࡿࠋ

ࡋ࠿ࡋࠊ⁐ᾮࡢᾮᛶ࡟ᛂࡌࡓⰍ࡜ࡑࡢศᏊᵓ㐀࡜ࡢ㛵ಀ࡟ࡣΰ஘ࡀࡳࡽࢀࠊᮍࡔࡣࡗࡁࡾ࡜ࡣࡋ࡚࠸࡞࠿ࡗ
ࡓࠋࡇࡢࡓࡵࠊࣈࣟࣔࢳ࣮ࣔࣝࣈ࣮ࣝࡢศᏊᵓ㐀ࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡟◊✲ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬࡟ࡣ Gaussian 16 ࢆ⏝࠸ࡓࠋྍど྾཰ࢫ࣌ࢡࢺࣝ࡟ᑐࡋከኚ㔞ゎᯒࢆ⾜࠺ࡇ࡜࡛ᚓࡓ᝟ሗ࡟ᇶ

࡙ࡁࠊೃ⿵࡜࡞ࡿࣈࣟࣔࢳ࣮ࣔࣝࣈ࣮ࣝศᏊࡢ㦵᱁ᵓ㐀ࢆ⤠㎸ࡳࠊࡑࢀࡽ࡟ᑐࡋ DFT ィ⟬࡟ࡼࡾᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ᭱Ᏻᐃᵓ㐀࡟ᑐࡋࠊTD-DFT ィ⟬࡟ࡼࡾྍど྾཰ࢫ࣌ࢡࢺࣝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊᐇ㦂⤖ᯝ࡜ẚ㍑ࡋࡓࠋ

3◊✲ᡂᯝࣈࣟࣔࢳ࣮ࣔࣝࣈ࣮ࣝỈ⁐ᾮࡣ㓟ᛶ࡛㯤Ⰽࠊ୰ᛶ࡛⥳Ⰽࠊሷᇶᛶ࡛㟷Ⰽࢆ♧ࡍࠋࡇࡢ࠺ࡕ㟷Ⰽࢆ♧ࡍศᏊ࡜㯤Ⰽࢆ♧ࡍࣈࣟࣔࢳ࣮ࣔࣝࣈ࣮ࣝศᏊᵓ㐀ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ⁐ᾮࡀ♧ࡍ⥳Ⰽࡣࠊ㯤Ⰽ࡜㟷Ⰽࢆ♧ࡍศᏊࡢΰྜ⁐ᾮ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡑࢀࡒࢀࡢᵓ㐀࡟ᑐࡋ࡚ࠊTD-DFT ィ⟬࡟ࡼࡾᚓࡓྍど྾཰ࢫ࣌ࢡࢺࣝࡣࠊ
ᐇ㦂࡛ᚓࡽࢀࡓྍど྾཰ࢫ࣌ࢡࢺࣝࢆᐃᛶⓗ࡟෌⌧ࡍࡿࡶࡢ࡛࠶ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬ᓥ⏣ ㏱ࠊᰳෆ⬌᱈ࠊ㛗㇂ᕝ ೺ࠊ͆ྍど྾཰ศගἲ࠾ࡼࡧ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓࢳ࣮ࣔࣝࣈ࣮ࣝࡢศᏊ
ᵓ㐀ゎᯒ͇ࠊᖹᡂ 31 ᖺᗘ ᪥ᮏศගᏛ఍ᖺḟㅮ₇఍㸦2019 ᖺ 5 ᭶ࠊி㒔㸧‫ ۻ‬ᓥ⏣ ㏱ࠊᰳෆ⬌᱈ࠊ㛗㇂ᕝ ೺ࠊ͆㓟ሷᇶᣦ♧⸆ࢳ࣮ࣔࣝࣈ࣮ࣝࡢศᏊᵓ㐀ゎᯒ͇ࠊ2019 ᖺᗘ໬Ꮫ⣔Ꮫ༠఍ᮾ໭኱఍ ໬Ꮫᩍ⫱◊✲༠㆟఍ᮾ໭኱఍㸦2019 ᖺ 9 ᭶ࠊᒣᙧ㸧‫ ۻ‬ᓥ⏣ ㏱ࠊᰳෆ⬌᱈ࠊ㛗㇂ᕝ ೺ࠊ͆㔞Ꮚ໬Ꮫィ⟬ࢆ฼⏝ࡋࡓࢳ࣮ࣔࣝࣈ࣮ࣝࡢศᏊᵓ㐀Ỵᐃ͇ࠊ᪥ᮏ⌮⛉ᩍ⫱Ꮫ఍ ➨ 58 ᅇᮾ໭ᨭ㒊኱఍㸦2019 ᖺ 11 ᭶ࠊ⛅⏣㸧‫ ۻ‬ᓥ⏣ ㏱ࠊ͆ࢳ࣮ࣔࣝࣈ࣮ࣝ࡜ࣈࣟࣔࢳ࣮ࣔࣝࡢⰍኚ໬ࡢẚ㍑͇
ࠊ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍㸦2020 ᖺ 3
᭶ࠊᮾி㸧

5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Toru Shimada, Kurumi Tochinaia, Takeshi Hasegawa㸪” Determination of pH dependent structures of thymol blue
revealed by cooperative analytical method of quantum chemistry and multivariate analysis of electronic absorption
spectra” Bulletin of the Chemical Society of Japan 92, 1759-1766 (2019).
‫ۻ‬ᓥ⏣ ㏱ࠊ͆㓟ሷᇶᣦ♧⸆ࡢⰍ࡜ศᏊᵓ㐀ࡢ㛵ಀ㸫㛗ᖺࡢΰ஘࡟Ỵ╔ࢆࡘࡅࡿ㸟͇ࠊ໬Ꮫ 75ࠊ30-34 (2020).

- 36 -

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

Fine Control of Chiral-at-Metal and Elucidation of their Properties
:+ '<$

;)5132!=1 13/.üĆ¨ãÂ( $oñ¡ß*źÏ(ŰŌ'ĦĭŘŽ% 5Ĝ³%1ķģ(Ħĭ7$ 6'4)»)ő½*ķÅ(ŕŒ7Cdfů|¾8Ğ6ÞŌ 5źÏ(ŋŸ'ů|¾ÞŌ'·¨ 6üĆ¨ãÂ( $ųÊrÝCdfŴ}8Ğ6&%7+ŋŸ'ů|¾8Ğ &1oñ¡ßŨņ6)%*' &łÿĦĭĤģ*ųÊrÝoñ)ŕ
Œj¨ãČ8ĝŚŒĴ&ÄƀÂ)qŻ(35ħįĒďjļø(6źÆĩųÊŴ})ăŧj¡ßàjģë8¾g[f%Őõ6&% 6ųÊŴ})ılů|²)źÆĩ(µ#ƁÓ'oñő½¡ß2CdfÐŇÜ(ŷ6Ħĭ8ņ!

2 13"&84"&þăŧ)ăĶ*ļø X ľăŧŐā(35ċÃÔą8Ğ $ņ ăŧúūÅÓĊŷïČƂDFTƃ8Ğ $µÒęâ8ŒĴĈ(÷ŶÀÅÓĊŷïČƂTD-DFTƃ8Ğ $Šęâ8ŒĴ.ŹŅŒĴ2uĈģ'ĥv~Ğ8ōĬ16)( NBO 7 YhFda8ĞDFT
3, TD-DFT ŒĴ*$ Gaussian 16 YhFda8Ğ77)ŒĴ(Ğ ĊŷïĲ*zn)Ŧ5%ăŧúūƆB3LYP/Lanl2DZ (ųÊ)B3LYP/6-31G(d) ()x)Ĺ)?TfDkŒĴƆ
B3LYP/Lanl2DZ(ųÊ)B3LYP/6-311+G(d) ()x)Ĺ)8Ğ 

3 13%
 ųÊ=Ai(Æ;Cdf'źÆĩů|¾&Ô)oñŉµ8Ŵ}Ùã6&(35ųÊrÝoñ8ü6Łîčà'¯Ż}´Ŵ})¨ã8ņ!¨ãdK`}(Æoñŉ8
6&%ĕ)H;IOgA_k}-)ŗÇ8ņ!¯Ż}´Ŵ}&oñŉ4'6H;IOgA_k}ĉ8ĝŚŒĴ%ōĬ16&%ů|¾2oñŉ)¾ŕŒ8ņ H;IOgAŭæģ¨ã8ņ!4(ÿŴ}oñő½('6&8ō)%wÛĝŚŒĴ
(36¡ßĆă)Őõ8ĤêƂŚðđrƃ ųÊů8Ą'ŵj¼%ķÅ(Ü6&*ųÊ=Ai)ïīſů(Ęü)ò
 Ź¾ăŧ8Ģ60(ÞŌo¥ć% 6ÿĦĭ%*ēĹXgka8rÝ(ų¾8ů
6äČ8Äƀ4õ4(ĝŚŒĴ(36)àşŐõ8ņ!ēĹ¾)®5( 6 ")ų¾8ůŻ}´ųEdIMk¾)àşŐõ8ĤêăŧúūìŒĴŠęâƂĺº¥Ŏ¬¢I\EPfƃ)ŒĴ8ņ

ųÊ4ů|¾-)ŬĪƂMLCTƃ%6&8ōů|¾8ŕŒ6&%EdIMk)Ģ Ęà8řĵ6&%ƂFigure 1, ŚðãĂ 14ƃ
4(ġ'6ųÊ8Ļ/Ť9 ZOhųÊEdIMk(6&%)àş¹8ĝŚŒĴ4tĐů|¾)Ă(36ųEdIMk)àş¹8XhiO<;šŪ4ŜŚ6&¥Ń% 6wÛ*Ģ bBSJa)Őõ8ņ Ų¾¢ě)«m8±6ƂŚðđrƃ

- 37 -

   + ;98=3/; 928%2+7 9;,3=+6< 90 >  -6><=/;    $; , %37>6+=/. +,<9;:=398 90 >
-6><=/;-%-2/7+=3-;/:;/</8=+=39890=2/9;,3=+6/8/;13/<+8./8/;1B1+:<90> -6><=/;< $; $; $$2 4 -7<13 =(6<2 =

<

90,=

 ŵğĎlƄ ´ĹŬĪųÊĹŶ(»Űļ¨8ü6 $#! Ŵ})Ŋ&ńÌĻŀ)Ü ŋ Ñ  û¨;SAi}{ŜGi^H>aƁűË¼Â ôűĽ¾ ŵğĎl ¸ŝ ÚųÊrÝ(CdeO<k8é"ACLVRH>aŴ})¨ã&)ģoñŗÇ  ı  °Ŵ}ÂœŚ{ $ B+59389  

ª¤ÉÍ  !3=<>2359%23989B+ Ñ  û

%B8=2/<3<+8.B8+73-23;+68.>-=39890&/=;+2/.;+6#A9(+8+.3>797:6/A/<@3=2+23;+6!/=+6/8=/; ôÿÂ{ı

öÁÑ{   űğÍÑû &9;> ,32+;+     !3=<>2359 %23989B+

%B8=2/<3< 90 + &/=;+2/.;+6 23;+6+=;98 97:6/A

,/+;381+8-23;+6'8<B77/=;3-+63./8=+=/ 31+8.+8.3=<6>-3.+=39890$;9:/;=3/<  ôÿÂ{ı{ $  űğÍ

öÁÑ

Ñ û

  /3*2/8$/3)3+9 33=9<23',/    !3=<>2359%23989B+"2/=/;9-B-63--+;,/8/:;9=/A=/.

2/=/;97/=+663-196.-6><=/;<@3=22B:/;-99;.38+=/.-+;,98+8.=2/631+8./00/-=<38<=;>-=>;/+8.6>738/<-/8-/ôÿÂ{ı

öÁÑ{ $ űğÍ B+59 389  Ñ û   !3=<>2359 %23989B+

-98=;9690=2/3;7/=+6-/8=/;/.-23;+63=B $+-303-2/7
   +@+33'%

   &9;> ,32+;+ !3=<>2359 %23989B+

3;98-97:6/A@3=27/=+6-/8=/;/.-23;+63=B $+-303-2/7
  /3 *2/8 3=9<23 ',/  %B8=2/<3< 90 -23;+6 =/=;+2/.;+6 7/=+6 -97:6/A/< +8.
Ñ

ûtÃ

%B8=2/<3< +8. +<B77/=;3- 38.>-=398 90 + =/=;+2/.;+6
+@+33'%

   !3=<>2359 %23989B+

Ñ

ûtÃ

!>6=3.37/8<398+6 631+8. /00/-=< 98 =2/

:29<:29;/<-/8= :;9:/;=3/< +8. 38=;+-/66>6+; +-=3?3=3/< 902/=/;9-B-63- -+;,/8/:;9=/-=/. >1 -6><=/;<$+-303-2/7

+@+33'%

  /3*2/8  

Ñ

ûtÃ

  3=9<23',/!3=<>2359%23989B+ 31+8./00/-=<98=2/:29=9:2B<3-+6:;9:/;=3/<90.33<9:;9:B6,/8C373.+C96B63./8/:;9=/-=/.-/8=/;/.2/A+196.-6><=/;<        # 

49;1+8-2/7



 

   B+59 389 !3=<>2359 %2389B+<B77/=;3- 8.>-=398 90 &/=;+2/.;+6 23;+6+=(+8+.3>7

-97:6/A/<   

- 38 -

࢖࣑ࢲࢡࣟࣉࣜࢻࡢගศゎ㐣⛬ࡢゎ᫂࡞ࡽࡧ࡟つ๎Ⅳ⣲ゐ፹࡟࠾ࡅࡿ཯ᛂ⌮ゎ
Photochemistry of Imidacloprid and Reaction Mechanism in Ordered Carbon
Catalysts‫ۑ‬ᒣᮏ 㞞⣡㸦ᮾ໭኱Ꮫ ከඖ≀㉁⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ

⢭ຊⓗ࡟฼⏝ࡉࢀ࡚࠸ࡿ㎰⸆ࡢ୍ࡘ࡟࢖࣑ࢲࢡࣟࣉࣜࢻࡀ࠶ࡿࠋ⏦ㄳ⪅ࡽࡣࠊࡑࡢග໬Ꮫⓗศゎ㐣⛬ࡢゎ᫂ࢆ㒊ศⓗ࡟࡛ࡣ࠶ࡿࡀᐇ㦂ⓗ࡟㐩ᡂࡋ࡚࠸ࡿࠋࡲࡓࠊࡑࡢග⏕ᡂ≀ࡢ୍ࡘࡢᵓ㐀㐨⛬ࢆ⾜࠺࡜࡜ࡶ࡟ࠊࡑ
ࡢⓎගࢆ฼⏝ࡋࡓᐃ㔞ศᯒἲࢆ☜❧ࡋࡓࠋᮏ◊✲ㄢ㢟࡟࠾࠸࡚ࡣࠊ୺࡟ࡇࡢ㎰⸆࠾ࡼࡧග໬Ꮫ཯ᛂ୰㛫య࡟
ᑐࡍࡿTD-DFTࢆ⾜࠺ࡇ࡜࡛ࠊග໬Ꮫ཯ᛂࡢࡉࡽ࡞ࡿ㏿ᗘㄽⓗ⌮ゎࢆ῝ࡵࡿࡇ࡜࡟࠶ࡿࠋࡲࡓࠊ⏦ㄳ⪅ࡽࡀ᳨ウ୰ࡢつ๎Ⅳ⣲ゐ፹࡟࠾ࡅࡿ≀㉁ኚ᥮཯ᛂ࡟࠾ࡅࡿ㑄⛣≧ែ᥈⣴ࢆ⾜࠺ࡇ࡜࡛ࠊࡑࡢ㏿ᗘㄽⓗ⌮ゎࢆ῝ࡵࡿࠋ2◊✲᪉ἲࠊィ⟬᪉ἲࡲࡎࡣヱᙜ㎰⸆ࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓᚋࠊ⤖ྜゅᗘࢆኚ࠼࡞ࡀࡽࡢTD-DFTࢆ⾜࠺ࡇ࡜࡛ບ㉳≧ែᏳᐃᛶ࡞ࡽࡧ࡟ග໬Ꮫ཯ᛂ㐍⾜࡜࠸࠺ᐇ㦂⤖ᯝࡢ┦⿵ⓗ⌮ゎࢆᮇࡍࡿࠋࡲࡓࠊྍ⬟࡛࠶ࢀࡤࡑࢀࡽ཯ᛂ࡟࠾ࡅࡿ㑄⛣≧ែ᥈⣴ࢆ㐺ᐅ⾜࠺ࡇ࡜࡛⇕཯ᛂࡢ㏿ᗘㄽⓗ⌮ゎ࡟ࡘ࠸࡚ࡶేࡏ࡚┠ᣦࡍࠋࡑࡢ࠺࠼࡛ࠊᚓࡽࢀࡓィ⟬⛉Ꮫⓗ▱ぢ࡜ࠊࡍ࡛࡟ᚓ࡚࠸ࡿᐇ㦂ⓗ▱ぢࢆేࡏ࡚Ꮫ⾡ㄽᩥ࡜ࡋ࡚ࡢⓎ⾲ࢆ┠ᣦࡋࡓࠋ

3

◊✲ᡂᯝ

࢖࣑ࢲࢡࣟࣉࣜࢻࡢග໬Ꮫ࡟ࡘ࠸࡚ࡣࠊᇶᗏ≧ែィ⟬ࢆ௒ᖺᗘ᏶஢ࡋࡓࠋ௚᪉ࠊⅣ⣲ࡢ໬Ꮫ࡟࠾࠸࡚ࡣࠊ
Ⅳ⣲㔜ྜ㐣⛬ࡢ⇕ຊᏛࡢᐇ㦂࡜ィ⟬ࡢ┦⿵ⓗ᳨ウࢆ⾜ࡗࡓࠋຍ࠼࡚ࠊ᳨
᳨ウࡢ㐣⛬࡛ࠕⅣ⣲ᮦᩱศゎ཯ᛂࡢ⌮ゎࢆィ⟬໬Ꮫⓗ࡟㐩ᡂ࡛ࡁࡿࠖ࡜╔᝿ࡋࠊ2 ᗘ࡟ࢃࡓࡿⅬᩘ㏣ຍࢆ㡬࠸ࡓ࠺࠼࡛ࡇࢀࢆ᳨ウࡋࡓ࡜ࡇࢁࠊⅣ⣲ᮦᩱࢆ㟁ᴟᮦᩱ࡟⏝࠸ࡓࢫ࣮ࣃ࣮࢟ࣕࣃࢩࢱ࡟࠾ࡅࡿ༝㟁఩༳ຍ᮲௳࡛ࡢᇶ㉁-Ⅳ⣲㛫┦஫స⏝࡟㛵ࡍࡿᐇ㦂⤖ᯝ࡜┦⿵ⓗ࡞ィ⟬⤖ᯝࢆᚓࡿ࡟⮳ࡾ2019ᖺᗘ୰࡟Journal of Power Sourceㄅ࡟ㄽᩥⓎ⾲ࢆ⾜ࡗࡓࠋ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

1. ᭷ᶵ໬Ꮫ࠾ࡼࡧⅣ⣲ᮦᩱ⛉Ꮫ࡟࠾ࡅࡿィ⟬࣭ศᯒ໬Ꮫᒣᮏ 㞞⣡୰㒊኱Ꮫ ᛂ⏝⏕≀Ꮫ㒊ࠊ2019 ᖺ 11 ᭶ 26 ᪥㸦ᣍᣍᚅㅮ₇㸧
2. Chemistry of carbon materials: Fundamentals and applications
Masanori Yamamoto
School of Biological and Chemical Sciences, Queen Mary, University of London, 2020 ᖺ 2 ᭶ 6 ᪥㸦ᣍᣍᚅㅮ₇㸧
3. ࢔࣑ࣝࢼࢼࣀ⢏Ꮚࢆ⏝࠸ࡓࢢࣛࣇ࢙࣓ࣥࢯࢫ࣏ࣥࢪࡢస〇࠾ࡼࡧⅣ⣲ᡂ㛗ᶵᵓࡢゎ᫂ᚋ⸨ 㥴㍜ࠊ㔝ᮧ ၨኴࠊᒣᮏ 㞞⣡ࠊすཎ ὒ▱ࠊఀ⸨ ோࠊෆᮧ ඔᐉࠊி㇂ 㝯➨ 46 ᅇⅣ⣲ᮦᩱᏛ఍ᖺ఍ࠊᒸᒣ኱Ꮫࠊ2019 ᖺ 11 ᭶ 28 ᪥㸦ᮌ㸧㹼11 ᭶ 30 ᪥㸦ᅵ㸧4. ᵝࠎ࡞㔠ᒓ࣏ࣝࣇ࢕ࣜࣥ㢮ࢆ๓㥑య࡜ࡋࡓつ๎ᵓ㐀ᛶ࣮࢝࣎ࣥ࢔ࣟ࢖ࡢస〇㧗ᶫ ࿴㤿ࠊᒣᮏ 㞞⣡ࠊすཎ ὒ▱ࠊ኱࿴⏣ ┿⏕ࠊி㇂ 㝯ࠊᒾ℩ ࿴⮳ࠊ⚄㇂ ࿴⚽ࠊ୸ᒣ ⣧ࠊ㇂ ᩥ㒔ࠊVarisara Deerattrakul➨ 46 ᅇⅣ⣲ᮦᩱᏛ఍ᖺ఍ࠊᒸᒣ኱Ꮫࠊ2019 ᖺ 11 ᭶ 28 ᪥㸦ᮌ㸧㹼11 ᭶ 30 ᪥㸦ᅵ㸧5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

1. ‫ۻ‬Effect of Carbon Surface on Degradation of Supercapacitors in Negative Potential Range
Rui Tang, Masanori Yamamoto, Keita Nomura, Emilia Morollon, Diego Cazorala-Amoros, Hirotomo Nishihara, andTakashi Kyotani
J. Power Sources 2020, 457, 228042
DOI: 10.1016/j.jpowsour.2020.228042
2. ‫ۻ‬Direct fluorometry of imidacloprid in agricultural products using alkali photolysis
M. Yamamoto, N. Yamato, C. Tomizawa, K. Yagi, K. Kikukawa, S. Kodama, R. Yamamoto, and A. Yamamotoin preparation- 39 -

ගㄏ㉳㐣Ώᵓ㐀ኚ໬ࢆ฼⏝ࡋࡓศᏊ㛫཯ᛂ㛤Ⓨ
Development of intermolecular reactions utilizing light-induced transient
deformation‫ۑ‬ṇ஭ ᏹࠊ㔠Ꮚ ಇ୍㸦ᮾி኱Ꮫ኱Ꮫ㝔⥲ྜᩥ໬◊✲⛉㸧

1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲࡛ࡣࠊ㔠ᒓ㘒యࡢศᏊ㛫཯ᛂࡀගບ㉳࡟కࡗ࡚ຍ㏿ࡍࡿຠᯝ࡟╔┠ࡋࠊࡑࡢᚑ᮶࡟࡞࠸཯ᛂᙧᘧࡢ

ᇶ♏Ꮫ⌮ࢆゎ᫂ࡍࡿࠋࡇࢀ࡟ࡼࡗ࡚ࠊᮏ⌧㇟ࢆ⏝࠸ࡓ௚ศ㔝࡬ࡢᛂ⏝Ⓨᒎ࡟࠾ࡅࡿᇶ♏ⓗ▱ぢࢆ☜❧ࡍࡿࠋ⏦ㄳ⪅ࡣࡇࢀࡲ࡛ȧඹᙺศᏊ࡜㑄⛣㔠ᒓ㘒యࢆ⏝࠸ࡓᶵ⬟ᛶᮦᩱ㛤Ⓨࡢ◊✲࡟ᦠࢃࡗ࡚ࡁࡓࠋࡑࡢ୰࡛ࠊⓑ㔠㘒యࢆ⏝࠸ࡓ HCl ࢞ࢫࢭࣥࢧᮦᩱࡢ㛤Ⓨ࡟ᡂຌࡋࡓࠋࡇࡢࢭࣥࢧࡣ HCl ࡟ࡼࡗ࡚ⓑ㔠࢔ࢭࢳࣜࢻ㘒యࡀศゎࡍࡿࡇ࡜ࢆ㘽࡜ࡋ࡚࠸ࡿࠋࡑࡢ㝿അ↛࡟ࡶࠊࡇࡢ཯ᛂࡀඹᙺ㒊఩ບ㉳ࡢග↷ᑕ࡟ࡼࡗ࡚ຍ㏿ࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡑࡢຍ㏿ຠᯝࡣ኱ࡁࡃࠊග↷ᑕ࡞ࡋࡢᑐ↷ᐇ㦂࡟ẚ࡭࡚ 2000 ศࡢ 1 ࡢప⃰ᗘ HCl ࡟ᑐࡋ࡚ࠊᚑ᮶ࡢ
50 ಸࡢᛂ⟅㏿ᗘ࡛཯ᛂࡋࡓࠋࡑࡇ࡛⏦ㄳ⪅ࡣࠊࡇࡢᚑ᮶࡟࡞࠸ග཯ᛂࡢᐇែ࡟ᑐࡋ࡚ࠊDFT ィ⟬࡜ᐇ㦂ࢆ⤌ࡳྜࢃࡏࡓᇶ♏ࣞ࣋ࣝࡢ◊✲࡟ࡼࡗ࡚ࡑࡢヲ⣽ࢆ᫂ࡽ࠿࡟ࡋࠊගㄏ㉳ࡢ㓄఩Ꮚ஺᥮཯ᛂ㛤Ⓨ࡬࡜Ⓨᒎࡉࡏࡿࡇ࡜࡛ࠊ᪂ࡓ࡞Ꮫ⌮ᵓ⠏ࢆ┠ᣦࡍࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
ඛ㏙ࡋࡓගࡀ㛵୚ࡋࡓࠊⓑ㔠࢔ࢭࢳࣜࢻ㘒య࡜ HCl ࢆ⏝࠸ࡓ᪂཯ᛂ࡟࠾ࡅࡿᴟࡵ࡚⯆࿡῝࠸Ⅼ࡜ࡋ࡚ࠊග

ບ㉳㒊఩࡜཯ᛂ㒊఩ࡀ୍⮴ࡋ࡚࠸࡞࠸Ⅼࡀᣲࡆࡽࢀࡿࠋ༶ࡕⓑ㔠࢔ࢭࢳࣜࢻ㘒యࡢࣇࣟࣥࢸ࢕࢔㌶㐨ࡣඹᙺ㒊఩࡟ᒁᅾ໬ࡋ࡚࠾ࡾࠊ཯ᛂ࡛㛤⿣ࡍࡿⓑ㔠࢔ࢭࢳࣜࢻ⤖ྜࡀ㛵୚ࡋ࡚࠸࡞࠸ࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊGaussian
09 ࠾ࡼࡧ 16 ࢆ฼⏝ࡋ࡚ࠊDFT ࠾ࡼࡧ TD-DFT ィ⟬࡟ᇶ࡙ࡃບ㉳ᵓ㐀ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡛ࠊ≉␗࡞཯ᛂᛶ
ࢆᘬࡁ㉳ࡇࡋ࡚࠸ࡿ≉ᚩⓗ࡞Ṕୖᵓ㐀ཬࡧศᏊ㌶㐨ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ≉࡟ࠊᵝࠎ࡞᭷ຠඹᙺ㛗ࢆ᭷ࡍࡿ㓄఩Ꮚࡢඹᙺ⣔ࢆ⣔⤫ⓗ࡟᥈⣴ࡍࡿࡇ࡜࡛ࠊ཯ᛂάᛶ࡟࠾ࡅࡿ྾཰Ἴ㛗ࡢ౫Ꮡᛶࢆ᥈⣴ࡍࡿࠋ▷Ἴ㛗ࢆ྾཰ࡍࡿ
㓄఩Ꮚ࡜ࡋ࡚࢜ࣜࢦࣇ࢙ࢽࣞࣥࠊ㛗Ἴ㛗྾཰ࡍࡿ㓄఩Ꮚ࡜ࡋ࡚࢜ࣜࢦࢳ࢜ࣇ࢙ࣥ࡞࡝ࢆ᥇⏝ࡋࠊ཯ᛂ㏿ᗘࡢἼ㛗౫Ꮡᛶࢆ᫂ࡽ࠿࡟ࡍࡿࠋࡇࡢᐇ㦂⤖ᯝ࡜ᮏ◊✲⏦ㄳ࡛ࡶࡓࡽࡉࢀࡿィ⟬⤖ᯝ࡜ࡢ┦㛵ࢆ᫂ࡽ࠿࡜ࡍࡿࡇ
࡜࡛ࠊග࡟ࡼࡗ࡚⏕ࡌࡓບ㉳ศᏊࡀࠊ୍᫬ⓗ࡟ᵓ㐀ࢆኚ໬ࡉࡏࡿࡇ࡜࡛ᇶᗏ≧ែ࡛ࡣ㐩ᡂࡉࢀ࡞࠿ࡗࡓ㧗཯ᛂᛶࢆ⋓ᚓࡍࡿ࡜࠸࠺ᚑ᮶࡟࡞࠸᪂ࡋ࠸཯ᛂᙧᘧࢆᐇドࡍࡿࠋࡇࢀࡽࡢ᥈⣴ࡢ⤖ᯝࠊศゎ཯ᛂࡢἼ㛗౫Ꮡᛶࡀ᫂ࡽ࠿࡟࡞ࢀࡤࠊ」ᩘࡢⓑ㔠࢔ࢭࢳࣜࢻ㘒య࠿ࡽ≉ᐃࡢ㘒యࢆἼ㛗㑅ᢥⓗ࡟ศゎࡍࡿ⣔ࡢᐇ⌧ࡸࠊ㘒యΰྜୗ࡟࠾ࡅࡿ࢔ࣝ࢟ࣥᮎ➃ࡢẁ㝵ⓗ࡞ಟ㣭࡞࡝ࠊᚑ᮶ࡢ᭷ᶵ
㔠ᒓ໬Ꮫ࡛ࡣ㐩ᡂ୙ྍ⬟࡞㑅ᢥⓗ཯ᛂࢆᐇ⌧ࡍࡿࠋ⥆࠸࡚ࠊ㔠ᒓ୰ᚰ࡜཯ᛂࡍࡿᇶ㉁ࢆࣈࣞࣥࢫࢸࢵࢻ㓟௨እ࡬࡜ᒎ㛤ࡍࡿࠋග↷ᑕ࡟ࡼࡗ࡚≉ᚩⓗ࡞ບ㉳≧ែࡢᙧᡂࡀ᫂ࡽ࠿࡟࡞ࡗࡓሙྜࠊ౛࠼ࡤ㖡࢔ࢭࢳࣜࢻᏑᅾ
ୗ࡛ࡣ࢔ࢭࢳࣜࢻ㓄఩Ꮚ஺᥮཯ᛂࢆຍ㏿ࡍࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋࡉࡽ࡟ࡇࡇ࡛ࠊ྾཰Ἴ㛗ࡢ␗࡞ࡿ࢔ࢭࢺࣜ
ࢻ㓄఩ᏊࢆඹᏑࡉࡏࡿࡇ࡜࡛ࠊ↷ᑕࡍࡿගࡢἼ㛗࡟ࡼࡗ࡚㑅ᢥⓗ࡞㓄఩Ꮚ஺᥮཯ᛂࡀᐇ⌧ࡍࡿࠋࡇࡢࡼ࠺࡞
㔠ᒓ㘒యࡢ㓄఩Ꮚ஺᥮཯ᛂࢆἼ㛗㑅ᢥⓗ࡟ᐇ⌧ࡋࡓ౛ࡣ࡞ࡃࠊᮏ᪂つ཯ᛂࡢ᭷⏝ᛶࡀ♧ࡉࢀࡿࠋ- 40 -

3◊✲ᡂᯝ࢜ࣜࢦࣇ࢙ࢽ࢚ࣞࣥࢳࢽࣞࣥࡀ㐃⤖ࡋࡓⓑ㔠࢔ࢭࢳࣜࢻ㘒య࡟ᑐࡍࡿ TD-DFT ィ⟬ࢆ⾜ࡗࡓࠋỗ㛵ᩘ࡜ࡋ

࡚ࡣ B3LYP ࡶࡋࡃࡣ cam-B3LYP ࢆ⏝࠸࡚ࠊ㔜ඖ⣲ࡢつᐃ㛵ᩘࡣ Lanl2DZ ࢆ㑅ᢥࡋࠊࡑࡢ࡯࠿ࡢඖ⣲࡟ࡣ
6-31G*ࢆ㐺⏝ࡋ࡚࠸ࡿࠋ࢔ࢽ࢜ࣥᛶࡢ㓄఩Ꮚࢆྵࡴࡓࡵ୍㒊ࡢཎᏊ࡟ࡣศᴟ㛵ᩘࢆ⏝࠸ࡓࠋィ⟬ࡢ⤖ᯝࠊᅗ㸯࡟♧ࡍࡼ࠺࡟ࠊᇶᗏ≧ែ࡟ẚ࡭࡚ບ㉳≧ែࡣⓑ㔠࿘ࡾࡢ㓄఩Ꮚࡀ 90 ᗘᅇ㌿ࡋࡓࠋࡑࢀ࡟కࡗ࡚ᇶᗏ≧ែ࡛ࡣඹᙺ㓄఩Ꮚ࡟ᒁᅾ໬ࡋ࡚࠸ࡓࣇࣟࣥࢸ࢕࢔㌶㐨ࡀࠊᵓ㐀⦆࿴࡟కࡗ࡚ບ㉳≧ែ࡛ࡣⓑ㔠୰ᚰ࡬࡜⛣ືࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋᚑࡗ࡚ࠊගບ㉳࡟క࠺ⓑ㔠࢔ࢭࢳࣜࢻ㘒యࡢ≉␗࡞཯ᛂᛶࡣࠊບ㉳ᚋࡢᵓ㐀⦆࿴࡟ࡼࡗ࡚ᚓࡽࢀࡿ≉␗࡞㐣Ώⓗᵓ㐀࡛࠶ࡿࡇ࡜ࡀࠊィ⟬࡟ࡼࡗ࡚ᙉࡃᨭᣢࡉࢀࡓࠋ
⥆ࡅ࡚ࠊࡇࡢᵓ㐀ኚ໬ࡢ㥑ືຊ࡟ࡘ࠸࡚ࡢ

䐠 upper SOMO (S1)(vertical transition)⪃ᐹࢆ⾜ࡗࡓࠋᅗ㸯࠿

DFT and TD-DFT (Nstates=50) calculations
B3LYP/LANL2DZ for Pt, 6-31G(d) for P, C 6-31G(d,p) for Hࡽࠊⓑ㔠࢔ࢭࢳࣜࢻ㘒
S1యࡣᇶᗏ≧ែ࡟࠾࠸࡚ࠊղp ᖹ㠃࡜ⓑ㔠㘒య࡟࠾

relaxation

S-S* transitionࡅࡿ✵㓄ᗙࡢ㌶㐨ࡣ┤S0⾜ࡋ࡚࠸ࡿࠋࡑࡢ୍᪉
䐟 HOMO (S0)(steady state)࡛ࠊග↷ᑕ࡟ࡼࡗ࡚ඹ

E

ᙺ⣔ࡀ࢟ࣀ࢖ࢻᵓ㐀ࢆ

ճ

hX

ձ

䐡 Excited state after relaxation
upper SOMO (S1)(activated state)ᙧᡂࡍࡿ㝿ࡣࠊⓑ㔠࿘ࡾࡢ㓄఩Ꮚࡀ 90 ᗘᅇ㌿ࡍࡿࡇ࡜࡛ࡑࡢ࢟ࣀ࢖
ࢻᵓ㐀ࡀᣑᙇ ࡉࢀ࡚

ᅗ 1. DFT ࠾ࡼࡧ TD-DFT ࢆ⏝࠸ࡓⓑ㔠࢔ࢭࢳࣜࢻ㘒యࡢࠊձᇶᗏ≧ែࠊղᆶ┤࠸ࡿࡇ࡜ࡀ᫂ ࡽ࠿࡜㑄⛣ᚋࠊճບ㉳≧ែ࡟࠾ࡅࡿᵓ㐀࡜ศᏊ㌶㐨ゎᯒ࡞ࡾࠊࡇࢀ࡟ࡼࡗ࡚ᚓ
ࡽࢀࡿ࢚ࢿࣝࢠ࣮ࡢᏳᐃ໬ࡀᵓ㐀ኚ໬ࡢ㥑ືຊ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋᐇ㝿ࠊNBO ゎᯒ࡟ࡼࡗ࡚ࠊᵓ㐀ኚ໬๓ᚋ࡟࠾ࡅࡿ࢔ࢭࢳࣜࢻ㓄఩Ꮚࡢᮎ➃Ⅳ⣲࡜ⓑ㔠ཎᏊࡢ㟁Ꮚ≧ែࡢኚ໬ࢆゎᯒࡋࡓ࡜ࡇࢁࠊບ㉳≧ែ࡟࠾ࡅࡿᅇ㌿࡟ࡼࡗ࡚ࠊ࢔ࢭࢳࣜࢻࡢⅣ⣲ࡢ Pz ㌶㐨࠿ࡽⓑ㔠ࡢ Pz ㌶㐨࡟㟁Ꮚࢆ౪୚ࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ
ᚑࡗ࡚ࠊDFT ࠾ࡼࡧ TD-DFT ィ⟬ࢆ⾜࠺ࡇ࡜࡛ࠊⓑ㔠࢔ࢭࢳࣜࢻࡢຍ㏿ⓗ࡞㓄఩Ꮚ⨨᥮཯ᛂࡢ࣓࢝ࢽࢬ࣒
ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ௒ᚋࡣࡇࢀࡽࡢィ⟬⤖ᯝࢆศᏊタィ࡬࡜ࣇ࢕࣮ࢻࣂࢵࢡࡍࡿࡇ࡜࡛ࠊ⌮ㄽ࡜ᐇ㦂ࡢᩚྜᛶࢆ☜ㄆࡍࡿணᐃ࡛࠶ࡿࠋࡲࡓᮏ◊✲ᡂᯝ࡟ࡘ࠸࡚ࡣࠊ⌧ᅾㄽᩥᇳ➹୰࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ㔠Ꮚ࣭ ṇ஭࣭⋢ᮌ࣭ᑎᑿ, ᪥ᮏ໬Ꮫ఍➨ 99 ᫓Ꮨᖺ఍2019 ⏥ᗓ㔠Ꮚ࣭ ᮧ⏣࣭ṇ஭࣭⋢ᮌ࣭ᑎᑿ, ➨ 66 ᅇ᭷ᶵ㔠ᒓ໬Ꮫウㄽ఍

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬㔠Ꮚ࣭ᮧ⏣࣭ṇ஭࣭ᑎᑿࠊᢞ✏ணᐃ- 41 -

2019 ᮾிẼ┦ࢼࣀ⢏Ꮚࡢ㍺㏦࡜Ⲵ㟁࡟㛵ࡍࡿศᏊືຊᏛⓗゎᯒ
Molecular dynamics analysis of nanoparticle's transport/charging in gas‫▱ ⯓⋢ۑ‬ஓ㸦㔠ἑ኱Ꮫ኱Ꮫ㝔࣭⮬↛⛉Ꮫ◊✲⛉࣭༤ኈᚋᮇㄢ⛬㸧
1◊✲┠ⓗࠊෆᐜ
㟁Ẽ⛣ືᗘศᯒἲ㸦IMS㸧࡞࡝࡟ࡼࡗ࡚኱Ẽ୰࡟ᾋ㐟ࡍࡿᚤ⢏Ꮚ㸦࢚࢔ࣟࢰࣝ㸧ࠊ≉࡟ࢼࣀ⢏Ꮚࢆ⢭ᗘ㧗ࡃศᯒࡍࡿ࡟ࡣࠊ⢏Ꮚࡢ㸯㸧㍺㏦ࢲ࢖ࢼ࣑ࢡࢫ࠾ࡼࡧࠊ㸰㸧Ẽ୰࢖࢜ࣥ࡜ࡢ⾪✺࡟ࡼࡿⲴ㟁࣭୰࿴࡟㛵ࡍࡿࢲ࢖ࢼ࣑ࢡࢫࢆ͆ศᏊ͇࡛ࣞ࣋ࣝ⌮ゎࡍࡿᚲせࡀ࠶ࡿࠋᮏ◊✲ࡣศᏊືຊᏛἲࢆ⏝࠸࡚㸯㸧㍺㏦࡜㸰㸧Ⲵ㟁࣭୰࿴ࣉࣟࢭࢫࢆゎᯒࡍࡿࡶࡢ࡛࠶ࡾࠊᮏ✏࡛ࡣ୺࡟ᮏᖺᗘ࡟ྲྀࡾ⤌ࢇࡔ㸰㸧ࡢ୰࿴ࣉࣟࢭࢫࡢࡳ♧ࡍࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ⾪✺㏿ᗘᐃᩘࡢィ⟬ἲ࡜ࡋ࡚ᚑ᮶⏝࠸ࡽࢀ࡚࠸ࡿࣇࣛࢵࢡࢫ࣐ࢵࢳࣥࢢἲࢆᛂ⏝ࡋࠊศᏊ࢖࢜ࣥ㏆ഐࡢື

ⓗᣲືࢆ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾゎࡃ Continuum-Molecular dynamics (C-MD)ἲࢆ㛤ⓎࡋࡓࠋձNH4+࢖࢜
ࣥ࡜ NO2-࢖࢜ࣥࡢ⾪✺㏿ᗘᐃᩘࠊղከ౯ᖏ㟁 Polyethylene-glycol㸦PEG㸧࢖࢜ࣥ࡜ NO2-࢖࢜ࣥࡢ⾪✺㏿ᗘᐃᩘࢆィ⟬ࡋࡓࠋ፹యศᏊࡣձHe ࢆࠊղN2 ࢆ⏝࠸ࡓࠋィ⟬࡟ࡣ⮬సࡢࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ

3◊✲ᡂᯝձ࡟࠾࠸࡚ࠊᅽຊࢆࣃ࣓࣮ࣛࢱ㸦1㹼1000kPa㸧࡜ࡋ࡚ィ⟬ࡍࡿ࡜ࠊ㧗ᅽୗ࡛ࡣ㐃⥆య㡿ᇦ࡟࠾ࡅࡿྂ඾ⓗ࡞⾪✺㏿ᗘ⌮ㄽ࡜Ⰻዲ࡟୍⮴ࡋࠊᅽຊࡢῶᑡ࡜࡜ࡶ࡟⮬⏤ศᏊ㡿ᇦ㸦ྂ඾ㄽ㸧࡬࡜㑄⛣ࡋࡓࠋࡇࡢ㑄⛣㐣⛬
ࡣ LD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽồࡵࡓ᥎ᐃ⥺ࡸᐇ㦂್࡜Ⰻዲ࡟୍⮴ࡋࡓࡇ࡜࠿ࡽࠊC-MD ἲࡢጇᙜᛶࡀ♧ࡉࢀࡓࠋࡲࡓࠊղ࡛ࡶᐇ㦂⤖ᯝࢆⰋዲ࡟෌⌧ࡋࠊ୰࿴࡟క࠺ PEG ศᏊࡢኚᙧࡶ☜ㄆࡉࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬T. Tamadate, C. J. Hogan, H. Higashi, Y. Otani & T. Seto, “A Hybrid Continuum-Molecular Dynamics Flux

Matching Calculation Method for Collision Rate Coefficients”, The American Association for Aerosol Research 2019,
9AP.19, US, Nov 2019.
‫ ۻ‬T. Tamadate, H. Higashi, M. Kumita, Y. Otani & T. Seto, “Molecular dynamics study on charging process ofaerosol nanoparticles”, Asian Aerosol Conference 2019, 260, Hong Kong, May 2019.
‫▱⯓⋢ ۻ‬ஓࠊᮾ⚽᠇ࠊỮ⏣ᖿኵࠊ኱㇂ྜྷ⏕ࠊ℩ᡞ❶ᩥࠊࠕศᏊືຊᏛἲࢆ⏝࠸ࡓ࢞ࢫ୰࡟࠾ࡅࡿ࢖࢜ࣥ㛫⾪✺㏿ᗘᐃᩘࡢ⟬ฟࠖࠊ໬ᏛᕤᏛ఍➨ 85 ᖺ఍ࠊC217ࠊ࢜ࣥࣛ࢖ࣥࠊ2020 ᖺ 3 ᭶௒ᚋࡢⓎ⾲ணᐃ AAAR2020ࠊ࢚࢔ࣟࢰࣝウㄽ఍ 2020ࠊ໬ᏛᕤᏛ఍⛅Ꮨ኱఍࡞࡝ࢆணᐃ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬T. Tamadate, H. Higashi, T. Seto & C. J. Hogan, “Calculation of the Ion-Ion Recombination Rate Coefficient via a

Hybrid Continuum- Molecular Dynamics Approach” The Journal of Chemical Physics, 152(9), 094306, 2020, DOI:
10.1063/1.5144772⌧ᅾࠊ1 ሗᇳ➹୰㸦≀⌮໬Ꮫ⣔ࡢ㞧ㄅ࡟ᢞ✏ணᐃ㸧

- 42 -

㹂㹄㹒ィ⟬ࢆ⏝࠸ࡓ཯ᛂᶵᵓࡢゎ᫂࡟ࡼࡿ㑅ᢥⓗ᭷ᶵྜᡂ཯ᛂࡢ㛤Ⓨ
Development of selective synthetic reactions by elucidation of reaction
mechanisms using DFT calculations‫ۑ‬ᒣᓮ ⚈Ꮚ㸦ዉⰋᩍ⫱኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ
1.1 ⨨᥮ࢫࢳࣞࣥㄏᑟయࢆ⏝࠸ࡓศᏊ㛫࠾ࡼࡧศᏊෆ⎔໬௜ຍ⨨᥮ࢩࢡࣟࣈࢱࣥࡢ❧య㑅ᢥⓗྜᡂࡣ⏕≀άᛶ໬ྜ≀ࡢྜᡂࡸࠊ᭷ᶵྜᡂ࡛ࡢά⏝࡛㔜せ࡛࠶ࡿࠋ⨨᥮ࢫࢳࣞࣥㄏᑟయࢆ⏝࠸ࡓศᏊ㛫[2+2]⎔໬௜ຍ(ᅗ 1)࠾ࡼࡧศᏊෆ[2+2]⎔໬௜ຍཬࡧ[4+2]⎔໬௜ຍ࡟ࡼࡿ❧య㑅ᢥⓗࡢ㛤Ⓨࢆ⾜ࡗࡓࠋ཯ᛂࡀ㐍⾜ࡍࡿ㘽࡜࡞ࡿᅉᏊ࡟ࡘ࠸࡚ࠊィ⟬໬Ꮫࢆ⏝࠸࡚཯ᛂ⤒㊰ࢆㄪ࡭ࡿࡇ࡜࡟ࡼ
ࡾࠊ཯ᛂᛶࠊ㑅ᢥᛶࡢ㐪࠸ࢆㄪ࡭ࡓࠋ
ᅗ 1. ศᏊ㛫[2+2]⎔໬௜ຍ཯ᛂ

EtO2C

1.0 equiv.
SnCl4(or SnBr4)

CO2Et
+
X

RO2C
R=Et,CH2Ph,
allyl, i-Pr, MeAr

CH2Cl2
r.t. 1h or-78 C

X = H, Br
Ar=4-YC6H4(Y = H,F,Cl,Br,Me)

MeO
EtO2C
EtO2C

Ar
X

MeO

O

O

SnCl4

O
MeO

RO2C
X = H, SnCl4
X = Br, SnBr4

H
A1

Cl4
Sn
O
O

TS1

Ph

H
H
[ G =0kcal/mol][+12.33
kcal/mol]

TS2[+5.76kcal/mol]

MeO

OMe

MeO

Ph
H

O B1
[+1.88 kcal/mol]

MeO
MeO2C

O SnCl4
O

OMe
C1 Ph
[-1.77 kcal/mol]

1.2 ᭷ᶵⓎගᛶ≀㉁ྜᡂ◊✲࣓ࢱࣝࣇ࣮ࣜ᭷ᶵ࢔ࣥࣔࢽ࣒࢘ሷⓎගᛶ≀㉁࡟ࡘ࠸࡚ࠊບ㉳≧ែࡢࣔࢹࣝィ⟬ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ
GAUSSIAN 09, GAUSSIAN 16 ࢆ⏝࠸࡚ DFT ィ⟬ࢆ⾜ࡗࡓࠋ཯ᛂᶵᵓࢆ B3LYP/6-31G*, LANL2DZ (Sn), ࠾ࡼࡧ PCM ⁐፹ຠᯝࢆྵࡵࡓィ⟬࡛ㄪ࡭ࡓࠋ⁐፹ຠᯝࢆྵࡵ࡚⢭ᗘࢆ㧗ࡵࡓ RB3LYP/6-311+G(d,p) , SDD (Sn)SCRF = (PCM, solvent) ࡛࢚ࢿࣝࢠ࣮ΔG ࡲࡓࡣ ΔE㸩ZPE ࡢ㸯Ⅼィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝ
ᅗ 1 ࡟♧ࡋࡓࢫࢳࣞࣥ࡜࢚ࢸࣥࢺࣜ࢝ࣝ࣎ࣥ㓟ㄏᑟయࡢ❧య㑅ᢥⓗ[2+2]⎔໬௜ຍ࡟ࡘ࠸࡚ࠊẁ㝵ⓗ࡞཮ᛶ࢖࢜ࣥࢆ㏻ࡿ⤒㊰ࡀồࡵࡽࢀࡓࠋ⏕ᡂ≀ࡢ㑅ᢥⓗ 1,3-cis ❧య໬Ꮫࡣࠊࢩࢡࣟࣈࢱࣥ⎔ᙧᡂࡢ㑄⛣≧ែ࠾ࡼࡧ⏕ࡌࡓ SnCl4 㓄఩⏕ᡂ≀࡟࠾ࡅࡿ᭷฼࡞ 1,3-࢚ࢡ࢔ࢺࣜ࢔ࣝᵝ㓄ᗙ࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡑࡢ࡯࠿ࡢ཯ᛂ
ཬࡧ᭷ᶵⓎගᛶ≀㉁ࡢⓎග࡟ࡘ࠸࡚ࡶᐇ㦂⤖ᯝࢆㄝ᫂ࡋ࡚࠸ࡿࠋ

4Ⓨ⾲ணᐃ‫ۻ‬Inter- and Intramolecular Cycloaddition Reactions of Ethenetricarboxylates with Styrenes and Halostyrene, S.

Yamazaki, Z. Wang, K. Iwata, K. Katayama, Y. Mikata, T. Morimoto, and A. Ogawa,Ⓨ⾲ணᐃ- 43 -

ศᏊືຊᏛἲ࡟ࡼࡿỈࡢ㸱ḟඖ࣐࣭ࣛࣥTHz ᣺ືศගἲ
Calculation of 3 dimensional Raman and THz vibrational spectra of liquidwater using molecular dynamics simulation‫ۑ‬㇂ᮧ ྜྷ㝯ࠊᱵཎ ୍㉳㸦ி㒔኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉ 㔞Ꮚ໬Ꮫ◊✲ᐊ)

1◊✲┠ⓗࠊෆᐜ

ከḟඖ᣺ືศගἲࡣ㠀ㄪ࿴ⓗ᣺ືࠊ᣺ື࣮ࣔࢻ࣮ࣔࢻ࢝ࢵࣉࣜࣥࢢࠊ᣺ື࢚ࢿࣝࢠ࣮ࡢ⦆࿴㐣⛬࡞࡝  ḟඖ᣺ືศගἲ࡛ࡣゎᯒ࡟㝈⏺ࡀ࠶ࡿỈࡢືⓗᛶ㉁ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋỈࡢᵝࠎ࡞≉␗࡞ᛶ㉁ࡣỈ⣲⤖ྜ࡟ࡼࡿࡶࡢ࡞ࡢ࡛ࠊ≉࡟ศᏊ㛫᣺ືࡢࢩࢢࢼࣝࢆゎᯒࡍࡿࡇ࡜ࡣỈࢆ⌮ゎࡍࡿୖ࡛㔜せ࡛࠶ࡿࠋ7+] ࣃࣝࢫࡣ⛗ື࣮ࣔࢻࢆᙉࡃບ㉳ࡍࡿࡀࠊ୪㐍᣺ື࡟క࠺཮ᴟᏊኚ໬ࡀᑠࡉ࠸ࡇ࡜࠿ࡽ୪㐍࣮ࣔࢻࢆᙉࡃບ㉳ࡏ
ࡎࠊ7+] ࣃࣝࢫࡢࡳࢆ⏝࠸ࡓศග࡛ࡣศᏊ㛫ࡢືⓗᛶ㉁ࡢゎᯒࡀᅔ㞴࡛࠶ࡿࠋ୍᪉࡛࣐ࣛࣥࣃࣝࢫ࡛࠶ࢀࡤ
୪㐍࣮ࣔࢻࢆᙉࡃບ㉳ࡍࡿࡢ࡛୪㐍࣮ࣔࢻࢆ⤡ࡵࡓືⓗᛶ㉁ࡢゎᯒࡀྍ⬟࡛࠶ࡿ࡜ᮇᚅࡉࢀࡿࠋ᭱㏆࡟࡞ࡗ࡚ศᏊෆ࡛࡞ࡃศᏊ㛫ࡢ㟁Ⲵ⛣ືࡶ⪃៖ࡋࡓ⢭ᗘࡢ㧗࠸ศᴟ⋡㛵ᩘ &)&7',' ࡀ㛤Ⓨࡉࢀࠊ࣐ࣛࣥࣃࣝࢫࢆ⏝࠸ࡓಙ㢗ᛶࡢ㧗࠸ከḟඖ᣺ືศගࢆ⾜࠺ࡇ࡜ࡀྍ⬟࡜࡞ࡗࡓࠋᮏ◊✲࡛ࡣࠊᖖỈ࡟ᑐࡋ࡚ 7+] ࣃࣝࢫ࡜ࣛ

࣐ࣥࣃࣝࢫࢆ⤌ࡳྜࢃࡏࡓከḟඖ᣺ືศගࡢィ⟬ࢆ⾜࠸ࠊࡑࡢゎᯒࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛ࡣᖖỈ  ศᏊ࡟࠾ࡅࡿ  ḟඖ ,5࣭࣐ࣛࣥ᣺ືศගࢫ࣌ࢡࢺࣝࢆᖹ⾮㠀ᖹ⾮ࣁ࢖ࣈࣜࢵࢻἲ࡟ࡼ

ࡾࠊࣇࣝศᏊືຊᏛἲ࠿ࡽ⟬ฟࡍࡿࠋᖹ⾮㠀ᖹ⾮ࣁ࢖ࣈࣜࢵࢻἲࡣஂಖබᘧ࡟ࡼࡾ⥺ᙧᛂ⟅ࢆᖹ⾮್࠿ࡽィ⟬ࡍࡿᖹ⾮ἲ࡜ࠊᐇ㦂ࢫ࣮࣒࢟ࢆࡑࡢࡲࡲࢩ࣑࣮ࣗࣞࢺࡋࡓ㠀ᖹ⾮ἲࢆ⤌ࡳྜࢃࡏ࡚㧗ḟࡢᛂ⟅㛵ᩘࢆィ⟬ࡍࡿᡭἲ࡛࠶ࡿࠋᚑ᮶࠿ࡽࢺࣛࢪ࢙ࢡࢺ࣮ࣜࡢࢧࣥࣉࣜࣥࢢᡭἲ࡜ࡋ࡚㸱ḟඖศගࢆィ⟬ࡍࡿࡢ࡟⏝࠸ࡽࢀ࡚࠸ࡓ backward-forward ἲ࡛ࡣศᏊᩘࡀᑡ࡞࠸⣔࡛ CFCT-DID ࢆ౑ࡗࡓሙྜ࡟ṇࡋ࠸ࢫ࣌ࢡࢺࣝࢆ୚࠼࡞࠸
ࡇ࡜ࡀุ᫂ࡋࡓࡓࡵࠊforward-forward ἲࢆ⏝࠸࡚ィ⟬ࢆ⾜ࡗࡓࠋࡲࡓࠊ࣏ࢸࣥࢩࣕࣝ࡜ࡋ࡚ 7,33 ࢆ⏝࠸ࠊ཮ᴟᏊ࣮࣓ࣔࣥࢺཬࡧศᴟ⋡ࡢィ⟬࡟ࡣ &)&7',' ࢆ⏝࠸ࡓࠋ
&)&7',' ࡣศᏊ㛫㟁Ⲵ⛣ືࡢຠᯝࢆྲྀࡾධࢀࡿࡓࡵࠊ௨ୗࡢᘧ࠿ࡽศᏊ㛫㟁Ⲵ⛣ື࡟ࡼࡗ࡚⏕ࡌࡿศᏊ L ୰ࡢ┦஫స⏝ࢧ࢖ࢺ N ࡢ㟁Ⲵࡇࡇ࡛ࡣศᏊ L ୰ࡢ┦஫స⏝ࢧ࢖ࢺ N ࡜ศᏊ M ୰ࡢ┦஫స⏝ࢧ࢖ࢺ O ࡢ㛫࡛ศᏊ㛫㟁Ⲵ⛣ືࢆチᐜࡍࡿ㟁Ⲵ⛣ືศᴟ⋡࡛࠶ࡾࠊ3ࢆィ⟬ࡍࡿࠋ

࡜ᐃ⩏ࡍࡿࠋ

◊✲ᡂᯝ- 44 -              ᅗ 1. ࣇ࣐ࣝࣛࣥศගࡢࢫ࣌ࢡࢺࣝࡢ᫬㛫ኚ໬
ᅗ 1 ࡣ㸰Ⓨ┠࡜㸱Ⓨ┠ࡢ࣏ࣥࣉࣃࣝࢫࡢ᫬㛫㛫㝸ࢆ t2 ࡜ࡋ࡚ࠊt2=0,20,40,60fs ࡟࠾ࡅࡿ RRRR ࡢ㸱ḟඖ᣺ືࢫ࣌ࢡࢺࣝࢆࡑࢀࡒࢀ♧ࡋࡓࡶࡢ࡛࠶ࡿࠋࡇࡇ࡛ R ࡣ࣐ࣛࣥࣃࣝࢫࢆ⾲ࡋࠊ㸱ᅇࡢ࣏ࣥࣉࣃࣝࢫ࡜㸯ᅇࡢࣉ࣮ࣟࣈࣃࣝࢫ඲࡚ࡀ࣐ࣛࣥࣃࣝࢫ࡛࠶ࡿࡇ࡜ࢆ␎グࡍࡿࠋ
40fs ࡲ࡛ࡣ(Ȱ1,Ȱ3)=(250,200)࡟ translation ࣮ࣔࢻࡢࣆ࣮ࢡࡀほࡉࢀࡿࡀࠊᛴ㏿࡟ࣆ࣮ࢡᙉᗘࡣῶᑡࡋ࡚

࠸ࡁ 60fs ࡛ࡣ࡯࡜ࢇ࡝ࣆ࣮ࢡࡀᾘ⁛ࡋ࡚࠸ࡿࠋ0fs ࡛ぢࡽࢀࡿ㠀ㄪ࿴ࣆ࣮ࢡ㸦㟷Ⰽࡢࣆ࣮ࢡ㸧࡟ࡼࡗ࡚translation ࣮ࣔࢻࡢ㠀ㄪ࿴ᛶࡀ㠀ᖖ࡟኱ࡁ࠸ࡇ࡜ࡀศ࠿ࡾࠊࡉࡽ࡟᫬㛫ࡢ⤒㐣࡜ඹ࡟ࡑࡢࣆ࣮ࢡࡀప࿘Ἴഃ
࡬࡜⛣ືࡍࡿᵝᏊࡶほࡉࢀࡿࠋࡇࡢࡇ࡜࠿ࡽࠊບ㉳ࡉࢀࡓ 250cm-1

ࡢ O-O ఙ⦰᣺ືࡀỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࢆᦂࡿࡀࡋ࡚ቯࡋ࡞ࡀࡽࠊ
~60cm-1 ௨ୗࡢ O-O-O ኚゅ᣺ື࡟ 60fs ௨ୗࡢ㠀ᖖ࡟㏿࠸᫬㛫ࢫࢣ࣮࡛࢚ࣝࢿࣝࢠ࣮⛣ືࢆ㉳ࡇࡋ࡚࠸ࡿࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋ㸯ḟඖ࣐ࣛࣥࢫ
࣌ࢡࢺ࡛ࣝࡣ libration ࣮ࣔࢻࡀ translation ࣮ࣔࢻ௨ୖࡢᙉᗘ࡛᫂☜࡟ほࡉࢀࡿ࡟ࡶ㛵ࢃࡽࡎࠊᅗ 2 ࡢ TTTT㸦࣐ࣛࣥྠᵝ THz ࢆ T ࡜␎グࡍࡿ㸧࡜ࡣ␗࡞ࡾ RRRR ࡢ(Ȱ1,Ȱ3)=(700,700)௜㏆࡟ࡣᑐᛂࡍࡿࣆ࣮ࢡࡀほࡉࢀ࡚࠸࡞࠸ࠋ࣐࡛ࣛࣥࡣ㸯ḟඖ࡟࠾ࡅࡿ libration ࣮ࣔࢻࡀ࡯ࡰኚࢃࡽ࡞࠸ᙉᗘ࡛ 400~1000cm-1 ࡟ᗈࡃศᕸࡋ࡚࠸ࡿࡓࡵࠊྛ࿘Ἴ
ᩘࡢࣆ࣮ࢡࡀ࢝ࢵࣉࣜࣥࢢࣆ࣮ࢡ࡜㔜࡞ࡾ┦ẅࡋ࡚࠸ࡿ࠿ࡽࡔ࡜⪃࠼ ᅗ 2 .TTTT ࡢࢫ࣌ࢡࢺࣝ(t2=0fs)

ࡽࢀࡿࠋࡇࢀࡽࡢ⤖ᯝࡣศᏊ㛫ࡢ㟁Ⲵ⛣ືࢆ⪃៖ࡋ࡞࠸ศᴟ⋡㛵ᩘ࠿ࡽᚓࡽࢀࡿࢫ࣌ࢡࢺࣝ࡜ࡣ኱ࡁࡃ␗࡞ࡾࠊtranslation ࣮ࣔࢻࡶ⤡ࡵࡓ᏶඲࡞ศᏊ㛫᣺ືࢲ࢖ࢼ࣑ࢡࢫࡢゎᯒ࡟࠾ࡅࡿ CFCT-DID ࡢ㔜せᛶࢆᙉࡃ♧ࡋ࡚࠸ࡿࠋRRRR ࡛ࡣ translation ࡢᙉ࠸ࣆ࣮ࢡࡢࡳࡀほࡉࢀࠊ࣐ࣛࣥࣃࣝࢫࡀ translation ࣮ࣔࢻࡢゎᯒ࡟㐺ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀ࡟ࡼࡾࠊ THz ࣃࣝࢫ࡜࣐ࣛࣥࣃ
ࣝࢫࡢ࢔ࢡࢸ࢕ࣈ࣮ࣔࢻࡢ㐪࠸ࢆ฼⏝ࡋ࡚ TTRRࠊRRTT ࡛ࡣ࢝ࢵࣉࣜࣥࢢࣆ࣮ࢡ࡟ࡼࡿ libration ࡜translation 㛫ࡢ࢚ࢿࣝࢠ࣮⛣ື࡟ࡘ࠸࡚ࡢ▱ぢࡀᚓࡽࢀࡿ࡜ᮇᚅࡉࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 45 -

⏕యศᏊࡢᶵ⬟Ⓨ⌧཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲
7KHRUHWLFDOUHVHDUFKRQUHDFWLRQPHFKDQLVPVLQELRPROHFXOHV‫ۑ‬ᫍ㔝 ᛅḟࠊ▞ Ⰻࠊຍⱱ ኱ᆅࠊᏱబ⨾ ⍆ࠊ኱┒ 㞙ேࠊ㯮⏣ ᆂ୍㸦༓ⴥ኱Ꮫ኱Ꮫ㝔⸆Ꮫ◊✲㝔㸧

1◊✲┠ⓗࠊෆᐜ
ࢱࣥࣃࢡ㉁ࡢศᏊィ⟬࡛ࡣࠊศᏊࡢฟⓎᵓ㐀࡜ࡋ࡚ ; ⥺⤖ᬗᵓ㐀ゎᯒࡢཎᏊᗙᶆࢆ౑࠺ࡇ࡜ࡀከ࠸ࠋ; ⥺⤖ᬗᵓ㐀ゎᯒ࡛ࡣࠊࢱࣥࣃࢡ㉁ࡢ⤖ᬗࡀᚓࡽࢀࡿ࠿ྰ࠿ࡀ㔜せ࡞ࢫࢸࢵࣉ࡜࡞ࡗ࡚࠸ࡿࠋ⤖ᬗ໬๣࡜ࡋ࡚ࠊ
◲㓟࢔ࣥࣔࢽ࣒࢘ࡸ࣏࢚ࣜࢳࣞࣥࢢࣝࢥ࣮ࣝ㸦3(*㸧ࡀⰋࡃ౑⏝ࡉࢀࡿࠋࢱࣥࣃࢡ㉁ࡢ✀㢮࡟ࡼࡾࠊ◲㓟࢔ࣥࣔࢽ࣒࡛࢘⤖ᬗࡀᚓࡽࢀࡸࡍ࠸ࡶࡢࠊ㏫࡟ᚓࡽࢀ࡟ࡃ࠸ࡶࡢࡀ࠶ࡿࠋᮏ◊✲࡛ࡣࠊࡇࡢ㐪࠸ࡀఱ࡟㉳ᅉࡋ࡚࠸ࡿࡢ࠿ࢆㄪ࡭ࡿࡓࡵ࡟ࠊ㧗࠸⃰ᗘࡢ◲㓟࢔ࣥࣔࢽ࣒࡛࢘⤖ᬗࡀᚓࡽࢀࡓ  ✀㢮ࡢࢱࣥࣃࢡ㉁ࡢ㟼㟁࣏ࢸࣥࢩࣕࣝࢆィ⟬ࡋࡓࠋࡇࡢ⤖ᯝࢆࠊẚ㍑ⓗప࠸⃰ᗘࡢ◲㓟࢔ࣥࣔࢽ࣒࡛࢘⤖ᬗࡀᚓࡽࢀࡓ  ✀㢮ࡢࢱࣥ
ࣃࢡ㉁ࠊ࣏࢚ࣜࢳࣞࣥࢢࣜࢥ࣮ࣝ㸦3(*㸧࡛⤖ᬗࡀᚓࡽࢀࡓ  ✀㢮ࡢࢱࣥࣃࢡ㉁ࠊࡑࡢ௚ࡢ᮲௳࡛⤖ᬗࡀᚓࡽࢀࡓ  ✀㢮ࡢࢱࣥࣃࢡ㉁࡜ẚ㍑ࡋࡓࠋࡑࡢୖ࡛ࠊ◲㓟࢔ࣥࣔࢽ࣒࡛࢘⤖ᬗࡀᚓࡽࢀࡸࡍ࠸ࢱࣥࣃࢡ㉁࡜
ᚓࡽࢀ࡟ࡃ࠸ࢱࣥࣃࢡ㉁ࡢ㛫࡛ࠊ㟼㟁࣏ࢸࣥࢩࣕࣝࡢศᕸ࡟㐪࠸ࡀ࠶ࡿ࠿࡝࠺࠿ࢆㄪ࡭ࡓࠋ


2◊✲᪉ἲࠊィ⟬᪉ἲ㟼㟁࣏ࢸࣥࢩࣕࣝࡢィ⟬ᮏ◊✲࡛ศᯒࡋࡓ⤖ᬗᵓ㐀ࡣ௨ୗࡢᇶ‽࡛ࢱࣥࣃࢡ㉁ࢹ࣮ࢱࣂࣥࢡ 3'% ࠿ࡽࢲ࣮࢘ࣥࣟࢻࡋࡓࠋ ࡢᵓ㐀࡟ࡘ࠸࡚ࡣࠊࢱࣥࣃࢡ㉁ࡣ 0 ௨ୖࡢ㧗⃰ᗘ࡛ $6 ࡟ࡼࡾ⤖ᬗ໬ࡋࠊ⤖ᬗࡣࣜ࢞ࣥࢻࡲࡓࡣ㜼ᐖ๣࡞ࡋ࡛࢔࣏ᆺ࡛ᡂ㛗ࡋࡓࡶࡢࢆ㑅ࢇࡔࠋ ࡢᵓ㐀࡟ࡘ࠸࡚ࠊ0 ௨ୗࡢప⃰ᗘ࡛ $6 ࡟ࡼࡾࢱࣥࣃࢡ㉁ࢆ⤖ᬗ໬ࡋࡓࡶࡢࢆ㑅ࢇࡔࠋẚ㍑ࡢࡓࡵ࡟ࠊ3(* ࢆ฼⏝ࡋ࡚ᚓࡽࢀࡓ  ࡢ⤖ᬗᵓ㐀ࢆຍ࠼ࡓࠋࡉࡽ࡟ࠊ௚ࡢ✀㢮ࡢሷࡲࡓࡣ⸆ရ࡟ࡼࡾ⤖ᬗ໬ࡋࡓࢱࣥࣃࢡ㉁ࡢ  ࡢᵓ㐀ࢆྵࡵࡓࠋ
◊✲࡛ࡣ඲㒊࡛  ࡢ⤖ᬗᵓ㐀ࢆㄪ࡭ࡓࠋ ࢲ࣮࢘ࣥࣟࢻࡋࡓ⤖ᬗᵓ㐀ࢆィ⟬ࣔࢹࣝ࡜ࡋ࡚ࠊྛࢱࣥࣃࢡ㉁࿘㎶ࡢ㟼㟁࣏ࢸࣥࢩࣕࣝࢆᥥ࠸ࡓࠋ⤖ᬗᵓ㐀୰ࡢḞᦆṧᇶࢆ 0RGHOOHU࡟ࡼࡿ࣍ࣔࣟࢪ࣮ࣔࢹࣜࣥࢢἲ࡛㏣ຍࡋࡓࠋS.D ࡢィ⟬ࡣ 3UR3ND࡟ࡼ
ࡗ࡚⾜ࢃࢀࠊࣉࣟࢺࣥ໬≧ែࡢኚ໬ࡍࡿṧᇶࡢ S.D ್ࡣ㟼㟁㐃⥆⌮ㄽ࡟ࡼࡗ࡚ண

ࡋࡓࠋྛṧᇶࡢࣉࣟࢺࣥ

໬≧ែࡣࠊ࠶ࡿ S+ࡍ࡞ࢃࡕ➼㟁Ⅼ࡛඲ࢱࣥࣃࢡ㉁ࡢ඲㟁Ⲵࡀࢮࣟ࡟࡞ࡿࡼ࠺࡟㑅ᢥࡋࡓࠋỈ⣲ཎᏊࡣ
$PEHU7RROV ࡢ OHDSPRGXOH ࡟ࡼࡗ࡚⏕ᡂࡋࡓࠋ㟼㟁࣏ࢸࣥࢩࣕࣝࡣ 'HOSKL ࡟ࡼࡿ 3RLVVRQ̺%ROW]PDQQ᪉⛬ᘧࢆゎࡃ᪉ἲ࡟ࡼࡾᚓࡽࢀࠊ࣏ࢸࣥࢩ࣐ࣕࣝࢵࣉࡣ &KLPHUD ࢆ⏝࠸࡚ྍど໬ࡋࡓࠋ ࢱࣥࣃࢡ㉁ࡢ⤖ᬗ໬౛኱⭠⳦ 5RVHWWD '( S/\V6 ᰴࢆ࢟ࢺࢧࢼ࣮ࢮࢆࢥ࣮ࢻࡍࡿ㑇ఏᏊࢆྵࡴ S(7E ࣋ࢡࢱ࣮ 1RYDJHQ ࡛
ᙧ㉁㌿᥮ࡋࡓࠋ
࢟ࢺࢧࢼ࣮ࢮࡣ S(7E ࣋ࢡࢱ࣮ࡢ౑⏝࡟ࡼࡾ +LV ⼥ྜ 1XV̺WDJ ඹᙺᆺ࡜ࡋ࡚Ⓨ⌧ࡋࡓࠋ/% ᇵᆅ࡛ r& ࡛๓ᇵ㣴ࡋࡓᚋࠊP0,37* ࡛ㄏᑟࡋࠊ୍ᬌ r& ࡛ 2' ್  ࡛Ⓨ⌧ࡉࡏࠊ」ྜࢱࣥ
ࣃࢡ㉁ࢆ &R 㔠ᒓ࢔ࣇ࢕ࢽࢸ࢕࣮ࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡛⢭〇ࡋࠊ+LV ⼥ྜ 1XV ࢱࢢࢆ +59& ࣉࣟࢸ࢔࣮
ࢮ࡛ษ᩿ࡋࡓࠋษ᩿ࡉࢀࡓ 1XV̺WDJ+59̺& ࣉࣟࢸ࢔࣮ࢮࠊ࠾ࡼࡧᮍษ᩿⤖ྜࢱࣥࣃࢡ㉁ࢆ 1L̺17$ ᶞ⬡- 46 -

࡛㝖ཤࡋࡓࠋࢱࣥࣃࢡ㉁ࢆࠊS+ ࠾ࡼࡧ P01D&O ࡛ࡢ P07ULV+&O ࡢࣛࣥࢽࣥࢢ⦆⾪ᾮ࡛ࡢࢤࣝ
ℐ㐣࡟ࡼࡗ࡚ࡉࡽ࡟⢭〇ࡋࡓࠋ᭱ᚋ࡟ࠊࢱࣥࣃࢡ㉁ࢆ PJP/ ࡟⃰⦰ࡋࡓࠋ࢟ࢺࢧࢼ࣮ࢮࡢ༢⤖ᬗࢆ r&ࡢ⵨Ẽᣑᩓἲ࡛⫱ᡂࡋࠊ⤖ᬗ໬ᾮ⁲ࢆㄪ〇ࡍࡿࡓࡵࠊP00(6 ࠿ࡽ࡞ࡿỿẊ๣⁐ᾮ ȣ/ S+ࠊ0$6 ࡟ࢱࣥࣃࢡ㉁⁐ᾮ ȣ/ ࢆΰྜࡋࠊỿẊ๣⁐ᾮ ȣ/ ࢆ‶ࡓࡋࡓ࢙࢘ࣝෆࡢࣉࣛࢫࢳࢵࢡࣉ࣮ࣞࢺࢆ
⏝࠸࡚⤖ᬗࢆᡂ㛗ࡉࡏࡓࠋ; ⥺ᅇᯒࡢᐇ㦂᫬࡟ࡣ⤖ᬗࢆ  YY ࢢࣜࢭ࣮ࣟࣝྵ᭷⁐ᾮ࡟▷᫬㛫ᾐₕࡋࡓᚋࠊᾮయ❅⣲୰࡛෾⤖ࡋࡓࠋᅗ 㸸඾ᆺⓗ࡞㟼㟁࣏ࢸࣥࢩࣕࣝࢆ♧ࡋࡓ  ✀㢮ࡢࢱࣥࣃࢡ㉁ࡢ࿘ࡾࡢ࣏ࢸࣥࢩࣕࣝࡢṇ࡜㈇ࡢ➼⾲㠃ࠋ ✀㢮ࡢ࠺ࡕࠊ ✀㢮ࡢࢱࣥࣃࢡ㉁ࡣ㧗⃰ᗘࡢ $6 ࡟ࡼࡗ࡚⤖ᬗ໬ࡋࠊ ✀㢮ࡣ 3(* ࡟ࡼࡗ࡚⤖ᬗ໬ࡉࢀ࡚࠸ࡿࠋṇ࡜㈇ࡢ➼್㠃ࡣࠊࡑࢀࡒࢀ㟷࡜㉥ࡢ࣓ࢵࢩࣗ⾲⌧࡛⾲♧ࡉࢀ࡚࠸ࡿࠋ➼㧗㠃ࡢ್ࡣ N7H ༢఩࡛ ࡜ ࡛࠶ࡿࠋ

3◊✲ᡂᯝ㧗࠸⃰ᗘࡢ◲㓟࢔ࣥࣔࢽ࣒࡛࢘⤖ᬗ໬ࡉࢀࡓ࡯࡜ࢇ࡝ࡢࢱࣥࣃࢡ㉁ࡣࠊ㟼㟁࣏ࢸࣥࢩࣕࣝࡢ➼⾲㠃࡟ඹ㏻ࡢᙧࢆࡋ࡚࠸ࡓ ᅗ㸯 ࠋ㟼㟁࣏ࢸࣥࢩࣕࣝࡢṇࡢ㡿ᇦ࡜㈇ࡢ㡿ᇦࡣ࡯ࡰ➼ࡋࡃศ㞳ࡉࢀࠊྛ㡿ᇦࡣ⌫≧ࡢ࣮ࣟࣈᙧ≧ࢆᣢࡕࠊࢱࣥࣃࢡ㉁ศᏊࡣ  ࡘࡢ㡿ᇦࡢ୰ᚰ࡟఩⨨ࡍࡿࠋṇ࡜㈇ࡢ㡿ᇦࡢ㛫ࡢ᥋ゐ㡿ᇦࡣࢱࣥࣃࢡ㉁ࡢ✵㛫࡟࡯ࡰ㝈ᐃࡉࢀࠊ᥋ゐ㡿ᇦࡢ㟼㟁࣏ࢸࣥࢩࣕࣝࡣࡁࢀ࠸࡛࠶ࡿࠋ୍᪉ࠊ3(* ࡟ࡼࡗ࡚⤖ᬗ໬ࡉࢀࡿ

- 47 -

ࢱࣥࣃࢡ㉁࡟ࡘ࠸࡚ࡣࠊṇࡢ㡿ᇦ࡜㈇ࡢ㡿ᇦ࡜ࡢ㛫ࡢศ㞳ࡣࡑࢀ࡯࡝᫂☜࡛ࡣ࡞࠸ࠋ≉࡟ࠊ㟼㟁࣏ࢸࣥࢩࣕ
ࣝࡢṇ࡜㈇ࡢ㡿ᇦࡣ᩿∦ⓗ࡛࠶ࡾࠊ᥋ゐ㡿ᇦࡢ➼⾲㠃ࡣ」㞧࡛࠶ࡿࠋࡇࢀࡽࡢ▱ぢࡣ◲㓟࢔ࣥࣔࢽ࣒࢘ࡢ࢖
࢜ࣥ࡜ࢱࣥࣃࢡ㉁ศᏊ㛫ࡢᒁᡤⓗ┦஫స⏝ࡔࡅ࡛࡞ࡃࠊࢱࣥࣃࢡ㉁ࡢ࿘ᅖࡶࢱࣥࣃࢡ㉁⤖ᬗࡢ᰾ᙧᡂ࡜ᡂ㛗࡟㛵୚ࡍࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋ㟼㟁࣏ࢸࣥࢩࣕࣝࡢゎᯒࢆࠊ ✀㢮ࡢࢱࣥࣃࢡ㉁࡟㐺⏝ࡋ࡚⾜ࡗࡓሙྜࡶྠᵝ࡟ࠊ◲㓟࢔ࣥࣔࢽ࣒࡛࢘⤖ᬗ໬ࡉࢀࡓ࡯࡜ࢇ࡝ࡢࢱࣥࣃࢡ㉁࡛ࡣࠊ㟼㟁࣏ࢸࣥࢩࣕࣝࡢṇࡢ㡿ᇦ࡜㈇ࡢ㡿ᇦࡣ࡯ࡰ➼ࡋࡃศ㞳ࡉࢀࠊྛ㡿ᇦࡣ⌫≧ࡢ࣮ࣟࣈᙧ≧ࢆᣢࡗ࡚࠸ࡓ㸦ᅗ㸰㸧ࠋᅗ㸰㸸඲  ⺮ⓑ㉁ࡢ㟼㟁࣏ࢸࣥࢩࣕࣝࠋṇ࡜㈇ࡢ➼㧗㠃ࡢ್ࡣࠊN7H ༢఩࡛ࡑࢀࡒࢀ ࡜ ࡛࠶ࡿࠋṇ࡜㈇ࡢ➼㧗㠃ࡣ㟷࡜㉥ࡢ࣓ࢵࢩ࡛ࣗ⾲♧ࡉࢀࠊࢱࣥࣃࢡ㉁ศᏊࡣ⥳ࡢₔ⏬࡛⾲♧ࡉࢀ࡚࠸ࡿࠋ
㟼㟁࣏ࢸࣥࢩࣕࣝࡢ⤖ᬗᡂ㛗࡟࠾ࡅࡿ᝟ሗࡢ᭷⏝ᛶࢆᐇドࡍࡿࡓࡵ࡟ࠊ㐣ཤࡢሗ࿌࡛ࡣ 3(* ࡛⤖ᬗ໬ࡉࢀ࡚࠸ࡓ࢟ࢺࢧࢼ࣮ࢮ㸦3'%YF㸧ࢆࠊ◲㓟࢔ࣥࣔࢽ࣒࡛࢘⤖ᬗ໬ࡉࡏࡓࠋࡇࡢࢱࣥࣃࢡ㉁ࡣࠊ㟼㟁࣏ࢸ- 48 -

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ྜᡂ࡞ࡽࡧ࡟άᛶホ౯ࠖ㺂᪥ᮏ⸆Ꮫ఍➨  ᖺ఍ி㒔  5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] Ailiken, G., Kitamura, K., Hoshino, T., Satoh, M., Tanaka, N., Minamoto, T., Rahmutulla, B., Kobayashi, S., Kano,
M., Tanaka, T., Kaneda, A., Nomura, F., Matsubara, H., Matsushita, K. : Posttranscriptional regulation of BRG1 by
FIRᶭexon2 in gastric cancer, Oncogenesis 9, 26 (2020)
մ[2] Mori, D., Yoneda, T., Suzuki, M., Hoshino, T., Neya, S. : meso-Diketopyripentaphyrin and Diketopyrihexaphyrin
as Macrocyclic Tripyrrinone Ligands for NiII Ions, Chem. Asian J. 14 (23), 4169-4173 (2019)մ[3] Kitahara, M., Fudo, S., Yoneda, T., Nukaga, M., Hoshino, T.: Anisotropic Distribution of Ammonium Sulfate Ionsin Protein Crystallization, Cryst. Growth Des., 19, 6004-6010 (2019)մ[4] Qu, L., Fudo, S., Matsuzaki, K., Hoshino, T. : &RPSXWDWLRQDO6WXG\RQWKH$VVHPEO\RI$P\ORLGȕ-Peptides in the
Hydrophobic Environment, Chem. Pharm. Bull. 67, 959-965 (2019).
[5] Kobayashi, S., Hiwasa, T., Ishige, T., Bahityar, R., Kano, M., Hoshino, T., Minamoto, T., Shimada, H., Nomura, F.,
Matsubara, H., Matsushita : Anti-),5ǻH[RQDVSOLFLQJYDULDQWIRUPRI38)DXWR-antibody is detected in thesera of esophageal squamous cell carcinoma, Cancer Science 110, 2004–2013 (2019).

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ƶ§Ʒ,'ť©&Ƨ8ųŁ?WiCnºèƶÝ»`RlHdiƷ- 57 -ƾ ƺŊŻÍū¸ƩyƊûéƉı
1.

ÖĒ Free Energy Calculations: Entering the Fourth Decade of Adventure in Chemistry and Biophysics,
Santa Fe, NM, USA, June 16-21, 2019.

2.

ÖĒ [Plenary Talk] The 4th International Conference on Computational Science and Engineering (ICCSE-4),
Ho Chi Minh City, Vietnam, July 24-27, 2019.

3.

ÖĒ The 10th Toyota RIKEN International Workshop on Science of Life Phenomena Woven by Water andBiomolecules, Nagakute, Aichi, Japan, September 4-6, 2019.

4.

ÖĒ Molecular Simulation 2019 Meeting, Hangzhou, China, October 12-13, 2019.

5.

ÖĒ [Plenary Talk] The 5th International Conference on Molecular Simulation (ICMS 2019),
Jeju, Korea, November 3-6, 2019.

6.

ÖĒ Focused Lectures on Molecular Modeling and Theory, Daejeon, Korea, November 7, 2019.

ƿƺĹÍū
ũƅmƁƅmčŠ7.

ğÖĒ in Computational Methods to Study the Structure and Dynamics of Biomolecules andBiomolecular Processes – from Bioinformatics to Molecular Quantum Mechanics
A. Liwo (ed.) (Springer-Verlag, Berlin Heidelberg, 2019) pp. 203-256.

8.

ÖĒ   74, 388-389 (2019).

9.

ÖĒ  

Biophysics and Physicobiology 16, 344-366 (2019).

ƈĆ
10.

ÂŐÖĒÄĔ         

Scientific Reports 9, 6853 (11 pages) (2019).

11. įĨĜÙě×T\LlÖĒ   Proteins 87, 635-645 (2019).
12.

ėÖĒ   

Physical Review E 100, 043304 (2019).

- 58 -

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࣮㘒యࡢ㟁Ꮚ≧ែィ⟬ࡣࠊࡋࡤࡋࡤከཧ↷㟁Ꮚ≧ែ⌮ㄽ࡟ࡼࡿᐃ㔞ⓗ࡞ィ⟬ࡀᚲせ࡜ཤࢀࠊࡲࡓࠊࡑࢀ࡜ྠ
᫬࡟ィ⟬⤖ᯝࡢṇࡋ࠸ゎᯒࡶồࡵࡽࢀࡿࠋ᭱㏆࡛ࡣࠊ⁐ᾮෆࡢᏙ❧ศᏊࡤ࠿ࡾ࡛࡞ࡃࠊศᏊᛶ⤖ᬗෆ࡛ࡢ྾
཰࣭Ⓨගࢫ࣌ࢡࢺࣝࡸບ㉳≧ែ࡟ࡶᐇ㦂ⓗ࡞⯆࿡ࡀ㞟ࡲࡗ࡚࠾ࡾࠊ⤖ᬗࡢຠᯝࢆྲྀࡾࡇࢇࡔ㟁Ꮚ≧ែィ⟬ࡀồࡵࡽࢀ࡚࠸ࡿࠋ⤖ᬗࡢ㟁Ꮚ≧ែィ⟬ࡣ࿘ᮇቃ⏺᮲௳ࢆ⏝࠸ࡓ ')7 ἲࡀከ⏝ࡉࢀ࡚࠸ࡿࡀࠊࡇࡢ᪉ἲࡣບ㉳≧ែࡸⓎගࢫ࣌ࢡࢺࣝࡢ◊✲࡟ࡣ㐺ࡋ࡚࠸࡞࠸ࠋບ㉳≧ែࡢศᏊࡢ SRSXODWLRQ ࡣᇶᗏ≧ែࡢศᏊ࡟ẚ࡭࡚ࡣࡿ࠿࡟ᑠࡉࡃࠊ࿘ᮇቃ⏺᮲௳ィ⟬ἲࢆ㐺⏝ࡍࡿሙྜ࡟ࡣ༢఩ࣘࢽࢵࢺࡀ㠀ᖖ࡟኱ࡁࡃ࡞ࡾࠊ஦ᐇୖィ⟬ࡀᅔ㞴࡟࡞ࡿࡓࡵ࡛࠶ࡿࠋࡇࡢࡼ࠺࡟ࠊ」ྜ㟁Ꮚ⣔ࡢ⌮ㄽ◊✲࡟ࡣ㟁Ꮚ≧ែࠊ⤖ྜᛶ࡟㛵ࡍࡿṇࡋ࠸▱㆑࡜ศᏊ≀ᛶࡸ཯ᛂᛶࠊゐ፹స⏝࣓࢝ࢽࢬ࣒࡜ࡢ㛵㐃࡟㛵ࡍࡿ▱㆑࡟ຍ࠼࡚ࠊᚑ᮶ࡢ⌮ㄽⓗ᪉ἲࡔࡅ࡛࡞ࡃࠊ᪂ࡋ࠸
⌮ㄽィ⟬ἲࡶᚲせ࡜ࡉࢀࡿࠋࡉࡽ࡟ࠊ໬Ꮫ⤖ྜࡸ཯ᛂ㐣⛬࡟ᑐࡍࡿ᪂ࡋ࠸どⅬࠊ᪂ࡋ࠸ᴫᛕࡶᚲせ࡜ࡉࢀࡿࡇ࡜࠿ࡽࠊ㑄⛣㔠ᒓࢆྵࡴ」ྜ㟁Ꮚ⣔ࡣศᏊ⛉Ꮫ◊✲ࠊ⌮ㄽ໬Ꮫ㺃ィ⟬໬Ꮫ◊✲ࡢᐆᗜ࡛࠶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 㘒య࡟ࡼࡿ VS &+ ⤖ྜࡢ࣎ࣜࣝ໬ゐ፹཯ᛂࡢ཯ᛂᶵᵓ࡜཯ᛂࡢ఩⨨㑅ᢥᛶࡢゎ᫂ࠊ1L , 㘒య࡟ࡼ- 59 -

ࡿࣆࣜࢪࣥ࠾ࡼࡧ㢮ఝ໬ྜ≀ࡢࣄࢻࣟࢩࣜࣝ໬཯ᛂࡢ཯ᛂᶵᵓゎ᫂࡜ணࠊ LL  㔠ᒓ㘒యࡢᵓ㐀࡜⤖ྜ࡟㛵ࡍࡿ◊✲࡛ࡣࠊ᭱㏆ࠊሗ࿌ࡉࢀࡓ 5K$O ┤᥋⤖ྜࢆࡶࡘ 5K , 㘒యࡢᵓ㐀࡜ 5K$O ⤖ྜࡢ≉ᚩࠊࢺࣛࣥࢫᙳ㡪ࢆ᫂ࡽ࠿࡟ࡋࠊ LLL  㔠ᒓᚤ⢏Ꮚ㛵ಀ࡛ࡣࠊ$J ࠾ࡼࡧ &X ࢡࣛࢫࢱ࣮ᚤ⢏Ꮚୖ࡛ࡢ 12 ஧㔞໬཯ᛂࡢᶵᵓ࡜㟁Ꮚ≧ែኚ໬ࡢゎ᫂ࠊ&X ࢡࣛࢫࢱ࣮ᚤ⢏Ꮚୖ࡛ࡢ 12 ஧㔞໬ࢆ⤒⏤ࡍࡿ 12&2 ཯ᛂࡢ཯ᛂᶵᵓゎ᫂ࠊ5X5K
3G $J ࢡࣛࢫࢱ࣮ᚤ⢏Ꮚ࡛ࡢ 12 ཯ᛂᣲືࡢ┦㐪ࢆ㟁Ꮚ≧ែ࠿ࡽゎ᫂ࡋࠊ LY  ศᏊᛶ⤖ᬗ㛵ಀ࡛ࡣࠊ$X ,㘒యࡢศᏊᛶ⤖ᬗ࡛ࡢ྾཰ࢫ࣌ࢡࢺࣝࠊບ㉳≧ែᵓ㐀ࠊⓎගࢫ࣌ࢡࢺࣝࡢ⤖ᬗᵓ㐀౫Ꮡᛶࢆゎ᫂ࡋࡓࠋ⣬㠃ࡢ㒔ྜୖࠊ୍㒊ࢆ㝖࠸࡚ࠊ௨ୗ࡟ᴫせࢆ㏙࡭ࡿࠋ

2◊✲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⏝࠸ࡓࠋ㑄⛣㔠ᒓඖ⣲ࡢෆẆ㟁Ꮚࡣ Hay-Wadt ࡶࡋࡃࡣ Stuttgart-Dresden-Bonn ࢢ࣮ࣝࣉࡢ᭷ຠෆẆ࣏ࢸࣥࢩࣕ
ࣝ(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 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⿦ࡋࡓࡶࡢ࡛࠶ࡾࠊQM ศᏊ࡜ MM ศᏊࡢᵓ㐀ࠊ㟁Ⲵศᕸࢆself-consistent ࡟ồࡵࠊMM ศᏊࡣቃ⏺᮲௳ࢆ౑⏝ࡋࠊ↓㝈⣔ࢆ෌⌧ࡍࡿࡼ࠺࡟⨨࠸ࡓࠋ

3

◊✲ᡂᯝ

3.1 Ir 㘒య࡟ࡼࡿ sp3 C-H ⤖ྜࡢ࣎ࣜࣝ໬཯ᛂࡢ⌮ㄽⓗ◊✲㸸(phen)Ir(Bpin)3 ࡟ࡼࡿ THF ࡞࡝ࡢ sp3-C-H ⤖ྜࡢ࣎ࣜࣝ໬཯ᛂࡀ᭱
㏆ሗ࿌ࡉࢀࡓ(Scheme 1)ࠋࡇࡢ཯ᛂ࡛ࡣࠊ཯ᛂᛶ࡟ஈࡋ࠸ sp3 C-H⤖ྜࡀษ᩿ࡉࢀࠊࡑࡇ࡟࣎ࣜࣝᇶ(Bpin)ࡀᑟධࡉࢀࡿࡇ࡜ࠊࡲࡓࠊ

Scheme 1. Ir-catalyzed borylation of THF

C-H ⤖ྜ࢚ࢿࣝࢠ࣮ࡀᑠࡉ࠸Ș఩࡛࡞ࡃࠊO ཎᏊ࠿ࡽ㐲ࡃ C-H ⤖ྜࡢᙉ࠸ș఩࡟㑅ᢥⓗ࡟࣎ࣜࣝᇶࡀᑟධࡉࢀࡿࡇ࡜࡞࡝ࠊ᭷ᶵ཯
ᛂㄽⓗ࡟⯆࿡῝࠸ࠋ཯ᛂ⤒㊰ࢆ᳨ウࡋࠊࡇࡢ཯ᛂࡣ(phen)Ir(Bpin)5
ࢆ resting state, (phen)Ir(Bpin)3 ࢆάᛶ✀࡜ࡋࠊTHF ࡢ C-H ⤖ྜࡢ
Ir(III)࡬ࡢ㓟໬ⓗ௜ຍࠊ⏕ᡂࡋࡓ࢜࢟ࢯࣛࢽࣝᇶ࡜ Bpin ࡜ࡢ㑏ඖ⬺㞳ࢆྵࡴ Ir(III)/Ir(V)ゐ፹ࢧ࢖ࢡࣝ㸦Scheme 2㸧࡛㐍⾜ࡍࡿࡇ࡜ࠊ
ᚊ㏿ࡣ㑏ඖ⬺㞳࡛࠶ࡿࡇ࡜ࠊ఩⨨㑅ᢥᛶࡣ㑏ඖ⬺㞳࡛Ỵᐃࡉࢀ࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊᐇ㦂࡛ࡣ㔜Ỉ⣲ຠᯝࡀぢฟࡉࢀ

Scheme 2. Ir(III)/Ir(V)-Catalytic cycle of
Ir-catalyzed borykatruon of THF

࡚࠾ࡾࠊᚊ㏿ࡀ C-H ⤖ྜάᛶ໬㐣⛬࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡓ
ࡀࠊᚊ㏿ࡀ㑏ඖ⬺㞳࡛ࡶࠊ㔜Ỉ⣲ຠᯝࡀฟ࡚ࡃࡿࡇ࡜ࢆィ⟬໬Ꮫⓗ࡟ࡶᩘ್࡜ࡋ࡚᫂ࡽ࠿࡟ࡋࠊࡲࡓࠊࡑࡢ
⌮⏤ࢆ㑄⛣≧ែ࡜୰㛫యࡢᵓ㐀ⓗ≉㛗࠿ࡽ᫂ᛌ࡟ㄝ᫂ࡋࡓࠋ௨ୖࡢࡼ࠺࡟ࠊ㘒యゐ፹໬Ꮫ࡜ࡋ࡚ࡶ⯆࿡ࡀ࠶ࡾࠊ᭷ᶵ཯ᛂㄽⓗ࡟⯆࿡ࡢ࠶ࡿ཯ᛂࡢ≉ᚩࢆ᫂ࡽ࠿࡟ࡋࡓࠋ㸦R. Zhong, S.Sakaki, J. Am. Chem. Soc. 141,9854-9866 (2019).㸧
3.2 Rh(I)-Aluminyl 㘒యࡢ㟁Ꮚ≧ែࠊ⤖ྜࠊࢺࣛࣥࢫᙳ㡪ࡢ⌮ㄽⓗ◊✲㸸 Al ࢆ㓄఩ཎᏊ࡜ࡍࡿࣆࣥࢧ࣮ᆺ

- 60 -

㸱ᗙ㓄఩Ꮚ(PAlP)ࡀ᭱㏆ࠊᐇ㦂ศ㔝࡛ྜᡂࡉࢀࠊࡑࡢ Rh(I)㘒య㸦௨ୗࠊRh(PAlP)࡜␎
ࡍ; Scheme 3㸧ࡣ C-H ⤖ྜάᛶ໬ࢆ⤒⏤ࡍࡿ࢝ࢵࣉࣜࣥࢢ཯ᛂࡢゐ፹స⏝ࢆ♧ࡍࡇ࡜ࡀRhሗ࿌ࡉࢀࡓࠋࡇࡢ Rh(PAlP)㘒యࡣ⯆࿡-࠶ࡿ Rh-Al ┤᥋⤖ྜࢆᣢࡗ࡚࠸ࡿࠋࡇࡢ㘒య࠾ࡼࡧ㢮ఝ㘒యࡢ⌮ㄽⓗ◊✲ࢆ DFT ἲ࡛⾜࠸ࠊRh-Al ⤖ྜᛶ㌶㐨ࡣࠊRh(G-)-Al(G+)࡜ศᴟ

Scheme 3.

ࡋ࡚࠾ࡾࠊ㏻ᖖࡢ㓄఩⤖ྜ࡜ࡣ㏫࡛࠶ࡿࡇ࡜ࠊࡲࡓࠊࡑࡢࢺࣛࣥࢫᙳ㡪ࡣ࣎ࣜࣝ㓄఩Ꮚࡼࡾࡣᙅ࠸ࡀࠊࢩࣜࣝ㓄఩Ꮚࡼࡾࡣᙉ࠸ࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋPAlP 㓄఩Ꮚࢆࢺࣛࣥࢫᙳ㡪ࡀᙉࡃࠊȪ౪୚ᛶࡢᙉ࠸࣎ࣜࣝ (BR2)ࠊࢩࣜࣝ(SiMe3), ࢔ࣝ࢟ࣝ(CH3)ࠊࢺࣛࣥࢫᙳ㡪ࡀᙅ࠸ ClࠊOMe 㓄఩Ꮚ࡞࡝࡜ẚ㍑ࡋࠊ
ࢺࣛࣥࢫ఩ࡢ NH3 ࡢ㓄఩࢚ࢿࣝࢠ࣮ࠊRh-N ㊥㞳ࢆẚ㍑ࡋࡓࠋࡇࢀࡽࡢ᳨ウ࠿ࡽࠊࢺࣛࣥࢫᙳ㡪ࡣ㏻ᖖࠊ㓄఩Ꮚࡢ HOMO ࡢ㌶㐨࢚ࢿࣝࢠ࣮࡟౫Ꮡࡋ࡚Ỵࡲࡿ࡜⪃࠼ࡽࢀࡿࡀࠊ㌶㐨࢚ࢿࣝࢠ࣮࡜ඹ࡟ࠊ㌶㐨ࡢ㔜࡞ࡾ࡟ࡶᙳ㡪ࡍࡿࡇ࡜ࠊ㌶㐨ࡢ㔜࡞ࡾ࡟ᙳ㡪ࡍࡿཎᏊ㊥㞳ࢆࣃ࣓࣮ࣛࢱ࣮࡟ᑟධࡍࡿᚲせࡀ࠶ࡿࡇ࡜ࠊ㓄఩Ꮚ E ࡢࢺࣛࣥࢫᙳ㡪࡟ࡼࡿࢺࣛࣥࢫ఩ࡢ NH3 ࡜ Rh ࡢ⤖ྜ㊥㞳 R(Rh-NH3)ࡣࠊ⤒㦂ⓗ࡟ḟࡢ㛵ಀ࡛୚࠼ࡽࢀࡿࡇ࡜ࢆ᫂
ࡽ࠿࡟ࡋࡓ㸸R(Rh-NH3) = 2.530 + 0.035 H(HOMO of E) – 0.027 R(E) ࡇࡇ࡛H(HOMO of E)ࡣ㓄఩Ꮚ E ࡢ SOMOࠊ
R(E)ࡣ㓄఩ཎᏊ E ࡢཎᏊ༙ᚄ࡛࠶ࡿࠋࡇࡢ㛵ಀࡣࠊ࿘ᮇࡢ␗࡞ࡿ㓄఩Ꮚࡢࢺࣛࣥࢫᙳ㡪ࢆ⪃ᐹࡍࡿ㝿࡟᭷ຠ࡛࠶ࡿࠋ(N. Kriakose, S. Sakaki, et al. Inorg. Chem., 58, 48944906 (2019)).
3.3 Au(I)㘒యࡢศᏊᛶ⤖ᬗෆ࡛ࡢ྾཰࠾ࡼࡧⓎගࢫ࣌ࢡࢺࣝ࡜ບ㉳≧ែᵓ㐀ࡢ⌮ㄽⓗ◊✲㸸Au(I)ࣇ࢙ࢽ࣭ࣝ
࢖ࢯࢩ࢔ࢽࢻ㘒య Au(CNPh)(Ph)ࡢศᏊᛶ⤖ᬗࡣᶵᲔⓗእ㒊่⃭࡟ࡼࡾ┦㌿⛣ࢆㄏ㉳ࡋࠊⓎගࢫ࣌ࢡࢺࣝࡀኚ໬ࡍࡿࡇ
࡜ࡀ᭱㏆ᐇ㦂ⓗ࡟ሗ࿌ࡉࢀࠊ㘒య໬Ꮫࠊᮦᩱ⛉Ꮫࠊ≀⌮໬Ꮫⓗ࡟⯆࿡ࢆ㞟ࡵ࡚࠸ࡿࠋࡋ࠿ࡋࠊບ㉳≧ែࡢᖐᒓࡶᅛయ
ࡢࡓࡵࠊ᫂ࡽ࠿࡛࡞࠿ࡗࡓࠋ࿘ᮇቃ⏺᮲௳ QM/MM ἲ࡛ᇶᗏ≧ែࡢᵓ㐀ࢆ᭱㐺໬ࡋࠊࡑࡢᇶᗏ≧ែࡢᵓ㐀࠿ࡽὀ┠ࡍࡿ Au(I)㘒యࡢࡳࡢບ㉳≧ែᵓ㐀ࢆ᭱㐺໬ࡍࡿࡇ࡜࡛ࠊศᏊ
≧⤖ᬗෆ࡛ࡢບ㉳≧ែࢆィ⟬ࡋࡓࠋFig.1 ࡟♧ࡍࡼ࠺࡟ 1a ┦࡛ࡣ Au 㘒య㛫࡟ CH-ȧ┦஫స⏝ࡢࡳࡀ⏕ᡂࡋ࡚࠸ࡿࡀࠊᶵ

Fig. 1. Partially optimized geometry in phase 1aand 1y of Au(Ph)(CNPh)Ეⓗ่⃭࡟ࡼࡾ┦㌿⛣ࡋࡓ 1y ࡛ࡣ CH-ȧ࡟ຍ࠼ȧ-ȧ┦஫స⏝ࡶྵࡲࢀ࡚࠾ࡾࠊ1y ࡀࡼࡾᏳᐃ࡛࠶ࡿ⌮⏤ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊບ㉳≧ែᵓ㐀ࡣ⤖ᬗ┦࡟ࡼࡾ␗࡞ࡾࠊ1b ┦࡛ࡣ Fig.2 ࡟♧ࡍࡼ࠺࡟ࠊ㸰ࡘࡢ㓄఩Ꮚ㛫ࡢȧ-ȧ*ບ㉳࡛࠶ࡿࡀࠊ1y ┦࡛ࡣ㸰ศᏊࡢ Au 㘒య㛫࡟ dV-dVࡢ཯⤖ྜᛶ㌶㐨ࡀᙧᡂࡉࢀࠊࡑࡢ㌶㐨࠿ࡽ㓄఩Ꮚࡢȧ*㌶㐨࡬ࡢ୍㟁Ꮚບ㉳࡟ࡼࡿ࠸ࢃࡺࡿ MMLCT ບ㉳࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࢀࡣ 1b ࡛ࡣ Au-Au 㛫㊥㞳ࡀ㛗ࡃࠊ
Au 㛫࡟┦஫స⏝ࡀ⏕ࡲࢀ࡞࠸ࡇ࡜ࠊ
1y ࡛ࡣ Au-Au 㛫㊥㞳ࡀ▷ࡃࠊບ㉳≧ែ࡛ dV-dV

Fig. 2 Triplet excited states of Au(Ph)(CNPh) in molecular⤖ྜᛶࠊ཯⤖ྜᛶ㌶㐨ࡀ⏕ࡲࢀࡿࡇ࡜࠿ࡽ⌮ゎ

crystals 1b and 1y.

࡛ࡁࡿࠋǼSCF ィ⟬࠿ࡽồࡵࡓⓎග࢚ࢿࣝࢠ࣮ࡣᐇ㦂⤖ᯝ࡜ࡼࡃ୍⮴ࡋࠊ1b ࡛ࡢⓎගࢫ࣌ࢡࢺࣝ࡟ẚ࡭ࠊ1y࡛ࡢࡑࢀࡣ㧗࢚ࢿࣝࢠ࣮ࢩࣇࢺࡋ࡚࠸ࡿഴྥࡀࡼࡃ෌⌧࡛ࡁࡓࠋ௨ୖࡢࡼ࠺࡟࿘ᮇቃ⏺᮲௳ QM/MM ἲࡣศ- 61 -

Ꮚᛶ⤖ᬗࡢບ㉳≧ែ࠾ࡼࡧⓎගࢫ࣌ࢡࢺࣝࡢ⌮ㄽ◊✲࡟ᙉຊ࡞ᡭἲ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ(S. Aono, T. Seki,
H. Ito, S. Sakaki, J. Phys. Chem. C, 58, 48944906 (2019)).
3.4 Cu38 ᚤ⢏Ꮚ࡛ࡢ NO-CO ཯ᛂࡢ⌮ㄽⓗ◊✲㸸Cu ࡜ Ru ࡢྜ㔠ᚤ⢏Ꮚࡣ CO-NO ཯ᛂࡢゐ፹࡟࡞ࡿࡇ࡜ࡀᐇ㦂ศ㔝࡛ሗ࿌ࡉࢀ
ࡓࠋࡑࡢ⌮⏤ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊࡲࡎࠊCu ࡢࡳࡢᚤ⢏Ꮚ࡛NO-CO ཯ᛂࡀ㐍⾜ྍ⬟࠿ࠊ᳨ウࡋࡓࠋከᩘࡢ㑄⛣≧ែࡸ୰㛫యࢆィ⟬ࡍࡿᚲせࡀ࠶ࡿࡇ࡜࠿ࡽࠊẚ㍑ⓗᑠࡉ࠸ Cu38 ᚤ⢏Ꮚࢆ᥇⏝ࡋࡓࠋCO ࡟ẚ࡭ࠊNO ࡢ྾╔࢚ࢿࣝࢠ࣮ࡣ኱ࡁࡃࠊࡲࡎࠊNOࡀ Cu ⾲㠃࡟྾╔ࡍࡿࡇ࡜ࠊࡋ࠿ࡋࠊRh 㔠ᒓ࡛⪃࠼ࡽࢀ࡚࠸ࡿ
ࡼ࠺࡞ゎ㞳྾╔ࡣ㐍⾜ࡏࡎࠊNO ࡢ஧㔞໬ࡀ㐍⾜ࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓ(Scheme 4)ࠋࡑࡢᚋࠊN-O ⤖ྜࡀ୍ࡘษ᩿ࡉࢀࠊN2O ࡜྾╔
O ཎᏊࡀ⏕ᡂࡋࠊN2O ࡀ྾╔ᵓ㐀ࢆኚ໬ࡉࡏࠊࡶ࠺㸯ࡘࡢ N-O

Scheme 4. Catalytic cycle of NO-CO
reaction on Cu38

⤖ྜࡀษ᩿ࡉࢀࠊN2 ࡀ⏕ᡂࡍࡿࠋṧࡗࡓ྾╔ O ཎᏊࡣ CO ࡜཯ᛂࡋࠊCO2 ࢆ⏕ᡂࡍࡿ࡜࡜ࡶ࡟ࠊCu38 ࢆ෌⏕ࡍࡿ཯ᛂᶵᵓ࡛㐍⾜ࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋᚊ㏿ࡣ CO ࡜྾╔ O
ཎᏊࡢ཯ᛂ࡛࠶ࡿࠋᐇ㝿࡟ࠊᐇ㦂ࢢ࣮ࣝࣉ࡟ࡼࡾ N2O ࡀ཯ᛂ୰࡟᳨ฟࡉࢀ࡚࠾ࡾࠊ⌮ㄽィ⟬࡛♧ࡋࡓゐ፹ࢧ࢖ࢡࣝࡢጇᙜᛶࡀ♧ࡉࢀࡓࠋ(N. Takagi, R. Fukuda, M. Ehara, S. Sakaki, et al. ACS Omega, 4, 2596-2609 (2019)).
3.4 Ru55, Rh55, Pd55, Ag55 ᚤ⢏Ꮚ࡛ࡢ NO ཯ᛂᣲືࡢ⌮ㄽⓗ◊✲㸸NO ࡣ㔠ᒓ࡟ゎ㞳྾╔ࠊศᏊ≧྾╔ࠊ஧㔞໬࡞࡝ࡢ཯ᛂᛶࢆ♧ࡍࡀࠊ㔠ᒓࡢ࿘ᮇ⾲ୖࡢ఩⨨࡛ࡑࢀࡽࡀ␗࡞ࡿࠋࡇࡢ NO ྾╔ᣲືࡣ⮬ື㌴᤼Ẽ࢞ࢫί໬
ゐ፹࡛ᇶᮏⓗ࡞▱ぢ࡛࠶ࡿࡢ࡟࠿࠿ࢃࡽࡎࠊࡑࡢ⌮⏤ࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋ4d 㔠ᒓࡢ 8 ᪘࠿ࡽ 11 ᪘ࡲ࡛ࡢ㔠ᒓඖ⣲ࢆྲྀࡾୖࡆࠊ55 ཎᏊ⣔ࡢᚤ⢏Ꮚ࡛ NO ࡢ཯ᛂᣲືࢆ᳨ウࡋࡓࠋRu, Rh ࡛ࡣゎ㞳྾╔ࡀࠊPd ࡛ࡣศᏊ≧྾╔ࡀࠊAg ࡛ࡣ஧㔞໬ࡢ㐍⾜ࡀ♧ࡉࢀࡓࠋࡇࢀࡽࡢᣲືࡣ㔠ᒓᚤ⢏Ꮚࡢ valence band-top ࡢ࢚ࢿࣝࢠ
࣮࡜ᡂศ࡟ࡼࡿࡇ࡜ࠊd ㌶㐨ᡂศࡀ valence band-top ࡛࢚ࢿࣝࢠ࣮‽఩ࡀ㧗࠸࡜ NO ゎ㞳྾╔ࡀࠊd ㌶㐨࡛࢚ࢿࣝࢠ࣮‽఩ࡀప࠸࡜ศᏊ≧྾╔ࡀࠊs ㌶㐨ࡀ valence-band top ࡟࡞ࡿ࡜஧㔞໬ࡀ㐍⾜ࡍࡿࡇ࡜ࡀ㟁Ⲵ⛣ືࠊ㌶㐨ࡢ㔜࡞ࡾ࡞࡝࠿ࡽࠊ᫂ࡽ࠿࡟࡞ࡗࡓࠋ(Takagi, Ehara,, Sakaki, J. Phys. Chem. A, 123, 7021-7033 (2019)).

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

ཎⴭㄽᩥ‫ۻ‬N. Takagi, M. Nakagaki, K. Ishimura, R. Fukuda, M. Ehara, and S. Sakaki, J. Comput. Chem., 40, 181–190(2019). ‫ۻ‬N. Takagi, K. Ishimura, H. Miura, T. Shishido, R. Fukuda, M. Ehara, and S. Sakaki1, ACS Omega, 4,
2596–2609 (2019). T. Yoshimoto, H. Hashimoto, N. Takagi, S. Sakaki, N. Hayakawa, T. Matsuo, and H. Tobita, Chem.
Eur. J. 25, 3795 – 3798 (2019). ‫ ۻ‬S. Aono, T. Seki, H. Ito, and S. Sakaki, J. Phys. Chem. C, 123, 4773–4794 (2019).
‫ۻ‬N. Kuriakose, J.-J. Zheng, T. Saito, N. Hara, Y. Nakao, and S. Sakaki, Inorg. Chem., 58, 4894 – 4906 (2019). ‫ۻ‬V.
Singh, S. Sakaki, and M. M. Deshmukh, J. Comput. Chem., 40, 2119–2130 (2019). ‫ۻ‬R.-L. Zhong and S. Sakaki, J.
Am. Chem. Soc., 141, 9854 – 9866 (2019). ‫ۻ‬N. Takagi, K. Ishimura, R. Fukuda, M. Ehara, and S. Sakaki, J. Phys.
Chem. A, 123, 7021-7033 (2019). ‫ۻ‬K. Fujimoto, R. S.Payal, T. Hattori, W. Shinoda, M. Nakagaki, S. Sakaki, S.
Okazaki, J. Comput. Chem., 40, 2571-2576 (2019). Ꮫ఍Ⓨ⾲㸸01DNDJDNL6$RQR0<RVKLGD$.RED\DVKL7
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7KHRUHWLFDO DQG &RPSXWDWLRQDO &KHPLVWV $3$7&&  6HSW  WR 2FW ¶UG 8QLYHUVLW\ RI 6\GQH\ 6\GQH\ $XVWUDOLD,QYLWHG  ⌮ㄽ໬Ꮫウㄽ఍㸹ཱྀ㢌Ⓨ⾲㸯௳ࠊ࣏ࢫࢱ࣮Ⓨ⾲㸱௳ࠊศᏊ⛉Ꮫウㄽ఍㸹ཱྀ㢌Ⓨ⾲㸯௳ࠊ࣏ࢫࢱ࣮Ⓨ⾲  ௳ࠊゐ፹ウㄽ఍㸹ཱྀ㢌Ⓨ⾲  ௳ࠊ㘒య໬Ꮫウㄽ఍㸹ཱྀ㢌Ⓨ⾲㸯௳- 62 -

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[B1] K. Okada, T. Tonami, T. Nagami, M. Nakano, J. Phys. Chem. C, 123, 15403-15414 (2019). [B2] M. Nakano,
J. Chem. Phys., 150, 234305-1-18 (2019). [B3] T. Tonami, T. Nagami, K. Okada, W. Yoshida, M. Nakano, ACS
Omega, 4, 16181-16190 (2019). [B4] J. E. Barker, J. J. Dressler, A. Cárdenas Valdivia, R. Kishi, E. T. Strand, L. N.
Zakharov, S. N. MacMillan, C. J. Gómez-García, M. Nakano, J. Casado, M. M. Haley, J. Am. Chem. Soc., 142, 15481555 (2020). [B5] J. J. Dressler, A. Cárdenas Valdivia, R. Kishi, G. E. Rudebusch, A. M. Ventura, B. E. Chastain, C.
J. Gómez-García, L. N. Zakharov, M. Nakano, J. Casado, M. M. Haley, Chem, DOI: 10.1016/j.chempr.2020.02.010 (2020).
[B6] T. Nagami, K. Okada, H. Miyamoto, W. Yoshida, T. Tonami, M. Nakano, J. Phys. Chem. C, in press (2020). [B7] W. Yoshida, K. Okada, H. Miyamoto, T. Tonami, T. Nagami, M. Nakano, J. Phys. Chem. C, (2020), in press. [B8] M. Nakano, K. Okada, T. Nagami, T. Tonami, R. Kishi, Y. Kitagawa, Molecules 24, 541 (2019).  17 6Þ.JL'I¦ß.

- 66 -

86ሙࡢ㔞Ꮚㄽ࡟ᇶ࡙ࡃᒁᡤ≀⌮㔞࡟ࡼࡿ㔞Ꮚ≀ᛶࡢ◊✲
Condensed matter physics research by local quantities based on
quantum field theory‫℩ۑ‬Ἴ ኱ᅵ, ΎỈ ᬛつ, ᯇỌ 㞙἞, 㯮⏣ ┤ஓ, 㧗ᯇ ுኴᮁ㸦ி㒔኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࢢ࣮ࣝࣉࡣࠊ࢝࢖ࣛࣝ࡞ᵓ㐀ࢆᣢࡘศᏊ୰࡟ࡣ㟁Ꮚࡢ࢝࢖ࣛࣜࢸ࢕࡟㠀ᑐ⛠ᛶࡀ࠶ࡿࡇ࡜ࢆ♧ࡋࡓ(&&0(OHFWURQ&KLUDOLW\LQ&KLUDO0ROHFXOH ࠋࡇࡢ㟁Ꮚࡢ࢝࢖ࣛࣜࢸ࢕ࡀ࡝ࡢࡼ࠺࡟⏕ࡳฟࡉࢀࠊ࡝ࡢ
ࡼ࠺࡞໬Ꮫ࣭≀⌮ࡢ⌧㇟࡟ᙺ❧ࡘࡢ࠿ࢆ◊✲ࡋ࡚࠸ࡿࠋ≉࡟ࠊࡇࡢ (&&0 ࡀ⮬↛⏺ࡢ +RPRFKLUDOLW\ ࡢ㉳※࡜࡞ࡗ࡚࠸ࡿ࠿࡝࠺࠿ࡢ◊✲ࢆ୰ᚰ࡟⾜ࡗ࡚࠸ࡿࠋ
ࡲࡓࠊሙࡢ㔞Ꮚㄽ࡟ࡼࡿཎᏊ࣭ศᏊ࡟ᑐࡍࡿ໬Ꮫ࣭≀⌮ࡢ⌧㇟࡟ᑐࡍࡿ◊✲ࢆ⾜ࡗ࡚࠸ࡿࠋሙࡢ㔞Ꮚㄽࡣ┦ᑐᛶ⌮ㄽ࡜ᩚྜࡍࡿ㔞Ꮚㄽࡢᯟ⤌ࡳ࡛࠶ࡾࠊ⌧ᅾᐃᘧ໬ࡉࢀࡓ≀⌮ࡢᇶ♏⌮ㄽࡣ㔞ᏊຊᏛ࡛ࡣ࡞ࡃሙࡢ㔞Ꮚㄽ࠸ᇶ࡙࠸࡚࠸ࡿࠋࡑࢀ࡛ࠊᮏ◊✲࡛ࡣࠊ㐣ཤ࡟㔞ᏊຊᏛ࡟ᇶ࡙ࡁゎᯒࡀ⾜ࢃࢀⓎᒎࡋ࡚ࡁࡓ஦㇟ࡢ⌮ゎࢆሙࡢ㔞Ꮚㄽ࡟ᇶ࡙ࡁ෌⪃ࡋ㔞Ꮚ໬Ꮫศ㔝࡟᪂ࡓ࡞Ⓨᒎⓗ⌮ゎࢆྲྀࡾ㎸ࡴ◊✲ࢆ᥎㐍ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲᅛయ࡞࡝ࡢ࿘ᮇ⣔ィ⟬࡟ࡣᐦᗘỗ㛵ᩘ⌮ㄽࢆ⏝࠸ࡓ OpenMX ࡟ࡼࡿィ⟬ࢆ⾜ࡗࡓࠋศᏊ࡟ᑐࡍࡿ㟁Ꮚᵓ㐀ィ⟬࡟ࡘ࠸࡚ࡣࠊ┦ᑐㄽຠᯝࢆྲྀࡾධࢀࡓィ⟬࡟ࡘ࠸࡚ࡣ DIRAC ࢆ, ┦ᑐㄽຠᯝࢆྲྀࡾධࢀ࡞࠸ィ⟬࡟ࡣ
Gaussian ࢆ౑⏝ࡋ࡚ィ⟬ࡋࡓࠋィ⟬ࡋ࡚ᚓࡓἼື㛵ᩘ࡟ᑐࡋ࡚, 㟁Ꮚ࢝࢖ࣛࣜࢸ࢕ࡸࢫࢺࣞࢫࢸࣥࢯࣝ࡞࡝ࡢ
✀ࠎࡢ≀⌮㔞ࡣ QEDynamics (https://github.com/mfukudaQED/QEDalpha) ࢆ⏝࠸࡚ィ⟬ࡋࡓࠋ

3◊✲ᡂᯝ࢔࣑ࣝࢽ࣒࢘ࢡࣛࢫࢱ࣮࡟㟁ὶࢆὶࡍࡇ࡜࡛໬Ꮫ⤖ྜࡀ኱ࡁࡃኚ໬ࡍࡿ࡜ࡢඛ⾜◊✲ሗ࿌ࢆ☜ㄆࡍࡿ◊✲ࢆ⾜ࡗࡓࠋඛ⾜◊✲࡛ࡣࢡࣛࢫࢱ࣮࡟࡝ࡢࡼ࠺࡟㟁ὶࢆὶࡍ࠿᳨ウࡉࢀ࡚࠸࡞࠿ࡗࡓࡢ࡛ࠊ㟁ὶࢆὶࡍࡇ࡜
ࡀྍ⬟࡞ࢼࣀ࣡࢖ࣖᵓ㐀ࢆ᥇⏝ࡋ࡚ࠊ㠀ᖹ⾮ࢢ࣮ࣜࣥ㛵ᩘἲࢆ⏝࠸࡚㟁Ẽఏᑟࡀ໬Ꮫ⤖ྜ࡟୚࠼ࡿᙳ㡪࡟ࡘ࠸࡚◊✲ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ㏻ᖖࡢࢹࣂ࢖ࢫ࡛౑⏝ࡉࢀࡿࡼ࠺࡞㟁ὶࡢ⠊ᅖ࡛ࡣ໬Ꮫ⤖ྜ࡟᭷ព࡞ኚ໬ࢆ
୚࠼࡞࠸ࡇ࡜ࢆ♧ࡋࡓࠋሙࡢ㔞Ꮚㄽࡢᥥീࠊ≉࡟ඛ⾜◊✲࡛㧗࠸ホ౯ࢆཷࡅ࡚࠸ࡓࢫࢺࣞࢫࢸࣥࢯࣝ࡟ࡼࡿᥥീ࡟࠾࠸࡚ࠊỈ⣲⤖ྜࡀ࡝ࡢࡼ࠺࡟⾲⌧ࡉࢀࡿ࠿ࢆ◊✲ࡋࡓࠋඛ⾜◊✲࡛ࡣࠊඹ᭷⤖ྜࠊ㔠ᒓ⤖ྜࠊ࢖࢜ࣥ⤖ྜࡀㄪ࡭ࡽࢀ࡚࠾
ࡾࠊỈ⣲⤖ྜࡢ◊✲ࡀᮃࡲࢀ࡚࠸ࡓࠋࡇࡢ◊✲࡟ࡼࡾࠊỈ⣲⤖ྜ࡛ࡣඹ᭷⤖ྜ࡜࢖࢜ࣥ⤖ྜࡢ୧᪉ࡢ≉ᚩࢆేࡏᣢࡘࡇ࡜ࢆ♧ࡋࡓࠋࡍ࡞ࢃࡕࠊඹ᭷⤖ྜࡢᣢࡘࢫࣆࣥࢻࣝᵓ㐀ࢆ♧ࡍࠋࡓࡔࡋࠊࡑࡢࢫࢺࣞࢫࢸࣥࢯࣝ
ࡢ᭱኱ᅛ᭷್ࡸ⤖ྜḟᩘࡣ඾ᆺⓗ࡞ඹ᭷⤖ྜࡼࡾࡶᑠࡉ࠸ࡶࡢ࡛࠶ࡗࡓࠋ࢖࢜ࣥ⤖ྜࡢ♧ࡍ≉ᚩ࡛࠶ࡿࠊ㐠ື࢚ࢿࣝࢠ࣮ᐦᗘࡢࢮࣟ㠃ࡢศ㞳ࡶ☜ㄆࡉࢀࡓࠋỈ⣲⤖ྜ࡜࢖࢜ࣥ⤖ྜࡢศ㢮ࡀ㞴ၥ࡛࠶ࡗࡓࡀࠊᙅ࠸࡞ࡀ
ࡽඹ᭷⤖ྜࡀసࡾฟࡍࢫࢺࣞࢫࢸࣥࢯࣝࡢ᪉ྥᛶ࡟ࡼࡾศ㢮ࡀྍ⬟࡛࠶ࡿࡇ࡜ࢆ♧ࡋࡓࠋ- 67 -

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] Masato Senami, (Oral, Invited), “The Electron Chirality in Chiral Molecules”, International Conference ofComputational Methods in Sciences and Engineering (ICCMSE), 2019/5/1-5, Sheraton Hotel, Rhodes, Greece.
‫[ۻ‬2] Masato Senami, (Oral, Invited), “Asymmetry of electron chirality between enantiomeric pair molecules and theorigin of homochirality in nature”, Exploration of Particle Physics and Cosmology with Neutrinos Workshop2019
2019/6/12-14, Hill Hotel Sunpia Iga, Iga, Japan[3] Masahiro Fukuda, Masato Senami, Akitomo Tachibana, (Poster), P-114 “Electronic stress tensor density based on
the quantum field theory in surface material systems”, The 22nd Asian Workshop on First-Principles Electronic
Structure Calculations (ASIAN-22), 2019/10/28-30, Osaka University, Toyonaka, Japan[4] Naoya Kuroda, Masato Senami, (Poster), “Effects of molecular structure of polyatomic polar molecules on spin
dynamics and effective electric field”, The 3rd Univ. Ryukyus International Symposium of Theoretical andComputational Science (RIS-TCS) 2020/3/20-22, University of the Ryukyus, Okinawa, Japan[5] Tomoki Shimizu, Masato Senami, “The asymmetry of electron chirality induced by chiral structure of molecule”,
The 3rd Univ. Ryukyus International Symposium of Theoretical and Computational Science (RIS-TCS) 2020/3/20-22,
University of the Ryukyus, Okinawa, Japan‫[ۻ‬6] ᯇỌ 㞙἞, ℩Ἴ ኱ᅵ, (࣏ࢫࢱ࣮), P98 ͆ᖹ㠃ᵓ㐀ᮦᩱ࡟࠾ࡅࡿ㟁Ẽఏᑟ୰ࡢ࣮ࣟࣞࣥࢶຊᐦᗘ࡜ࢸࣥ
ࢩࣙࣥᐦᗘࡢ⌮ㄽⓗ◊✲͇, ➨ 22 ᅇ ⌮ㄽ໬Ꮫウㄽ఍, 2019/5/27-29, ໭ᾏ㐨኱Ꮫ (ᮐᖠ).
[7] ΎỈ ᬛつ, ఀ⸨ ᆂே, ℩Ἴ ኱ᅵ, (࣏ࢫࢱ࣮), P99 ͆㙾ീ␗ᛶయ࡟࠾ࡅࡿ㟁Ꮚ࢝࢖ࣛࣜࢸ࢕ࡢ⌮ㄽⓗ◊✲͇,➨ 22 ᅇ ⌮ㄽ໬Ꮫウㄽ఍, 2019/5/27-29, ໭ᾏ㐨኱Ꮫ (ᮐᖠ).
[8] ⚟⏣ ᑗ኱㸪℩Ἴ ኱ᅵ, ❧ⰼ ᫂▱, ᑿᓮ Ὀຓ (ཱྀ㢌), 13aK25-3 ͆≀㉁⾲㠃࡟࠾ࡅࡿሙࡢ㔞Ꮚㄽ࡟ᇶ࡙ࡃ
ᒁᡤ≀ᛶホ౯᪉ἲ͇,᪥ᮏ≀⌮Ꮫ఍ 2019 ᖺ ⛅Ꮨ኱఍,2019/9/10-13, ᒱ㜧኱Ꮫ (ᒱ㜧).
[9] 㧗ᯇ ுኴᮁ㸪㧗ᶫ ಇ㈗㸪℩Ἴ ኱ᅵ, (࣏ࢫࢱ࣮), 1P107 ͆La2/3-xLi3xTiO3 ෆ࡛ᙧᡂࡉࢀࡿ໬Ꮫ⤖ྜࡢ⌮ㄽⓗ◊✲͇,➨ 13 ᅇ ศᏊ⛉Ꮫウㄽ఍,

2019/9/10-13, ྡྂᒇ኱Ꮫ (ྡྂᒇ)[10] 㯮⏣ ┤ஓ㸪㔝᭮ཎ ┤அ㸪℩Ἴ ኱ᅵ, 4P109 ͆➨ 14 ᪘ඖ⣲ࡢ 2 ḟඖ⣔≀㉁࡟࠾ࡅࡿࢫࣆࣥ࡜㟁ὶࡢ㛵ಀ͇, (࣏ࢫࢱ࣮), ➨ 13 ᅇ ศᏊ⛉Ꮫウㄽ఍, 2019/9/17-20, ྡྂᒇ኱Ꮫ (ྡྂᒇ).
‫[ ۻ‬11] ᯇỌ 㞙἞㸪℩Ἴ ኱ᅵ, (࣏ࢫࢱ࣮), 4P114 ͆ᖹ㠃ᵓ㐀ᮦᩱ࡟࠾ࡅࡿ㟁Ẽఏᑟ୰ࡢ࣮ࣟࣞࣥࢶຊᐦᗘ࡜
ࢸࣥࢩࣙࣥᐦᗘࡢ⌮ㄽⓗ◊͇, ➨ 13 ᅇ ศᏊ⛉Ꮫウㄽ఍, 2019/9/17-20, ྡྂᒇ኱Ꮫ (ྡྂᒇ).
[12] ⚟⏣ ᑗ኱㸪℩Ἴ ኱ᅵ, ❧ⰼ ᫂▱ (ཱྀ㢌), 16aK29-11 ࢚͆ࢿࣝࢠ࣮༊㛫ࡈ࡜࡟ぢࡿ㟁Ꮚࢫࢺࣞࢫࢸࣥࢯ
ࣝᐦᗘࡢᥥീ͇, ᪥ᮏ≀⌮Ꮫ఍ ➨ 75 ᅇᖺḟ኱఍, 2020/3/16-19, ྡྂᒇ኱Ꮫ (ྡྂᒇ).

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

մ[1] Masato Senami, Shunji Matsunaga, “The effect of electric current on chemical bonding of hydrogen adsorption on
an aluminum nanowire”, Int. J. Quantum. Chem. 119, e26004 (2019).
մ[2] M. Senami, N. Kuroda, T. 7DNDKDVKL³(൵HFWVRIH[WHUQDOHOHFWULF¿HOGDQGLQWHUQXFOHDUOHQJWKRQH൵HFWLYHHOHFWULF
¿HOGIRUPHDVXUHPHQWRIHOHFWURQHOHFWULFGLSROHPRPHQW´-. Comput. Metthods Sci. Eng., acceptedմ[3] Masato Senami, Keito Ito, “Identification of Hydrogen Bonds Using Quantum Electrodynamics”, Int. J. Quantum
Chem., accepted- 68 -

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1.1

QZF?Bãĵ$3ýhqö<K[>`%óĪĦÝ

ğúĮ%gåãĵ%¸Ä$&çĊĎ·ł53gåãĵe%çĊĎ<K[>`6©Ľû$

ĤĂ.3!&ğúĮ%Ąpãĵ¸Äó%óĦ$¦%ÍĜ$.¹ĄÚÿă & α QZF?B$310 QZF?B 0( π QZF?B%çĊĎ<K[>`6Ľ¦§ħć$02ĩ*α X[ROP/ 4 2<? K4I_aA 3.6 [ROPA 5 
1.2

2<_aA 4.4 `?`@?3:*310 X[ROP 3  2<_aA 3  `*π X

K4I+

9?E^% ATPase Áäã%ĦÝ

9?E^&Ćēď6¸Ä3fģ#D^L?Į%ap3Ļ3!

39?E^N:YU^H6¸ÄĆđ!%ĩĈ6Ç$+4
ATP&Ľp% G-9?E^jÑaě%ČĖ$.9?E^&¤Ľ

1Đďñ$Ļ F-9?E^)!ãĵ¢3!

çĦëÂ6×30 $#3! þ14 2% ATP4+ ¼14# !

ĦÓ$4# F-9?E^% ATPcĳ%çĦëÂ H\FITZ^@!

'439?E^%aÑû$ĶĠ3¦½ôķ6ō3!Ĕ#Ħs¶% F-9?E^%ãĵgĻ17%ČĖ|ãĵ

143

1% ATP# 1

çĦ%Áäã&ØçĦÁ%ĨČ#¦äã%ĦÓ6üû!Ĳ´¼14 1.2 Å %ŎĦs¶% X ĐĎÕãĵ6.!$ONIOM é$03Áčİ%óĪĦÝ6Ġ

2ÿăÑéħćÑé
2.1

QZF?Bãĵ$3ýhqö<K[>`%óĪĦÝ

310 QZF?Bπ QZF?B$44Whole helical structure (WH)VG[6qÄ%ãĵ6
$Single turn (ST)VG[Minimal hydrogen bond (MH)VG[6qÄ4.SZ9YJ^% N
Ùą69CE[(Ace)C Ùą6UE[(Nme) =WFP¦(Ace-Alan-Nme) 3WH VG[%ãĵ&gŉĥ6©Öĸ6ĠŒ310 QZF?BŘϕ = -26°, ψ = -49°(π QZF?BŘϕ = -70°, ψ = -57°œçĊĎ<K[>`& negative fragmentation approach $02è-ħć$& B97D/6-31+G(d)é6ö
1$¦ (Amber99SB)$03çĊĎ<K[>`%ħćŒMMœ.Ġ- 69 -

2.2

9?E^% ATPase Áäã%ĦÝ

xÿăĕ02Ër4 F-actin %ŎĦs¶ĎÕãĵ6.!$ONIOM
é6öÁčİ%Êċ6ĠQM Ŋ!D^L?Į%Ö®Ń%ëÂĹmŒ 1œ62~.%ŒQM1œ#1($4$ ATP !çĊĎ3 P1, P2 [`P%fŀ6
2X/6-31G(d)\R[.%ŒQM2œ6öQM Ŋ& M06-

2Æ4k£%Ĺm& Amber ff96 2ÆQM Ŋ%,ãĵÖĸ6ĠMM Ŋ&ĎÕãĵ$©

3

ÿăÄß
3.1

QZF?Bãĵ$ŗ F-actin %ëÂĹm

YL@

3ýhqö<K[>`%óĪĦÝ
MV\N^K"'?3:W]RT36K

2 ?4+

α X[ROP_AH`-FB π X[ROP_PiH`;A WH
ZS\< ST ZS\;#,MV\N^/GJ:-H*=7GE MH ZS\<0/#,+ 2. QZF?BVG[$ 3çĊĎ<K[>`ŖAH: α QZF?BŔ3 10H: 310 QZF?BŔPiH: π QZF?BŖ

;*310 X[ROP_3_10H`;A WH ZS\@C
0/>8:,6+1@0@%,KG.?4I

6D? 310 X[ROP?9,: ST ZS\@? 2 959YWQU K$36ZS\K3: MV
\N^K!36*WH ZS\?#,/GJ6+1JA*310 X[ROP;A*@b)@X[ROP<A
>H*@0@(/& <>I1<K 3:,I+
3.2

9?E^% ATPase Áäã%ĦÝ

 3 $Úÿă Ĥ~4 F-actin % ATPçĦÁ%<K[>`P]N8;[644% QM Ŋ%ÛlŒQM1,2œ$ĀÒ$Å%u%ħć
ĶĠPO3

ŕF-9?E^% ATPĘŇeŁñÃ6čõÄð$Ě3!

çĦ& dissociative pathwayĀ4 iÐ$PO Ď%ĦŇ$u7eŁp6¨©3-% lytic water%}ĺ į3! Ā4+»Ĵæń 3 PO3–)% lytic water%èàÎÌ%<K[>`Ņ¡&9?E^% P1,P2 [`P!%çĊĎ6 QM Ŋ$2v43! û$nb3! 5 

4 3. F-actin % ATPase ÁęùġªĒ
4.1 ŋùġŒC^D`ö$03.%w 5 l

ø<K[>`P]N8;[Èºīî 2 lœŏļ1International Congress on Pure & Applied Chemistry Yangon 2019 Èºīî#"
4.2 SBD`ùġŒC^D`ö$03.%w 14 lœŏļ1The 60th Sanibel Symposium SBD`ùġ #"5~ïªĒŒĪÏw 4 lœĲĞáÞŐ÷Ō÷Ŀ«eļêÚŏļ"Effects of a remote mutation from the contact paratope on
the structure of CDR-H3 in an anti-HIV neutralizing antibody PG16"Sci. Rep. 2019, 9, 19840- 70 -

⏕యศᏊࡢᵓ㐀࡜ᶵ⬟࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Studies on Structures and Functionsof Biological Molecules‫◁⨾ ⏣┦ۑ‬Ꮚ㸪㉥℩ ኱㸪Ώ㒊 㞝኱㸪ຊᒣ ࿴᫭㸪⚟ཎ ኱㍤㸦ᗈᓥ኱㝔⌮㸧1◊✲┠ⓗ㸪ෆᐜ
⏕⌮άᛶศᏊࡸ⏕యศᏊࡢᵓ㐀ࡢ≉ᚩࡸ཯ᛂࡢ࣓࢝ࢽࢬ࣒㸪ࡲࡓ㸪ࡑࢀࡽ࡬ࡢ⁐፹ࡸ࿘ࡾࡢ⎔ቃࡢ㛵୚ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚㸪୺࡟㠀⤒㦂ⓗศᏊ㌶㐨ἲ㸪ศᏊືຊᏛἲ㸪ࣔࣥࢸ࢝ࣝࣟἲࢆ㸪ࡲࡓ㸪ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ◊✲ࢆ㐍ࡵࡓࠋ◊✲ࡢෆᐜࡣ㸪1) QM/MM ἲ࡟ࡼࡿ⏕⌮άᛶศᏊࡢỈ⁐ᾮ୰࡟࠾ࡅࡿ≉ᚩࡢゎ᫂㸪2㸧⁐፹ỈศᏊࡢศᕸࡢゎᯒ㸪3) ᐇ㦂ⓗ࡟⯆࿡ࡢ࠶ࡿ⌧㇟ࡢ⌮ㄽⓗゎ᫂㸪࡛࠶ࡿࠋ

2◊✲᪉ἲ㸪ィ⟬᪉ἲ౑⏝ࣉࣟࢢ࣒ࣛࡣ㸪୺࡜ࡋ࡚㸪 Gaussian09㸪 Gaussian16㸪 HONDO ࡛࠶ࡿࠋQM/MM ἲィ⟬࡟ࡣ㸪⊂⮬࡛㛤Ⓨࢆ㐍ࡵ࡚࠸ࡿ HONDO ࢆ౑⏝ࡋ࡚࠸ࡿࠋゎᯒ࡟ࡣ⊂⮬࡟సᡂࡋࡓࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚࠸ࡿࠋ

3

◊✲ᡂᯝ

3.1 QM/MM-MD ἲ࡟ࡼࡿ㸪Ỉ⁐ᾮ୰࡟࠾ࡅࡿ⏕⌮άᛶศᏊࡢᵓ㐀࡜ࡑࡢỈ࿴ᵓ㐀ḟࡢ 2 ✀ࡢศᏊࡣ㸪ᾐ㏱ᅽㄪᩚ≀㉁࡜ࡋ࡚▱ࡽࢀࡿࡀ㸪ࢱࣥࣃࢡ㉁࡟ᑐࡋ࡚┦཯ࡍࡿస⏝ࢆࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡍ࡞ࢃࡕ㸪TMG ࡣࢱࣥࣃࢡ㉁ࡢ㧗ḟᵓ㐀ࢆᏳᐃ໬ࡋ㸪Urea ࡣࢱࣥࣃࢡ㉁ࡢኚᛶ๣࡛࠶ࡿࠋࡑࡢ
㐪࠸ࡢཎᅉࡣ㸪ࡑࢀࡽࡢศᏊࡢ࿘ᅖࡢỈ࿴ᵓ㐀ࡢ≉ᚩ࡟࠾ࡅࡿ㐪࠸࡟࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
࣭N, N, N-ࢺ࣓ࣜࢳࣝࢢࢩࣥ㸦TMG㸧ࡣ㸪୰ᛶ࡟࠾࠸࡚཮ᛶ࢖࢜ࣥࡢᵓ㐀ࢆ࡜ࡾ㸪࿘ᅖࡢỈศᏊ࡜ᙉࡃ┦஫స⏝ࡍࡿࠋTMG ࡜ᙉ࠸┦஫స⏝ࡢ࠶ࡿỈศᏊࡣ 26 ಶ⛬ᗘ࡛࠶ࡾ㸪ࢱࣥࣃࢡ㉁ࢆኚᛶࡉࡏࡿྍ⬟ᛶࡢ࠶ࡿ୍౯࢝ࢳ࢜ࣥࡀࡑࡢࢿࢵࢺ࣮࣡ࢡ࡟ྲྀࡾ㎸ࡲࢀࡿࡇ࡜ࢆぢฟࡋࡓࠋࠝⓎ⾲ࣜࢫࢺ  ࠞ࣭ᒀ⣲㸦Urea㸧ࡣ㸪Ỉ⁐ᾮ୰࡟࠾࠸࡚ᖹᆒ࡛ 4㹼5 ಶࡢỈศᏊ࡜┤᥋Ỉ⣲⤖ྜࡋ࡚࠾ࡾ㸪ࡑࡢ࠺ࡕ㸪࢝ࣝ࣎ࢽࣝᇶࡢ㓟⣲ཎᏊࡣ⣙ 2 ಶࡢỈศᏊ࡜Ỉ⣲⤖ྜࡋ࡚࠸ࡿࡀ㸪࢔࣑ࣀᇶࡢ❅⣲ཎᏊ࡟ࡣ࡯࡜ࢇ࡝Ỉ⣲⤖ྜࡋ࡚࠸࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡍ࡞ࢃࡕ㸪Urea ࡢ࿘ࡾࡢỈ࿴ࡣ㸪TMG ࡼࡾ㸪࠿࡞ࡾᙅ࠸ࠋ
ࠝⓎ⾲ࣜࢫࢺ  ࠞ
3.2 ⁐፹ỈศᏊࡢศᕸࡢゎᯒࠝⓎ⾲ࣜࢫࢺ  ࣭ࠞNMR 㐽ⶸᐃᩘࡢᩘ್ࡣ㸪 ᐃ໬ྜ≀ࡢᵓ㐀ࡔࡅ࡛࡞ࡃ㸪ࡑࢀࢆྲྀࡾᕳࡃ⎔ቃ࠿ࡽࡶᙳ㡪ࢆཷࡅࡿࠋ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ồࡵࡓ㸪Ỉ⁐ᾮ୰ࡢ࣓ࢱࣀ࣮ࣝࡢ 1H-NMR 㐽ⶸᐃᩘࢆ┠ⓗኚᩘ࡜ࡋ㸪ᐃ໬ྜ≀ࡢᵓ㐀࠾ࡼࡧ⁐፹ỈศᏊࡢ㓄⨨࠿ࡽᚓࡽࢀࡿཎᏊ㛫㊥㞳ࡸ⤖ྜゅࢆㄝ᫂ኚᩘ࡜ࡋ࡚㸪ᶵᲔᏛ⩦ࢆ⏝࠸࡚㸪㧗࠸ணᗘࡢࣔࢹࣝࢆᵓ⠏ࡋ࡚࠸ࡿࠋNMR 㐽ⶸᐃᩘࢆண

⢭ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࣔࢹࣝࢆ㛤Ⓨࡍࡿࡇ࡜࠿ࡽ㸪NMR 㐽ⶸᐃᩘࡢ⁐፹ຠᯝ࡟㛵ࡍࡿ▱ぢࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋ

3.3 ᐇ㦂ⓗ◊✲⪅࡜ࡢඹྠ◊✲࣭Pramidimicin A (PRM-A) ࡣᨺ⥺⳦⏤᮶ࡢᢠ⏕≀㉁࡛࠶ࡾ㸪࣐ࣥࣀ࣮ࢫࢆྵࡴ⢾㙐࡟≉␗ⓗ࡟⤖ྜࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋPRM-A ࡀ࡝ࡢࡼ࠺࡟ࡋ࡚㸪࣐ࣥࣀ࣮ࢫࢆ≉␗ⓗ࡟ㄆ㆑ࡍࡿࡢ࠿㸪ࡑࡢ࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ

- 71 -

࠿࡟ࡍࡿࡓࡵ࡟㸪Ca2+ࢆ௓ࡋࡓ PRM-A ࡢ஧㔞య࡜࣐ࣥࣀ࣮ࢫㄏᑟయࡢ஧㔞యࡢ⤖ྜᵝᘧࢆ㸪DFT ィ⟬࡟ࡼࡗ࡚᫂ࡽ࠿࡟ࡋࡓࠋࡑࢀࡣ㸪NMR ࠿ࡽࡢᐇ㦂ࢹ࣮ࢱࢆࡼࡃㄝ᫂ࡍࡿࡶࡢ࡛࠶ࡿࠋࠝฟ∧ࣜࢫࢺ>@㸪>@࣭ࠞ᫬㛫ศゎ㉥እ྾཰ศග࡟ࡼࡾ㸪᫬㛫࡜࡜ࡶ࡟୺࡜ࡋ࡚ほࡉࢀࡿศᏊ✀ࡀኚ໬ࡍࡿࡇ࡜ࡀᐇ㦂ⓗ࡟ぢฟࡉࢀࡓ⁐ᾮ୰࡟࠾ࡅࡿ཯ᛂ⣔࡟ࡘ࠸࡚㸪ᵓ㐀࡜᣺ືᩘࡸᙉᗘࢆ DFT ィ⟬࡟ࡼࡗ࡚ồࡵ㸪཯ᛂ㐣⛬ࢆ≉ᐃࡋࡓࠋࠝฟ∧ࣜࢫࢺ[3]㸪[4]ࠞ
࣭ぶỈᛶ࡜␯Ỉᛶࡢࣈࣟࢵࢡࢆ୍ᮏ㙐ෆ࡟஺஫࡟」ᩘᅇ㓄⨨ࡍࡿ୧ぶ፹ᛶ࣐ࣝࢳࣈࣟࢵࢡඹ㔜ྜయࢆྜᡂ
ࡋ㸪ࡑࡢỈ⁐ᾮ≀ᛶࢆᐇ㦂ⓗ࡟᫂ࡽ࠿࡟ࡋࡓࠋࡑࡢࡼ࠺࡞≀ᛶࡀ⌧ࢀࡿཎᅉࢆ⌮ㄽⓗ࡟᫂ࡽ࠿࡟ࡍࡿ◊✲ࢆ㛤ጞࡋ࡚࠸ࡿࠋ
ࠝฟ∧ࣜࢫࢺ>@ࠞ

4

Ⓨ⾲ᐇ⦼

‫(ۻ‬1) ⚟ཎ㸪㉥℩㸪┦⏣ࠕTMG ࡀỈࢆᙉࡃಖᣢࡍࡿ⬟ຊ࡟㛵ࡍࡿ⌮ㄽ໬Ꮫⓗ◊✲ࠖ➨ 22 ᅇ⌮ㄽ໬Ꮫウㄽ఍
㸦2019 ᖺ 5 ᭶ 27 ᪥㸫29 ᪥㸪ᮐᖠᕷ㸧‫(ۻ‬2) ⚟ཎ㸪㉥℩㸪┦⏣ࠕỈ⁐ᾮ୰࡟࠾ࡅࡿ TMG ࡜୍౯࢖࢜ࣥ࡜ࡢ㛫ࡢ┦஫స⏝࡟㛵ࡍࡿ⌮ㄽ໬Ꮫⓗ◊✲ࠖ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍㸦2019 ᖺ 9 ᭶ 17 ᪥㸫20 ᪥㸪ྡྂᒇᕷ㸧‫(ۻ‬3) ⚟ཎ㸪㉥℩㸪┦⏣ࠕࢺ࣓ࣜࢳࣝࢢࣜࢩࣥࡢỈ࿴ᵓ㐀࡬ࡢሷࡢᙳ㡪࡟㛵ࡍࡿ⌮ㄽ໬Ꮫⓗ◊✲ࠖ᪥ᮏࢥࣥࣆ
࣮ࣗࢱ໬Ꮫ఍ 2019 ⛅Ꮨᖺ఍㸦2019 ᖺ 10 ᭶ 24 ᪥㸫25 ᪥㸪ᗈᓥᕷ㸧‫(ۻ‬4) ୗᒸ㸪㉥℩㸪┦⏣ࠕỈ⁐ᾮ୰࡟࠾ࡅࡿᒀ⣲ࡢỈ࿴ᵓ㐀࡟ࡘ࠸࡚ࡢ QM/MM-MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼ
ࡿ⌮ㄽ໬Ꮫⓗ◊✲ࠖ2019 ᖺ᪥ᮏ໬Ꮫ఍୰ᅜᅄᅜᨭ㒊኱఍㸦2019 ᖺ 11 ᭶ 16 ᪥㸫17 ᪥㸪ᚨᓥᕷ㸧‫(ۻ‬5) ⋢㔝㸪㉥℩㸪┦⏣ࠕᶵᲔᏛ⩦ࢆ⏝࠸ࡓ NMR 㐽ⶸᐃᩘࡢ⁐፹ຠᯝ࡟ࡘ࠸࡚ࡢ⌮ㄽ໬Ꮫⓗ◊✲ࠖ2019 ᖺ᪥ᮏ໬Ꮫ఍୰ᅜᅄᅜᨭ㒊኱఍㸦2019 ᖺ 11 ᭶ 16 ᪥㸫17 ᪥㸪ᚨᓥᕷ㸧

5

ฟ∧ᐇ⦼

‫[ۻ‬1] Yu Nakagawa, Takashi Doi, K. Takegoshi, Takahiro Sugahara, Dai Akase, Misako Aida, Kazue Tsuzuki, Yasunori
Watanabe, Tomohiko Tomura, Makoto Ojika, Yasuhiro Igarashi, Daisuke Hashizume, Yukishige Ito, “Molecular
Basis of Mannose Recognition by Pradimicins and their Application to Microbial Cell Surface Imaging,” Cell
Chemical Biology, 26(7), 950-959 (2019). DOI: 10.1016/j.chembiol.2019.03.013‫[ۻ‬2] Yasunori Watanabe, Fumiya Yamaji, Makoto Ojika, Takahiro Sugawara, Dai Akase, Misako Aida, Yasuhiro
Igarashi, Yukishige Ito, Yu Nakagawa, “The endocyclic oxygen atom of D-mannopyranose is involved in its
binding to pradimicins,” Tetrahedron Letters, 61(9), 151530 (2020). DOI: 10.1016/j.tetlet.2019.151530‫[ۻ‬3] Masato Kondoh, Akira Sakuta, Kazuki Okazawa, Dai Akase, Misako Aida, and Taka-aki Ishibashi㸪“Photo-Induced Ring-Opening Reaction of Flav-3-en-2-ol Monitored by Time-Resolved Infrared Spectroscopy,”
Journal of Physical Chemistry B, 123(40), 8499-8504 (2019). DOI: 10.1021/acs.jpcb.9b07108‫[ۻ‬4] Masato Kondoh, Chinatsu Takizawa, Kazuki Okazawa, Dai Akase, Misako Aida, Taka-aki Ishibashi㸪
“Time-resolved infrared study of photo-induced ring-closure reaction of trans-2-hydroxychalcone,” Journal of
Photochemistry and Photobiology A: Chemistry, 389, 112280 (2020). DOI: 110.1016/j.jphotochem.2019.112280[5] Kazuaki Rikiyama, Yusuke Sanada, Keisuke Watanabe, Misako Aida, and Yukiteru Katsumoto, “Unimer Structureand Micellization of Poly(ethylene oxide)-Stereocontrolled Poly(N-isopropylacrylamide) Alternating Multiblock
Copolymers in Aqueous Solution,” Macromolecules, 52, 7188-7196 (2019). DOI: 10.1021/acs.macromol.9b01172- 72 -

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໬ࢳ࢜࢔ࢭࢺࣥࡢ +)&& ࡢィ⟬ࢆ⾜ࡗࡓࠋࡲࡓࠊᡃࠎࡢࢢ࣮ࣝࣉࡣᛂ⏝ⓗ࡞◊✲࡜ࡋ࡚ࠊᐇ㦂ࡢࢢ࣮ࣝࣉ࡜
ඹྠࡋ࡚࢔ࢽ࢜ࣥㄆ㆑ࡢᶵ⬟ࢆᣢࡘ㓄఩Ꮚࡸṑ㌴≧୧ぶ፹ᛶศᏊ࡟ࡼࡾᙧᡂࡉࢀࡓࢼࣀ࣮࢟ࣗࣈࡢ◊✲ࢆ⾜ࡗ࡚ࡁࡓࠋ≉࡟ࢼࣀ࣮࢟ࣗࣈࡣࠕࢤࢫࢺศᏊࠖࢆໟᦤࡋࠊࡑࡢయ✚ࡀࢤࢫࢺศᏊ࡟ࡼࡾኚ໬ࡍࡿࡇ࡜ࡀᐇ㦂ⓗ࡟᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࢼࣀ࣮࢟ࣗࣈࡢయ✚ኚ໬ࡢ⌮ㄽⓗ࡞ゎ᫂ࢆ┠ᣦࡋ◊✲ࢆ⾜ࡗࡓࠋ ◊✲᪉ἲࠊィ⟬᪉ἲ ࣑࣮ࣗ࢜ࢽ࣒࢘໬ࢳ࢜࢔ࢭࢺࣥࡢ +)&& ࡢ⢭ᐦィ⟬ᙜ◊✲ᐊ࡛㛤Ⓨࡋࡓ⤒㊰✚ศศᏊືຊᏛ 3,0' ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ࠊ࣑࣮ࣗ࢜ࢽ࣒࢘໬ࢳ࢜࢔ࢭࢺࣥࡢ
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࣮ࣞࢩࣙࣥࡣ .DWP ࢆ┠ᶆ್࡜ࡍࡿ 137 ࢔ࣥࢧࣥࣈ࡛ࣝ⾜࠸ࠊIV ࡢ᫬㛫้ࡳ࡛ QV  ࢫࢸࢵࣉ ᫬㛫ⓎᒎࡉࡏࡓࠋỈ⣲ࢆྵࡴඹ᭷⤖ྜࡢ⤖ྜ㛗ࡣ 6+$.( ἲࢆ⏝࠸࡚ᅛᐃࡋࡓࠋ
ศᏊຊሙࡣ *HQHUDO$0%(5)RUFH )LHOG *$)) ຊሙࢆ⏝࠸ࠊྠࡌࡃ $PEHU  ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࡼࡾ౑⏝ྍ⬟࡛࠶ࡿ [OHDS ࠾ࡼࡧ$QWHFKDPEHU ࢆ⏝࠸࡚ຊሙࡢ๭ࡾᙜ࡚ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓࢺࣛࢪ࢙ࢡࢺࣜ࠿ࡽయ✚ࢆ௨ୗࡢ  ࡘࡢ᪉ἲ࡛ồࡵࡓࢼࣀ࣮࢟ࣗࣈࡢᑐゅ⥺ࢆ┤ᚄ࡜ࡍࡿ⌫ࡢయ✚ࠊ ࢼࣀ࣮࢟ࣗࣈࢆᖹ⾜භ㠃య࡜㏆ఝࡋࡓ᫬ࡢయ✚ࠋ- 73 - ◊✲ᡂᯝ ࣑࣮ࣗ࢜ࢽ࣒࢘໬ࢳ࢜࢔ࢭࢺࣥࡢ +)&&
࣑࣮ࣗ࢜ࢽ࣒࢘໬ࢳ࢜࢔ࢭࢺࣥࡢ 3,0' ィ⟬࡟ࡣࠊ⹫᫬㛫้ࡳᖜ IVࠊࢫࢸࢵࣉᩘ ࠊࣅ࣮ࢬᩘ ࡢ᮲௳࡛⾜ࡗࡓࠋ3,0' ࡟࠾ࡅࡿ +)&& ࡢᮇᚅ್ࡣࠊ 0+] ࡛࠶ࡗࡓࠋỈ⣲໬ࢳ࢜࢔ࢭࢺࣥࡢ 3,0'ィ⟬࡟ࡣࠊ⹫᫬㛫้ࡳᖜ  IV ࢫࢸࢵࣉᩘ ࠊࣅ࣮ࢬᩘ  ࡢ᮲௳࡛⾜࠸ࠊ+)&& ࡢᮇᚅ್  0+]ࢆᚓࡓࠋ࡞࠾ࠊ࣑࣮ࣗ࢜ࢽ࣒࢘໬ࢳ࢜࢔ࢭࢺࣥࡢ᭱Ᏻᐃᵓ㐀࡟࠾ࡅࡿ +)&& ࡣ 0+] ࡛࠶ࡗࡓࠋ

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)LJ D +)&& ࡢศᕸ E +)&& ࡢ҆6&0X ࡟ᑐࡍࡿኚ໬
+)&& ࡢศᕸࢆㄪ࡭ࡿ࡜  0+] ௜㏆ࡢ㗦࠸ࣆ࣮ࢡࡢ௚࡟  0+] ௜㏆࡟ࣈ࣮ࣟࢻ࡞ࣆ࣮ࢡࡀ☜ㄆࡉࢀࡓ )LJ  D ࠋ ࡘࡢ࣓ࢳࣝᇶࡢ㓄ྥᛶ࡟౫Ꮡࡍࡿࡶࡢࡢࠊ+)&& ࡢ್ࡣ҆6&0X ࡟౫Ꮡࡋࠊ≉࡟࣓ࢳࣝᇶࡀHFOLSVHG ᆺࡢ㓄ྥࢆྲྀࡿ࡜ࡁࡣ ௜㏆࡛ᛴ⃭࡟ +)&& ࡢ್ࡀ  ࡟ኚ໬ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ )LJ E ࠋ୍⯡࡟ +)&& ࡣཎᏊ᰾ୖࡢ≀ᛶ್࡛࠶ࡾ 6202 ࡢᐤ୚ࡀ㔜せ࡛࠶ࡿࠋィ⟬⤖ᯝ࠿ࡽ◲㯤ࡢ px, py, pz ㌶㐨ࡀ6202 ࡟኱ࡁࡃᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࡀࠊ҆6&0X ࡢኚ໬࡟ࡼࡾࢳ࢜࢔ࢭࢺࣥࡢ 6202 ࡢᑐ⛠ᛶࡀ a'࠿ࡽ a"࡟ኚ໬ࡋࠊࢳ࢜࢝ࣝ࣎ࢽࣝᇶ࡟ྵࡲࢀࡿⅣ⣲ཎᏊ࡜◲㯤ཎᏊࡢ 6202 ࡬ࡢᐤ୚ࡀᑠࡉࡃ࡞ࡗ࡚࠸ࡓࡇ
࡜ࡀࠊ+)&& ࡢ๻ⓗ࡞ኚ໬ࢆࡶࡓࡽࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ

 ṑ㌴≧୧ぶ፹ᛶศᏊ࡟ࡼࡾᙧᡂࡉࢀࡿࢼࣀ࣮࢟ࣗࣈࡢࢤࢫࢺศᏊ࡟ࡼࡿయ✚ኚ໬ᖹ⾜භ㠃య㏆ఝ࡟ࡼࡾᚓࡽࢀࡓࢼࣀ࣮࢟ࣗࣈࡢయ✚ࡣࠊ7%0DT3&&3 ࢆໟ᥋ࡍࡿࡇ࡜࡟ࡼࡾࠊࡑࢀࡒࢀ
Ⴒ ࡜࡞ࡗࡓࠋࡲࡓ⌫య㏆ఝ࡟ࡼࡾᚓࡽࢀࡓయ✚ࡣࠊႲ ࡛࠶ࡗࡓࠋඹ
ྠ◊✲ඛ࡟ࡼࡾᐇ㦂ⓗ࡟ぢ✚ࡶࡽࢀࡓయ✚ࡣࠊࡑࢀࡒࢀ Ⴒ ࡛࠶ࡗࡓࠋᖹ⾜භ㠃య㏆ఝࡣᐇ㦂್ࢆ㐣ᑠホ౯ࡋࡓࠋᐇ㦂࡟࠾࠸࡚ࢼࣀ࣮࢟ࣗࣈࡢయ✚ࡣࢼࣀ࣮࢟ࣗࣈࡢ⛣ືᗘ࠿ࡽ࢔࢖ࣥࢩࣗࢱ࢖ࣥࢫ
ࢺ࣮ࢡࢫࡢ㛵ಀᘧࡼࡾὶయຊᏛⓗ༙ᚄࢆồࡵࠊࡑࢀࢆ⌫ࡢయ✚ࡢබᘧ࡟௦ධࡍࡿࡇ࡜࡛ᚓ࡚࠸ࡿࠋ⌫య㏆ఝࡢ᪉ࡀᐇ㦂࡛⏝࠸࡚࠸ࡿ㏆ఝ࡜㏆࠸ࡓࡵᚓࡽࢀࡓయ✚ࡢ࣮࢜ࢲ࣮ࡀ㏆ࡃ࡞ࡗࡓ࡜⪃࠼ࡽࢀࡿࠋ

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)LJ ᐇ㦂࡟࠾ࡅࡿࢼࣀ࣮࢟ࣗࣈࡢࢤࢫࢺศᏊ࡟ࡼࡿయ✚ኚ໬୍᪉ࠊィ⟬࡛♧ࡋࡓయ✚ࡢ㡰ᗎࡀᅗ࡟♧ࡋࡓᐇ㦂ࡢ㡰ᗎ࡜୍⮴ࡋ࡞࠿ࡗࡓཎᅉ࡜ࡋ࡚ࠊᐇ㦂࡛ࡢయ✚ࡀ⁐፹࡜ࡢ┦஫స⏝࡞࡝ࡢᙳ㡪ࢆཷࡅ࡚࠸ࡿྍ⬟ᛶࡀᣲࡆࡽࢀࡿࠋ⛣ືᗘࡣศᏊືຊᏛィ⟬࠿ࡽࡶィ⟬ࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡾࠊィ⟬࡟࠾࠸࡚ࡶᐇ㦂࡜ྠᵝ࡟ὶయຊᏛ༙ᚄࢆ⏝࠸ࡓయ✚ࢆ⏝࠸ࡿࡇ࡜࡛ᐇ㦂್࡜ྠᵝࡢయ✚- 74 -

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- 80 -

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- 81 -

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6SHFWUDO$QDO\VLVIURP7HUDKHUW]WR0LG,QIUDUHG5HJLRQRQ&RPSOH[6\VWHPV ᐩỌ ᆂ௓㸦⚄ᡞ኱ᏛศᏊࣇ࢛ࢺࢧ࢖࢚ࣥࢫ◊✲ࢭࣥࢱ࣮㸧 ◊✲┠ⓗࠊෆᐜࢸࣛ࣊ࣝࢶᖏ㸦㏻ᖖࠊ7+] ࠿ࡽ 7+] ࢆᣦࡍࠋ7+] FP㸧࠿ࡽ㉥እ㡿ᇦ㸦FPaFP㸧࡟࠾ࡅࡿ࿘ἼᩘᖏࡣࠊศᏊ⣔ࡢศᏊෆ࠾ࡼࡧศᏊ㛫᣺ື࣮ࣔࢻ࡟┦ᙜࡋࠊỈ⣲⤖ྜ⣔ᾮయࡸ⁐ᾮࠊࡲࡓࢱࣥ
ࣃࢡ㉁ࠊᑟ㟁ᛶ㧗ศᏊ➼ࡢ」㞧ศᏊ⣔࡟࠾ࡅࡿືⓗᣲືࡸᒁᡤᵓ㐀ࠊศᏊ㛫ࡢ┦஫స⏝➼ࢆ⌮ゎࡍࡿ࠺࠼࡛㔜せ࡞࿘Ἴᩘᖏ࡛࠶ࡿࠋᡃࠎࡢࢢ࣮ࣝࣉ࡛ࡣࠊ᫬㛫㡿ᇦࢸࣛ࣊ࣝศගࡸ᫬㛫ศゎࢸࣛ࣊ࣝࢶศගࠊࡲࡓ஧ḟඖ᣺ືศගࠊ࣓࢞࣊ࣝࢶ࠿ࡽ㐲㉥እ㡿ᇦ࡟ࢃࡓࡿᗈᖏᇦㄏ㟁ศග➼ࢆ⏝࠸࡚ࠊࡇࢀࡽࡢ」㞧ศᏊ⣔࡟㛵ࡍࡿศගᏛⓗ࡞◊✲ࢆ᥎㐍ࡋ࡚࠸ࡿࠋᮏ◊✲ㄢ㢟࡛ࡣࠊࡇࢀࡽࡢᐇ㦂⤖ᯝ࠿ࡽᐃ㔞ⓗ࡞᝟ሗࢆᚓࡿࡓࡵ࡟ࠊ኱ᆺ
ィ⟬ᶵࢆ⏝࠸ࡓ⢭ᐦィ⟬ࢆ⾜࠺ࠋලయⓗ࡟ࡣ௨ୗࡢ  ࡘࡢࢸ࣮࣐ࢆ⾜࠺ࠋ㸬 ஧ḟඖ᣺ືศගࢫ࣌ࢡࢺࣝࡢゎᯒ㸹Ỉ⁐ᾮ୰࡟࠾ࡅࡿ⁐㉁࢖࢜ࣥࡢ᣺ືᩘᦂࡽࡂ࡜ࡑࡢάᛶ໬࢚ࢿࣝࢠ࣮㸬 ศᏊᛶ⤖ᬗࡢࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࡢゎᯒ㸹࢔ࣛࢽࣥࡢࣛࢭ࣑యࠊ࠾ࡼࡧ࣌ࣟࣈࢫ࢝࢖ࢺᆺ໬ྜ
≀௨ୖ࡟ࡘ࠸࡚ࠊྛ㡯┠࡟ࡘ࠸࡚㏙࡭ࡿࠋ ◊✲᪉ἲࠊィ⟬᪉ἲ஧ḟඖ᣺ືศග㸸Ỉ⁐ᾮ୰࡟࠾ࡅࡿࣇࣝ࢜ࣞࣀࣥㄏᑟయࡢ &2 ఙ⦰᣺ືࡢ᣺ືᩘᦂࡽࡂࢆᐃ㔞ⓗ࡟ồࡵࡿࡓࡵࠊ9LEUDWLRQDO6WDUNVKLIW ἲ࡟ࡼࡿィ⟬ࢆ⾜࠺ࠋྂ඾ 0' ィ⟬࠿ࡽᚓࡓࢺࣛࢪ࢙ࢡࢺ࣮ࣜࢆ౑⏝ࡋࠊ㐺ษ࡞ࣃ࣓࣮ࣛࢱࢆồࡵࡿࡇ࡜࡛ࠊࢺࣛࢪ࢙ࢡࢺ࣮ࣜࡢྛ᫬้࡟࠾ࡅࡿ )/ ࡢ᣺ືᩘࢆィ⟬ࡍࡿࠋィ⟬ᡭἲࡢヲ⣽ࡣ
௨ୗࡢ㏻ࡾ࡛࠶ࡿࠋx )/ ࿘ࡾ࡟ỈศᏊࡀ a ಶ࠶ࡿ㓄⨨ࢆࠊ0' ࢺࣛࢪ࢙ࢡࢺ࣮ࣜ࠿ࡽィ  ✀ࢧࣥࣉࣜࣥࢢࡍࡿࠋx ୖグࡢࢧࣥࣉࣜࣥࢢ࡟࠾࠸࡚ࠊ&2 ᇶ࡜Ỉ⣲⤖ྜࡋ࡚࠸ࡿỈศᏊᩘࡢ๭ྜࡀࠊࢺࣛࢪ࢙ࢡࢺ࣮ࣜ඲య࡛

⪃࠼ࡓ࡜ࡁ࡜ྠࡌ๭ྜ࡟࡞ࡿࡼ࠺࡟ㄪᩚࡍࡿࠋ
x

 *DXVVLDQ ࢆ⏝࠸ࠊ%/<3*GS ࡛ࣞ࣋ࣝࢡࣛࢫࢱ࣮ࡢᵓ㐀᭱㐺໬ࠊᇶ‽᣺ືゎᯒࢆ⾜࠺ࠋ

9LEUDWLRQDO6WDUNVKLIW ἲࢆ⏝࠸ࠊᇶ‽᣺ືゎᯒ࠿ࡽᚓࡽࢀࡓ᣺ືᩘZ I ࡜ࠊ)/ ࡢ j ␒┠ࡢ┦஫స⏝Ⅼ࡟࠾ࡅࡿ⁐፹ศᏊ࡟ࡼࡿ㟁఩࣏ࢸࣥࢩࣕࣝIj ࢆ⤖ࡧ௜ࡅࡿ lj ࣃ࣓࣮ࣛࢱࢆ௨ୗࡢᘧ  ࡼࡾỴᐃࡍࡿࠋ'Z Z I  Z I



Nsolu

¦ l jI j
j 

Nsolu

ZLWK ¦ l j





j 

࡞࠾ࠊZ I  ࡣ )/ ༢య࡛ࠊ┿✵୰࡛ィ⟬ࢆ⾜ࡗࡓ᫬ࡢ⤖ᯝ࡛࠶ࡿࠋồࡵࡓ lj ࣃ࣓࣮ࣛࢱ࠿ࡽ 0' ࢺࣛࢪ࢙ࢡࢺ࣮ࣜࡢྛ᫬้࡟࠾ࡅࡿ᣺ືᩘࢆỴᐃࡋࠊ᣺ືᩘᦂࡽࡂࡢホ౯ࢆ⾜ࡗࡓࠋ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⪃៖ࡋࠊ%/<3' ࢆ⏝࠸ࡓࠋᇶᗏ㛵ᩘ࡜ࡋ࡚ * GI SG ࢆ⏝࠸ࡓࠋᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ᣺ືᩘィ⟬- 82 -

ࢆ⾜࠺ࠋ ◊✲ᡂᯝ
ᚓࡽࢀࡓࣃ࣓࣮ࣛࢱࢆ⏝࠸ࠊ᣺ືᩘᦂࡽࡂࡢ᫬㛫┦㛵㛵ᩘ㸦))7&)㸧ࢆồࡵࡓ⤖ᯝࢆᅗ  ࡟♧ࡍࠋ))7&) ࡣ஧ࡘࡢᣦᩘ㛵ᩘ࡛⾲⌧ࡍࡿࡇ࡜ࡀ࡛ࡁࠊ஧ࡘࡢ᫬ᐃᩘࠊ SV࡜ SV ࢆᚓࡓࠋᚋ⪅࡟ࡘ࠸࡚ࠊᐇ㦂࡛ࡣ࠾ࡼࡑ SV ࡢ್࡛࠶ࡾࠊ኱ࡁࡃ␗࡞ࡿࠋࡲࡓࠊ㐜࠸᫬㛫ᖏ࡟࠾࠸࡚ ))7&)
ࡣ᏶඲࡟  ࡬࡜ῶ⾶ࡋ࡚࠾ࡾࠊᐇ㦂࡛ほ ࡉࢀࡓ SV ௨ୖ࡜ぢ✚ࡶࡽࢀࡿ㠀ᖖ࡟㐜࠸ῶ⾶ࡣほࡉࢀ࡞࠿ࡗࡓࠋ௨ୖ

஧Ⅼࡢᕪ␗࡟ࡘ࠸࡚ࠊィ⟬࡟࠾࠸࡚ỈศᏊࡢศᴟ⋡ࢆ⪃៖ᅗ 㸬)/ ࡢ ))7&)㸦㉥㸧ࠋ஧ࡘࡢᣦᩘ㛵ᩘ࡟ࡋ࡚࠸࡞࠸ࡇ࡜ࡀせᅉࡢ୍ࡘ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋᮏ◊✲ࡼࡿࣇ࢕ࢵࢸ࢕ࣥࢢ㸦㟷㸧

࡛ࡣࠊ0' ィ⟬࡟ 7,33 ỈศᏊࣔࢹࣝࢆ⏝࠸ࡓࡓࡵࠊศᴟ
⋡ࡢᐤ୚ࡣ࡞࠸ࠋ᣺ືᩘᦂࡽࡂࡣࠊ᣺ື㒊఩㏆ഐࡢỈศᏊࡢ㐠ື࡟ᴟࡵ࡚ᩄឤ࡛࠶ࡾࠊࡑࡢỈศᏊࡢỈ⣲⤖ྜ⏕ᡂࠊ㛤⿣㐣⛬࡟ࡼࡿ㐠ືࡣศᴟ⋡ࢆ⪃៖ࡍࡿࡇ࡜࡟ࡼࡗ࡚⣙ ಸࠊ᫬㛫ࢫࢣ࣮ࣝࡀ㐜ࡃ࡞ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡑࡢࡓ
ࡵࠊ SV ࡜  SV ࡢ㐪࠸ࡀ⏕ࡌࡓ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ
SV ௨ୖࡢ㠀ᖖ࡟㐜࠸ῶ⾶ࡣࠊᴟࡵ࡚㐜࠸ỈศᏊࡢ୪㐍㐠ືࡀ཯ᫎࡉࢀ࡚࠸ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡑࡢ
㐠ືࢆ⪃៖ࡍࡿ࡟ࡣࠊỈศᏊ㛫ࡢ┦஫స⏝ࢆ⢭ᗘࡼࡃィ⟬ࡍࡿᚲせࡀ࠶ࡾࠊࢺࣛࢪ࢙ࢡࢺ࣮ࣜࡢྛ᫬้ࠊྛཎᏊ࡟࠾
ࡅࡿศᴟ⋡ࡢ᝟ሗࡣ㔜せ࡛࠶ࡿࠋࡼࡗ࡚ࠊᐇ㦂⤖ᯝࢆ෌⌧ࡍࡿࡇ࡜ࡣฟ᮶࡞࠿ࡗࡓࡶࡢࡢࠊ9LEUDWLRQDO 6WDUN VKLIW ἲ࡟ࡼࡗ࡚ồࡵࡽࢀࡓ᣺ືᩘᦂࡽࡂ࡟ࡣࠊ⁐፹ศᏊ࡛࠶ࡿỈศᏊࡢศᴟ⋡ࡀ㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋ
ḟ࡟ࠊ᣺ືࣉ࣮ࣟࣈ㒊఩ &2 ᇶ࡟Ỉ⣲⤖ྜࡋ࡚࠸ࡿỈศᏊᩘ࡜ࠊ)/ ࡢᇶ‽᣺ືᩘ࡜ࡢ㛵㐃ᛶ࡟ࡘ࠸࡚ᐃᛶⓗ࡞ホ౯ࢆᅗ 㸬 D ྛ᫬้࡟࠾࠸࡚ &2 ᇶ࡟Ỉ⣲⤖ྜ⾜࠺ࠋᅗ  D ࠊ E ࡟ࡑࢀࡒࢀࡢ⤖ᯝࢆ♧ࡍࠋࡲࡓࠊࢺࣛࢪ

㸦+%㸧ࡋ࡚࠸ࡿỈศᏊᩘࠋ E ྛ᫬้࡟࠾ࡅ

࢙ࢡࢺ࣮ࣜ඲య࡛⪃࠼ࡓ᣺ືᩘศᕸࢆࠊ1+% ࡢ㐪࠸࡛ศࡅࡓ

ࡿ )/ ࡢ &2 ఙ⦰᣺ືᩘ

⤖ᯝࢆᅗ  ࡟♧ࡍࠋᅗ  ࡼࡾࠊỈ⣲⤖ྜᮏᩘ㸦1+%㸧ࡀῶᑡࡍࡿ࡜᣺ືᩘࡀࣈ࣮ࣝࢩࣇࢺࡋࠊቑຍࡍࡿ࡜ࣞࢵࢻࢩࣇࢺ
ࡋ࡚࠸ࡿഴྥࡀぢ࡚ྲྀࢀࡿࠋ᣺ື㒊఩࡜ࡢศᏊ㛫Ỉ⣲⤖ྜ࡟ࡼࡿᇶ‽᣺ືᩘ࡬ࡢᙳ㡪ࡣ኱ࡁࡃࠊ≉࡟⤖ྜᮏᩘ࡟౫Ꮡ
ࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋᅗ  ࡟ࡘ࠸࡚ࠊ᣺ືᩘ'ZࡢṤ࡝ࡀ㈇ࡢ್ࢆ♧ࡋ࡚࠾ࡾࠊࡼࡾᑠࡉ࡞ศᏊ࡛ )/ ࡟ఝࡓ⣔ࠊ࢔ࢭࢺ࡛ࣥィ⟬ࡉࢀࡓࡶࡢ࡜ྠࡌഴྥ࡛࠶ࡿࠋࡋ࠿ࡋࠊlj ࣃ࣓࣮ࣛࢱࢆẚ㍑ࡍࡿ࡜ࠊ2 ཎᏊ࡛ࡢ್ࡢṇ㈇ࡀ␗࡞ࡿࠋ࢔ࢭࢺࣥᅗ 㸬࠶ࡿỈ⣲⤖ྜᮏᩘ 1+% ࡟࠾ࡅࡿ )/ ࡢ᣺ືᩘศᕸ

- 83 -

ࡣ㈇࡛࠶ࡿࡀࠊ)/ ࡣṇ࡛࠶ࡿࠋࡓࡔࡋࠊ)/ ࡣ㞄ࡢ  ␒┠ࡢ & ཎᏊࡢ್ࡀᴟ➃࡟㈇࡟࡞ࡗ࡚࠸ࡿࡓࡵࠊ&2 ఙ⦰᣺ື࡜࠸࠺ᣓࡾ࡛⪃࠼ࡿ࡜'Zࡣ㈇࡟࡞ࡿࠋ& ཎᏊࡢ್ࡀᴟ➃࡟ᙉㄪࡉࢀ࡚࠸ࡿࡇ࡜ࡣࠊ)/ ࡢ &2 ఙ⦰᣺ື࡟ࡣ &2 ᇶ࡟┤᥋Ỉ⣲⤖ྜࡋ࡚࠸ࡿỈศᏊࡔࡅ࡛࡞ࡃࠊ& ཎᏊ㏆ഐࡢỈศᏊࠊ༶ࡕⰾ㤶⎔ୖ࡟ᏑᅾࡍࡿỈศᏊࡢᙳ㡪ࡶࡲࡓ㔜せ࡛࠶ࡿࡇ࡜ࢆ♧၀ࡍࡿࠋࡋࡓࡀࡗ࡚ࠊᅗ  D ࠊ E ࡟࠾࠸࡚ࠊ'Z࡜ 1+% ࡢᑐᛂࡀ᏶඲࡟୍
⮴ࡏࡎࠊᅗ  ࡟♧ࡋࡓ 1+% ࡈ࡜ࡢ᣺ືᩘศᕸࡢ㔜࡞ࡾࡀ኱ࡁ࠸ࡇ࡜࡬ࡢ⌮⏤࡜ࡋ࡚ࠊ࢔ࢭࢺ࡛ࣥࡣᏑᅾࡋᚓ
࡞࠸ࠊⰾ㤶⎔ୖ࡛ᙅࡃ┦஫స⏝ࡍࡿከᩘࡢỈศᏊࡢᏑᅾࡀ㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋ
㸬'/࢔ࣛࢽࣥࡢࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝ
'࢔ࣛࢽࣥ࡜ /࢔ࣛࢽࣥࢆ➼㔞ΰྜࡉࡏࡓࣛࢭ࣑యࡢప᣺ືࢫ࣌ࢡࢺࣝࡣࠊ/࢔ࣛࢽࣥࡢࡑࢀ࡜ẚ㍑ࡍࡿ
࡜ࠊ⤖ᬗᵓ㐀ࡀఝ࡚࠸ࡿ࡟ࡶ㛵ࢃࡽࡎ኱ࡁࡃ␗࡞ࡿࡀ⚟஭኱㐲㉥እ㡿ᇦ㛤Ⓨ◊✲ࢭࣥࢱ࣮ࡢࢢ࣮ࣝࣉ࡟ࡼࡾ
ሗ࿌ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡑࡢ⌮⏤ࡣ୙࡛᫂࠶ࡗࡓࠋ௒ᅇࠊᅛయᐦᗘỗ㛵ᩘἲࢆ⏝࠸ࡓィ⟬ࢆ⾜࠺ࡇ࡜࡟ࡼ
ࡾࠊᇶ‽᣺ື࣮ࣔࢻࡸࡑࡢ㉥እάᛶᗘࢆィ⟬ࡋࠊ'/࢔ࣛࢽࣥ࡜ /࢔ࣛࢽࣥࡢࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࡢ㐪࠸ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ'/ ࢔ࣛࢽࣥ࠾ࡼࡧ / ࢔ࣛࢽࣥࡢࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࡢィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊ ᐃ⤖ᯝࢆࡼࡃ෌⌧ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊ୧⣔࡜ࡶࠊ࡯ࡰྠࡌἼᩘ࡟ᇶ‽᣺ືࢆᣢࡘࠋࡇࢀࡣ஧ࡘࡢ
⣔࡛⤖ᬗᵓ㐀ࡀ㢮ఝࡋ࡚࠸ࡿࡇ࡜࡟ࡼࡿ࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊ㉥እάᛶᗘࡣ஧ࡘࡢ⣔࡛␗࡞ࡾࠊ/ ࢔ࣛࢽ࡛ࣥࡣ  ੉ၱ ௜㏆ࡢ᭱పἼᩘࡢ࣮ࣔࢻࡣ㉥እ୙άᛶ࡛࠶ࡿࡀࠊ'/ ࢔ࣛࢽ࡛ࣥࡣ  ੉ၱ ௜㏆ࡢ࣮ࣔࢻࡣ㉥እάᛶ࡛࠶ࡿࠋ'/ ࢔ࣛࢽࣥࡢᑐ⛠ᛶࡣ Pna21 ࡛࠶ࡾ C2v ࡟ᒓࡍࡿࡀࠊ/ ࢔ࣛࢽࣥࡣ P212121 ࡛࠶ࡾ D2 ࡟ᒓࡍࡿࠋ
ࡑࡢࡓࡵࠊᇶ‽᣺ື࣮ࣔࢻࡢ㉥እάᛶࠊ㉥እ୙άᛶࡀ࠿ࢃࡿࠋࡑࡢࡓࡵ᣺ື࣮ࣔࢻࡢᙧࡀఝ࠿ࡼࡗ࡚࠸࡚ࡶ
㉥እࢫ࣌ࢡࢺࣝࡣ኱ࡁࡃ␗࡞ࡿࡇ࡜ࡀ࠶ࡿࠋ

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7UDQVODWLRQ/LEUDWLRQ ] /LEUDWLRQ [,QWUDPROHFXDOU9LEᅗ 㸬D '/ ࢔ࣛࢽࣥࠊ' ࢔ࣛࢽࣥࠊ/ ࢔ࣛࢽࣥࡢ 7+] ᖏࡢࢫ࣌ࢡࢺࣝ㸦IURP<DPDJXFKLHWDO App. Phys. Lett.
 㸧 E &5<67$/ ࡟ࡼࡾィ⟬ࡋࡓ '/ ࢔ࣛࢽࣥ࡜ / ࢔ࣛࢽࣥࡢ 7+] ࢫ࣌ࢡࢺࣝࠋ F  E ୰࡟♧ࡍ୕ࡘࡢ᣺ືࣂࣥࢻࢆ୪㐍ࠊࣛ࢖ࣈ࣮ࣞࢩࣙࣥ㸦;<=㸧ࠊศᏊෆ᣺ືࡢ୕ࡘࡢᐤ୚࡟ศゎࡋࠊࡑࢀࡒࢀࡢ
ᐤ୚ࡢ㉥እάᛶᗘࢆィ⟬ࡋࡓᅗࠋ
㸬↓ᶵ᭷ᶵ࣌ࣟࣈࢫ࢝࢖ࢺ໬ྜ≀㸦0$3E%U0$ ࣓ࢳࣝ࢔ࣥࣔࢽ࣒࢘㸧ࡢప᣺ືࢫ࣌ࢡࢺࣝ㸹㧗ຠ⋡࡞ኴ㝧㟁ụࡢᮦᩱ࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿ࣌ࣟࣈࢫ࢝࢖ࢺ໬ྜ≀࡟ࡘ࠸࡚ࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࡢィ⟬ࢆ⾜ࡗࡓࠋ࠸ࡃࡘ࠿ࡢ◊✲ࢢ࣮ࣝࣉ࠿ࡽ 0$3E%U ࡢࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࡣሗ࿌ࡉࢀ࡚࠸ࡿࡀࠊࡑࢀࡽࡣ
஫࠸࡟␗࡞ࡗ࡚࠸ࡿࠋᡃࠎࡣ

ᐃ๓ᚋࡸᐃ⏝ヨᩱ࣌ࣞࢵࢺసᡂ๓ᚋ࡛ ; ⥺ᅇᢡࢆᐃࡍࡿ࡞࡝ࠊៅ㔜࡟

0$3E%U ࡢࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝࢆ ᐃࢆ⾜ࡗࡓࠋ↓ᶵ᭷ᶵ࣌ࣟࣈࢫ࢝࢖ࢺ໬ྜ≀ࡢࢸࣛ࣊ࣝࢶࢫ࣌ࢡࢺࣝ
ࢆィ⟬ࡋࡓ࡜ࡇࢁࠊ ᐃ⤖ᯝࢆ‶㊊࡟ㄝ᫂ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋ≉࡟ࠊ ੉ၱ ࠿ࡽ  ੉ၱ ࡟࠿ࡅ࡚ࠊ
ᐃ⤖ᯝ࡛ࡣࣈ࣮ࣟࢻ࡞ࣂࣥࢻࡀほࡉࢀࡿࡀࠊィ⟬⤖ᯝࡣࢩ࣮ࣕࣉ࡞ᵓ㐀ࢆ୚࠼ࡓࠋ⤖ᬗ୰࡛࣓ࢳࣝ࢔ࣥࣔ

ࢽ࣒࢘ࡣ⮬⏤࡟ᅇ㌿࡛ࡁࡿࡇ࡜࡟╔┠ࡋࠊ༢఩᱁Ꮚ୰ࡢ  ࡘࡢ࣓ࢳࣝ࢔ࣥࣔࢽ࣒࢘ࡢྥࡁࢆ  ㏻ࡾྲྀࢀࡿ࡜

- 84 -

ࡍࡿ↓⛛ᗎᛶࢆᑟධࡋࡓࠋ඲㒊࡛  ㏻ࡾࡢ␗࡞ࡿ⤖ᬗᵓ㐀ࡀᚓࡽࢀࡿࠋࡇࡢ  ࡢࢫ࣌ࢡࢺࣝࢆ඲㒊㊊ࡋྜ
ࢃࡏࡓ࡜ࡇࢁࠊᐇ㦂⤖ᯝࢆࡼࡃ෌⌧ࡋࡓࠋࢸࣛ࣊ࣝࢶศගࡣ↓⛛ᗎᛶࡢㄪ࡭ࡿ࠺ࡇ࡜ࡀ࡛ࡁࡿࡇ࡜ࢆ♧ࡋࡓࠋ
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ᅗ 㸬ᕥ㸸↓ᶵ᭷ᶵ࣌ࣟࣈࢫ࢝࢖ࢺ໬ྜ≀㸦0$3E%U㸧ࡢᵓ㐀ࠋ୰㸸༢఩᱁Ꮚ୰࡟࣓ࢳࣝ࢔ࣥࣔࢽ࣒࢘ࡣ ࡘ࠶ࡾࠊࡑࡢ཮ᴟᏊ࣮࣓ࣔࣥࢺࡣ஧㏻ࡾࡢྥࡁࡀ࠶ࡿࠋࡍ࡞ࢃࡕࠊ༢఩᱁Ꮚ࡛඲㒊࡛␗࡞ࡿ࣓ࢳࣝ࢔ࣥࣔࢽ
࣒࢘ࡢྥࡁࡀ  ㏻ࡾ࠶ࡿࠋྑୖ㸸 ᐃ࠿ࡽồࡵࡓ 0$3E%U ࡢ 7+] ᖏࡢࢫ࣌ࢡࢺࣝࠋྑୗ㸸 ㏻ࡾࡢࢫ࣌ࢡ
ࢺࣝࢆィ⟬ࡋࠊࡑࢀࢆ඲࡚㊊ࡋྜࢃࡏࡓࡶࡢࠋ
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6HSWHPEHU    ‫ۻ‬³$ *HQHUDO 5XOH RI 7+] 0RGH $VVLJQPHQW IRU 0ROHFXODU &U\VWDOV´ )=KDQJ +RQJ:HL :DQJ .HLVXNH
7RPLQDJD0LFKLWRVKL+D\DVKL7HWVXR6DVDNL63,(3KRWRQLFV$VLD+DQJ]KRX2FWREHU    ‫ۻ‬³7+] 6SHFWURVFRS\ LQ 0ROHFXODU &U\VWDOOLQH 6\VWHPV´ )=KDQJ .HLVXNH 7RPLQDJD 0LFKLWRVKL +D\DVKL7HWVXR6DVDNL7KH)RXUWK<RXQJ6FKRODUV)RUXPDW)X]KRX8QLYHUVLW\)X]KRX'HFHPEHU    ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
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:DQJ.HLVXNH7RPLQDJD0LFKLWRVKL+D\DVKL7HWVXR6DVDNLJ. Phys. Chem. A      ‫ۻ‬³+LJKUHVROXWLRQ 7+] 6SHFWURVFRS\ DQG 6ROLGVWDWH 'HQVLW\ )XQFWLRQDO 7KHRU\ &DOFXODWLRQV RI 3RO\F\FOLF
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Infrared Milli Terahz Waves, Special Issue on the Interpretation of Terahertz Spectra LQ SUHVV '2,V)LUVW2QOLQH6HSWHPEHU
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ࢼࣀࣂ࢖࢜≀㉁ࡢ㟁Ꮚ≧ែ࣭ᵓ㐀࣭ᶵ⬟ࡢ┦㛵
Correlation among electron states, structures and functions of
nano-bio materials‫ۑ‬ᢲᒣ ῟ࠊࣈ࢖ ࢩ࢚࢟࢘ ࣑ࠊไ㔝࠿࠾ࡾࠊ஭ᮏ ᩥ⿱ࠊ㛗ᕝ೺ኴࠊཎᔱᗤ௓
㸦ྡྂᒇ኱Ꮫᮍ᮶ᮦᩱ࣭ࢩࢫࢸ࣒◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
ࢼࣀࢫࢣ࣮ࣝ⾲㠃࣭⏺㠃ࡣ≀㉁ࡀᙧᡂࡉࢀࡿ⯙ྎ࡛࠶ࡿࠋẼ┦࡜ᅛయ┦࡜ࡢ⏺㠃࡛ࡢ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ࠊ࢔ࣔࣝࣇ࢓ࢫ┦࡜ᅛయ┦࡛ࡢࢹࣂ࢖ࢫ⏺㠃ᙧᡂ࡞࡝ࠊ⏺㠃ᡂ㛗⌧㇟ࡢ㔜せᛶࡣᇶ♏⛉Ꮫࡢ⠊␪࡟࡜࡝ࡲࡽࡎࠊ
ᗈ⠊࡞ᛂ⏝ศ㔝࡛ࡢ㔜せᛶࢆ᭷ࡋ࡚࠸ࡿࠋᮏㄢ㢟࡛ࡣࠊᡃࠎࡀ㛤Ⓨࡋࡓࠊ୪ิ࢔࣮࢟ࢸࢡࢳࣕୖ࡛ࡢ኱つᶍ㧗㏿࣭㧗⢭ᗘィ⟬ࢆྍ⬟࡟ࡍࡿᐇ✵㛫ᐦᗘỗ㛵ᩘἲ㸦RSDFT㸧ࢥ࣮ࢻࠊᐇ✵㛫 Car-Parrinello ศᏊືຊᏛ
㸦RS-CPMD㸧ࢥ࣮ࢻࢆ㍈࡟ࡍ࠼ࠊࡲࡓ㏆ᖺⓎᒎⴭࡋ࠸῝ᒙᏛ⩦࡟ࡼࡿࠊ࣮࢜ࢲ࣮㸦N㸧orbital-free DFT ࡢ㛤Ⓨࠊ㔞Ꮚㄽᑐᛂࡢྂ඾ຊሙ⏕ᡂ࡞࡝ࢆ᪉ἲㄽⓗࢱ࣮ࢤࢵࢺ࡜ࡋࠊࡑࢀ࡟ࡼࡾࠊࢼࣀ࣓࣮ࢺࣝࢫࢣ࣮ࣝ⌧㇟࡛࠶ࡿ⾲㠃⏺㠃ᡂ㛗ࡢᶵᵓゎ᫂ࢆ┠ᣦࡍࡶࡢ࡛࠶ࡿࠋලయⓗ࡞≀㉁⛉Ꮫࡢࢱ࣮ࢤࢵࢺ࡜ࡋ࡚ࡣࠊࣃ࣮࢚࣡ࣞࢡ
ࢺࣟࢽࢡࢫࡢᇶᖿᮦᩱ࡜ࡋ࡚ὀ┠ࢆ㞟ࡵ࡚࠸ࡿⅣ໬ࢣ࢖⣲(SiC)ࠊ❅໬࣒࢞ࣜ࢘(GaN)ࠊ࠾ࡼࡧࡑࡢࢤ࣮ࢺ⤯⦕⭷(SiO2ࠊAl2O3ࠊ࠾ࡼࡧࡑࢀࡽࡢΰᬗ)࡟ࣇ࢛࣮࢝ࢫࡋࠊ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗⾲㠃ࡢᵓ㐀ゎ᫂ࠊᡂ㛗ࡢ⣲㐣⛬ゎ᫂ࠊ࢔ࣔࣝࣇ࢓ࢫ࣭ࢤ࣮ࢺ⤯⦕⭷ࡢ≀ᛶゎ᫂ࠊ༙ᑟయ୰㌿఩ࡢ㟁Ꮚⓗ≉ᛶゎ᫂ࠊࢆ⾜࠺ࠋ2◊✲᪉ἲࠊィ⟬᪉ἲᮏᖺᗘࡢ◊✲ᡂᯝࡢ୺࡞ࡿࡶࡢࡣࠊᐦᗘỗ㛵ᩘ⌮ㄽ㸦DFT: Density Functional Theory㸧࡟ᇶ࡙ࡃ Kohn-Sham᪉⛬ᘧࢆᐇ✵㛫ࡢ࣓ࢵࢩࣗୖ࡛ゎࡃᐇ✵㛫ᐦᗘỗ㛵ᩘἲ㸦ࢥ࣮ࢻྡ㸻RSDFTࠊReal-Space Density-Functional
Theory㸧࠾ࡼࡧࣛࢢࣛࣥࢪ࢙ᙧᘧࡢ᫬㛫౫Ꮡ᪉⛬ᘧࢆゎࡃᐇ✵㛫 Car-Parrinello ศᏊືຊᏛἲ㸦ࢥ࣮ࢻྡ㸻
RS-CPMDࠊReal-Space Car-Parrinello Molecular Dynamics㸧࡟ࡼࡗ࡚ᚓࡽࢀ࡚࠸ࡿࠋࡇࢀࡽࡢࢥ࣮ࢻࡣ⊂⮬㛤Ⓨࡢࡶࡢ࡛࠶ࡾࠊ࣏ࢫࢺࠕிࠖࢥࣥࣆ࣮ࣗࢱࣉࣟࢪ࢙ࢡࢺࡢࢥࢹࢨ࢖࣭࣮ࣥ࣡࢟ࣥࢢࢢ࣮ࣝࣉࡢࢱ࣮ࢤࢵࢺ࢔
ࣉ࡛ࣜࡶ࠶ࡿࠋ࠸ࡎࢀࡢࢥ࣮ࢻ࡛ࡶࠊཎᏊ᰾࡜Ẇ㟁Ꮚࡣ➨୍ཎ⌮ⓗ࡟ᵓᡂࡉࢀࡿᨃ࣏ࢸࣥࢩ࡛ࣕࣝࢩ࣑ࣗࣞ
࣮ࢺࡉࢀࠊ౯㟁Ꮚྠኈࡢ┦஫స⏝ࡣᐦᗘỗ㛵ᩘ⌮ㄽࡢࠊᒁᡤᐦᗘ㏆ఝ㸦LDA㸧ࠊᒁᡤࢫࣆࣥᐦᗘ㏆ఝ㸦LSDA㸧ࠊ୍⯡໬㸦ࢫࣆࣥ㸧ᐦᗘ໙㓄㏆ఝ㸦GGA㸧ࠊࡉࡽ࡟ࡣࣁ࢖ࣈࣜࢵࢻ㏆ఝ࡛グ㏙ࡉࢀ࡚࠸ࡿࠋ
ࡲࡓࠊ௒ᖺᗘ࡟ࡣࠊ῝ᒙᏛ⩦࡟ࡼࡿ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘ(KEDF)ࡢ㛤Ⓨࠊࡑࢀ࡟⥆ࡃ orbital-free ࡢ DFTィ⟬(OFDFT)ࢫ࣮࣒࢟ࢆ㛤Ⓨࡋࡓࡀࠊࡑࡢࢥ࣮ࢻࡢࢥ࢔࡜࡞ࡿ㒊ศࡣ RSDFT ࢥ࣮ࢻࢆά⏝ࡋ࡚࠸ࡿࠋ㛤Ⓨࡋࡓ OFDFT ࢫ࣮࣒࢟ࡢ㦵Ꮚࡣࠊձ ከ㔜ࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ࡟ࡼࡿ KEDF ࡢ᪂ࡓ࡞㛤Ⓨࠊղorbital-free ࡟ᑐᛂࡍࡿ➨୍ཎ⌮ᒁᡤ(local)ᨃ࣏ࢸࣥࢩࣕࣝࡢ㛤Ⓨࠊճ KEDF ࡢỗ㛵ᩘᚤศࢆྵࡴ Euler ᪉⛬ᘧࡢゎἲࠊࡢ 3
Ⅼ࠿ࡽᡂࡗ࡚࠸ࡿࠋヲ⣽ࡣูࡢᶵ఍࡟ㆡࡿࡀࠊࢲ࢖ࣖࣔࣥࢻࡢ KEDF ỗ㛵ᩘᚤศࢆᐇ✵㛫࣓ࢵࢩࣗⅬ࡛Ꮫࡤࡏࡿࡇ࡜࡟ࡼࡾࠊ㧗ᛶ⬟ KEDF ࡀ㛤Ⓨࡉࢀ࡚࠾ࡾࠊ༙ᑟయ Siࠊ༙ᑟయ SiCࠊfcc-Alࠊbcc-Li ࡜࠸࠺ᗈ⠊࡞≀㉁⩌࡛ࡢ᭷ຠᛶࡀ☜࠿ࡵࡽࢀࡓࠋࡲࡓࠊ࣮࢜ࢲ࣮(N)ࡢィ⟬᫬㛫ࡶᐇドࡉࢀ࡚࠸ࡿࠋ௒ᚋࠊ๓౛ࢆࡳ࡞࠸จ⦰⣔኱つᶍ DFT ィ⟬ࡀᮇᚅࡉࢀࡿࠋ

- 86 -

3◊✲ᡂᯝ
SiC ⾲㠃ࢫࢸࢵࣉࡢཎᏊᵓ㐀࡜࢚ࢼ࣮ࢪ࢙ࢸ࢕ࢡࢫ [ฟ∧ࣜࢫࢺ 1,2,5]
༙ᑟయ࢚ࣆࢱ࢟ࢩࣕࣝⷧ⭷ᡂ㛗ࡣࠊࢹࣂ࢖ࢫ〇㐀ࡢ᰿ᖿᢏ⾡࡛࠶ࡿࠋࡑࡢⷧ⭷ᡂ㛗ࡣ⾲㠃ࡢཎᏊᒙࢫࢸ
ࢵࣉ࡛ࡢ໬Ꮫ཯ᛂࡀ⣲㐣⛬࡛࠶ࡿࡀ㸦ࢫࢸࢵࣉࣇ࣮ࣟᡂ㛗㸧ࡑࡢヲ⣽ࡣ඲ࡃࢃ࠿ࡗ࡚࠸࡞࠸ࠋ⣲㐣⛬ゎ᫂ࡢࡓࡵ࡟ࡣ⯙ྎ࡜࡞ࡿࢫࢸࢵࣉᵓ㐀ࡢྠᐃࡀᚲせ࡛࠶ࡿࡀࠊࡇࢀࡶᐇ㦂ⓗ࡟ࡣ⾜ࢃࢀ࡚࠾ࡽࡎࠊィ⟬⛉Ꮫࡢฟ␒࡛࠶ࡿࠋᡃࠎࡣ SiC(0001)㠃㸦㏻ᖖࢹࣂ࢖ࢫ〇㐀࡟౑ࢃࢀࡿ㠃㸧࡛ࡢࠊ༢ཎᏊᒙࢫࢸࢵࣉࡢ⤖ᬗᏛⓗ࡟ྍ⬟࡞ࡍ࡭࡚ࡢࢫࢸࢵࣉࡢᵓ㐀࡜ࡑࡢ⏕ᡂ࢚ࢿࣝࢠ࣮ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ    
ᅗ 1: SiC(0001)㠃࡛ࡢྛ✀ࢫࢸࢵࣉࡢ⏕ᡂ࢚ࢿࣝࢠ࣮ࠋ㠃ࡢഴࡁ᪉ྥ࡟ࡼࡾࠊSi ࡜ C ୧⪅ࡀࢫࢸࢵࣉ➃࡟⌧ࢀࡿ SC ࢫࢸࢵࣉࠊSi ࠶ࡿ࠸ࡣ C ࡔࡅࡀ⌧ࢀࡿ Si2, Si3, C1, C2 ࢫࢸࢵࣉ࡞࡝ࡀྍ⬟ࠋᅗ㸰㸸ᅗ 1 ࡛ᚓࡽࢀࡓ࢚ࢼ࣮ࢪ࢙ࢸ࢕ࢡࢫ࡟ࡼࡾୖᅗࡢ
ࡼ࠺࡞ࢪࢢࢨࢢᙧ≧ࡢࢫࢸࢵࣉࡀᏳᐃ࡛࠶ࡿࡇ࡜ࡀィ⟬ุ࡛᫂ࡋࠊࡇࢀࡣᐇ㦂ࢆぢ஦࡟ㄝ᫂ࡍࡿࠋ

GaN ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗⾲㠃࡛ࡢ Ga ᭱⾲㠃ᒙࡢᾮయ໬ࡢⓎぢ [ฟ∧ࣜࢫࢺ 3]
GaN ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗࡛ࡣࠊGa-rich ࡞ᡂ㛗⾲㠃࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡑࡢᡂ㛗⾲㠃࡛ࡢཎᏊࢫ
ࢣ࣮࡛ࣝࡢືⓗ᣺ࡿ⯙࠸ࢆㄪ࡭ࡿࡓࡵࠊCar-Pariinello Molecular Dynamics ィ⟬ࢆ⾜ࡗࡓࠋᡂ㛗
1300K ࡛࠶ࡿࡀࠊࡑࡢ

ᗘࡲ࡛⣔ࢆ

ᗘࡣ⣙

ࡵࡿ࡜ࠊ㦫ࡃ࡭ࡁࡇ࡜࡟ࠊ᭱ୖᒙࡢ Ga ཎᏊࡣᾮయ໬ࡍࡿࡇ࡜ࡀࢃ࠿

ࡗࡓࠋᅗ 3 ࡣ᭱ୖᒙ Ga ࡢືᚄศᕸ㛵ᩘ࡛࠶ࡿࡀࠊᡂ㛗ᗘ࡛ࠊ✺ዴ Ga ཎᏊࡣจ㞟ࢆጞࡵ࡚࠸ࡿࠋࡑࡢจ

㞟ᙧែࡣࠊືᚄศᕸ㛵ᩘࡢᙧែ࠿ࡽࠊᅛయ࠶ࡿ࠸ࡣࢡࣛࢫࢱ࣮࡛࡞࠸ࡇ࡜ࡣ♧၀ࡉࢀࡿࡀࠊᅗ 4 ࡟♧ࡍᣑᩓಀᩘࡣࠊࡑࢀࡀ㸰ḟඖᾮయ࡛࠶ࡿࡇ࡜ࢆᙉࡃ♧ࡋ࡚࠸ࡿࠋ࢚ࣆࢱ࢟ࢩࣕࣝᡂ㛗ࡣࠊᅛయ⾲㠃ୖࡢ໬Ꮫ཯
ᛂ࡛ࡣ࡞ࡃࠊ㸰ḟඖᾮయ໬࡟ࡼࡿ཯ᛂ࡛࠶ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ

GaN-MOSFET ࡢ(Al2O3)1-x(SiO2)x ࢔ࣔࣝࣇ࢓ࢫ⤯⦕⭷࡛ࡢ㓟⣲✵Ꮝ࡜ࢹࣂ࢖ࢫ≉ᛶゎ᫂ [ฟ∧ࣜࢫࢺ 7]
GaN ࡣග࢚ࣞࢡࢺࣟࢽࢡࢫ࡟࠾ࡅࡿᇶᖿᮦᩱ࡛࠶ࡿࡀࠊࡑࡢࣂࣥࢻࢠࣕࢵࣉࡢᗈࡉࠊᴟ㝈⎔ቃ࡛ࡢሀ∼ࡉࡺ࠼࡟ࠊࣃ࣮࢚࣡ࣞࢡࢺࣟࢽࢡࢫࡢ㔜せᮦᩱ࡜ࡋ࡚ᮇᚅࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࡑࡢࢹࣂ࢖ࢫᛂ⏝࡛ࡢၥ㢟
ⅬࡣⰋዲ࡞ࢤ࣮ࢺ⤯⦕⭷ࡢḞዴ࡛࠶ࡿࠋ㏆ᖺࠊ㇏⏣୰ኸ◊✲ᡤ࡟ࡼࡾ(Al2O3)1-x(SiO2)x ΰᬗ࢔ࣔࣝࣇ࢓ࢫ⤯⦕యࡀⰋዲ࡞ࢹࣂ࢖ࢫ≉ᛶࢆ♧ࡍࡇ࡜ࡀሗ࿌ࡉࢀࡓࠋ௒ᅇࠊࢹࣂ࢖ࢫ≉ᛶࢆỴᐃ࡙ࡅࡿ㓟⣲ཎᏊ✵ᏍࡢཎᏊᵓ㐀ࠊ⏕ᡂ࢚ࢿࣝࢠ࣮ࠊ㟁Ꮚ‽఩ࢆィ⟬ࡋࠊࡇࡢΰᬗ࢔ࣔࣝࣇ࢓ࢫ࡛ࡢ㓟⣲✵Ꮝ࡟ࡣᵝࠎ࡞ࡶࡢࡀ࠶ࡾ
ᚓࡿࡀࠊ⏕ᡂ࢚ࢿࣝࢠ࣮ࡢప࠸㸦ࡘࡲࡾ abundant ࡞㸧㓟⣲✵Ꮝࡣ GaN ࢠࣕࢵࣉ୰࡟࣮࢟ࣕࣜࣖࢺࣛࢵࣉࢆ
ᘬࡁ㉳ࡇࡉ࡞࠸ࡇ࡜ࡀุ᫂ࡋࡓࠋAlSiO ⤯⦕⭷ࡀࠊ௒ᚋࡢࣃ࣮࢚࣡ࣞࢡࢺࣟࢽࢡࢫ࡟࠾ࡅࡿ㔜せ࡞఩⨨ࢆ- 87 -

༨ࡵࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ  ᅗ 3: GaN(0001)㠃࡛ࡢ᭱ୖᒙ Ga ཎᏊࡢ࣌࢔ศᕸ㛵ᩘࠋ   ᅗ 4: GaN(0001)㠃࡛ࡢ᭱ୖᒙ Ga ཎᏊࡢᣑᩓಀᩘࠋ
1100K ௨ୗ࡛ࡣప ᒙ࡛ࡢᏳᐃ㓄⨨ࡢ࿘ᅖࡢ⇕㐠ືࡀ㢧ⴭ࡛࠶ࡿࡀࠊ࢚ࣆᡂ㛗 ᗘ࡛ࡣࠊGa
ཎᏊࡣ✺ዴᣑᩓࡋࠊจ㞟ࡍࡿࠋMD ࢹ࣮ࢱ࠿ࡽஂಖබᘧ࡟ࡼࡾ⟬ฟࡉࢀࡓࠋᡂ㛗ᗘ࡛ᣑᩓಀᩘࡣࢪࣕࣥࣉࡋࠊ஧ḟඖᾮయ໬ࢆ♧၀ࡋ࡚࠸ࡿࠋ

GaN ࡢ㌿఩ᵓ㐀࡜࢔ࢡࢭࣉࢱ࣮୙⣧≀ࡢ┦஫స⏝ [ฟ∧ࣜࢫࢺ 8]
SiCࠊGaN ࡞࡝ࡢ᪂ᮦᩱࡀ⌧ᅾࡢ Si ࢸࢡࣀࣟࢪ࣮ࢆ⨨ࡁ᥮࠼ࡿ࡟⮳ࡗ࡚࠸࡞࠸᰿ᮏⓗ࡞⌮⏤ࡣࠊࡑࡇ࡛
ࡢḞ㝗ไᚚ࡛࠶ࡿࠋ࡜ࡃ࡟⤖ᬗ୰⥺Ḟ㝗ࡢ௦⾲࡛࠶ࡿ㌿఩࡟ࡘ࠸࡚ࡣࠊSi ⤖ᬗ࡛ࡣ↓㌿఩⤖ᬗࡀసᡂࡉࢀ
࡚ஂࡋ࠸ࡀࠊ໬ྜ≀ࢹࣂ࢖ࢫ࡛ࡣ࠸ࡲࡔ࡟ࡑࡢไᚚࡣ኱ࡁ࡞ၥ㢟࡛࠶ࡿࠋ௒ᅇᡃࠎࡣࠊࡑࡢ኱つᶍᛶࡢࡺ࠼࡟ࠊ࠸ࡲࡔ⾜ࢃࢀ࡚࠸࡞࠸㌿఩ࡢ➨୍ཎ⌮ィ⟬ࢆ GaN ࡟ᑐࡋ࡚ᐇ⾜ࡋࡓࠋࡑࡢືᶵࡣࠊྡྂᒇ኱Ꮫኳ㔝ࢢ࣮ࣝࣉ࡟࠾ࡅࡿࠊGaN pn ᥋ྜ࡟࠾ࡅࡿ₃ࢀ㟁ὶࡀ㌿఩ࡢ⟠ᡤ࡛㉳ࡁ࡚࠸ࡿ࡜࠸࠺ሗ࿌࡛࠶ࡿࠋୡ⏺࡛ึࡵ࡚ࡢ㌿఩ࡢᵓ㐀ࡢྠᐃࢆ⾜࠸ࠊࡉࡽ࡟ p-ᆺࢆᙧᡂࡋ࡚࠸ࡿ Mg ୙⣧≀࡜ࡢ┦஫స⏝ࢆ᫂ࡽ࠿࡟ࡋࠊMg
ࡀ㌿఩࡟ࢺࣛࢵࣉࡉࢀࠊࡑࢀ࡟ࡼࡾ࢔ࢡࢭࣉࢱ࣮‽఩ࡀᾘ⁛ࡋࠊ㏫࡟ࢻࢼ࣮‽఩ࡀฟ⌧ࡍࡿࡇ࡜ࡀぢ࠸ࡔࡉࢀࡓࠋࡇࢀ࡟ࡼࡾࠊpn ᥋ྜࡀᔂቯࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

ᅜ㝿Ꮫ఍ㅮ₇
1.

K. Seino and A. Oshiyama, “Microscopic identification of surface steps of SiC by the density-functional
calculations” International Conference on Silicon Carbide and Related Materials 2019㸦September, Kyoto㸧

2.

K. M. Bui, M. Boero, K. Shiraishi and A. Oshiyama, “Gallium Diffusion and Ammonia Decomposition on
Growing GaN Surface: First Principles Molecular Dynamics Simulations” International Conference on Solid State
Devices and Materials 2019 (Nagoya, September)

3.

T. Nakano, K. Chokawa, Y. Harashima, M. Araidai, K. Shiraishi, A. Oshiyama, A. Kusaba, Y. Kangawa, A. Tanaka,
Y. Honda, H. Amano, “Microscopic Reason for the Leakage Current due to the Mg-Attached Dislocation in GaN”
International Conference on Solid State Devices and Materials 2019 (Nagoya, September)

4.

F. Shintaku, Y. Kangawa, J. I. Iwata, A. Oshiyama, K. Shiraish, A. Tanaka, H. Amano, “Theoretical approach tooxygen incorporation mechanism in vicinal m-GaN MOVPE” International Conference on Solid State Devices
and Materials 2019 (Nagoya, September)- 88 -

5.

Y. Harashima1, T. Nakano, A. Oshiyama, K. Shiraishi, “Modeling of the Leakage Current in GaN mediatedthrough the Dislocation-Impurity Complex” International Conference on Solid State Devices and Materials 2019
(Nagoya, September)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

Ⓨ⾲ㄽᩥ
‫ۻ‬

1.

K. Seino and A. Oshiyama, ``Energetics of the surface step and its morphology on the 3C-SiC(111) surface
clarified by the density-functional theory" Appl. Phys. Exp. 13, 015506 (2020).

‫ۻ‬

2.

K. Seino and A. Oshiyama, ``Microscopic Identification of Surface Steps on SiC by Density-Functional
Calculations" Proc. Int. Conf. SiC Related Materials (ICSCRM2019) (September 2019, Kyoto).

‫ۻ‬

3.

K. M. Bui, M. Boero, K. Shiraishi and A. Oshiyama, ``A two-dimensional liquid-like phase on Ga-rich GaN(0001) surfaces evidenced by first principles molecular dynamics" Jpn. J. Appl. Phys. 59, SGGK04 (2020).

4.

F. Shintaku, D. Yosho, Y. Kangawa, J.-I. Iwata, A. Oshiyama, K. Shiraishi, A. Tanaka aand H. Amano,``Computational study of oxygen stability in vicinal m(10-10)-GaN growth by MOVPE" Appl. Phys. Exp. 13,055507 (2020)

‫ۻ‬

5.

K. Seino and A. Oshiyama, ``Density-Functional Calculations for Structures and Energetics of Atomic Steps andtheir Implication for Surface Morphology on Si-face SiC Polar Surfaces" Phys. Rev B 101, 195307 (2020).

6.

D. Yosho, F. Shintaku, Y. Inatomi, Y. Kangawa, J.-I. Iwata, A. Oshiyama, K. SHiraishi, A. Tanaka and H. Amano,``Oxygen incorporation kinetics in vicinal m(10-10)-GaN growth by MOVPE" Phys. Sta. Solidi - Rapid Res. Lett.
2000142 (2020).

‫ۻ‬

7.

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

8.

T. Nakano, Y. Harashima, K. Chokawa, K. Shiraishi, A. Oshiyama et al., ``Screw dislocation that converts p-type
GaN to n-type: Microscopic study on the Mg condensation and the leakage current in p-n diodes" submitted toAppl. Phys. Lett.

- 89 -

ࣁࣟ㓟⬺ࣁࣟࢤࣥ໬㓝⣲࡜ࢩࢫࢸ࢖ࣥྜᡂ㓝⣲ࡢ཯ᛂᶵᵓゎᯒ࡜ࡑࢀ࡟ᇶ࡙࠸ࡓ㧗ᶵ⬟㓝⣲ࡢࢹࢨ࢖ࣥ
Analysis of reaction mechanism of haloacid dehalogenase
and cysteine synthase and the design for highly functional enzymes
based on their mechanisms‫ ۑ‬୰ᮧ ༟ࠊᑠ⃝ ᣅᐇ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⣽⳦⏤᮶ࡢ⪏⇕ᛶࢩࢫࢸ࢖ࣥྜ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 ࡜࠸ࡗࡓᐦᗘỗ㛵ᩘἲ㸦DFT㸧࡟ࡼࡾィ⟬ࡋࠊᐇ㦂⤖ᯝ࡜ᑐᛂࡍࡿ཯ᛂ⤒㊰ࢆỴᐃࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋOPSS ࡟㛵ࡋ࡚ࡣࠊL-DEX ࡢィ⟬ࢆ㔜Ⅼⓗ࡟⾜ࡗ࡚ィ⟬ࡍࡿ᫬㛫ࡀ࡞࠿ࡗࡓࡓࡵࠊL-DEX ࡢィ⟬⤖ᯝ࡟ࡘ࠸࡚௨ୗ࡟ሗ࿌ࡍࡿࠋ㸰 ◊✲᪉ἲࠊィ⟬᪉ἲ
L-DEX ࡜ L-2-CPA ࡜ࡢ」ྜయࡢ QM/ศᏊຊᏛ㸦MM㸧ィ⟬࡟ࡘ࠸࡚ࠊ᫖ᖺᗘࡣࡇࢀࡲ࡛ࡢᐇ㦂ࡸィ⟬⤖ᯝ࡛άᛶ࡟㔜せࡔ࡜᥎ᐃࡉࢀ࡚࠸ࡿṧᇶࡢ୰࠿ࡽࠊAsp10, Arg41, Lys151, Asp180 ࡢഃ㙐㒊ศࡢྜィ 59 ཎᏊࡢ⣔ࠊ59 ཎᏊࡢ⣔࡟ Thr14, Asn177 ࡢഃ㙐㒊ศࢆ㏣ຍࡋࡓ 75 ཎᏊࡢ⣔ࠊ75 ཎᏊࡢ⣔࡟ࡉࡽ࡟ Ser118 ࡢഃ㙐㒊ศࢆ㏣ຍࡋࡓ 80 ཎᏊࡢ⣔ࢆ QM 㡿ᇦ࡟ᣦᐃࡋࡓࡀࠊ2019 ᖺᗘࡣࠊ80 ཎᏊࡢ⣔࡟ᚋ༙ࡢຍỈศゎ཯ᛂ࡟㛵ࢃࡿ࡜ᛮࢃࢀࡿṧᇶ㸦Ser175㸧ࡢഃ㙐㒊ศࢆࡉࡽ࡟ຍ࠼ࡓ 85 ཎᏊࢆ QM 㡿ᇦࠊࡑࢀ௨እࢆ MM 㡿ᇦ࡜ࡋ࡚
Gaussian09 ࡢ Our own N-layered Integrated molecular Orbital 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⏝࠸ࡓࠋ཯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⟬ࡔࡅ࡛࡞ࡃࠊNudged Elastic Band㸦NEB㸧ἲ࡟ࡼࡾ᥎ᐃୖࡢ཯ᛂ๓ࠊTSࠊ཯ᛂᚋࡢᵓ㐀࠿ࡽ- 90 -

TS ᵓ㐀ࡸ཯ᛂ⤒㊰ࢆ⮬ື᥈⣴ࡍࡿࢯࣇࢺ࢙࢘࢔ Reaction Plus Pro2㸦HPC ࢩࢫࢸ࣒ࢬ㸧ࡶ౑⏝ࡋࡓࠋᚓࡽ
ࢀࡓ TS ೃ⿵ᵓ㐀ࢆᇶ࡟ TS ᵓ㐀᭱㐺໬ࠊ᣺ືᩘゎᯒࠊIRC ィ⟬ࢆ⾜ࡗࡓࠋ㸱 ◊✲ᡂᯝ
2018 ᖺᗘ࡟⾜ࢃࢀࡓࠊL-DEX ࡟ࡼࡿ L-2-CPA ࡢ 2 ẁ㝵┠ࡢຍỈศゎ཯ᛂࡢ QM/MM ィ⟬࡟ࡘ࠸࡚ࡣࠊ80ཎᏊࡢ⣔࡛ B3LYP/6-31G (d)࡛ࣞ࣋ࣝᚓࡽࢀࡓάᛶ໬࢚ࢿࣝࢠ࣮ࡀࠊ40.4 kcal/mol ࡜࡞ࡾࠊPM3 ࡛ࣞ࣋ࣝᚓ
ࡽࢀࡓάᛶ໬࢚ࢿࣝࢠ࣮(34.4 kcal/mol)ࡼࡾࡶ኱ࡁࡃࠊᐇ㦂⤖ᯝ࡜ࡶᑐᛂࡋ࡞࠸⤖ᯝ࡜࡞ࡗࡓࠋࡑࡇ࡛ 2019ᖺᗘࡣຍỈศゎ཯ᛂ࡟㛵ࢃࡿ࡜ᛮࢃࢀࡿṧᇶ㸦Ser175㸧ࡢഃ㙐㒊ศࢆࡉࡽ࡟ຍ࠼ࡓ 85 ཎᏊࢆ QM 㡿ᇦ࡜ࡋ࡚ࠊྠᵝ࡟ NEB ἲ࡟ࡼࡾ཯ᛂ⤒㊰ࢆ⮬ື᥈⣴ࡋࠊᐇ㦂⤖ᯝ࡜ᑐᛂࡍࡿࡼ࠺࡞཯ᛂ⤒㊰ࢆぢࡘࡅࡿࡇ࡜ࡀ࡛ࡁ
࡞࠸࠿᳨ウࡋࡓࠋࡇࢀࡲ࡛ࡣࠊLys151 ࡢഃ㙐ࡢ࢔࣑ࣀᇶ࠿ࡽ L-2-CPA ࡢ࢝ࣝ࣎࢟ࢩᇶ࡟Ỉ⣲ࡀ⛣ືࡍࡿືࡁࡀぢࡽࢀ࡚ࡶỈ⣲ࢆ↓⌮࡟ Lys151 ࡢ࢔࣑ࣀᇶ࡜⤖ྜࡉࡏ࡚ィ⟬ࡋ࡚࠸ࡓࡀࠊ௒ᖺᗘࡣỈ⣲ࢆ L-2-CPA ࡢ࢝ࣝ࣎࢟ࢩᇶ࡟ࡘ࡞࠸࡛ィ⟬ࡋࡓࠋࡲࡓࠊ4 ࡘ⪃࠼ࡽࢀࡿ཯ᛂᗙᶆࡢ࠺ࡕࠊ2 ࡘ࡟↔Ⅼࢆ⤠ࡗ࡚ࠊ⥙⨶ⓗ࡟ SCANィ⟬ࢆ⾜࡞࠺ࡇ࡜ࡶヨࡳࡓࠋࡑࡢ⤖ᯝࠊReaction Plus Pro2 ࡛ࡣ」ᩘࡢ TS ೃ⿵ᵓ㐀ࢆỴᐃ࡛ࡁࡓࡶࡢࡢࠊIRC
ィ⟬࡛ TS ᵓ㐀࠿ࡽ཯ᛂ๓ࡢᵓ㐀㸦࢚ࢫࢸࣝ୰㛫యᵓ㐀㸧࡟ᡠࡽ࡞࠿ࡗࡓࡓࡵࠊάᛶ໬࢚ࢿࣝࢠ࣮ࢆィ⟬࡛ࡁ࡞࠿ࡗࡓࠋࡲࡓࠊScan ィ⟬࡛ࡣ TS ೃ⿵ᵓ㐀ࢆぢࡘࡅࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋ
௒ᚋࡢㄢ㢟࡜ࡋ࡚ࡣࠊᐇ㦂⤖ᯝ࡜ᑐᛂࡍࡿ཯ᛂ⤒㊰ࢆ≉ᐃࡍࡿࡓࡵ࡟
1. QM 㡿ᇦࡢཎᏊᩘࢆࡉࡽ࡟ᑡࡋࡎࡘቑࡸࡍࠋ
2. PM3 ࡛ᚓࡽࢀࡓィ⟬⤖ᯝࡢᵓ㐀ࡶ฼⏝ࡍࡿ࡞࡝ࠊィ⟬࡟౑⏝ࡍࡿึᮇᵓ㐀ࢆᩘከࡃ⏝ពࡋ࡚෌ィ⟬ࡍࡿࠋ
3. 㓝⣲࠿ࡽᇶ㉁࡬ࡢࣉࣟࢺࣥ⛣ື࡞࡝ࡇࢀࡲ࡛⪃࠼࡚࠸࡞࠸཯ᛂ⤒㊰ࢆ᥎ᐃࡋ࡚෌ィ⟬ࡍࡿࠋ࡞࡝ࡢ᪉ἲࢆ᳨ウࡋ࡚ィ⟬ࢆ㐍ࡵ࡚࠸ࡃணᐃ࡛࠶ࡿࠋ

㸲 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ  ࡞ࡋ㸳 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ  ࡞ࡋ

- 91 -

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⣴ࠊᐑཎ ཭ኵ㸦㔞Ꮚ໬Ꮫ◊✲༠఍㸧ࠕ㠉᪂ⓗ㔞Ꮚ⛉Ꮫ࡜኱つᶍࢩ࣑࣮ࣗࣞࢩࣙࣥ⛉Ꮫࡢ๰㐀ࠖࡢࢸ࣮࣐ࡢࡶ࡜ࠊ᫖ᖺᗘࡣ୺࡟ࠕṇ☜࡞ணゝⓗ㔞Ꮚ໬Ꮫ⌮ㄽࡢᵓ⠏࡜ᒎ㛤ࠖ࡜࠸࠺ࢸ࣮࣐࡟ὀຊࡋࡓࠋࡶ࠺୍ࡘࡢᰕ࡛࠶ࡿࠕບ㉳≧ែࡢ㔞Ꮚ໬Ꮫ࡜ග⏕≀Ꮫ࡬ࡢᒎ㛤ࠖ࡟ࡘ࠸࡚ࡣࠊ-3K\V&KHP$  ࠊ-&RPSXW&KHP   ➼ࡢㄽᩥ࡟グ㍕
ࡋࡓࡢ࡛ࠊࡇࡇ࡛ࡣ๭ឡࡋࠊᮏሗ࿌᭩࡛ࡣࠊ୺࡟๓⪅ࡢㄢ㢟࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ

◊✲┠ⓗ࡜ィ⟬ࡢ᪉ἲ໬Ꮫࡢ⛉Ꮫⓗᇶ♏ࡣ୺࡟ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ࡟ࡼࡗ࡚ᨭ㓄ࡉࢀ࡚࠸ࡿࡢ࡛ࠊࡇࡢ᪉⛬ᘧࢆṇ☜࠿ࡘᐜ᫆࡟ゎࡃ⌮ㄽࡀᏑᅾࡋࠊࡑࢀࢆㄡࡶࡀ౑࠼ࡿィ⟬ࣉࣟࢢ࣒ࣛ࡜ࡋ࡚᏶ᡂࡋ࡚࠸ࢀࡤࠊ໬Ꮫ⪅ࡣ໬Ꮫ⌧㇟ࢆᐇ㦂ࡢࡳ࡛࡞ࡃ⌮ㄽ࡜ィ⟬࡟ࡼࡗ࡚ࡶṇ☜࡟ணゝࡍࡿࡇ࡜ࡀ࡛ࡁࡿࡢ࡛ࠊ໬Ꮫࡢ㐍Ṍࡣᛴ㏿࡟㛤ࡅࡿࡇ࡜࡟
࡞ࡿࠋᮏ◊✲ㄢ㢟ࡢ௦⾲⪅ࡣ  ᖺ࡟ཎᏊ࣭ศᏊࡢࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࢆṇ☜࡟ゎࡃࡇ࡜ࡢ࡛ࡁࡿ୍
⯡⌮ㄽ)UHH&RPSOHPHQW )& WKHRU\ ⮬⏤᏶ဨ㛵ᩘ⌮ㄽ ࢆⓎ⾲ࡋࡓ 3K\V5HY/HWW  ࠋ௨ᚋࠊ4&5, ࡛ࡣࠊඹྠ◊✲⪅࡜୍୸࡜࡞ࡗ࡚ࠊࡇࡢ⌮ㄽࢆⓎᒎࡉࡏࠊṇ☜࡛౑࠸᫆࠸ணゝⓗ㔞Ꮚ໬Ꮫࡢᘓタࢆ┠ᣦࡋࡓ◊✲ࢆ⥆ࡅ࡚ࡁࡓࠋ)& ⌮ㄽࢆཎᏊศᏊ࡟ᛂ⏝ࡍࡿ㝿ࠊఏ⤫ⓗ࡞ኚศἲࢆ⏝࠸ࡿ࡜ࠊࡈࡃᑠࡉ࡞ᑐ㇟ࢆ㝖࠸࡚ࠊ඲࡚ࡢ✚ศࢆィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞࠸࡜࠸࠺ၥ㢟࡟ᙜࡓࡿࠋࡋ࠿ࡋ࡞ࡀࡽࡑࢀࡀ࡛ࡁࡿ⣔࡟ᑐࡋ࡚ࡣࠊ)& ⌮ㄽᮏ᮶ࡢᴟࡵ࡚
㧗⢭ᗘ࡞ィ⟬⤖ᯝࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡇࡇ࡛ࡣࡑࡢ  ౛࡜ࡋ࡚ࠊ㛗࠸᫬㛫ࢆ࠿ࡅ࡚Ỉ⣲ศᏊࡢᇶᗏ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩ࣭࣮ࣕࣝ࢝ࣈ࡜ࠊࡑࢀ࡟ᇶ࡙ࡃ᣺ື≧ែゎᯒࢆ⾜ࡗࡓ⤖ᯝࢆሗ࿌ࡍࡿࠋȊ≧ែࡣ  ᖺࠊȈ≧ែࡣ  ᖺ࡟ 3&&3 ࡟Ⓨ⾲ࡉࢀࡓࠋ
୍⯡࡟ࡣࡇࡢ✚ศࡢၥ㢟ࡀ࠶ࡿࡓࡵࠊ ᖺᗘࡲ࡛ࡢ◊✲࡛ࡣࠊᒁᡤࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ /6( ἲ࡜࠸࠺ࢧࣥࣉࣜࣥࢢἲ࡟ࡼࡗ࡚ゎࡃ᪉ἲࢆⓎᒎࡉࡏࡓࠋ౛࠼ࡤࠊ ᖺࡢ -&KHP3K\V   ࡣࠊࡑࡢ⥲ᣓⓗㄽᩥ࡜ゝ࠼ࡿࠋࡑࡇ࡛ࡣ 6FDOHG6FKU|GLQJHU ᪉⛬ᘧ࡟ྵࡲࢀࡿⓎᩓ㡯ࢆྲྀࡾ㝖ࡃ VFDOLQJIXQFWLRQ ࡜
ࡋ࡚ࠊJ UL$ULM ࢆ⏝࠸ࠊ඲࡚ࡢ➨  ࿘ᮇཎᏊ࡜࣒࣍ࣝ࢔ࣝࢹࣄࢻ࡞࡝ࡢ⡆༢࡞ศᏊ࡟ࡘ࠸࡚ࠊ⤯ᑐ࢚ࢿࣝࢠ
࣮࡛໬Ꮫ⢭ᗘ (1 kcal/mol ௨ୗ) ࡜࠸࠺࡜࡚ࡶṇ☜࡞ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ゎࢆࠊຠ⋡ⓗ࠿ࡘᐜ᫆࡟ィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡋ࠿ࡋࠊࡑࡇ࡛ࡶࠊࢧࣥࣉࣜࣥࢢἲ࡟≉ᚩⓗ࡞ UDQGRPQHVV ࡟ᇶ࡙ࡃ࢚࣮ࣛࢆ᏶඲࡟㐽᩿ࡍࡿࡇ࡜ࡣ࡛ࡁ࡞࠿ࡗࡓࠋ
ࡇࡢ⤒㦂࡟ᇶ࡙࠸࡚ࠊ ᖺᗘ࠿ࡽ  ᖺᗘ࡟࠿ࡅ࡚ࠊ✚ศኚศἲ࡟ࡼࡗ࡚ )& ⌮ㄽࡢἼື㛵ᩘࢆࠊ୍⯡ࡢཎᏊ࣭ศᏊ࡟ࡘ࠸࡚ࡶồࡵࡿࡇ࡜ࡢ࡛ࡁࡿ⌮ㄽࡢᵓ⠏࡟ὀຊࡋࡓࠋኚศἲࡣࠊኚศཎ⌮࡟⿬௜ࡅࡉࢀࡿᏳ
ᐃ࡞ィ⟬ἲ࡛࠶ࡿࡀࠊἼື㛵ᩘࢆᵓᡂࡍࡿࡍ࡭࡚ࡢ㛵ᩘ࡟ࡘ࠸࡚ࡑࡢࣁ࣑ࣝࢺࢽ࢔ࣥ✚ศ࡞࡝ࡀィ⟬࡛ࡁࡿࡇ࡜ࡀ๓ᥦ࡛࠶ࡿࠋࡑࡢࡓࡵࠊᑐ㇟࡜࡛ࡁࡿ⣔ࡣࡈࡃᑠࡉ࡞ࡶࡢ࡟㝈ࡽࢀࡿࠋࡋ࠿ࡋࠊ⪃࠼࡚ࡳࢀࡤࠊscaling
function ࡢ୰ࡢ㟁Ꮚ̿㟁Ꮚ㡯ࡣ rij ࡛࡞ࡃࠊsij = rij2 ࡛࠶ࡗ࡚ࡶࠊ✚ศࡢⓎᩓࡣ㜵ࡄࡇ࡜ࡣ࡛ࡁࡿࠋࡋ࠿ࡶࠊsij= rij2=(xi-xj)2 +(yi-yj)2 +(zi-zj)2 ࢆ౑࠼ࡤࠊἼື㛵ᩘࢆ  㟁Ꮚ㛵ᩘࡢࡳ࡛᭩ࡃࡇ࡜ࡀ࡛ࡁࠊィ⟬ࡣ㸯࣭㸰㟁Ꮚ✚ศࡢࡳ࡛ྍ⬟࡟࡞ࡾࠊᬑ㏻ࡢศᏊィ⟬ࡢດຊ࡛ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ゎ࡟㏆࠸⤖ᯝࢆᚓࡽࢀࡿ࡜࠸࠺ྍ⬟ᛶࡀᗈࡀࡿࠋࡓࡔࡑࡢ௦ൾ࡜ࡋ࡚ࠊe-e cusp condition ࡣ‶ࡓࡉࢀ࡞ࡃ࡞ࡿࡀࠊ඲࢚ࢿࣝࢠ࣮࡬ࡢᙳ㡪ࡣᑠࡉ࠸ࠋࡇࡢ
⌮ㄽ࡟ࡘ࠸࡚ࡣ᫖ᖺᗘࡢሗ࿌᭩࡟ࡲ࡜ࡵࠊㄽᩥࡶࡑࡢึሗࡣ 3K\V5HY$LQSUHVV ࡟࠶ࡿࡢ࡛ᮏሗ࿌࡛ࡣ㏙࡭

- 92 -

࡞࠸ࠋゎࡢ DFFXUDF\ ࡣࠊᚑ᮶ࡢ )&ULM ⌮ㄽ࡟ཬࡤ࡞࠸ࡀࠊࡑࢀࡼࡾࡶ✚ศࡀ 1࣭2 㟁Ꮚ✚ศࡢ⠊ᅖෆ࡟཰ࡲࡿ
࡜࠸࠺ᐇ⏝ୖࡢỗ⏝ᛶࡀ኱ࡁࡃࠊ኱ࡁ࡞ศᏊ⣔ࡶྵࡵࡓ໬Ꮫࢆࠊṇ☜࡞ணゝ⬟ࡢ࠶ࡿ⌮ㄽ࡟ࡼࡗ࡚᥎ࡋ㐍ࡵ࡚࠸ࡃୖ࡛ᮇᚅࡉࢀࡿࠋᮏ 2019 ᖺᗘࡢィ⟬ᶵ฼⏝࡛ࡣࠊ᏶ဨ㛵ᩘ㑅ᢥἲ࡜⥺ᙧ໬ኚศἲࢆᑟධࡋ࡚ )& VLM ⌮ㄽࡢຠ⋡ࢆࡉࡽ࡟㧗ࡵࡓ◊✲ࠊ)& ULM ⌮ㄽࢆ VLM ⌮ㄽ࡛࢔ࢩࢫࢺࡋᐇ㉁ⓗ࡟ 3࣭4 㟁Ꮚ✚ศࡲ࡛ィ⟬ࡍࡿ᪉ἲࠊ
➼ࡢ◊✲ࢆሗ࿌ࡍࡿࠋ
ࡉࡽ࡟⚾㐩ࡣࠊ6FDOHG6FKU|GLQJHU ᪉⛬ᘧࡢ J 㛵ᩘࢆ୍⯡໬ࡋࠊ6FKU|GLQJHU ᪉⛬ᘧࡔࡅ࡛ࡣᚓࡿࡇ࡜ࡀ࡛ࡁ
࡞࠿ࡗࡓ㟁Ꮚ≧ែ⌮ㄽࡢ῝໬ࢆ⾜࠺ࡇ࡜ࡀ࡛ࡁࡓࠋ6FDOHG6FKU|GLQJHU ᪉⛬ᘧࡣ 6FKU|GLQJHU ᪉⛬ᘧ࡜ྠࡌゎࢆᣢࡕ

J + ( \ ࡛୚࠼ࡽࢀࠊࡑࡢ VFDOLQJIXQFWLRQ ࡣ୍⯡ⓗ࡟
J

¦J
L $

L$

UL$  ¦ JLM ULM 
L M࡜᭩ࡃࡇ࡜ࡀ࡛ࡁࡿࠋࡇࡢ J 㛵ᩘࢆࠊᚑ᮶ࡢ UL$ ࠊ ULM ࡼࡾࠊࡼࡾ≀⌮ⓗ࡟ṇࡋ࠸㛵ᩘ࡛⾲⌧ࡋࠊ῝ࡵࡿࡇ࡜࡟
ࡼࡗ࡚ࠊ᪤Ꮡࡢ⌮ㄽ࡟ࡣ࡞࠸᪉ἲ࡛ H[DFW ゎࢆࡼࡾຠ⋡ⓗ࡟ィ⟬ࡍࡿ⌮ㄽࢆ㛤Ⓨࡋࡓࠋ୍⯡ⓗ࡟ࡣ✚ศࡀᅔ㞴࡛ࡶἼື㛵ᩘࡢ H[DFWQHVV ࡀྥୖࡍࢀࡤࠊࢧࣥࣉࣜࣥࢢ౫Ꮡᛶࡀ㍍ῶࡍࡿࡓࡵࠊ/6( ἲࢆࡼࡾ᭷⏝࠿ࡘᐜ᫆࡟
ά⏝ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡇࡢᵝ࡟ࠊ✚ศኚศἲ࡜ /6( ἲ࡟ࡼࡿィ⟬ࢆే⏝ࡋࠊྛࠎࡢ฼Ⅼࢆ⏕࠿ࡋࡓ⌮ㄽ㛤
Ⓨࢆ㐍ࡵࡓࠋ
ࡲࡓࠊ┦ᑐㄽⓗࢹ࢕ࣛࢵࢡ࣭ࢡ࣮ࣟࣥ᪉⛬ᘧࡢゎἲࡢ◊✲ࡶ㐍ࡵࠊ」⣲ࢫࢣ࣮ࣜࣥࢢἲ࡛࢔ࢩࢫࢺࡍࡿ㏫
ࣁ࣑ࣝࢺࢽ࢔ࣥἲࡢᒎ㛤࡟ࡘ࠸࡚ࡶࡲ࡜ࡵࡓࠋQRQ%RUQ2SSHQKHLPHU ࣞ࣋ࣝࡢ⌮ㄽ㛤Ⓨࡶ⥅⥆ࡋ࡚㐍ࡵ࡚࠸
ࡿࠋ



◊✲ᡂᯝ

$ Ỉ⣲ศᏊࡢH[DFW SRWHQWLDO FXUYHࡢィ⟬࡜᣺ືࣞ࣋ࣝࡢィ⟬ᇶᗏ≧ែࡢᖹ⾮᰾㛫㊥㞳࡟࠾ࡅࡿỈ⣲ศᏊࡢ6FKU|GLQJHU᪉⛬ᘧࡢH[DFW࡞ゎࡣ)UHH &RPSOHPHQWἲ࡟ࡼࡾ᪤࡟ᚓࡽࢀ
࡚࠸ࡿ 3K\V5HY$  ࠋᮏ◊✲࡛ࡣࠊྠ⌮ㄽࢆ⏝࠸࡚ࠊᵝࠎ࡞ບ㉳≧ែ࡟ࡘ࠸࡚ࡶH[DFW࡞࣏ࢸࣥࢩࣕࣝ
࣮࢝ࣈࢆồࡵࡓࠋᮏ◊✲ࡢึᮇ㛵ᩘࡣࠊゎ㞳ᴟ㝈࡟࠾ࡅࡿỈ⣲ศᏊࡢH[DFW࡞Ἴື㛵ᩘ࡜ࡋࡓࠋࡍ࡞ࢃࡕࠊỈ⣲ཎᏊࡢᇶᗏ ≧ ែ ࡜ ບ ㉳ ≧ ែ + V  + Q  ཬ ࡧ+ Q  ࡢ✚ࢆึᮇ㛵ᩘ\  ࡟ྵࡵࠊ࡝ࡢ
≧ែࡢィ⟬ࡶඹ㏻࡟ࠊ ᅗ 1. Free Complement ἲ࡟ࡼࡿỈ⣲ศᏊࡢᇶᗏ࣭ບ㉳≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈ࡜᣺ືࣞ࣋ࣝ. ᕥ: 6J 㯮  6X ⥳  6J ㉥  ཬࡧ
6X 㟷  ≧ែ ྑ3J 㯮 3X 㟷 3J ㉥  ཬࡧ 3X ⥳  ≧ែ

- 93 -

\3ÖVSLQ 3ÖVSDFH ª¬H[S U $  U %

 H[S U $   U %   U %
 H[S U $   U %   U %  U% @ ;   <L/࡜ࡋࡓࠋࡇࡇ࡛ 3ÖVSLQ ཬࡧ 3ÖVSDFH ࡣࡑࢀࡒࢀࢫࣆ࣭ࣥ
ࢫ࣮࣌ࢫ✵㛫࡟㛵ࡍࡿ ཯ ᑐ⛠໬₇⟬Ꮚ࡛࠶ࡾࠊ 㔜㡯ཪࡣ  㔜㡯≧ែࠊཬࡧ JHUDGH ཪࡣ XQJHUDGH≧ែࢆṇࡋࡃ⾲⌧ࡋࠊࡇࢀࡽࡢ⤌ࡳྜࢃࡏ࡟ࡼࡾ  ࡘࡢ␗࡞ࡿ≧ែࢆྠ➼࡟ồࡵࡿࡇ࡜ࡀ࡛ࡁ

ࡿࠋᮎ㡯ࡣศᏊ㍈࿘ࡾࡢゅ㐠ື㔞ࢆ⾲ࡋ࡚࠾ࡾࠊ ᅗ 2. EF1ѷg ≧ែࡢ double well potential ࡜᣺ືࣞ࣋ࣝȈ ≧ែ ȁ  ཪࡣ Ȇ ≧ែ ȁ  ࢆ⾲⌧ࡍࡿࠋࡇࡢ
ึᮇ㛵ᩘࢆ⏝࠸ࡿࡇ࡜࡛ࠊṇࡋ࠸ゎ㞳≧ែ࡟཰᮰ࡍࡿࡇ࡜ࡀಖドࡉࢀࡿࠋࡇࡢึᮇ㛵ᩘ࡟ )& ⌮ㄽࢆ㐺⏝ࡋࡓࠋᚓࡽࢀࡿ )& Ἴື㛵ᩘࡣࠊ␗࡞ࡿ≧ែ㛫࡛ࡣᚲࡎ┤஺ࡋࠊࡲࡓࣁ࣑ࣝࢺࢽ࢔ࣥ┤஺ࡍࡿࡇ࡜ࡀ⌮ㄽⓗ࡟ಖドࡉࢀ࡚࠸ࡿࠋRUGHU  ࡟࠾࠸࡚ᚓࡽࢀࡓཬࡧ Ȇ ≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࢆᅗ  ࡟♧ࡋࡓࠋ࡝ࡢ≧ែࡶ
PKDUWUHH ௨ୖࡢ⢭ᗘ࡛ồࡲࡗ࡚࠾ࡾࠊ≉࡟᰾㛫㊥㞳ࡀ኱ࡁࡃ࡞ࡿ࡟ࡘࢀ࡚ࡼࡾ⢭ᐦ࡟ồࡲࡾࠊ࡝ࡢᩥ⊩್ࡼࡾࡶṇ☜࡟ᚓࡽࢀ࡚࠸ࡿࠋࡉࡽ࡟ࠊ)& ἲ࡟ࡼࡾᚓࡽࢀࡓ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈࢆ⏝࠸࡚ࠊศᏊ᣺ືࣞ࣋ࣝࢆィ⟬ࡋࡓࠋ౛࡜ࡋ࡚ ()J ≧ែࡢ᣺ືࣞ࣋ࣝࢆᅗ  ࡟♧ࡋࡓࠋࡇࡢ≧ែࡣ GRXEOHZHOO ࡟࡞ࡗ࡚࠸ࡿࡓࡵࡑࡢ᣺
ື‽఩ࡢ㛫㝸ࡀ≉␗ⓗ࡛࠶ࡾ⯆࿡῝࠸ࠋࡇࡢ௚࡟ࡶ඲࡚ࡢ≧ែ࡟ࡘ࠸࡚ࡶ᣺ືࣞ࣋ࣝࢆồࡵࠊࡑࡢࢹ࣮ࢱࡣ
ㄽᩥ୰ 6XSSOHPHQWDO'DWD ࡜ࡋ࡚බ㛤ࡋ࡚࠸ࡿࠋᮏィ⟬࡛ᚓࡽࢀࡓ࡝ࡢ≧ែࡢ࣏ࢸࣥࢩ࣮ࣕࣝ࢝ࣈཬࡧ᣺ືࣞ
࣋ࣝࡶࠊྠࡌึᮇ㛵ᩘࢆ⏝࠸ࡓ )& ἲ࡟ࡼࡿ⤫୍ⓗ࡞᪉ἲ࡛ᚓࡽࢀࡓࡶࡢ࡛࠶ࡾࠊ௒ᚋ UHIHUHQFH ࢹ࣮ࢱ࡜ࡋ
࡚ᐇ㦂ࢹ࣮ࢱࡸ௚ࡢ⌮ㄽࡢ᳨ド࡟኱ኚ᭷⏝࡛࠶ࢁ࠺ࠋ
௨ୖࡢᡂᯝࡣࠊ≧ែ࡟ࡘ࠸࡚ࡣࠊ3K\V&KHP&KHP3K\V   ࡟ᥖ㍕ࡉࢀ 3&&3 ㄅࡢ⾲⣬࡟᥇⏝ࡉࢀࡓࠋȆ ≧ែ࡟ࡘ࠸࡚ࡶࠊ3&&3 ㄅ࡟ᥖ㍕ணᐃ࡛࠶ࡿࠋ%  )&sij ⌮ㄽ ᏶ဨ㛵ᩘ㑅ᢥἲ࡜⥺ᙧ໬ኚศἲࡢᑟධ
FC sij ⌮ㄽࢆຠ⋡໬ࡍࡿࡓࡵࠊ࢚ࢿࣝࢠ࣮ᐤ୚ࡢ኱ࡁ࡞㔜せ࡞᏶ဨ㛵ᩘࢆ㑅ᢥࡍࡿ᏶ဨ㛵ᩘ㑅ᢥἲ(cf 㑅ᢥἲ)ࢆ㛤Ⓨࡋࡓࠋࡲࡓࠊྛ cf ࡢ Slater ࡲࡓࡣ Gauss 㛵ᩘࢆ」ᩘࡢ㌶㐨ᣦᩘ(3 㡯࠿ࡽ 5 㡯⛬ᗘ)࡛ᒎ㛤ࡍࡿ⥺ᙧ໬ኚศἲࢆᥦ᱌ࡋࡓࠋ౛࠼ࡤࠊ➨஧࿘ᮇཎᏊ࡛ 1s ㌶㐨
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ЍFI 㑅ᢥ0    ([DFW
D

Q  ࡢ FI ࡣ 3ULPDU\ 㛵ᩘ࡜ࡋ࡚᥇⏝EVV ㌶㐨ࢆࡑࢀࡒࢀ  ಶࡢ㌶㐨ᣦᩘ࡛ᒎ㛤F'RXEOH]HWD ึᮇ㛵ᩘ3K\V5HY$LQSUHVV- 94 -ᗘ(exact ゎ࡜ࡢ࢚ࢿࣝࢠ࣮ᕪࡀ 1 kcal/mol ⾲ )&sijFI 㑅ᢥἲ࡜⥺ᙧ໬ኚኚศἲࡢ %H ཎᏊ࡬ࡢᛂ⏝ DE௨ୗ)ࢆᚓࡿࡓࡵ࡟ n=4, M=222 ࡀᚲせ࡛ࠊM

cf 㑅ᢥἲࢆ㐺⏝ࡋࡓᚋࡶ 37 ಶࡢ cf ࢆせࡋ

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

I,


V

VV
ࡓࡀ(Phys. Rev. A, in press)ࠊ⥺ᙧ໬ኚศἲ
VVVࢆ㐺⏝ࡍࡿ࡜ഹ࠿ 9 ಶ࡛ࡇࢀࢆ㐩ᡂࡋࡓࠋ
UV
UV
ྛ⾜(cf 㑅ᢥࡢ⤖ᯝ)࡛࢚ࢿࣝࢠ࣮ࡢᕪศ
VVV(ǻǻ()ࢆぢࡿ࡜ࠊn=0,1 ࡢ cf (M=7)࡟ VVV
UV

UV
ࢆྲྀࡾධࢀࡿ࡜ 2.9 kcal/molࠊḟ࡟ VVV ࡛
UVVVV
0.7 kcal/mol ࢚ࢿࣝࢠ࣮ࡀపୗࡋࠊ1s 㟁Ꮚ
VVV
VVVVVVྠኈࡢ┦㛵㡯ࡀࡲࡎ㔜せ࡟ᐤ୚ࡋ࡚࠸ࡿ
͐ࡇ࡜ࡀศ࠿ࡿࠋࡑࡋ࡚ࠊࡇࡢ 2 㡯ࡢࡳࢆຍUVVVV
UVUV¶ VVV࠼ࡿࡇ࡜࡛ࠊ໬Ꮫ⢭ᗘࢆ㐩ᡂࡋ࡚࠸ࡿࠋ
UVUVVVV⾲ 2 ࡣࠊBe ཎᏊ࡟ )& VLM ἲ n(order)=4UVVVVVVV
UVVVV(Slater 㛵ᩘ)࡟⥺ᙧ໬ኚศἲࢆ㐺⏝ࡋࡓ⤖UVVVVᯝࢆ♧ࡍࠋࡑࡢ⤖ᯝࠊ44 ಶࡢ cf ࡛໬Ꮫ⢭UVVVV
UVUVVVVVVVᗘࢆ㐩ᡂࡋࠊsij assisted - FC rij ἲ࡜ࡶྠ⛬)&VLM Q 0  Fᗘ ࡢ ຠ ⋡ ࡛ ໬ Ꮫ ⢭ ᗘ ࡢ ゎ ࡀ ᚓ ࡽ ࢀ ࡓ ࠋ VLMDVVLVWHG)&ULM Q 0  G
([DFW
n=0,1 ࡢ cf (M=8)ࡢḟ࡟㔜せ࡞ cf ࢆぢࡿ࡜ࠊD

2s ࡢᨵⰋ࡟ᐤ୚ࡍࡿ UVVVV ࡀࡲࡎ㔜せ࡛ࠊǻE E)&EH[DFWǻǻE
NFDOPRO 
NFDOPRO                                 ͐͐͐                        



(QHUJ\ DX 

Q  ࡢ FI ࡣ 3ULPDU\ 㛵ᩘ࡜ࡋ࡚᥇⏝EVV ㌶㐨ࢆࡑࢀࡒࢀ  ಶࡢ㌶㐨ᣦᩘ࡛ᒎ㛤F6LQJOH]HWD ึᮇ㛵ᩘG-&KHP3K\V  ḟ࡟ 1s 㟁Ꮚྠኈࡢ┦㛵㡯 VVVࠊࡉࡽ࡟ 1s,
2s ࡢ┦㛵㡯ྠኈࡢ unlinked 㡯 VVVVVV ࡀຠ࠸࡚࠸ࡓࠋ
 Rࡇࡢࡼ࠺࡟ࠊ᏶ဨ㛵ᩘ㑅ᢥἲ࡜⥺ᙧ໬ኚศἲ࡟ࡼࡗ ⾲ sijDVVLVWHG)&rij ⌮ㄽࡢ & ཎᏊ 6 VS ≧ែ ࡬ࡢᛂ⏝n࡚ࠊᑡ࡞࠸ cf ࡛㧗⢭ᗘ࡞Ἴື㛵ᩘࢆᵓ⠏ࡍࡿࡇ࡜ࡀ࡛M

(QHUJ\ DX ǻE E)&EH[DFWNFDOPRO 

sijDVVLVWHG)&rijWKHRU\D

2 㟁Ꮚ✚ศࡢ⠊ᅖෆ࡛ィ⟬ࡉࢀࠊࡉࡽ࡟పḟ order(㧗࠸



ゅ㐠ື㔞ࡢ✚ศࡀ୙せ)࡛ゎࡀᚓࡽࢀࡿࡓࡵࠊィ⟬ୖࡢ
E



࣓ࣜࢵࢺࡶ኱ࡁ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ

FIVHOHFWLRQ 
  &sijDVVLVWHG)&rij⌮ㄽ࡟ࡼࡿH[DFWゎࡢኚศィ⟬
  ḟ࡟ࠊ)&ULM ⌮ㄽࢆ VLM ⌮ㄽ࡛࢔ࢩࢫࢺࡍࡿ VLMDVVLVWHG
  
  
FC rij ⌮ㄽࡢィ⟬ࢆ⾜ࡗࡓࠋࡇࡇ࡛ࠊsij assisted ࡜ࡣࠊ✚
  ศィ⟬ࡢᅔ㞴ࢆᅇ㑊ࡍࡿࡓࡵ࡟ࠊrij 㡯ࡀ 2 ✀௨ୖྠ᫬
  )XOO&,UHIHUHQFHF
࡟Ꮡᅾࡍࡿ㡯(rijrkl)࡛ࡣ∦᪉ࢆ sij ࡟ኚ᥮ࡍࡿ(rijskl,
DXJFFS9'=G 


sijrkl)᧯స࡛࠶ࡿࠋ୍᪉ࠊᚑ᮶ࡢ Hylleraas-CI ἲࡢࡼ࠺ DXJFFS97=H  

&9%I



࡟༢⊂ࡢ rij 㡯ࢆ࣮࣋ࢫ࡜ࡋࡓἼື㛵ᩘ࡛ࡣࠊ4 㟁Ꮚ⣔&9%J



Be ཎᏊࡲ࡛ࡣ 1 kcal/mol ௨ୗࡢ໬Ꮫ⢭ᗘࡀᚓࡽࢀ࡚࠸
&9%K
 
([DFW
LࡁࠊἼື㛵ᩘࡢ⌮ゎ࡟ࡶ⧅ࡆࡸࡍ࠸ࠋࡲࡓࠊ✚ศࡣ 1࣭

ࡿࡀ(J. S. Sims and S. A. Hagstrom, Phys. Rev. A 83,

032518 (2011))ࠊ5 㟁Ꮚ⣔ࡢ B ཎᏊ࡛ࡍ࡛࡟୙ྍ⬟࡟࡞
ࡿ(M. B. Ruiz, Prog. in Theoret. Chem. Phys. 22, 105D

VLM 㡯ࡢᒎ㛤ࡢ⮬⏤ᗘࡶྲྀࡾධࢀࡿࡓࡵ J ULULULM EULM 㡯ࡣ  ḟࡲ࡛ F'K V\PPHWU\ G*DXVVLDQ  EDVLV  H*DXVVLDQ  EDVLV  I6ODWHU
 EDVLV  J6ODWHU  EDVLV  K6ODWHU  EDVLV  L(&* PHWKRG .
6WUDVEXUJHU3K\V5HY$   

- 95 -

(2011))ࠋ
VLMDVVLVWHGFC rij ⌮ㄽ࡟ࡼࡿኚศἲࡢィ⟬࡛ࡣࠊᚲせ࡞✚ศィ⟬ࡣ 1㹼4 㟁Ꮚ✚ศࡢ⠊ᅖෆ࡟཰ࡲࡿࠋᡃࠎ
ࡣࠊཎᏊ 1 ୰ᚰ Slater 㛵ᩘ࡟ᑐࡍࡿ 3࣭4 㟁Ꮚ✚ศࣃࢵࢣ࣮ࢪࢆ⊂⮬࡟సᡂࡋ࡚ィ⟬ࢆ⾜ࡗࡓࠋ⾲ 3 ࡟ࠊC ཎ
Ꮚ: 5So, sp3 ≧ែ࡟㐺⏝ࡋࡓ⤖ᯝࢆ♧ࡍࠋorder ࢆୖࡆࡿ࡜࢚ࢿࣝࢠ࣮ࡣ exact ゎ࡟ᛴ㏿࡟㏆࡙ࡁࠊn=3, M=4577
࡛ ǻ(=0.215 kcal/mol ࡜࡞ࡾ໬Ꮫ⢭ᗘ(1 kcal/mol ௨ୗ)ࢆ㐩ᡂࡋࡓࠋࡉࡽ࡟ࠊcf 㑅ᢥἲࢆ㐺⏝ࡍࡿ࡜ࠊഹ࠿ 129
ಶࡢ cf ࡛໬Ꮫ⢭ᗘࢆ㐩ᡂࡋࡓࠋFC sij ⌮ㄽ࡛ࡢ M=2942(Phys. Rev. A in press)࡜ẚ࡭ࡿ࡜㠀ᖖ࡟ᑡ࡞࠸ cf ࡢᩘ࡛
῭ࢇ࡛࠸ࡿࡀࠊ3࣭4 㟁Ꮚ✚ศࡢ኱ࡁ࡞ィ⟬㈇Ⲵ࡜୍⯡ⓗ࡞ศᏊ࡛ Slater 㛵ᩘ࡟ᑐࡍࡿ✚ศἲࡀ☜❧ࡋ࡚࠸࡞࠸ࡇ࡜ࢆ⪃࠼ࡿ࡜ࠊ1࣭2 㟁Ꮚ✚ศ࡛ィ⟬ྍ⬟࡞ FC sij ⌮ㄽࡢ᪉ࡀỗ⏝ᛶࡀ኱ࡁ࠸ࠋࢧࣥࣉࣜࣥࢢἲ(LSE ἲ)࡛ࡣࠊ✚ศἲࡀ୙せ࡞ࡓࡵ FC rij ⌮ㄽ࡛ᐜ᫆࡟ィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁࡿ(sij ࢔ࢩࢫࢺࡢᚲせࡶ࡞࠸)ࠋ⾲ 3 ࡟ࠊGaussᇶᗏ㛵ᩘ࡜ Slater ᇶᗏ㛵ᩘ࡛ࡢ Full CI ἲࡢ Reference ࡶ♧ࡋࡓࠋGauss ᇶᗏࡢ aug-cc-pVTZ ࡛ࡣࠊ㓄⨨ࡢᩘ(⮬⏤ᗘ)ࡀ M= ࡶ࠶ࡿࡢ࡟ ǻ(  NFDOPRO ࡛࠶ࡿࠋ6ODWHU ᇶᗏ࡛ࡣ⤯ᑐ࢚ࢿࣝࢠ࣮ࡀ኱ࡁࡃᨵၿࡉࢀ࡚
࠸ࡿࡀࠊ&9% ᇶᗏ 㓄⨨ࡢᩘ0  ⣙  ൨ ࡛ࡶ ǻ( NFDOPRO ࡛࠶ࡿࠋࡇࡢࡼ࠺࡟ࠊ)XOO&, ゎࡣࠊᇶᗏ✵㛫ࡢᗈࡀࡾ࡟ᑐࡍࡿ཰᮰ࡀ㐜ࡃࠊࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢ┿ࡢṇ☜࡞ゎ࡜ࡣ኱ࡁ࡞ࢠࣕࢵࣉࡀ࠶
ࡿࡇ࡜ࡀศ࠿ࡿࠋࡇࡢⅬ࠿ࡽࡶࠊᒁᡤⓗ⌮ㄽ࡟ᇶ࡙ࡃ )& ⌮ㄽࡀዴఱ࡟ຠ⋡ⓗ࡛࠶ࡿ࠿ࡀ⌮ゎࡉࢀࡿࠋ


D.

Scaled Schr|GLQger ᪉⛬ᘧ࡜ࡑࡢ g 㛵ᩘࡢ୍⯡໬࡟ࡼࡾᚓࡽࢀࡿ᪂ࡋ࠸㟁Ꮚ≧ែ⌮ㄽ

2004 ᖺ࡟Ⓨ⾲ࡋࡓ 6FDOHG6FKU|GLQJHU ᪉⛬ᘧ࡛ࡣࠊJ 㛵ᩘࡣࠊ6FKU|GLQJHU ᪉⛬ᘧࡢሙྜ࡟⏕ࡌࡿ✚ศࡢⓎᩓ࡜࠸࠺㠀≀⌮ⓗ࡞Ḟ㝗ࢆ㝖ࡁࠊṇࡋ࠸Ἴື㛵ᩘࢆィ⟬࡛ࡁࡿࡼ࠺࡟ࡍࡿࡓࡵ࡟ᑟධࡉࢀࡓࠋᡃࠎࡣࠊࡇࢀࢆ
୍⯡໬ࡋࠊࡼࡾ≀⌮ⓗ࡟ṇࡋ࠸ J 㛵ᩘ࡜ࡑࡢ 6FDOHG6FKU|GLQJHU ᪉⛬ᘧࢆᇶ♏࡜ࡍࡿࡇ࡜࡛ࠊ᪂ࡋ࠸㟁Ꮚ≧ែ⌮ㄽࡢᵓ⠏ࢆ┠ᣦࡋࡓࠋS࣭T ࡢ  ࡘࡢ⢏Ꮚࡢ⾪✺ⓗ┦஫స⏝ࢆ⾲⌧ࡍࡿ㛵ᩘ࡛࠶ࡿ J ST 㛵ᩘࢆᣢࡘ scaled
Schrödinger ᪉⛬ᘧࢆ⪃ᐹࡍࡿ࡜ࠊ J ST 㛵ᩘࡣḟࡢ 2 ࡘࡢᛶ㉁ࢆᣢࡘ࡭ࡁ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡿࠋ
 UЍU ⾪✺఩⨨  J ST 

UST

 

 UЍ ⾪✺ࡢ࡞࠸㡿ᇦ  J ST UST o ࠉᐃᩘ㸧 ࡣ⾪✺㡿ᇦ࡛ Kato ࡢ࢝ࢫࣉ᮲௳ࢆグ㏙࡛ࡁࡿࡇ࡜ࠊ(2)ࡣ⾪✺ࡢ࡞࠸㡿ᇦ UЍ࡟࠾࠸࡚ࡣࠊ6FDOHG
6FKU|GLQJHU ᪉⛬ᘧࡣ 6FKU|GLQJHU ᪉⛬ᘧ࡟₞㏆ࡍ࡭ࡁࡇ࡜ࠊ࡟ࡼࡿࠋᡃࠎࡣ J 㛵ᩘࢆୗࡢ  ࡘ࡟ศ㢮ࡋ࡚◊✲ࡋࡓࠋ    ࡜  ࢆඹ࡟‶ࡓࡍ≀⌮ⓗ࡟ṇࡋ࠸ J 㛵ᩘ㸹         ṇࡋ࠸㸦FRUUHFW㸧࡞ J 㛵ᩘ    ࢝ࢫࣉ᮲௳ ࡢࡳࢆ‶ࡓࡍ J 㛵ᩘ㸹                ࡲࡎࡲࡎ㸦UHDVRQDEOH㸧࡞ J 㛵ᩘ

UST ࢆ V ST ࡛⨨ࡁ᥮࠼ࡓ reasonable ࡟࡞ࡾᚓ࡞࠸ J 㛵ᩘ  ㏆ఝⓗ㸦DSSUR[LPDWH㸧࡞ J 㛵ᩘ⾲  ࡛ࡣࠊ≉࡟  㟁Ꮚ┦㛵ࢆ⾲ࡍ J 㛵ᩘ࡟ࡘ࠸࡚ࠊᵝࠎ࡞㛵ᩘᙧࢆ⪃࠼ࠊ✚ศࡢᐜ᫆࡞ +H ཎᏊࢆ⏝࠸᳨࡚ドࡋࡓࠋ㹼 ࡣ  ࡘࡢ㛵ᩘ࠿ࡽᡂࡿ J 㛵ᩘࠊ㹼 ࡣ」ᩘࡢ㛵ᩘ࠿ࡽ࡞ࡿ J 㛵ᩘ࡛࠶ࡿࠋࡇࢀࡽࡢ㛵ᩘࡣࠊୖࡢ⪃ᐹ࠿ࡽࡑࢀࡒࢀࠊFRUUHFWUHDVRQDEOHDSSUR[LPDWH
࡜ศ㢮ࡉࢀࡿࠋ´&RUUHFW´࡜´5HDVRQDEOH´ࡢࢡࣛࢫ࡛ࡣࠊ࡯ࡰⰋ࠸⤖ᯝࢆᚓ࡚࠸ࡿࡀࠊࡑࡢ୰ࡢ᭱ᝏࡣࡴࡋࢁᬑ
㏻࡟⏝࠸ࡽࢀࡿ ULM ࡛࠶ࡿࠋ≉࡟ࠊ´&RUUHFW´࡟ศ㢮ࡉࢀࡿ    H[S J  U  DUFWDQ J  U  ¦N  FN ª¬  H[S J N U º¼  F ª¬  H[S J  U º¼  F DUFWDQ J  U ࡣࠊࡑࡢྡࡢ㏻ࡾ㸦⌮ㄽ㏻ࡾ㸧㠀ᖖ࡟Ⰻ࠸⤖ᯝࢆ୚࠼࡚࠸ࡿࠋ´$SSUR[LPDWH´
ࡢ୰࡛ࡶࠊᚑ᮶ࡢ J V ࡜ẚ࡭ࡿ࡜ࡑࡢ௚ࡢ㛵ᩘࡢ⤖ᯝࡣ኱ࡁࡃᨵၿࡉࢀ࡚࠸ࡿࠋV ࡣࠊU ࡟ẚ࡭㟁Ꮚ⾪- 96 -

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ࡇࢀࡽࡢ J 㛵ᩘࡣࠊከ㟁Ꮚ⣔ࡢ୍⯡ⓗ࡞ཎᏊ࣭ศᏊ࡛ࡶ᭷ຠ࡛࠶ࡿ࡜⪃࠼ࡽࢀࠊࡼࡾࢥࣥࣃࢡࢺ࡞ FI ࡛ຠ⋡ⓗ࡟ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞ゎࢆᚓࡿ᪂ࡋ࠸㟁Ꮚ≧ែ⌮ㄽ࡟Ⓨᒎࡍࡿྍ⬟ᛶࡀ࠶ࡿࠋ⌧ᅾࠊ୍⯡ཎᏊ࣭ศᏊ࡟
࠾࠸࡚ࡶࠊࡇࢀࡽࡢ J 㛵ᩘࢆ⏝࠸ࡓィ⟬ࢆ⾜࠺ࡓࡵࡢ✚ศἲࡢ㛤Ⓨ࡜ࢧࣥࣉࣜࣥࢢἲ /6( ἲ ࡟ࡼࡿィ⟬ࢆే⏝ࡋ◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ
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- 97 - 

(  ┦ᑐㄽࢹ࢕ࣛࢵࢡࢡ࣮ࣟࣥ᪉⛬ᘧࡢゎἲ ㏫ࣁ࣑ࣝࢺࢽ࢔ࣥ」⣲ࢫࢣ࣮ࣜࣥࢢἲࡢᥦ᱌
㔜ඖ⣲໬Ꮫ࡛ࡣࠊ┦ᑐㄽຠᯝࡀᮏ㉁ⓗ࡟㔜せ࡛࠶ࡾࠊ㠀┦ᑐㄽࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧ࡟௦ࢃࡾ┦θ=0.01
θ=0.05 11S: (1s)2
θ=0.1
21S: (1s)(2s)
31S: (1s)(3s)θ=0.2Real axis

-0.2
-0.4

࡟᏶ഛ࡛࡞ࡃࠊLorentz ኚ᥮࡟ᑐࡍࡿ୙ኚᛶࡀ‶ࡓࡉ

-0.6
-6

ࢀ࡞࠸ࠋࡑࢀ࡛ࡶࠊ໬Ꮫ⌧㇟࡟࠾ࡅࡿ┦ᑐㄽຠᯝࡢ
グ㏙࡟ࡣ༑ศ࡟⢭ᐦ࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇ

ࡢ 2005 ᖺࡢㄽᩥ(Phys. Rev. Lett. 95, 050407 (2005).)

Im(Energy) (a.u.)

exact ࡛ࣞ࣋ࣝゎ࠿ࢀࡓ◊✲ࡣ࡯ࡰⓙ↓࡛࠶ࡾࠊᡃࠎ

-5

-4
-3
-2
Re(Energy) (a.u.)

Regularࡢࡼ࠺࡞ᛶ㉁ࡢࡓࡵࠊࢹ࢕ࣛࢵࢡ-ࢡ࣮ࣟࣥ᪉⛬ᘧࢆ

࡛ࡢ FC ⌮ㄽ࡟ࡼࡿ He ཎᏊ➼㟁Ꮚ⣔ࡢ exact ィ⟬ࡼࡾ௚࡟ࡣ࡞࠸ࠋ

Regularࡋࠊከ㟁Ꮚ⣔࡛ࡣࠊồࡵࡓ࠸㟁Ꮚ≧ែゎࡀ㐃⥆≧ែ࡟ᇙࡶࢀࡿ Brown-Ravenhall disease (㐃⥆≧ែゎ࡜ࡢ㠀≀⌮ⓗ┦஫స⏝)ࡀ㉳ࡇࡾᚓࡿࠋࡑࡇ࡛ࠊᡃࠎࡣࠊ
㏫ࣁ࣑ࣝࢺࢽ࢔ࣥἲ࡜ඹ࡟ඹ㬆≧ែࢆᢅ࠺」⣲ࢫࢣ࣮ࣜࣥࢢἲࢆᑟධࡍࡿࡇ࡜࡛ࠊኚศᔂቯࡢၥ㢟࡜㐃⥆≧ែゎࡢၥ㢟ࢆඹ࡟ゎỴࡍࡿ᪉ἲࢆᥦ᱌ࡋࡓࠋIm(Energy) (a.u.)

unbound problem (ኚศᔂቯࡢၥ㢟)ࢆゎỴࡋࡓࠋࡋ࠿

0.2
0
θ=0.01
θ=0.05
11S: (1s)2
21S: (1s)(2s)θ=0.1
31S: (1s)(3s)θ=0.2Real axis

-0.2
-0.4

-0.6
-1

0

-6

-5

Th88+ (Z=90)

1000
800
600
400
200
0
-200
-400
11S: (1s)2-600
21S: (1s)(2s)-800
31S: (1s)(3s)-1000-20000 -15000 -10000 -5000
Re(Energy) (a.u.)ࡇࡢ 2005 ᖺࡢㄽᩥ࡛ࡣࠊ㏫ࣁ࣑ࣝࢺࢽ࢔ࣥἲࢆ
ᑟධࡍࡿࡇ࡜࡛ࠊࢹ࢕ࣛࢵࢡ-ࢡ࣮ࣟࣥ᪉⛬ᘧࡢIm(Energy) (a.u.)0

Im(Energy) (a.u.)య┦஫స⏝(ࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝ)ࡢࡓࡵ┦ᑐㄽⓗ

0.4

0.2

0

Nh111+ (Z=113)

1000
800
600
400
200
0
-200
-400
11S: (1s)2-600
21S: (1s)(2s)
31S: (1s)(3s)
-800
-1000
-20000 -15000 -10000 -5000
Re(Energy) (a.u.)

0

-4
-3
-2
Re(Energy) (a.u.)-10Inverse

1000
800
600
400
200
0
-200
-400
11S: (1s)2-600
21S: (1s)(2s)
31S: (1s)(3s)
-800
-1000
-20000 -15000 -10000 -5000
Re(Energy) (a.u.)Im(Energy) (a.u.)ࡋ࠿ࡋࠊࢹ࢕ࣛࢵࢡ-ࢡ࣮ࣟࣥ᪉⛬ᘧࡣࠊྂ඾ⓗ࡞ 2

Inverse

0.6

0.4

Im(Energy) (a.u.)ᑐㄽࢹ࢕ࣛࢵࢡ-ࢡ࣮ࣟࣥ᪉⛬ᘧࢆゎࡃᚲせࡀ࠶ࡿࠋHe (Z=2)

Regular

0.6

0Inverse

1000
800
600
400
200
0
-200
-400
11S: (1s)2-600
21S: (1s)(2s)
31S: (1s)(3s)
-800
-1000
-20000 -15000 -10000 -5000
Re(Energy) (a.u.)0

ᅗ 3. ㏫ࣁ࣑ࣝࢺࢽ࢔ࣥ-」⣲ࢫࢣ࣮ࣜࣥࢢἲ࡟ࡼࡿ
ᅛ᭷್(」⣲࢚ࢿࣝࢠ࣮)ࡢศᕸ

ᅗ 3 ࡟ࠊ㏫ࣁ࣑ࣝࢺࢽ࢔ࣥ-」⣲ࢫࢣ࣮ࣜࣥࢢἲ࡟ࡼࡿ He ཎᏊ➼㟁Ꮚ⣔ࡢ」⣲࢚ࢿࣝࢠ࣮ࡢศᕸࢆ♧ࡋࡓࠋ㐃⥆≧ែࢆྵࡴ㠀≀⌮ⓗ࡞ゎࡣࠊ」⣲ᖹ㠃ࡢᅇ㌿ ș ࡟ࡼࡗ࡚」⣲ᗙᶆᖹ㠃࡛ᅇ㌿ࡍࡿࡀࠊ≀⌮ⓗ࡞㟁Ꮚ≧ែゎࡣȟ࡟౫Ꮡࡏࡎᐇ㍈ୖ࡟Ꮡᅾࡋ࡚࠸ࡿࠋᚑ᮶ࡢࣁ࣑ࣝࢺࢽ࢔ࣥ(Regular)࡛ࡣࠊ㟁Ꮚ≧ែゎࡢ࿘ࡾ࡟ከࡃࡢ
㠀≀⌮ⓗ࡞ゎࡀᏑᅾࡍࡿࠋ୍᪉ࠊ㏫ࣁ࣑ࣝࢺࢽ࢔ࣥἲࢆ⏝࠸ࡿ࡜ࠊኚศᔂቯࡢၥ㢟࡟㉳ᅉࡍࡿ㠀≀⌮ⓗ࡞ゎࡣ᭱ึ࠿ࡽᏑᅾࡋ࡞࠸ࠋࡑࡢࡓࡵࠊ㐃⥆≧ែゎ࡜ࡢ᭱ᑠ㝈ࡢ࢝ࢵࣉࣜࣥࢢࡢࡳࡀ」⣲ࢫࢣ࣮ࣜࣥࢢἲ࡟ࡼࡗ
࡚ゎ࠿ࢀࠊࢹ࢕ࣛࢵࢡ-ࢡ࣮ࣟࣥ᪉⛬ᘧࡢゎࡀṇࡋࡃồࡵࡽࢀࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋ㔜ඖ⣲࡟࡞ࡿ࡯࡝ࡇࡢ
ຠᯝࡣ㢧ⴭ࡛ࠊ」⣲ᗙᶆ㠃ୖࡢഹ࠿࡞ᅇ㌿࡛ࡶᏳᐃ࡟ゎࡀồࡵࡽࢀࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢᡂᯝࡣࠊChem.
Phys. Lett. 749, 137447 (2020).࡟ᥖ㍕ࡉࢀࡓࠋㅰ㎡ศᏊ◊ィ⟬ᶵࢭࣥࢱ࣮࡟ࡣࠊ ᖺᗘࡶᑓ᭷ࢡࣛࢫࢱ࣮ㄢ㢟ࡢ฼⏝ࢆㄆࡵ࡚㡬ࡁࠊࡑࡢィ⟬ᶵࣃ࣮࣡࡟ࡼࡗ࡚㔜せ࡞ᡂᯝࢆẚ㍑ⓗ㏿ࡃᚓࡿࡇ࡜ࡀ࡛ࡁࡲࡋࡓ஦ࠊࡇࡇ࡟῝ࡃឤㅰ⏦ࡋୖࡆࡿࠋ௒ᚋࡶࠊ㈗ࢭࣥࢱ࣮ࡢ
ィ⟬ᶵ㈨※ࢆࡼࡾຠ⋡ⓗ࡟฼⏝࡛ࡁࡿࡼ࠺ࠊᘬࡁ⥆ࡁ᪉ἲㄽ࡜ࣉࣟࢢ࣒ࣛࡢ㛤Ⓨ࣭ᨵⰋࢆ㐍ࡵࠊࡦ࠸࡚ࡣࠊ
㔞Ꮚ໬Ꮫࡢ◊✲ศ㔝ࢆඛᑟࡋ⥆ࡅࡽࢀࡿࡼ࠺࡞ࠊ໬Ꮫⓗ౯್ࡢ㧗࠸ィ⟬ࢆᐇ⾜ࡋ࡚࠸ࡁࡓ࠸ࠋ

- 98 -

Ⓨ⾲ࠊฟ∧ᐇ⦼ࡲࡓࡣணᐃ

Ⓨ⾲ㄽᩥ‫ ۻ‬1) Tomoo Miyahara and Hiroshi Nakatsuji, “Photoelectron Spectrum of NO2−: SAC-CI Gradient Study ofVibrational-Rotational Structures”, J. Comput. Chem., 40, 360-374 (2019).
‫ۻ‬2) Hiroshi Nakatsuji and Hiroyuki Nakashima, “Solving the Schrödinger equation with the free-complement
chemical-formula theory. Variational study of the ground and excited states of Be and Li atoms”, J. Chem. Phys., 150,
044105-1-24 (2019).
‫ ۻ‬3) Tomoo Miyahara and Hiroshi Nakatsuji, “Light-Driven Proton, Sodium Ion, and Chloride Ion Transfer
Mechanisms in Rhodopsins: SAC-CI Study”, J. Phys. Chem. A, 123, 1766-1784 (2019)‫ۻ‬4) 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 Σ symmetry”, Phys. Chem. Chem. Phys., 21, 6327-6340(2019).
‫ۻ‬5) 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).
‫ۻ‬6) 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., in press.
‫ۻ‬7) Hiroshi Nakatsuji, Hiroyuki Nakashima, and Yusaku I. Kurokawa, “Solving the Schrödinger equation of atoms andmolecules using one- and two-electron integrals only”, Phys. Rev. A, in press.
‫ۻ‬8) Hiroshi Nakatsuji, Hiroyuki Nakashima, and Yusaku I. Kurokawa, “Scaled Schrödinger equation and the accurate
variational theories therefrom”, to be submitted.
୺せ࡞Ꮫ఍Ⓨ⾲‫ۻ‬1) ୰㎷ ༤ࠊ³㔞Ꮚ⏕࿨⛉Ꮫ࡬ࡢ㔞Ꮚ໬Ꮫ࡟ࡼࡿ࢔ࣉ࣮ࣟࢳ´ࠊ 㔞Ꮚ⏕࿨⛉Ꮫ ➨ 1 ᅇ኱఍ࠊ ᮾி኱Ꮫᘺ⏕ㅮᇽࠊ 2019 ᖺ 5 ᭶ 23 ᪥ࠋᣍᚅㅮ₇ࠋ‫ۻ‬2) ୰㎷ ༤ࠊ୰ᔱ ᾈஅࠊ㯮ᕝ ᝆ⣴ࠊ“ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢṇ☜࡞ゎἲ࡟ᇶ࡙ࡃ᪂ࡋ࠸㔞Ꮚ໬Ꮫࡢᘓタ”, ➨  ᅇ⌮ㄽ໬Ꮫウㄽ఍ࠊᮐᖠ(໭ᾏ㐨኱Ꮫ)ࠊ2019 ᖺ 5 ᭶ 27-29 ᪥ࠋ‫ۻ‬3) ୰ᔱ ᾈஅࠊ㯮ᕝ ᝆ⣴ࠊ୰㎷ ༤ࠊ“)& ⌮ㄽ࡟ࡼࡿ H[DFW ࡟⮳ࡿィ⟬ࡢࡓࡵࡢ 6ODWHU ᆺ㛵ᩘࡢ✚ศἲ࡜ࣉࣟࢢ࣒ࣛࡢ㛤Ⓨ”, ➨  ᅇ⌮ㄽ໬Ꮫウㄽ఍, ᮐᖠ(໭ᾏ㐨኱Ꮫ)ࠊ2019 ᖺ 5 ᭶ 27-29 ᪥ࠋ‫ۻ‬4) 㯮ᕝ ᝆ⣴ࠊ୰ᔱ ᾈஅࠊ୰㎷ ༤ࠊ“&KHPLFDO)RUPXOD7KHRU\ ࡜ )UHH&RPSOHPHQW ἲ࡟ࡼࡿཎᏊ࣭ศᏊࡢ
ᇶᗏ࣭ບ㉳≧ែࡢኚศἲ࡟ࡼࡿィ⟬”ࠊ➨  ᅇ⌮ㄽ໬Ꮫウㄽ఍ࠊᮐᖠ(໭ᾏ㐨኱Ꮫ)ࠊ2019 ᖺ 5 ᭶ 27-29 ᪥‫ۻ‬5) ୰㎷ ༤ࠊ୰ᔱ ᾈஅࠊ㯮ᕝ ᝆ⣴ࠊ“ࢩ࣮ࣗࣞࢹ࢕࣮ࣥ࢞᪉⛬ᘧࡢṇ☜࡞ゎἲ࡟ᇶ࡙ࡃࠊ᪂ࡋ࠸㔞Ꮚ໬Ꮫࡢᘓタ”ࠊ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇ(ྡྂᒇ኱Ꮫ)ࠊ2019 ᖺ 9 ᭶ 17-20 ᪥ࠋ‫ۻ‬6) 㯮ᕝ ᝆ⣴ࠊ୰ᔱ ᾈஅࠊ୰㎷ ༤ࠊ“*DXVV ᆺᇶᗏࢆ⏝࠸ࡓ )&&)7 ἲ࡟ࡼࡿཎᏊ࣭ศᏊࡢィ⟬”ࠊ➨ ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇ(ྡྂᒇ኱Ꮫ)ࠊ2019 ᖺ 9 ᭶ 17-20 ᪥ࠋ‫ۻ‬7) ୰ᔱ ᾈஅࠊ㯮ᕝ ᝆ⣴ࠊ୰㎷ ༤ࠊ“6ODWHU ᆺ㛵ᩘࡢ✚ศࣉࣟࢢ࣒ࣛ㛤Ⓨ࡜ )& ⌮ㄽ࡟ࡼࡿཎᏊࡢ㧗⢭ᗘィ⟬”ࠊ➨  ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇ(ྡྂᒇ኱Ꮫ)ࠊ2019 ᖺ 9 ᭶ 17-20 ᪥ࠋ‫ۻ‬8) Hiroyuki Nakashima, Hiroshi, Nakatsuji, “Implementation of Slater-type one-center atomic integrals for accurate
variational calculations of small atoms by free complement theory”, The 9th Asia-Pacific Conference of Theoreticaland Computational Chemistry (APCTCC9), Sydney, Australia, Sep. 30-Oct. 4 (2019) (Invited).



ཷ㈹࡞࡝

ཷ㈹
‫ۻ‬1) Hiroyuki Nakashima, “2020 Pople Medal” from the Asia-Pacific Association of Theoretical & Computational
Chemists (APATCC).

- 99 -

Ⰽ⣲ቑឤ๣ࢆ⏝࠸ࡓㅖㄢ㢟࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical studies on several topics using dye-sensitizer‫ۑ‬໭ᑿ ಟࠊⲡ㛫 ோ㸦⏘ᴗᢏ⾡⥲ྜ◊✲ᡤ࣭ኴ㝧ගⓎ㟁◊✲ࢭࣥࢱ࣮㸧◊✲┠ⓗࠊෆᐜ
Ⰽ⣲ቑឤ๣ࢆ⏝࠸ࡓኴ㝧㟁ụ㸦Ⰽ⣲ቑឤኴ㝧㟁ụ㸧ࡣࠊ㓟໬≀༙ᑟయࠊ㓟໬㑏ඖ㟁ゎ㉁➼ࢆ⤌ࡳྜࢃࡏࡓ

」ྜᮦᩱ࡛ࠊᮦᩱ࠾ࡼࡧ〇㐀ࢥࢫࢺࡀᏳ౯࡞ࡇ࡜࠿ࡽḟୡ௦ᆺኴ㝧㟁ụࢹࣂ࢖ࢫ࡜ࡋ࡚ᮇᚅࡉࢀࠊ㥑ືᶵᵓ୪ࡧ࡟ኴ㝧㟁ụᛶ⬟ࡢᨭ㓄ᅉᏊ࡟㛵ࡍࡿヲ⣽࡞ゎ᫂ࡀᚅࡓࢀ࡚࠸ࡿࠋࡲࡓ⎔ቃ࡟ࡸࡉࡋ࠸ࢡࣟࣟࣇ࢕ࣝㄏᑟ
యࢆቑឤ๣୪ࡧ࡟࣮࣍ࣝ㍺㏦๣࡟⏝࠸ࡓ඲ᅛయᆺኴ㝧㟁ụࡢ㛤Ⓨࡶᮇᚅࡉࢀ࡚࠸ࡿࠋᮏㄢ㢟࡛ࡣࠊⰍ⣲ቑឤ๣࡟㛵ࡍࡿㅖ≀ᛶࢆ㠀⤒㦂ⓗ㔞Ꮚ໬Ꮫィ⟬ἲ࡛ྲྀࡾᢅ࠸ࠊࡇࢀࡽࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋලయⓗ࡟௨ୗ  ㄢ㢟࡟ࡘ࠸࡚ྲྀࡾ⤌ࢇࡔࠋ ࢡࣟࣟࣇ࢕ࣝㄏᑟయࢆቑឤ๣࡜࣮࣍ࣝ㍺㏦๣࡟⏝࠸ࡓ඲ᅛయᆺኴ㝧㟁ụ࡟ࡘ࠸᳨࡚ウࡋࡓࠋ ᨃࣁࣟࢤࣥࣞࢻࢵࢡࢫ 6H&1í± 6H&1  ࢆ⏝࠸ࡿⰍ⣲ቑឤኴ㝧㟁ụ࡟ࡘ࠸᳨࡚ウࡋࡓࠋ◊✲᪉ἲࠊィ⟬᪉ἲ*DXVVLDQ ࣉࣟࢢ࣒ࣛࢆ౑⏝ࡋࠊㄢ㢟  ࡛ࡣࢡࣟࣟࣇ࢕ࣝㄏᑟయࢆ ')7 ἲ࡟ࡼࡾᵓ㐀᭱㐺໬ࡋ୺せ㌶㐨ࢆᩚ⌮ࡋࠊ྾཰ࢫ࣌ࢡࢺࣝࢆ 7'')7 ἲ࡟ᇶ࡙࠸࡚ᵓᡂࡋࡓࠋㄢ㢟  ࡛ࡣⰍ⣲ศᏊࠊࣞࢻࢵࢡࢫศᏊࠊ୧⪅ࡢ」
ྜయࢆ ')7 ἲ࡟࡚ᵓ㐀᭱㐺໬ࡋࠊ⥆࠸࡚᣺ືゎᯒ࡜㟁Ꮚᐦᗘゎᯒࢆ⾜ࡗࡓࠋ



◊✲ᡂᯝ
 ࣮࣍ࣝ㍺㏦๣ࡢບ㉳ࢫ࣌ࢡࢺࣝ࡟㛵ࡋ࣏ࣝࣇ࢕ࣜࣥ⣔࡜ࢡࣟࣜࣥ⣔࡛㢧ⴭ࡞㐪࠸ࡀぢࡽࢀࡿࡀࠊ

7'')7 ἲ࡟ᇶ࡙ࡃゎᯒࡣᐇ㦂⤖ᯝࢆୖᡭࡃ෌⌧ࡋ୧⪅ࡢ㐪࠸ࢆㄝ࡛᫂ࡁࡓࠋ
 Ⰽ⣲㓟໬య±6H&1í」ྜయࡢィ⟬⤖ᯝ࠿ࡽࠊ௦⾲ⓗ࡞ 5X 㘒యⰍ⣲ 1 ࡣ  ࡘࡢ 6H&1í࡟ࡼࡿ㏲ḟ཯ᛂ࡟࡚ࠊ73$77$57$ ᭷ᶵⰍ⣲ࡣ  ࡘࡢ 6H&1íࡲࡓࡣ  ࡘࡢ 6H&1í࡟࡚෌㑏ඖࡉࢀࡿࡇ࡜ࢆぢ࠸ࡔࡋࡓࠋ



Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬໭ᑿࠊ⋤ࠊ$,67 ኴ㝧ගⓎ㟁◊✲ ᡂᯝሗ࿌఍ 㸦 ᖺ  ᭶ࠊࡘࡃࡤ㸧‫ⲡۻ‬㛫ࠊ$,67 ኴ㝧ගⓎ㟁◊✲ᡂᯝሗ࿌఍ 㸦 ᖺ  ᭶ࠊࡘࡃࡤ㸧 ୕▼ࠊ:DQJࠊబࠎᮌࠊዟ୰ࠊⲡ㛫ࠊᒣ⏣ࠊᇽචࠊబᒣࠊ$,67 ኴ㝧ගⓎ㟁◊✲ᡂᯝሗ࿌఍ 㸦 ᖺ ᭶ࠊࡘࡃࡤ㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬+LWRVKL.XVDPD-RXUQDORI3KRWRFKHPLVWU\DQG3KRWRELRORJ\$&KHPLVWU\  ‫ۻ‬+LWRVKL.XVDPD-RXUQDORI3KRWRFKHPLVWU\DQG3KRWRELRORJ\$&KHPLVWU\  - 100 -

⁐ᾮ⏺㠃ࡢᵓ㐀࡜ᶵ⬟ࡢィ⟬໬Ꮫ
Computational Chemistry on Structures and Functionsof Liquid Interfaces‫ۑ‬᳃⏣ ᫂ᘯࠊ㧗ᶫ ⱥ᫂ࠊ⋤ ⍅ࠊᖹ㔝 ᬛ೔ࠊᑠἨ ឡࠊෆ⸨ ᬸஓࠊ᳃ ΅ࠊఀ⸨Ꮧࠊబ⸨ ኱࿴㸦ᮾ໭኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧

1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊ୺࡟⁐ᾮ⏺㠃ࡢゎ᫂ࢆ┠ᣦࡋ࡚ᐇ㦂◊✲࡜ࡢඹྠࡢࡶ࡜࡟ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࡸ

㟁Ꮚ≧ែィ⟬࡟ࡼࡿ◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ⁐ᾮ⏺㠃ࡣᐇ㦂ⓗ࡟ศᏊ࡛ࣞ࣋ࣝ⢭ᐦ࡟ほࡍࡿࡇ࡜ࡀ㞴ࡋࡃࠊ⌮ㄽィ⟬࡜ࡢ༠ຊࡀ࡜ࡾࢃࡅᚲせ࡜ࡉࢀࡿࠋࡇࢀࡲ࡛ࡼࡾ⏺㠃㠀⥺ᙧศගࡢ⌮ㄽィ⟬ᡭἲࡢ㛤Ⓨ࡟ᇶ࡙࠸࡚ࡑ
ࡢᛂ⏝ࢆ㐍ࡵ࡚ࡁࡓࠋᮏᖺᗘ࡟ࡣ⌮ㄽゎᯒᡭἲࢆᅛᾮ⏺㠃࡟ᒎ㛤ࡋࠊ⏺㠃ศග⌮ㄽࢆ῝໬ࡉࡏࡿ࡜࡜ࡶ࡟஧
ḟ㟁ụ࡟㛵ࢃࡿ㟁ᴟ̺㟁ゎ㉁⏺㠃ࡢ◊✲ࢆ⾜ࡗࡓࠋࡲࡓࠊἜỈ⏺㠃࡛ࡢ࢖࢜ࣥ㍺㏦ࡢ◊✲ࢆ⾜࠸ࠊ࢖࢜ࣥ㍺㏦ࡢゐ፹ຠᯝࢆ♧ࡍᶵᵓࢆศᏊ࡛ࣞ࣋ࣝ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࡟ࡣศᴟࣔࢹࣝࢆᅛᾮ
⏺㠃࡬ᛂ⏝ࡍࡿ㛤Ⓨࢆᐇ᪋ࡋࡓࠋࡲࡓ࢖࢜ࣥ㍺㏦ࢆྲྀࡾᢅ࠺ࡓࡵࡢࣉࣟࢢ࣒ࣛ FreeFlex ࢆ㛤ⓎࡋࠊἜỈ⏺㠃ࡢᵓ㐀ࡺࡽࡂࡢᗙᶆࢆᣑᙇࡋ࡚ྲྀࡾධࢀࡿᐇ⿦ࡶ⾜ࡗࡓࠋ

3

◊✲ᡂᯝ

[1] ᅛᾮ⏺㠃ࡢ࿴࿘Ἴศග ࿴࿘Ἴศගࡢ᣺ືࢫ࣌ࢡࢺࣝࡣࠊ୍⯡࡟⏺㠃㠀⥺ᙧឤཷ⋡ࡢ᣺ືᩘ౫Ꮡᛶ࡟ࡼࡗ࡚⌮ゎࡉࢀࡿࠋࡋ࠿ࡋ⏺
㠃ศග࡟ࡣ୍⯡࡟⏺㠃ࣇࣞࢿࣝಀᩘࡶࢩࢢࢼࣝ࡟㛵୚ࡋࠊࡑࡢศᩓࡀࢫ࣌ࢡࢺࣝᙧ≧ࢆᨭ㓄ࡍࡿሙྜࢆ᫂ࡽ
࠿࡟ࡋࡓࠋ౛࠼ࡤ᭷ᶵ⁐ᾮࡢ࿴࿘Ἴศගゎᯒ࡛ࡋࡤࡋࡤ⏝࠸ࡿ C=O ఙ⦰ࣂࣥࢻࡣࠊ㠀ᖖ࡟኱ࡁ࡞㉥እ྾཰ࢆ♧ࡋࠊࣇࣞࢿࣝಀᩘࡢศᩓࡶ኱ࡁ࠸ࠋᐇ㦂ࢢ࣮ࣝࣉ࡜ඹྠ࡛ࡇࢀࡽࡢ᣺ືࣂࣥࢻࡢ」⣲ᒅᢡ⋡ࢆᐃ㔞ⓗ࡟᫂ࡽ࠿࡟ࡍࡿ࡜࡜ࡶ࡟ࠊࣇࣞࢿࣝಀᩘࡀ࿴࿘Ἴࢫ࣌ࢡࢺࣝࢆᨭ㓄ࡍࡿሙྜࡢ᮲௳ࢆ᫂ࡽ࠿࡜ࡋࡓࠋ࡜ࡃ࡟ᅛᾮ
⏺㠃ࡢࡼ࠺࡟㠀⥺ᙧឤཷ⋡ࡢ㠀ඹ㬆ࣂࢵࢡࢢࣛ࢘ࣥࢻࡀ኱ࡁ࠸ሙྜࠊࡑࡢຠᯝࡀ㢧ⴭ࡟࡞ࡾࠊࡇࢀࡣ஧ḟ㟁ụࡢ㟁ᴟࡢࡼ࠺࡞㠀Ỉ⁐፹ࡢᅛᾮ⏺㠃࡞࡝࡛ࡣᙉࡃ㛵ࢃࡿຠᯝ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

[2] ἜỈ⏺㠃࡟࠾ࡅࡿゐ፹ⓗ㍺㏦ࡢᶵᵓࡢゎ᫂ ◳ࡃ࡚ᑠࡉ࠸ぶỈⓗ࡞࢖࢜ࣥࡢἜỈ⏺㠃ࡢ⛣ືࡣ୍⯡࡟ᅔ㞴࡛࠶ࡿࡀࠊᚤ㔞ࡢ࢝࢘ࣥࢱ࣮࢖࢜ࣥࡢᏑᅾ࡟
ࡼࡗ࡚๻ⓗ࡟ಁ㐍ࡉࢀࡿࡇ࡜ࡀ࠶ࡿࠋࣇࢵ⣲࢖࢜ࣥ F- ࡢ⛣ືࡢሙྜࠊࢸࢺࣛ࣊࢟ࢩࣝ࢔ࣥࣔࢽ࣒࢘࢖࢜ࣥ
([N(CnH2n+1)4]+, n=6) ࡣ᫂ࡽ࠿࡞ゐ፹ຠᯝࢆ♧ࡍࡀࠊn=4 ࡛ࡣ♧ࡉ࡞࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣ࢖࢜ࣥ㍺㏦࡜࢝࢘ࣥࢱ࣮࢖࢜ࣥ࡜ࡢ࢖࢜ࣥ࣌࢔ᙧᡂࡢ୧᪉ࢆグ㏙ࡍࡿከḟඖ⮬⏤࢚ࢿࣝࢠ࣮㠃ࢆィ⟬ࡋ࡚ࠊࡑࡢ
ゐ፹ຠᯝࡢᶵᵓࡢ඲ㇺࢆゎ᫂ࡋࡓࠋnm ࣮࢜ࢲ࣮ࡢ⏺㠃ᒙ࡛ transient ࡞࢖࢜ࣥ࣌࢔ࢆᙧᡂࡍࡿሙྜ࡜ࡋ࡞࠸ሙ
ྜࡢ 2 ࡘࡢ཯ᛂ⤒㊰ࡀ୍⯡࡟Ꮡᅾࡍࡿࡀࠊࡑࢀࡒࢀࡢ┦ᑐⓗ࡞άᛶ໬㞀ቨ࡟ࡼࡗ࡚཯ᛂᶵᵓࡀ bifurcate ࡍࡿ- 105 -

ࡇ࡜ࢆ᫂ࡽ࠿࡜ࡋࡓࠋ⏺㠃࡛ࡢ࢖࢜ࣥ㍺㏦ࢆࢥࣥࢺ࣮ࣟࣝࡍࡿୖ࡛ࡶᚤどⓗ࡟㔜せ࡞ᡂᯝ࡜࡞ࡗࡓࠋ

[3] ᾮᾮ⏺㠃࡟࠾ࡅࡿ㟁Ꮚ⛣ື཯ᛂᶵᵓ ぶỈᛶࡢヨ⸆࡜␯Ỉᛶࡢヨ⸆ࡀἜỈ⏺㠃ࢆࡲࡓ࠸࡛㟁Ꮚ⛣ືࢆ㉳ࡇࡍ཯ᛂࡣࠊ࢚ࢿࣝࢠ࣮ᤕ㞟ࢹࣂ࢖ࢫ࡞
࡝࡬ࡢᛂ⏝ࡶᮇᚅࡉࢀࡿ⌧㇟࡛࠶ࡿࡀࠊࡑࡢ⏺㠃࡛ࡢ཯ᛂᶵᵓࢆ㟁Ẽ໬Ꮫᐃ࠿ࡽ᥎ᐃࡍࡿࡇ࡜ࡣ୍⯡࡟ࡣᅔ㞴ࢆక࠺ࠋ᭱ࡶ඾ᆺⓗ࡞㟁Ꮚ⛣ື࡛࠶ࡿぶỈᛶࡢ࣊࢟ࢧࢩ࢔ࣀ㕲࢖࢜ࣥ࡜␯Ỉᛶࡢࣇ࢙ࣟࢭࣥ࡜ࡢ㟁Ꮚ⛣ື࡛ࡶࠊ⏺㠃࡛㟁Ꮚ⛣ືࡀ㉳ࡇࡿࡢ࠿㸦୙ᆒ୍཯ᛂ㸧ࠊࣇ࢙ࣟࢭࣥࡀỈ୰࡟ධࡗ࡚཯ᛂࡍࡿࡢ࠿㸦ᆒ୍཯ᛂ㸧ㄽதࡀ࠶ࡗࡓࠋᮏ◊✲࡛ࡣࠊศᏊࡢ⏺㠃࡬ࡢ⛣ືࠊศᏊᑐࡢᙧᡂࠊ⁐፹࿴ᦂࡽࡂࡢ 3 ࡘࢆໟᣓⓗ࡟ྲྀࡾධࢀ
ࡿ 3 ḟඖ⮬⏤࢚ࢿࣝࢠ࣮㠃ࢆィ⟬ࡋ࡚ゎᯒࡋࠊࡇࡢ཯ᛂࡣ୙ᆒ୍཯ᛂࡢ⤒㊰ࢆྲྀࡿࡇ࡜ࢆ᫂ࡽ࠿࡜ࡋࡓࠋࡉ
ࡽ࡟ᐇ㦂ⓗ࡞ࢧ࢖ࢡࣜࢵࢡ࣎ࣝࢱ࣓ࣥࢺ࣮ࣜࡢゎᯒࡶ⾜࠸ࠊᚑ᮶ᆒ୍཯ᛂࢆ࡜ࡿドᣐ࡜⪃࠼ࡽࢀ࡚ࡁࡓᐇ㦂⤖ᯝࡣࠊᐇࡣ୙ᆒ୍཯ᛂ࡜ࡋ࡚⌮ゎࡉࢀࡿࡇ࡜ࡶ♧ࡋ࡚ࡇࡢၥ㢟ࢆゎỴࡋࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃմ⋤ ⍅ࠊElectrode/Electrolyte Interfaces: Observation and Analysis, ESICB 㟁Ꮚㄽ᳨ウ఍ࠊ὾ᯇࠊ2019. 12. 23-24.
մ᳃⏣ ᫂ᘯࠊᾮయ⏺㠃ࡢᵓ㐀࡜ᶵ⬟ࢆゎ᫂ࡍࡿィ⟬ศᏊ⛉Ꮫࠊࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣮࣡ࢡࢩࣙࢵࣉࠊᒸ
ᓮࠊ2019. 12. 19-20.
մL. Wang, S. Nihonyanagi, K. Inoue, K. Nishikawa, A. Morita, S. Ye, and T. Tahara, Microscopic Structure of
Electrode/electrolyte Interface Probed by Molecular Simulation and Sum Frequency Generation Spectroscopy(FI-13-P24), Materials Research Meeting (MRM) 2019, Yokohama, Japan, Dec. 10-14, 2019.
մᖹ㔝 ᬛ೔ࠊ᳃⏣ ᫂ᘯࠊἜỈ⏺㠃㟁Ꮚ⛣ືࡢከḟඖ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡟ࡼࡿ཯ᛂᶵᵓゎᯒ (234P)ࠊ➨ 33ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍ࠊྡྂᒇࠊ2019. 12.9-11.
մᑠἨ ឡࠊఀ⸨ Ꮧࠊᖹ㔝 ᬛ೔ࠊ᳃⏣ ᫂ᘯࠊࢪࢡ࣓ࣟࣟࢱࣥࡢศᏊࣔࢹࣝᨵⰋ࡜ࡑࡢศᏊືຊᏛࢩ࣑ࣗࣞ
࣮ࢩࣙࣥ࡟࠾ࡅࡿࣃࣇ࢛࣮࣐ࣥࢫ (274P)ࠊ➨ 33 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍ࠊྡྂᒇࠊ2019. 12.9-11.
մL. Wang and A. Morita, Molecular Dynamics Simulation and Sum Frequency Generation Study on the Structural
Order of Langmuir Monolayers, The 5th International Conference on Molecular Simulation, Jeju, Korea, Nov. 3-6,2019.
㧗ᶫ ⱥ᫂ࠊ㕥ᒸ ኱ᶞࠊ᳃⏣ ᫂ᘯࠊ኱つᶍ QM/MM ἲ࡟ࡼࡿ PSII ࣐ࣥ࢞ࣥࢡࣛࢫࢱ࣮ࡢ㓟໬⮬⏤࢚ࢿࣝࢠ࣮ゎᯒ (2O07)ࠊ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ⛅Ꮨᖺ఍ࠊᗈᓥࠊ2019. 10. 24-25.
մ᳃⏣ ᫂ᘯࠊ࿴࿘ἼⓎ⏕ศගࡢ⌮ㄽ࡜⁐ᾮ⏺㠃ࡢᵓ㐀ゎ᫂࡬ࡢᛂ⏝ࠊ᪥ᮏ໬Ꮫ఍㟷᳃ᆅ༊ㅮ₇఍ࠊᘯ๓ࠊ2019.
10. 11.
մA. Morita, Theory and Computational Analysis of Vibrational Sum Frequency Generation Spectroscopy, ChangchunInstitute of Applied Chemistry, Changchun, China, Sep. 30, 2019.
մL. Wang, Microscopic Investigation of Organic Interfaces, Jilin Normal University, Changchun, China, Sep. 29, 2019.
մA. Morita, Theory and Computational Analysis of Vibrational Sum Frequency Generation Spectroscopy, Jilin Normal
University, Changchun, China, Sep. 29, 2019.
մ⋤ ⍅ࠊUnderstanding Interfacial Molecular Structure through Computational Analysis of Sum Frequency Generation
Spectroscopy, ໬Ꮫ⣔Ꮫ༠఍ᮾ໭኱఍ࠊᒣᙧࠊ2019. 9. 21-22.

- 106 -⋤ ⍅ࠊ஧ᮏᰗ ⪽ྐࠊ஭ୖ ㈼୍ࠊすᕝ ៞ࠊ᳃⏣ ᫂ᘯࠊྔ ῝ࠊ⏣ཎ ኴᖹࠊEffect of Frequency-dependent Fresnel
Factor on the Lineshape of Vibrational Sum Frequency Generation Spectroscopy (1P051)ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊ
ྡྂᒇࠊ2019. 9. 17-20.
బࠎᮌ ఙ୍ࠊዟ㔝 ᑗᡂࠊ▼ᒣ 㐩ஓࠊ᳃⏣ ᫂ᘯࠊ▼ᶫ Ꮥ❶ࠊ✵Ẽ㸭㝧࣭㝜࢖࢜ࣥᛶΰྜ⏺㠃άᛶ๣Ỉ⁐ᾮ⏺㠃ࡢỈศᏊࡢ HD-VSFG ศග (2B05)ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019. 9. 17-20.
մఀ⸨ ᏗࠊᑠἨ ឡࠊᖹ㔝 ᬛ೔ࠊෆ⸨ ᬸஓࠊ᳃⏣ ᫂ᘯࠊᾮᾮ⏺㠃ࡢ࢖࢜ࣥ㍺㏦࡟࠾ࡅࡿᶆ‽㏿ᗘᐃᩘࡢホ
౯ (2P020)ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019. 9. 17-20.
㧗ᶫ ⱥ᫂ࠊ㕥ᒸ ኱ᶞࠊ᳃⏣ ᫂ᘯࠊQM/MM-ER ἲ࡟ࡼࡿ PSII ࣐ࣥ࢞ࣥࢡࣛࢫࢱ࣮ࡢග㓟໬ࡢ⮬⏤࢚ࢿࣝࢠ࣮ゎᯒ (2P087)ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019. 9. 17-20.
մᖹ㔝 ᬛ೔ ࠊ᳃⏣ ᫂ᘯࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿἜỈ⏺㠃㟁Ꮚ⛣ືࡢ཯ᛂ⤒㊰ゎᯒ (3B15)ࠊ➨
13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019. 9. 17-20.
մᑠἨ ឡࠊ⏣ཎ ᐶᩥࠊᖹ㔝 ᬛ೔ࠊᓊᮏ ┤ᶞࠊ᳃⏣ ᫂ᘯࠊἜỈ⏺㠃࡟࠾ࡅࡿ┦㛫⛣ືゐ፹ࡢᚤどⓗ◊✲ (3B17)ࠊ
➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019. 9. 17-20.
᳃ ΅ࠊᖹ㔝 ᬛ೔ࠊ⋤ ⍅ࠊ᳃⏣ ᫂ᘯࠊ࿴࿘ἼⓎ⏕ศග࡟࠾ࡅࡿࣂࣝࢡᅄ㔜ᴟຠᯝࡢỗ⏝ィ⟬ࣉࣟࢢ࣒ࣛࡢ
㛤Ⓨ (3P057)ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019. 9. 17-20.
մబ⸨ ኱࿴ࠊᖹ㔝 ᬛ೔ࠊ⋤ ⍅ࠊྔ ῝ࠊ᳃⏣ ᫂ᘯࠊࢪ࣓ࢳࣝࢫࣝ࣍࢟ࢩࢻ⁐ᾮ/ࢢࣛࣇ࢙ࣥ㟁ᴟ⏺㠃࡟࠾ࡅ
ࡿ࿴࿘ἼⓎ⏕ศග࡜⌮ㄽゎᯒ (4P055)ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019. 9. 17-20.
մෆ⸨ ᬸஓࠊ᳃⏣ ᫂ᘯࠊ⁐ᾮ⏺㠃࡟㐺⏝ࡉࢀࡿࢢࣛࣥࢻ࢝ࣀࢽ࢝ࣝศᏊືຊᏛἲࡢ㛤Ⓨ (4P103)ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019. 9. 17-20.
᳃⏣ ᫂ᘯࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜⌮ㄽ໬Ꮫࠊ➨ 13 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢫࢡ࣮ࣝ̿ᇶ♏࠿ࡽᛂ⏝ࡲ࡛̿ࠊᒸᓮࠊ2019. 9. 2-5.
մN. Naito, A. Morita, Development of Grand Canonical Molecular Dynamics Method Applied to Solution Interfaces,
Tohoku University's Chemistry Summer School 2019, Sendai, Aug. 27-28.
մA. Morita, Ion Transport Mechanisms through Liquid-Liquid Interfaces, Gordon Research Conference on Chemistry
and Physics of Liquids, Holderness, NH, USA, Aug. 4-9, 2019.
մA. Morita, Dynamics and Kinetics at Liquid-Liquid Interfaces, CPMD Meeting 2019, Lausanne, Switzerland, Jul.
22-24, 2019.
մA. Morita, Microscopic Structure and Dynamics at Water-Oil Interfaces, CECAM Workshop on "Dynamics of Waterin Complex Environments, Bridging the Gap between Molecular and Mesoscopic Interfaces", Paris, France, Jul. 15-17,
2019.
մA. Morita, Effect of Fresnel Dispersion in SFG Spectroscopy, The 2019 International Workshop on Nonlinear Optics
at Interfaces, Shanghai, China, Jun. 10-14, 2019.
մA. Morita, Molecular Dynamics Analysis of Catalytic Effect on Ion Transport through Liquid-Liquid Interface, 5thComputational Chemistry Symposium, ICCMSE2019, Greece, May 1-5, 2019.
մA. Morita, Theory and Computational Analysis of Liquid Interfaces and Spectroscopy, University of Cambridge, UK,
Apr. 30, 2019.

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5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

"In Situ Monitoring of the Unsaturated Phospholipid Monolayer Oxidation in the Ambient Air by HD-SFG
Spectroscopy"
Ken-ichi Inoue, Chunji Takada, Lin Wang, Akihiro Morita, and Shen Ye, J. Phys. Chem. B, in press (2020).
մ"Bi-layering at Ionic Liquid Surfaces: A Sum-Frequency Generation Vibrational Spectroscopy- and Molecular
Dynamics Simulation-based Study"
Takashi Iwahashi, Tatsuya Ishiyama, Yasunari Sakai, Akihiro Morita, Doseok Kim, and Yukio Ouchi, Phys. Chem.
Chem. Phys., in press (2020).
"Refractive Index of Nanoconfined Water Reveals Its Anomalous Physical Properties"
Thu H. H. Le, Akihiro Morita, and Takuo Tanaka, Nanoscale Horiz., in press (2020).
մ"Electron Transfer Mechanism at the Oil/Water Interface Revealed by Multidimensional Free Energy Calculations"
Tomonori Hirano and Akihiro Morita, J. Phys. Chem. B, 124(18), 3811-3827 (2020).
"Massively Parallel Implementation of HF-Exchange Energy on the Real-Space Grids Using 3D-Parallel FFT"
Hideaki Takahashi, Shun Sakuraba, and Akihiro Morita, J. Chem. Inf. Model., 60(3), 1376-1389 (2020).
մ"Revealing Transient Shuttling Mechanism of Catalytic Ion Transport through Liquid-Liquid Interface"Ai Koizumi, Hirofumi Tahara, Tomonori Hirano, and Akihiro Morita, J. Phys. Chem. Lett., 11(4), 1584-1588 (2020).
"Nonlinear Spectroscopy and Interfacial Structure and Dynamics"
Alexander Benderskii and Akihiro Morita, J. Chem. Phys., 151, 150401 (2019).
մ"Nuclear Quantum Effect on the Ȥ(2) Band Shape of Vibrational Sum Frequency Generation Spectra of Normal andDeuterated Water Surfaces"
Tatsuya Ishiyama and Akihiro Morita, J. Phys. Chem. Lett., 10, 5070-5075 (2019).
"Role of the Photosystem II as an Environment on the Oxidation Free Energy of the Mn Cluster from S1 to S2"
Hideaki Takahashi, Daiki Suzuoka, Shun Sakuraba, Akihiro Morita, J. Phys. Chem. B, 123(33), 7081-7091 (2019).
մ"Effect of Frequency-Dependent Fresnel Factor on the Vibrational Sum Frequency Generation Spectra for
Liquid/Solid Interfaces"
Lin Wang, Satoshi Nihonyanagi, Ken-ichi Inoue, Kei Nishikawa, Akihiro Morita, Shen Ye, Tahei Tahara, J. Phys. Chem.
C, 123(25) 15665-15673 (2019).
"Calculation of Solvation Free Energy Utilizing a Constrained QM/MM Approach Combined with a Theory of
Solutions"
Hideaki Takahashi, Hiroyuki Kambe, and Akihiro Morita, J. Chem. Phys. 150, 114109 (2019).
մ"Topologically Disordered Mesophase at Topmost Surface of Crystalline Ice between 120 and 200 K"
Toshiki Sugimoto, Yuji Otsuki, Tatsuya Ishiyama, Akihiro Morita, Kazuya Watanabe, and Yoshiyasu Matsumoto, Phys.
Rev. B 99, 121402 (2019).
մ"Molecular Structure and Vibrational Spectra at Water/Poly(2-methoxyethylacrylate) and Water/Poly(methyl
methacrylate) Interfaces: A Molecular Dynamics Simulation Study"
Sho Kishinaka, Akihiro Morita, and Tatsuya Ishiyama, J. Chem. Phys., 150, 044707 (2019).

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᪘㔠ᒓ࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࡢタィ࡜᭷ᶵࢹࣂ࢖ࢫࢆᣦྥࡋࡓⰾ㤶᪘໬ྜ≀ࡢタィ
Mechanistic studies on the olefin polymerization catalyzed by group 10
metal catalysts and design of aromatic compounds for organic
electronic devices‫ۑ‬㔝ᓮ ிᏊ㸦ᮾி኱Ꮫ኱Ꮫ㝔ᕤᏛ⣔◊✲⛉㸸໬Ꮫ⏕࿨ᕤᏛᑓᨷ㸧1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲࡛ࡣ“10 ᪘㔠ᒓ㘒య࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜゐ፹ࡢタィ”࠾ࡼࡧ“᭷ᶵࢹࣂ࢖ࢫࢆᣦྥࡋࡓⰾ㤶᪘໬ྜ≀ࡢタィ”ࢆ⾜࠸ࡲࡍࠋ᭱⤊ⓗ࡟ࡣ᪂つ໬ྜ≀タィ࡬ࡢ▱ぢࢆᚓ࡚ࠊᐇ㝿ࡢ໬ྜ≀ྜᡂ࡟཯ᫎࡉࡏࠊ᪂つᶵ⬟ࢆᣢࡘ໬ྜ≀ࡢྜᡂࢆ┠ᣦࡋࡲࡍࠋ
1.1 10 ᪘㔠ᒓ㘒య࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜࡢᶵᵓゎᯒ2019 ᖺᗘࡣࠊ10 ᪘㑄⛣㔠ᒓゐ፹ࢆࡶࡕ࠸ࡓ࢜ࣞࣇ࢕ࣥ㔜ྜࢆ┠ⓗ࡜ࡋࡲࡋࡓ (ᅗ 1)ࠋ

ᅗ 1.

ᅗ 2.

10 ᪘㑄⛣㔠ᒓࢆࡶࡕ࠸ࡓࣉࣟࣆࣞࣥࡢ㔜ྜ

Pd/IzQO ゐ፹࡟ࡼࡿࣉࣟࣆࣞࣥ࡜ᴟᛶࣔࣀ࣐࣮࡜ࡢඹ㔜ྜ࣏࢚ࣜࢳࣞࣥࡸ࣏ࣜࣉࣟࣆࣞࣥࡣ᪥ᮏᅜෆ࡛ᖺ㛫 200 ୓ t ௨ୖ⏕⏘ࡉࢀࡿ㠀ᖖ࡟㔜せ࡞ᮦᩱ࡛ࡍࡀࠊࡑࡢ
ᴟᛶࡢపࡉ࠿ࡽ┦⁐ᛶࡸ᥋╔ᛶ࡜࠸ࡗࡓᛶ㉁࡟ຎࡾࡲࡍࠋࡇࢀࡽࡢᛶ㉁ࡣᴟᛶᐁ⬟ᇶࢆᑟධࡍࡿࡇ࡜࡛ᨵၿ
ࡀྍ⬟࡛ࡍࠋࡇࡢࡓࡵࠊᴟᛶᐁ⬟ᇶᏑᅾୗ࡛ࡶάᛶࢆࡶࡘ 10 ᪘㑄⛣㔠ᒓゐ፹ࢆࡶࡕ࠸ࡓඹ㔜ྜ཯ᛂࡢ㛤Ⓨࡀ
㏆ᖺὀ┠ࢆ㞟ࡵ࡚࠸ࡲࡍࠋᡃࠎࡣ 2015 ᖺᗘ࡟ࠊ10 ᪘㔠ᒓゐ፹ࢆ⏝࠸ࡓ࢔ࢱࢡࢳࢵࢡ࣏ࣜࣉࣟࣆࣞࣥࡢྜᡂࠊ
࠾ࡼࡧࣉࣟࣆࣞࣥ࡜ᴟᛶࣔࣀ࣐࣮ࡢඹ㔜ྜࢆୡ⏺࡛ึࡵ࡚㐩ᡂࡋࡲࡋࡓࠋ(ᅗ 2; J. Am. Chem. Soc. 2015, 137,
10934.; Angew. Chem. Int. Ed.ǡ55ǡ͹ͷͲͷȂ͹ͷͲͻȋʹͲͳ͸ȌǤ) ࡋ࠿ࡋࠊࡑࡢ཯ᛂᶵᵓࡣᮍࡔ୙᫂࡞Ⅼࡀከࡃࠊᶵᵓゎᯒࡣゐ፹ᛶ⬟ࡢྥୖࡢࡓࡵ࡟㔜せ࡛ࡍࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣ࢜ࣞࣇ࢕ࣥ㔜ྜࡢᶵᵓࢆゎᯒࡋࠊゐ፹ᛶ⬟ྥୖࡢࡓࡵࡢᣦ㔪ࢆᚓࡿࡇ࡜ࢆ➨୍┠ᶆ࡜ࡋࡲࡋࡓࠋ⌮ㄽィ⟬࡛ᚓࡽࢀࡓ▱ぢ࠿ࡽ᪂つゐ፹ࢆྜᡂࡋࠊ᪤ሗࡢゐ፹- 109 -

ࢆ㉸࠼ࡿάᛶࠊ㧗ศᏊࡢศᏊ㔞ࠊ❧యไᚚࢆ㐩ᡂࡍࡿࡇ࡜ࢆ┠ᣦࡋࡲࡍࠋ
1.2 ᭷ᶵࢹࣂ࢖ࢫࢆᣦྥࡋࡓⰾ㤶᪘໬ྜ≀ࡢタィ㐣ཤ࡟ᡃࠎࡣࠊࢹࣂ࢖ࢫᵓ⠏ࢆᣦྥࡋࡓⰾ㤶᪘໬ྜ≀࡜ࡋ࡚ࠊ࣊ࣜࢭࣥᆺⰾ㤶᪘໬ྜ≀ࡢྜᡂ࡞࡝ࢆሗ࿌
ࡋ࡚࠸ࡲࡍ(ᅗ 3)ࠋ
ࡇࢀࡽࡢศᏊ࡟ᑐࡋ࡚ᑟධࡍࡿ࣊ࢸࣟඖ⣲ࢆኚ࠼ࡿࡇ࡜ࡸ, 㐺ษ࡞⨨᥮ᇶࡢᑟධ࡟ࡼࡾ, HOMO/LUMOࠊ‫ٷ‬फഀௗɼ‫ޭܮ‬ഀௗࢆࡣࡌࡵ࡜ࡍࡿㅖ≀ᛶࡢ⢭ᐦ࡞ไᚚࢆ⾜࠺ࡇ࡜ࡣ㠀ᖖ࡟㔜せ࡛ࡍࠋᮏ◊✲࡛ࡣ, DFT ィ⟬࡟ᇶ࡙ࡃ㟁Ꮚ≧ែࡢணࢆ᪂つศᏊᵓ⠏ࡢᣦ㔪࡜ࡋ, 㧗ᛶ⬟ࢹࣂ࢖ࢫᵓ⠏࡟ྥࡅࡓศᏊࡢ㛤Ⓨࢆຍ㏿ࡉࡏࡲࡍࠋ  ᅗ ⺯ගࢆⓎ⏕ࡍࡿࡽࡏࢇᆺⰾ㤶᪘໬ྜ≀ࡢ౛

2◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ࡣ඲࡚ Gaussian 09 ࡶࡋࡃࡣ Gaussian 16 ࢆ⏝࠸ DFT ィ⟬ࢆ⾜࠸ࡲࡋࡓࠋࡑࢀࡒࢀࡢィ⟬࡟⏝࠸ࡓỗ㛵ᩘ➼ࡣ௨ୗࡢ㏻ࡾ࡛ࡍࠋᵓ㐀᭱㐺໬㸸B3LYP-D3/Lanl2dz(㔠ᒓ)ࠊB3LYP-D3/6-31G(d)(ࡑࡢ௚ࡢඖ⣲) ࢚ࢿࣝࢠ࣮ィ⟬㸸B3LYP-D3 (SCRF)/Lanl2dz(㔠ᒓ)ࠊB3LYP-D3(SCRF)/6-31G(d)(ࡑࡢ௚ࡢඖ⣲) CD ࢫ࣌ࢡࢺࣝண

㸸

M06/6-31G(d,p)ࡲࡓࠊ⁐፹⿵ṇ࡟ࡣ SMD ࢆ⏝࠸ࡲࡋࡓࠋ

3

◊✲ᡂᯝ

3.1 10 ᪘㔠ᒓ㘒య࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜࡢゎᯒ
2014 ᖺ࡟ᡃࠎࡣࣜࣥୖࡢ⨨᥮ᇶ࡜ࡋ࡚㣬࿴࢔ࣝ࢟ࣝᇶࢆᣢࡘࣃࣛࢪ࣒࣭࢘࣍ࢫࣇ࢕ࣥࢫࣝ࣍ࢼ࣮ࢺゐ፹ࡢ࠿ࡉ㧗ࡉ࡛࠶ࡿ Sterimol ࡢ B5 ࣃ࣓࣮ࣛࢱࢆホ౯࡟⏝࠸ࡿࡇ࡜࡛ᚓࡽࢀࡿ࣏࣐࣮ࣜࡢศᏊ㔞ࢆㄝ᫂ࡍࡿࡇ࡜࡟
ᡂຌࡋࡲࡋࡓ(J. Am. Chem. Soc. 2014, 136, 11898̽11901.) ࡋ࠿ࡋࠊࡇࡢຠᯝࡣࡍ࡭࡚ࡢ Pd/PS 㘒య࡟㐺⏝࡛ࡁࡿࡶࡢ࡛ࡣ࠶ࡾࡲࡏࢇࠋࡑࡇ࡛ࠊ୍⯡ᛶࢆᣢࡘண

ἲࢆ┠ᣦࡋ࡚ࠊᶵᲔᏛ⩦ࢆ⏝࠸ࡓணࢆ⾜࠸ࡲࡋࡓࠋᅗ ࣃࣛࢪ࣒࣭࢘࣍ࢫࣇ࢕ࣥࢫࣝ࣍ࢼ࣮ࢺゐ፹ࢆ⏝࠸ࡓ࢚ࢳࣞࣥ㔜ྜ࡟ᑐࡍࡿ㓄఩Ꮚࡢ❧యⓗຠᯝ- 110 -

ࡑࢀࡒࢀࡢゐ፹ࡢᛶ㉁ࢆồࡵࡿࡓࡵ࡟ DFT ィ⟬ࢆ฼⏝ࡋࡲࡋࡓࠋᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓᚋ࡟ゐ፹ࡢ Sterimolࡢࣃ࣓࣮ࣛࢱ࡟௦⾲ࡉࢀࡿ❧యⓗᛶ㉁ࡸ NBO 㟁Ⲵ࡟௦⾲ࡉࢀࡿ㟁Ꮚⓗᛶ㉁࡞࡝ࢆィ⟬ࡋࡲࡋࡓࠋࡇࢀࡽࡢᛶ㉁ࢆグ㏙Ꮚ࡜ࡋ࡚ Pd/PS ࢆ⏝࠸ࡓ࢚ࢳࣞࣥ࡜࢔ࢡࣜࣝ㓟࣓ࢳࣝࡢඹ㔜ྜࡢணࢆᶵᲔᏛ⩦ࢆ⏝࠸࡚⾜࠸ࡲࡋࡓࠋࡑࡢ⤖ᯝࠊᅗ 5.ࡢ㏻ࡾ࡟࡞ࡾࡲࡋࡓࠋࡲࡓࠊ᭦࡞ࡿゎᯒࡢ⤖ᯝࠊࡇࢀࡲ࡛࡟ሗ࿌ࡉࢀࡓ Sterimol ࡢ B5ࣃ࣓࣮ࣛࢱ࡞࡝࡟ຍ࠼࡚ PȂPdȂO ࡢࣂ࢖ࢺ࢔ࣥࢢࣝࡀ኱ࡁ࡞ᙳ㡪ࢆཬࡰࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡾࡲࡋࡓࠋ

ᅗ 5. ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ Pd/PS ࡟ࡼࡿ࢚ࢳࣞࣥ/࢔ࢡࣜࣝ㓟࣓ࢳࣝඹ㔜ྜࡢ(ᕥ)ศᏊ㔞(ྑ)ゐ፹άᛶ࡟ᑐࡍࡿゎᯒࡢ⤖ᯝ

3.2 ᭷ᶵࢹࣂ࢖ࢫࢆᣦྥࡋࡓⰾ㤶᪘໬ྜ≀ࡢタィ ᡃࠎࡣࠊ⼺᪕≧ࡢศᏊ࣊ࣜࢭࣥࢆ⼺᪕㍈ࡀ┤஺ࡍࡿᙧ࡛஧ࡘ㐃⤖ࡋࡓศᏊࠊࢫࣆࣟࢲࣈࣝ࣊ࣜࢭࣥ㦵᱁ࡢᵓ⠏ࢆ⾜࠸ࡲࡋࡓ(ᅗ 6)ࠋᅗ࡟♧ࡍ㏻ࡾࠊࢫࣆࣟඖ⣲࡜ࡋ࡚ࢣ࢖⣲ࢆ⏝࠸ࡿࡇ࡜࡛ࢩࣛ[7]࣊ࣜࢭࣥࡀ஧ࡘ㐃⤖ࡋࡓᵓ㐀ࡢ໬ྜ≀ 1 ࡢྜᡂ࡟ᡂຌࡋ࡚࠸ࡲࡍࠋࡇࡢᵓ㐀࡟ࡼࡗ࡚ྠ୍ศᏊෆࡢ࣊ࣜࢭࣥ㒊఩ࡢ㓄ิ࡟ࡼࡿ㟁Ꮚ≀ᛶ࡬ࡢᙳ㡪ࢆホ౯ࡍࡿࡇ࡜ࡀྍ⬟࡛ࡍࠋᚓࡽࢀࡓⰾ㤶᪘໬ྜ≀ࡢᛶ㉁ࢆㄪ࡭ࡿࡓࡵ࡟ DFT ィ⟬ࢆ฼⏝ࡋࡲࡋࡓࠋ౛࠼ࡤࠊศᏊ୰ࡢ࣊ࣜࢭࣥ㒊఩ࡢࡽࡏࢇ཯㌿㞀ቨࢆㄪ࡭ࡿࡓࡵ࡟࢚ࢿࣝࢠ࣮ィ⟬(ᅗ 7)ࢆࠊ㦵᱁ࡢග≀ᛶ࡟㛵୚ࡍࡿศᏊ㌶㐨ࢆㄪ࡭ࡿࡓࡵ࡟ศ
Ꮚ㌶㐨ィ⟬(ᅗ 8)ࠊTD ィ⟬ࢆ⏝࠸ࡓ CD ࢫ࣌ࢡࢺࣝண(ᅗ 9)ࢆ⾜࠸ࡲࡋࡓࠋᅗ ࢫࣆࣟࢲࣈࣝࢩࣛ>@࣊ࣜࢭࣥ  ࡢྜᡂ- 111 -ᅗ  ࡢࡽࡏࢇ཯㌿㞀ቨ࢚ࢿࣝࢠ࣮ࡢィ⟬⤖ᯝ NFDOPRO ᅗ  ࡢศᏊ㌶㐨࡜ࡑࡢ࢚ࢿࣝࢠ࣮ࠊ୺せ࡞㑄⛣࡜ࡑࡢ᣺ືᏊᙉᗘࡢィ⟬⤖ᯝᅗ  ࡢ &'ࠊ&3/ ࢫ࣌ࢡࢺࣝ ᐇ⥺ ࡜ィ⟬࡛ண

ࡋࡓ &' ࢫ࣌ࢡࢺࣝ ◚⥺ 

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬Metal–Ligand Cooperative C–H Bond Formation and Cleavage by Cyclopentadienone Metal Complexes. Takuya

Higashi, Hideaki Ando, Shuhei Kusumoto, Kyoko Nozaki, 20th IUPAC International Symposium on Organometallic
Catalysis Directed Towards Organic Synthesis (OMCOS 20), Heidelberg Convention Center, Hidelberg, Germany,
2019/7/21–25, P-233 (Poster)‫ ۻ‬㔠ᒓ㓄఩Ꮚ༠ാⓗ C̽HࠊSi̽HࠊB̽H ⤖ྜࡢษ᩿࡜ゐ፹཯ᛂ࡬ࡢᛂ⏝ ᮾ ᣅஓ࣭ᴋᮏ ࿘ᖹ࣭㔝ᓮ ிᏊ ➨66 ᅇ᭷ᶵ㔠ᒓウㄽ఍ 㤳㒔኱Ꮫᮾி༡኱ἑ࢟ࣕࣥࣃࢫ ᮾி 2019 ᖺ 9 ᭶ 14̽16 ᪥ O2-06 (ཱྀ㢌)‫ࢺ࣮ࢼ࣍ࣝࢫࣥ࢕ࣇࢫ࣭࣒࣍࢘ࢪࣛࣃ ۻ‬㘒యࢆ⏝࠸ࡓ࢚ࢳࣞࣥ/ᴟᛶࣔࣀ࣐࣮ࡢඹ㔜ྜ཯ᛂࡢᶵᲔᏛ⩦ࢆ⏝࠸ࡓண⛅⏣ 㞙ᖹ࣭Guo Jing-Yao࣭Sigman S. Matthew࣭㔝ᓮ ிᏊ ➨ 66 ᅇ᭷ᶵ㔠ᒓウㄽ఍ 㤳㒔኱Ꮫᮾி༡኱

ἑ࢟ࣕࣥࣃࢫ ᮾி 2019 ᖺ 9 ᭶ 14̽16 ᪥ P3-77 (࣏ࢫࢱ࣮)‫ ۻ‬Cobalt/Lanthanide Multinuclear Complexes for Copolymerization of An Epoxide with Carbon Dioxide. ὸሙ ⿱

- 112 -

㈗࣭ᒾ㷂 Ꮥ⣖࣭㛗Ụ ᫓ᶞ࣭┿ᓥ ࿴ᚿ࣭㔝ᓮ ிᏊ 㘒య໬Ꮫ఍➨ 69 ᅇウㄽ఍ ྡྂᒇ኱Ꮫᮾᒣ࢟ࣕࣥࣃࢫ ឡ▱ 2019 ᖺ 9 ᭶ 21̽23 ᪥ 1Da-03 (ཱྀ㢌)‫[ࣛࢩࣝࣈࢲࣟࣆࢫ ۻ‬7]࣊ࣜࢭࣥࡢྜᡂ࡜ᛶ㉁ ᑎ⏣ ᮃ࣭᫬୸ ♸㍤࣭బ⸨ 㝧௓࣭㔝ᓮ ிᏊ ➨ 30 ᅇᇶ♏᭷ᶵ໬Ꮫウㄽ఍ ኱㜰ᅜ㝿஺ὶࢭࣥࢱ࣮ ኱㜰 2019 ᖺ 9 ᭶ 25̽27 ᪥ 2P059 (࣏ࢫࢱ࣮)‫[ࣛࢩࣝࣈࢲࣟࣆࢫ ۻ‬7]࣊ࣜࢭࣥࡢྜᡂ࡜ᛶ㉁ ᑎ⏣ ᮃ࣭᫬୸ ♸㍤࣭బ⸨ 㝧௓࣭㔝ᓮ ிᏊ ➨ 9 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2019 ࢱ࣮࣮࣡࣍ࣝ⯪ᇼ ᮾி 2019 ᖺ 10 ᭶ 15̽17 ᪥ P4-031 (࣏ࢫࢱ࣮)‫ࣥࣀ࢚ࢪࢱࣥ࣌ࣟࢡࢩ ۻ‬㔠ᒓ㘒య࡟ࡼࡿ㔠ᒓ̽㓄఩Ꮚ༠ാⓗ C̽H, Si̽H, B̽H ⤖ྜษ᩿࣭ᙧᡂ཯ᛂ ᮾ ᣅஓ࣭ᴋᮏ ࿘ᖹ࣭㔝ᓮ ிᏊ ➨ 9 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2019 ࢱ࣮࣮࣡࣍ࣝ⯪ᇼ ᮾி 2019 ᖺ 10 ᭶ 15̽17 ᪥ P6-060(࣏ࢫࢱ࣮)‫ࢺ࣮ࢼ࣍ࣝࢫࣥ࢕ࣇࢫ࣭࣒࣍࢘ࢪࣛࣃ ۻ‬㘒యࢆ⏝࠸ࡓ࢚ࢳࣞࣥ/ᴟᛶࣔࣀ࣐࣮ࡢඹ㔜ྜ཯ᛂࡢᶵᲔᏛ⩦ࢆ⏝࠸ࡓண⛅⏣ 㞙ᖹ࣭Guo Jing-Yao࣭Sigman S. Matthew࣭㔝ᓮ ிᏊ ➨ 9 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2019 ࢱ࣮࣮࣡࣍

ࣝ⯪ᇼ ᮾி 2019 ᖺ 10 ᭶ 15̽17 ᪥ E2-09 (ཱྀ㢌)࣭P9-069 (࣏ࢫࢱ࣮)‫ࢺ࣮ࢼ࣍ࣝࢫࣥ࢕ࣇࢫ࣭࣒࣍࢘ࢪࣛࣃ ۻ‬㘒యࢆ⏝࠸ࡓ࢚ࢳࣞࣥ/ᴟᛶࣔࣀ࣐࣮ࡢඹ㔜ྜ཯ᛂࡢᶵᲔᏛ⩦ࢆ⏝࠸ࡓண⛅⏣ 㞙ᖹ࣭Guo Jing-Yao࣭Sigman S. Matthew࣭㔝ᓮ ிᏊ ➨ 42 ᅇࢣࣔ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫウㄽ఍ ᮾி኱Ꮫᮏ㒓࢟ࣕࣥࣃࢫ ᮾி 2019 ᖺ 10 ᭶ 28̽29 ᪥ 1P15 (࣏ࢫࢱ࣮)‫ ۻ‬Metal-Ligand Cooperative Bond Cleavages and Application to Catalysis. ᴋᮏ ࿘ᖹ ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍ⱝ࠸ୡ௦ࡢ≉ูㅮ₇ ᮾி⌮⛉኱Ꮫ㔝⏣࢟ࣕࣥࣃࢫ ༓ⴥ 2020 ᖺ 3 ᭶ 22 ᪥ (ཱྀ㢌)‫ ۻ‬㔠ᒓ㓄఩Ꮚ༠ാస⏝࡟ࡼࡿ B̽H ⤖ྜࡢᴟᛶ㌿᥮ ᮾ ᣅஓ࣭ᴋᮏ ࿘ᖹ࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍ ᮾி⌮⛉኱Ꮫ㔝⏣࢟ࣕࣥࣃࢫ ༓ⴥ 2020 ᖺ 3 ᭶ 22̽25 ᪥ 3H2-06 (ཱྀ㢌)‫ ۻ‬Catalytic Performance Prediction of Ethylene/Methyl Acrylate Copolymerization Using Palladium/Phosphine̽Sulfonate by Machine Learning. ⛅⏣ 㞙ᖹ࣭Guo Jing-Yao࣭Sigman S. Matthew࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍ ᮾி⌮⛉኱Ꮫ㔝⏣࢟ࣕࣥࣃࢫ ༓ⴥ 2020 ᖺ 3 ᭶ 22̽25 ᪥ 3H2-46 (ཱྀ㢌)‫ ۻ‬Synthesis and Properties of Spiro Double Sila[7]helicene. ᑎ⏣ ᮃ࣭᳜ᯇ ၨ㍜࣭ᵽཱྀ ுኴ࣭᫬୸ ♸㍤࣭బ⸨ 㝧௓࣭୰㔝 ᖾྖ࣭㔝ᓮ ிᏊ ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍ ᮾி⌮⛉኱Ꮫ㔝⏣࢟ࣕࣥࣃࢫ ༓ⴥ 2020 ᖺ 3 ᭶ 22̽
25 ᪥ 2C4-13 (ཱྀ㢌)‫ ۻ‬Metal-ligand cooperative cleavage of C–O, C–H and B–H bonds. Shuhei Kusumoto, Kyoko Nozaki, Gabor A.

Somorjai Award for Creative Research in Catalysis: Symposium in honor of David Milstein, Philadelphia, PA, US,
2020/3/23 (Oral).

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

࣭Cyanide Free One-pot Synthesis of Methacrylic Esters from Acetone: M. Koyama, T. Kawakami, T. Okazoe, K.
Nozaki Chem. Eur. J. 2019, 25, 10913–10917. 10.1002/chem.201901933‫ ۻ‬Stepwise Reduction of Azapentabenzocorannulene: Z. Zhou, Z. Wei, Y. Tokimaru, S. Ito, K. Nozaki, M. A.

Petrukhina Angew. Chem. Int. Ed. 2019, 58, 12107–12111. 10.1002/anie.201906748
࣭Selective Synthesis of Primary Anilines from NH3 and Cyclohexanones by Utilizing Preferential Adsorption of
Styrene on the Pd Nanoparticle Surface: Y. Koizumi, X. Jin, T. Yatabe, R. Miyazaki, J. Hasegawa, K. Nozaki, N.
Mizuno, K. Yamaguchi Angew. Chem. Int. Ed. 2019, 58, 10893–10897. 10.1002/anie.201903841
࣭Reversible Polymer-Chain Modification: Ring-Opening and Closing of Polylactone: S. Moon, K. Masada, K. Nozaki
J. Am. Chem. Soc. 2019, 141, 10938–10942. 10.1021/jacs.9b03205- 113 -

࣭Synthesis of Polyethylene with in-chain α,β-Unsaturated Ketone and Isolated Ketone Units by Pd-catalyzed
Ring-opening Copolymerization of Cyclopropenones with Ethylene: X. Wang, F. W. Seidel, K. Nozaki Angew. Chem.
Int. Ed. 2019, 58, 12955–12959. 10.1002/anie.201906990
࣭ Single-molecule single-electron transistor (SM-SET) based on π-conjugated quinoidal-fused oligosilole andheteroepitaxial spherical Au/Pt nanogap electrodes: S. Lee, J. Kim, T. Tsuda, R. Takano, R. Shintani, K. Nozaki, Y.
Majima Appl. Phys. Express 2019, 12, 125007. 10.7567/1882-0786/ab56e5
࣭Synthesis of Fluorinated Dialkyl Carbonates from Carbon Dioxide as a Carbonyl Source: M. Sugiyama, M. Akiyama,
K. Nishiyama, T. Okazoe, K. Nozaki ChemSusChem 2020, 13, 1775–1784. 10.1002/cssc.202000090
࣭Cleavage of C–C and C–O bonds in β-O-4 Linkage of Lignin Model Compound by Cyclopentadienone Group 8 and 9
Metals Complexes: S. Kusumoto, M. Kishino, K. Nozaki Chem. Lett. 2020, 49, 477–480. 10.1246/cl.200037
࣭An Endergonic Synthesis of Single Sondheimer-Wong Diyne by Local Probe Chemistry: S. Kawai, H. Sang, L.
Kantorovich, K. Takahashi, K. Nozaki, S. Ito Angew. Chem. Int. Ed. in press. 10.1002/anie.202001268
࣭Synthesis of unsymmetrically substituted triarylamines via acceptorless dehydrogenative aromatization using a Pd/C
and p-toluenesulfonic acid hybrid relay catalyst: S. Takayama, T. Yatabe, Y. Koizumi, X. Jin, K. Nozaki, N. Mizuno, K.
Yamaguchi Chem. Sci., 2020, 11, 4074–4084 10.1039/C9SC06442G
࣭Copolymerization of Nonpolar Olefins and Allyl Acetate Using Nickel Catalysts Bearing a Methylene-bridged
Bisphosphine Monoxide Ligand: J. Jung, H. Yasuda, K. Nozaki Macromolecules 2020, 53, 2547–2556.
10.1021/acs.macromol.0c00183
࣭Reductive Coupling of Carbon Dioxide and an Aldehyde Mediated by a Copper(I) Complex toward the Synthesis of
α-Hydroxycarboxylic Acids: K. Masada, S. Kusumoto, K. Nozaki Org. Lett. in press. 10.1021/acs.orglett.0c00995
࣭Metal–Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes: S.
Deolka, O. Rivada, S. L. Aristizábal, R. R. Fayzullin, S. Pal, K. Nozaki, E. Khaskin, J. R. Khusnutdinova Chem. Sci. inpress. 10.1039/D0SC00646G
࣭Aluminum Porphyrins with Quaternary Ammonium Halides as Catalysts for Copolymerization of Cyclohexene Oxide
and CO2: Metal–Ligand Cooperative Catalysis: J. Deng, M. Ratanasak, Y. Sako, H. Tokuda, C. Maeda, J. Hasegawa, K.
Nozaki, T. Ema Chem. Sci. in press. 10.1039/D0SC01609H‫ ۻ‬Alternating Copolymerization of CO2 and Cyclohexene Oxide Catalyzed by Cobalt-Lanthanide Mixed Multinuclear

Complexes: H. Asaba, T. Iwasaki, M. Hatazawa, J. Deng, H. Nagae, K. Mashima, K. Nozaki Inorg.
Chem. accepted. 10.1021/acs.inorgchem.0c01156- 114 -

- 115 -- 116 -➨୍ཎ⌮཯ᛂࢲ࢖ࢼ࣑ࢡࢫ࡜ඛ㐍ⓗ㟁Ꮚ≧ែ⌮ㄽࡢከゅⓗᒎ㛤Divergent applications of ab initio reaction dynamics andadvanced electronic structure theories‫ۑ‬Ṋḟ ᚭஓ㸪Lyalin Andrey㸪ᑠᯘ ṇே㸪ᒾబ ㇦㸪ᑠ㔝 ࡺࡾᏊ㸪㉥㛫 ▱Ꮚ㸪㏆⸨ ᭷㍜㸪
Kumar Sonu㸪➉୰ ᑗᩯ㸪ሐ ᣅᮁ㸪⸨᳃ ಇ࿴㸪⋤ ዑ㸪⧊⏣ ⪔ᖹ㸪ᒾῲ 㞝ኴ㸪ᾏ⪁⃝ ಟ୍㸪኱ሙ ♸ử㸪ᑠす 㔛⥴㸪㧗ཎ 㔛ዉ㸪⏣௦ ၨ௓㸪ᐑ㉺ Ὧ஧㸪ẟ฼ ᗈ㔝㸪࿴⏣ ㄹ㸦໭ᾏ㐨኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ
Ab initio 㟁Ꮚ≧ែィ⟬࡛ᚓࡽࢀࡿ࣏ࢸࣥࢩࣕࣝ໙㓄࡟ᇶ࡙ࡃศᏊືຊᏛ㸦AIMD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DC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࿴ඖᖺᗘࡣ≉࡟ࠊ(1)ゎ㞳ᛶ෌⤖ྜ཯ᛂࡢ surface hopping AIMD ࢩ࣑࣮ࣗࣞࢩࣙࣥࠊ(2)⾲㠃྾╔ࣔࢹࣝィ⟬ࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜ࡑࡢ୙ᆒ୍ゐ፹άᛶண࡬ࡢᛂ⏝ࠊ(3)㔞Ꮚ໬Ꮫィ⟬࡜ྂ඾㟁☢ẼᏛࢩ࣑࣮ࣗࣞࢩࣙ

ࣥࡢ㐃ᡂ࡟ࡼࡿ⾲㠃ቑᙉ㉥እศගࢫ࣌ࢡࢺࣝィ⟬࡞࡝ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ(1)࡛ࡣ Molpro ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࠊ⯓⬥-ྂ㈡ࡢࢭࢢ࣓ࣥࢺᆺ 3 ಸᇶᗏ࡟㔝࿅-㛵㇂-ྂ㈡ࡢ┦㛵ᇶᗏࢆຍ࠼ࡓ TZP ࢡ࢜ࣜࢸ࢕ࡢᇶᗏ㛵ᩘࢆ฼⏝ࡋࡓ SA-CASSCF ィ⟬ࡼࡾ࢚ࢿࣝࢠ࣮࡜໙㓄ࠊ㠀᩿⇕⤖ྜ࣋ࢡࢺࣝィ⟬ࢆᐇ⾜ࡋࡓࠋືⓗ㟁Ꮚ┦㛵ࡢຠᯝࢆྲྀࡾ㎸ࡴࡓࡵ࡟ࠊCASPT2 ࢚ࢿࣝࢠ࣮࡟ࡼࡿ⿵ṇࢆຍ࠼ࡓࠋࢲ࢖ࢼ࣑ࢡ
ࢫィ⟬ࡣ⊂⮬ࡢࣉࣟࢢ࣒ࣛ࡟ࡼࡾ⾜ࡗࡓࠋ(2)࡛ࡣࠊ⊂⮬ࡢࣉࣟࢢ࣒ࣛࢆ౑ࡗ࡚ fcc (111)㠃ࠊ(100)㠃ࠊཬࡧ(211)㠃࡟ᑐࡍࡿึᮇ྾╔ᵓ㐀ࢆⓎ⏕ࡉࡏࠊ྾╔ᵓ㐀᭱㐺໬࡜࢚ࢿࣝࢠ࣮ィ⟬ࡣ SIESTA ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓ࿘ᮇቃ⏺᮲௳ィ⟬㸦GGA-PBE/DZP㸧࡟ࡼࡾᐇ⾜ࡋࡓࠋࡲࡓࠊR ゝㄒࡢ ncvreg ࣃࢵࢣ࣮ࢪࢆ฼⏝ࡋ࡚ᅇᖐศᯒࢆ⾜ࡗࡓࠋ(3)࡛ࡣࠊ㖟ࢼࣀ⢏Ꮚ࡟ p-ࢽࢺࣟᏳᜥ㤶㓟ࢆ྾╔ࡉࡏࡓ⣔࡟ᑐࡋ࡚ࠊSIESTA ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓ
GGA-PBE/DZP ࡛ࣞ࣋ࣝ㟁Ꮚ≧ែィ⟬ࢆ⾜࠸ࠊ㏆᥋ሙࡢィ⟬࡟ࡣቃ⏺せ⣲ἲࢆ⏝࠸ࡓ࣮࢜ࣉࣥࢯ࣮ࢫࡢ㟁☢
⏺ࢩ࣑࣮ࣗࣞࢩࣙࣥࣉࣟࢢ࣒ࣛ sucff-em ࢆ฼⏝ࡋࡓࠋ

3

◊✲ᡂᯝ

3.1 CH3+ࡢゎ㞳ᛶ෌⤖ྜ཯ᛂࡢ surface hopping AIMD ࢩ࣑࣮ࣗࣞࢩࣙࣥ ᴟప࣭㉸పᐦᗘ࡞⎔ቃୗ࡛㐍⾜ࡍࡿᫍ㛫ศᏊࡢ㐍໬㐣⛬࡛ࡣࠊ࢖࢜ࣥ-ศᏊ཯ᛂࡀ㔜せ࡞ᙺ๭ࢆᯝࡓࡍࠋ

࢖࢜ࣥ-ศᏊ཯ᛂ࡟ࡼࡾ⏕ᡂࡋࡓ㝧࢖࢜ࣥศᏊࡣࠊ㟁Ꮚ࡜ࡢゎ㞳ᛶ෌⤖ྜ㸦DR㸧཯ᛂ࡟ࡼࡗ࡚୰ᛶ໬ࡉࢀࡿࠋ
ぶศᏊࡀከཎᏊศᏊ࢖࡛࢜ࣥ࠶ࡿሙྜ࡟ࡣࠊ」ᩘࡢゎ㞳ࢳࣕࢿࣝࡀᏑᅾࡍࡿࡓࡵࠊゎ㞳⏕ᡂ≀ࡢศᒱẚࢆㄪ- 117 -

࡭ࡿࡇ࡜ࡀᫍ㛫ศᏊࡢ㐍໬㐣⛬ࢆ⌮ゎࡍࡿୖ࡛㔜せ࡜࡞ࡿࠋDR ཯ᛂ࡟ࡣࠊ㝧࢖࢜ࣥศᏊࡢᇶᗏ≧ែ࠿ࡽ୰ᛶ
ศᏊ✀ࡢゎ㞳ᛶཎᏊ౯≧ែ࡟┤᥋㑄⛣ࡍࡿ direct 㐣⛬࡜ࠊRydberg ≧ែࢆ⤒⏤ࡋ࡚ゎ㞳ࡀ㉳ࡁࡿ indirect 㐣⛬ࡀ࠶ࡿࠋDR ཯ᛂࡣከ≧ែࡢ㛵୚ࡍࡿከ⮬⏤ᗘࡢ㐣⛬࡛࠶ࡾࠊ㠀᩿⇕ຠᯝࡀᮏ㉁ⓗᙺ๭ࢆᢸࡗ࡚࠸ࡿࡓࡵࠊศ
ᒱẚࢆィ⟬࡟ࡼࡾồࡵࡿࡓࡵ࡟ࡣ㠀᩿⇕㑄⛣ࢆ⪃៖ࡍࡿᚲせࡀ࠶ࡿࠋᮏ◊✲࡛ࡣ CH3+ + e-ࢆᑐ㇟࡜ࡋࠊTullyࡢ fewest switches ࢔ࣝࢦࣜࢬ࣒࡟ᇶ࡙ࡃ㠀᩿⇕㑄⛣ࢆ⪃៖ࡋࡓ AIMD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋ࡚ゎ㞳⏕ᡂ≀ࡢศᒱẚࢆணࡋࡓࠋ ᅗ 1 ࡢ᭱ୖ㒊࡟ direct 㐣⛬ࢆ᝿ᐃࡋࡓࢩ
࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾồࡵࡽࢀࡓศᒱẚࢆ♧ࡍࠋ
96%ࡢࢺࣛࢪ࢙ࢡࢺࣜ࡟࠾࠸࡚ CH2 +H ࡀ⏕ᡂࡋࡓࡀࠊᐇ㦂⤖ᯝ࡛ࡣࡇࡢ⏕ᡂ≀࡬ࡢศᒱẚࡣ 35%࡛࠶ࡾࠊ኱ࡁࡃ␗࡞ࡿࠋ
ࡑࡇ࡛ࠊ㝧࢖࢜ࣥศᏊࡢᇶᗏ≧ែࡢ࣏ࢸࣥ
ࢩࣕࣝ㠃ࢆୗ᪉࡟ࢩࣇࢺࡍࡿࡇ࡜࡛
Rydberg ≧ែࡢ࣏ࢸࣥࢩࣕࣝ㠃ࢆᵓ⠏ࡋࠊ
indirect 㐣⛬ࢆ᝿ᐃࡋࡓࢩ࣑࣮ࣗࣞࢩࣙࣥ
ࢆᐇ⾜ࡋࡓࠋ࢚ࢿࣝࢠ࣮ࢩࣇࢺࢆ኱ࡁࡃࡋ
࡚࠸ࡃ࡜ࠊィ⟬࡛ồࡵࡽࢀࡓ CH2 + H ࡢศ

ᅗ1. ィ⟬࡟ࡼࡾdirect㐣⛬ཬࡧindirect㐣⛬ࢆ᝿ᐃࡋ࡚ồࡵᒱẚࡣᚎࠎ࡟ᑠࡉࡃ࡞ࡾࠊ㞽Ⅼ࢚ࢿࣝࢠ࣮

ࡓCH3+ࡢDR཯ᛂࡢศᒱẚ࡜ᐇ㦂್࡜ࡢẚ㍑ࠋ

㸦ZPE㸧ࡢ 2 ಸ࡟࡞ࡿ࡜ 42%࡜ᐇ㦂್࡜ࡢᑐᛂࡀ኱ࡁࡃᨵၿࡋࡓࠋࡲࡓࠊdirect 㐣⛬ࢆ᝿ᐃࡋࡓሙྜ࡟ࡣぢࡽࢀ࡞࠿ࡗࡓ C + H2 + H ࡸ CH + H2 ࡢ⏕ᡂศᒱẚࡀࠊ࢚ࢿࣝࢠ࣮ࢩࣇࢺࡢቑ኱࡜࡜ࡶ࡟ୖ᪼ࡍࡿࡇ࡜ࡀ☜࠿ࡵࡽࢀࡓࠋ
3.2 ⾲㠃྾╔ࣔࢹࣝィ⟬ࢹ࣮ࢱ࣮࣋ࢫࡢᵓ⠏࡜ࡑࡢ୙ᆒ୍ゐ፹άᛶண࡬ࡢᛂ⏝ ࣅࢵࢢࢹ࣮ࢱゎᯒࢆࡣࡌࡵ࡜ࡋࡓࢹ࣮ࢱ⛉ᏛⓗᡭἲࡢⓎᒎ࡟క࠸ࠊ࠶ࡲࡾ㔜どࡉࢀ࡚ࡇ࡞࠿ࡗࡓ
㔞Ꮚ໬Ꮫィ⟬ࡢࣁ࢖ࢫ࣮ࣝࣉࢵࢺ໬࡟ὀ┠ࡀ㞟ࡲࡗ࡚࠸ࡿࠋࡑࡇ࡛ࠊᡃࠎࡣ㔠ᒓ⾲㠃ࢆ෌⌧ࡋࡓ⾲㠃ࣔࢹࣝ࡬ᵝࠎ࡞໬Ꮫ✀ࡀ྾╔ࡋࡓ≧ែࡢィ⟬ࢆ⣔⤫ⓗ࡟ᐇ⾜ࡋࠊࡑࡢ⤖ᯝࢆ⵳✚ࡍࡿࡇ࡜࡟ࡼࡾࠊ୙ᆒ୍ゐ፹཯ᛂࡢゎᯒ࡟฼⏝ྍ⬟࡞ࢹ࣮ࢱ࣮࣋ࢫ
ࡢᵓ⠏ࢆ⾜ࡗࡓࠋࡲࡓࡇࡢࢹ࣮ࢱ࣮࣋ࢫࡢά⏝౛࡜ࡋ࡚ࠊ࣓ࢱࣥỈ⵨Ẽᨵ㉁཯ᛂ㸦MSR㸧ࢆᑐ㇟࡜ࡋࠊࢹ࣮ࢱ࣮࣋ࢫ࠿ࡽᚓࡽࢀࡓ᝟ሗ࡜ᩥ⊩࠿ࡽᚓࡓᐇ㦂᮲௳㸦ᢸయࡸ཯ᛂ

ᗘ࡞࡝㸧ࢆ⤌ࡳྜࢃࡏ࡚ࠊゐ፹άᛶࡢホ౯࡜άᛶᅉᏊࡢ≉ᐃࢆヨࡳࡓࠋ ༢୍ࡢㄽᩥ㸦D. Mei et al., J. Catal. 316, 11 (2014)㸧

ᅗ2. MC+ἲ࡟ࡼࡾண ࡉࢀࡓ࣓ࢱࣥ㌿໬⋡࡜ᐇ㦂್࡟グ㍕ࡉࢀࡓᆒ୍࡞ᐇ㦂᮲௳࡟ࡼࡿ㔠ᒓΎί⾲㠃ࡢ┦㛵ࠋୖ࡛ࡢ࣓ࢱࣥ㌿໬⋡ࡢᅇᖐࢆ⾜ࡗࡓࠋ⾲㠃⮬㌟࠾ࡼࡧ 1࣭2 ཎᏊ྾╔ࡋࡓ⾲㠃ࡢィ⟬⤖ᯝࢆࠊㄝ᫂ኚᩘ࡜ࡋ࡚
౑⏝ࡋࡓࠋࢫࣃ࣮ࢫࣔࢹࣜࣥࢢᡭἲࡢࡦ࡜ࡘ࡛࠶ࡿ MC+ἲ࡟ࡼࡾண

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ࡉࢀࡓ࣓ࢱࣥ㌿໬⋡࡜ᐇ㦂್ࡢ┦㛵ࢆᅗ 2 ࡟♧ࡍࠋMC+ἲ࡟ࡼࡿࣔࢹࣝࡢᅇᖐಀᩘࢆぢࡿ࡜ࠊ(111)㠃ୖ࡛ࡢ C2 ࡢ྾╔࢚ࢿࣝࢠ࣮ࡀ࣓ࢱࣥ㌿໬⋡࡜኱ࡁ࡞㈇ࡢ┦㛵ࢆ♧ࡋ࡚࠾ࡾࠊḟ࠸࡛(111)㠃ୖ࡛ࡢ C2 ྾╔✀ࡢ㠃࠿ࡽࡢ㊥㞳㸦㧗ࡉ㸧ࡀṇ࡟┦㛵ࡋ࡚࠸ࡿࡇ
࡜ࡀࢃ࠿ࡗࡓࠋC2 ࡣ┤᥋ MSR ཯ᛂ࡟㛵୚ࡋ࡞࠸ࡀࠊⅣ⣲ᯒฟ࡟ࡼࡿ୙ά໬ࢆ཯ᫎࡋ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿࠋ
ᮏࢹ࣮ࢱ࣮࣋ࢫࡣ MSR ཯ᛂ࡟≉໬ࡋࡓࡶࡢ࡛ࡣ࡞ࡃࠊ㔠ᒓ⾲㠃࡛㐍⾜ࡍࡿ୙ᆒ୍ゐ፹཯ᛂ୍⯡࡟㐺⏝࡛ࡁࡿᐇ⏝ᛶࡢ㧗࠸ࡶࡢ࡛࠶ࡿࠋࡲࡓࠊィ⟬࡛ࡣྲྀࡾ㎸ࡳ࡟ࡃ࠸ᗘࡸᢸయ࡜࠸ࡗࡓᐇ㦂᮲௳ࡢ୍㒊ࢆㄝ᫂ኚᩘ࡟

ຍ࠼ࡿࡇ࡜࡟ࡼࡾࠊ୙ᆒ୍࡞ᐇ㦂᮲௳ࢹ࣮ࢱ࡬ࡢ㐺⏝ࡸከᩥ⊩ࢆཧ↷ࡋࡓẚ㍑࡞࡝࡛ࡁࡿ࡜ᮇᚅࡉࢀࡿࠋ
3.3 㔞Ꮚ໬Ꮫィ⟬࡜ྂ඾㟁☢ẼᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ㐃ᡂ࡟ࡼࡿ⾲㠃ቑᙉ㉥እศගࢫ࣌ࢡࢺࣝィ⟬ ㏻ᖖࡢ㉥እศගἲ࡛ࡣࠊศᏊ࡜ගࡢ┦஫స⏝ࡣ཮ᴟᏊ㏆ఝ࡛ᢅ࠸ࠊศᏊࡣ≉ᐃࡢ㓄ྥࢆᣢࡓ࡞࠸࡜ࡉࢀࡿࠋࡋ࠿ࡋࠊ
㉥እ཯ᑕ྾཰ศගἲ㸦IRRAS㸧࡛ࡣ⾲㠃ᆶ┤᪉ྥࡢ㟁ሙࡀศᏊࢆບ㉳ࡋࠊ⾲㠃ቑᙉ㉥እศගἲ㸦SEIRAS㸧࡛ࡣ㔠ᒓࢼࣀᵓ㐀⾲㠃࡟ᒁᅾࡋࡓ㏆᥋ሙࡀศᏊࢆບ㉳ࡍࡿࡓࡵࠊ✵㛫ⓗ࡟㠀୍ᵝ࡞㟁ሙࢆ⪃៖ࡋࡓ⌮ㄽⓗᯟ⤌ࡳࡀᚲせ࡜࡞ࡿࠋᡃࠎࡣከ㔜ᴟࣁ࣑ࣝࢺࢽ࢔ࣥ࡟ᇶ࡙ࡁࠊ௵ពࡢ㟁ሙࢆ⪃៖ࡋࡓ᪉ἲㄽࢆ㛤Ⓨࡋ࡚ࡁࡓࠋᮏ◊✲࡛ࡣࠊࡇࡢ᪉ἲ࡟ቃ⏺
せ⣲ἲ࡟ࡼࡿ㟁ሙィ⟬ࢆ⤌ࡳ㎸ࡳࠊ㖟ࢼࣀᵓ㐀࿘㎶ࡢ㏆᥋ሙࢆ฼⏝ࡋࡓ SEIRAS ࢫ࣌ࢡࢺࣝࡢィ⟬࡬࡜ᛂ⏝ࡋࡓࠋ p-ࢽࢺࣟᏳᜥ㤶㓟ࡢ࣒࢝ࣜ࢘ሷ࡜ࡇࢀࢆ Ag3 ࡛ࣔࢹࣝ໬
ࡋࡓ㖟ࢼࣀᵓ㐀࡟྾╔ࡋࡓ⣔࡟ᑐࡋ࡚ᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊࡑࢀࡒࢀࢆ IR ィ⟬ࠊIRRAS/SEIRAS ィ⟬ࡢࣔࢹࣝ࡜ࡋ࡚฼
⏝ࡋࡓࠋᅗ 3(a)࡟ィ⟬ࡉࢀࡓ IRࠊIRRAS ཬࡧ SEIRAS ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋࡲࡓࠊᅗ 3(b)࡟ࡣᅗ 3(A)࡛♧ࡋࡓ 1㹼4 ཬ
ࡧ 1’㹼4’ࡢࣆ࣮ࢡ࡟ᑐᛂࡍࡿ᣺ື࣮ࣔࢻࢆ㯮▮༳࡛♧ࡋࡓࠋIR ཬࡧ IRRAS/SEIRAS ࣔࢹࣝ࡟ᑐࡋ࡚ᚓࡽࢀࡓ᣺ືᩘࠊ᣺
ື࣮ࣔࢻ࡟ࡣ኱ࡁ࡞ኚ໬ࡣぢࡽࢀ࡞࠿ࡗࡓࡀࠊIR ࢫ࣌ࢡࢺ࡛ࣝ኱ࡁ࡞ᙉᗘࡀぢࡽࢀࡓ 1, 2 ࡢࣆ࣮ࢡࡀ IRRAS/SEIRASࢫ࣌ࢡࢺ࡛ࣝࡣ࡯࡜ࢇ࡝ぢࡽࢀ࡞ࡃ࡞ࡗ࡚࠸ࡿࠋᅗ 3(b)࡟
ࡣ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢᇶ‽ᗙᶆᚤศࡶేࡏ࡚㉥▮༳࡛♧ࡋ࡚࠸ࡿࠋࡇࡢ⤖ᯝ࠿ࡽࠊࣆ࣮ࢡ 1, 2 ࡛ࡣ཮ᴟᏊ࣮࣓ࣔࣥ

ᅗ 3. p-ࢽࢺࣟᏳᜥ㤶㓟࡟ᑐࡋ࡚ィ⟬ࡉࢀࡓ IRࠊIRRASࠊཬࡧ SEIRAS ࢫ࣌ࢡࢺࣝ㸦a㸧࡜ᑐᛂࡍࡿ᣺ື࣮ࣔࢻ㸦b㸧ࠋ(b)࡛ࡣ཮ᴟᏊ࣮࣓ࣔࣥࢺࡢᇶ‽ᗙᶆᚤศࡢ᪉ྥࡶ㉥▮༳࡛♧ࡋ࡚࠸ࡿࠋ

ࢺࡢᇶ‽ᗙᶆᚤศࡀ⾲㠃࡜࡯ࡰᖹ⾜࡛࠶ࡿࡓࡵࠊ⾲㠃ᆶ┤᪉ྥࡢ᣺ືࡢࡳࢆ᳨ฟࡍࡿ IRRAS ࡛ࡣࣆ࣮ࢡࡀᾘ
ኻࡋࡓࠊ࡜⌮ゎࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡲࡓࠊ㖟ࢼࣀᵓ㐀࿘㎶࡟⏕ࡌࡿ㏆᥋ሙࡣ⾲㠃ᆶ┤᪉ྥ࡛࠶ࡿࡓࡵࠊࡇࢀ
࡜࡯ࡰ┤஺ࡍࡿࣆ࣮ࢡ 1, 2 ࡣ SEIRAS ࡛ࡶ࡯ࡰᾘኻࡋ࡚࠸ࡿࠋ୍᪉ࠊ3, 4 ࡢᇶ‽᣺ື࣮ࣔࢻ࡟ࡘ࠸࡚ࡢ཮ᴟ
Ꮚ࣮࣓ࣔࣥࢺᚤศࡣ⾲㠃࡜࡯ࡰ┤஺ࡋ࡚࠸ࡿࡓࡵࠊIRRAS/SEIRAS ࡛ࡶ኱ࡁ࡞ᙉᗘࢆᣢࡗ࡚࠸ࡿࠋࡇࡢィ⟬⤖ᯝࡣᐇ㦂࡜ࡶᑐᛂࡋ࡚࠾ࡾࠊᮏᡭἲࡣᑐ⛠ᛶࡔࡅ࠿ࡽ㆟ㄽࡍࡿࡇ࡜ࡀ㞴ࡋ࠸」㞧࡞ศᏊࡢ IRRAS ࡸSEIRAS ࢫ࣌ࢡࢺࣝࢆ➨୍ཎ⌮࠿ࡽண ࡍࡿᙉຊ࡞ࢶ࣮ࣝ࡜࡞ࡿࡶࡢ࡜ᮇᚅࡉࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

(1) T. Taketsugu, T. Tsutsumi, and Y. Ono “A new strategy for reaction path concept and dynamics effects” The 23rd

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International Annual Symposium on Computational Science and Engineering (ANSCSE23), 2019.6.27-28, Chiang Mai,
Thailand; (2) T. Taketsugu “Reaction pathways and dynamics of the excited-state branching reaction of stilbene
derivatives” International Symposium on Ultrafast Molecular Dynamics (UMD2019), 2019.7.5-6, Sendai, Japan; (3) T.
Taketsugu, T. Tsutsumi, S. Ebisawa, and Y. Ono “Reaction path concept: Intrinsic Reaction Coordinate, Anharmonic
Downward Distortion Following, and Ab Initio MD” The 9th Asia-Pacific Association of Theoretical andComputational Chemists (APATCC-9), 2019.9.30-10.3, Sydney, Australia; (4) M. Kobayashi, H. Onoda, and T.
Taketsugu “Surface model calculation database for predicting catalytic activity: An application to methane steam
reforming” The 9th Asia-Pacific Association of Theoretical and Computational Chemists (APATCC-9), 2019.9.30-10.3,
Sydney, Australia; (5) T. Taketsugu “Reaction path concept and dynamics effects: ab initio approach” ICReDD
workshop: International & Interdisciplinary Workshop on Chemical Reaction Dynamics - Mathematics Informatics, andPhysics Meet Chemistry, 2019.10.8, Sapporo, Japan; (6) Ṋḟᚭஓࠕ㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃࢲ࢖ࢼ࣑ࢡࢫ◊✲ࡢᒎ㛤ࠖ᪥ᮏ໬Ꮫ఍ 2019 㟷᳃ᆅ༊ㅮ₇఍, 2019.10.11, ᘯ๓; (7) T. Taketsugu “Excited-state branching reaction of
stilbene derivatives” Theoretical and High Performance Computational Chemistry 2019 (ICT-HPCC19), 2019.11.2-5,
Guiyang, China; (8) T. Taketsugu “Theoretical elucidation of photo-reaction mechanism: applications to stilbene
derivatives” The 15th Nanjing University-Hokkaido University-NIMS Joint Symposium, 2019.11.24-28, Nanjing, China;(9) ᑠᯘṇேࠕࢹ࣮ࢱ⛉Ꮫࢆ฼⏝ࡋࡓ⾲㠃྾╔⣔㔞Ꮚ໬Ꮫィ⟬⤖ᯝࡢゎᯒ࡜ゐ፹࡬ࡢᛂ⏝ࠖࣞ࢔࣭࢖࣋ࣥࢺࡢ

ィ⟬⛉Ꮫ ➨ 3 ᅇ࣮࣡ࢡࢩࣙࢵࣉ, 2019.12.8, ྡྂᒇ; (10) ᑠᯘṇேࠕ⾲㠃྾╔⣔㔞Ꮚ໬Ꮫィ⟬ࢹ࣮ࢱ࣮࣋ࢫࡢ
ᵓ⠏࡜ゐ፹άᛶゎᯒ࡬ࡢᛂ⏝ࠖESICB 㟁Ꮚㄽ᳨ウ఍, 2019.12.23-24, ὾ᯇ; (11) M. Kobayashi “Data ScientificAnalysis of Quantum Chemical Calculation Results for Surface Adsorption Systems and Its Application to Catalysis”➨ 36 ᅇィ⟬ᶵ࣐ࢸࣜ࢔ࣝࢬࢹࢨ࢖ࣥ(CMD)࣮࣡ࢡࢩࣙࢵࣉ, 2020.2.21, ኱㜰.㸦௨ୖᣍᚅㅮ₇ࡢ୍㒊ࠊ௚ከᩘ㸧5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1) ‫ۻ‬M. Kamiya and T. Taketsugu, J. Comput. Chem. 40, 456-463 (2019); (2) ‫ۻ‬M. Takenaka, Y. Hashimoto, T. Iwasa,
T. Taketsugu, G. Seniutinas, A. Balcytis, S. Juodkazise, and Y. Nishijima, J. Comput. Chem. 40, 925-932 (2019); (3) ‫ۻ‬
Y. Kuroda, M. Kobayashi, and T. Taketsugu, Chem. Lett. 48, 137-139 (2019); (4) ‫ۻ‬T. Iwasa, T. Sato, M. Takagi, M.
Gao, A. Lyalin, M. Kobayashi, K.-i. Shimizu, S. Maeda, and T. Taketsugu, J. Phys. Chem. A 123, 210-217 (2019); (5)‫ۻ‬A. Lyalin, V. G. Kuznetsov, A. Nakayama, I. V. Abarenkov, I. I. Tupitsyn, I. E. Gabis, K. Uosaki, and T. Taketsugu, J.
Electrochem. Soc. 166, A5362-A5368 (2019); (6) ‫ۻ‬T. Taketsugu and Y. Kobayashi, Comp. Theo. Chem. 1150, 1-9(2019); (7) ‫ۻ‬M. Ebina, Y. Kondo, T. Iwasa, and T. Taketsugu, Inorg. Chem. 58, 4686-4698 (2019); (8) ‫ۻ‬Y.
Harabuchi, R. Tani, N. DeSilva, B. Njegic, M. S. Gordon, and T. Taketsugu, J. Chem. Phys. 151, 064104 (2019); (9) ‫ۻ‬
N. A. Vinogradov, A. Lyalin, T. Taketsugu, A. S. Vinogradov, and A. Preobrajenski, ACS Nano 13, 14511-14518 (2019);(10) ‫ۻ‬M. Kobayashi, H. Onoda, Y. Kuroda, and T. Taketsugu, J. Comput. Chem. Jpn. 18, 251-253 (2019); (11) ‫ۻ‬T.
Machida, T. Iwasa, T. Taketsugu, K. Sada, and K. Kokado, Chem. Eur. J., in press; (12) ‫ۻ‬J. Li, M. Gao, S. Tong, C.
Luo, H. Zhu, T. Taketsugu, K. Uosaki, and M. Wu, Electrochim. Acta 340, 135977 (2020); (13) ‫ۻ‬Y. Ootani, A. Satoh,
Y. Harabuchi, and T. Taketsugu J. Comput. Chem. 41, 1549-1556 (2020); (14) ‫ۻ‬M. Takenaka, T. Taketsugu, and T.
Iwasa, J. Chem. Phys. 152, 164103 (2020); (15) ‫ۻ‬B. Wang, M. Gao, K. Uosaki, and T. Taketsugu, Phys. Chem. Chem.
Phys., in press; (16) ‫ۻ‬M. Kobayashi, M. Harada, H. Takakura, K. Ando, Y. Goto, T. Tsuneda, M. Ogawa, and T.
Taketsugu, ChemPlusChem, in press.

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㉸⌫㠃᥈⣴ἲࢆ⏝࠸ࡓศᏊᵓ㐀ࠊ⤖ᬗᵓ㐀ࡢ᥈⣴
Exploration of molecular structure and crystal structure using the SHS
method‫ۑ‬ᒣ㛛 ⱥ㞝ࠊ㧗⏣㇂ ྜྷᬛࠊ⟪ᅵ㊰ ♸ᕼࠊἈ ༟ே㸦࿴ḷᒣ኱Ꮫ㸧

1◊✲┠ⓗࠊෆᐜ
➹⪅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
௒ᅇࠊᕧ኱ศᏊࡢཎᏊࡢ࠺ࡕࡢࠗ㣕ࡧ㣕ࡧࡢ㝈ࡽࢀࡓ୺せ࡞(ẚ㍑ⓗᑡᩘࡢ)ཎᏊࡢᗙᶆࡢࡳࢆ SHS ἲ࡛ࡢୖࡾ᥈⣴ࡢᑐ㇟࡜ࡋࠊ௚ࡢ኱㒊ศࡢཎᏊࡣⴠ࡜ࡋ㎸ࡳ࡛ᑐฎࡍࡿࡇ࡜࡟ࡼࡾࠊศᏊࡢ࡜ࡾ࠺ࡿ኱ᒁⓗᵓ㐀ೃ⿵ࢆẚ㍑ⓗ▷᫬㛫࡛᥈⣴࡛ࡁࡿྍ⬟ᛶࡀ࠶ࡿࡢ࡛ࡣ࡞࠸࠿࠘࡜ࡢ௬ㄝࢆ❧࡚ࠊࡑࡢ᳨ドࢆヨࡳࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ❧య㓄ᗙ␗ᛶయ(ࢥࣥࣇ࢛࣐࣮)ࡢ᥈⣴ᑐ㇟ศᏊ࡜ࡋ࡚࢔ࣛࢽࣥศᏊ 3 ࡘࡀ⬺Ỉ⦰ྜࡋࡓศᏊࠊཬࡧࢩࢽࣙࣜ

ࣥࢆ㑅ࡧࠊࡲࡓィ⟬࡟ࡣ GRRM14 ࣉࣟࢢ࣒ࣛ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿȣ-ADDF ἲࠊཬࡧ࢚ࢿࣝࢠ࣮ィ⟬࡟ࡣ
Gaussian09 ࢆ౑⏝ࡋࡓࠋ

3◊✲ᡂᯝ࢔ࣛࢽࣥศᏊ 3 ࡘࡀ⤖ྜࡋࡓศᏊ(C9H17O4N3)࡟ࡘ࠸࡚ࠊ6 ࠿ᡤࡢཎᏊࢆୖࡾ᥈⣴ᑐ㇟࡟ᣦᐃࡋࡓ᥈⣴(LADD=3ࠊGauProc=16ࠊィ⟬ࣞ࣋ࣝ B3LYP/6-31G(d,p))࡟ࡼࡾࠊEQ Ⅼ 7 ಶ࡜ TS Ⅼ 4 ಶࢆᚓࡓࠋࡲࡓࠊࢩࢽ
ࣙࣜࣥศᏊ࡟ࡘ࠸࡚ࠊ10 ࠿ᡤࡢཎᏊࢆୖࡾ᥈⣴ᑐ㇟࡟ᣦᐃࡋࡓ᥈⣴(LADD=3ࠊGauProc=16ࠊィ⟬ࣞ࣋ࣝ PM3)
ࢆ⾜࠸ࠊEQ ᵓ㐀 5 ಶ࡜ TS ᵓ㐀 2 ಶࢆᚓࡓࠋࢩࢽࣙࣜࣥ࡟ࡘ࠸࡚ࠊึᮇᵓ㐀ࠊୖࡾ᥈⣴࡟㑅ࢇࡔཎᏊࠊᚓࡽ
ࢀࡓ EQ࣭TS ᵓ㐀ࢆᅗ 1 ࡟♧ࡍࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۑۻ‬㧗⏣㇂ࠊἈࠊ⟪ᅵ㊰ࠊᒣ㛛ࠊSRPS2019ࠊP21, 2019 ྡྂᒇ.
‫ۑۻ‬ᒣ㛛ࠊ㧗⏣㇂ࠊ⟪ᅵ㊰ࠊἈࠊศᏊ⛉Ꮫウㄽ఍ࠊ4P099, 2019 ྡྂᒇ.
‫ۑۻ‬ᒣ㛛ࠊ㧗⏣㇂ࠊ⟪ᅵ㊰ࠊἈࠊ᫬ᏊᒣࠊAPATCC 2019ࠊIC056,
2019 Sydney (Australia).
௚ 7 ௳(࠺ࡕ㸯௳‫)ۻ‬5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬㧗⏣㇂ࠊἈࠊᒣ㛛ࠊ᫬Ꮚᒣࠊ኱㔝ࠊChem. Phys. Lett., 718 (2019),
ᅗ 1.

32-37.

ࢩࢽࣙࣜࣥࡢึᮇᵓ㐀ࠊୖࡾ᥈⣴࡟㑅ᢥࡋࡓཎᏊࠊᚓࡽࢀࡓ㹃㹏࣭㹒

௚ 3 ௳(‫)ࡋ↓ۻ‬㹑ᵓ㐀- 121 -

ศᏊືຊᏛཬࡧ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸ࡓࢭ࣮ࣝࣟࢫ㛵㐃ศᏊ࠾ࡼࡧ㧗ศᏊࡢᵓ㐀࡜ᶵ⬟ࡢ◊✲ ̺ ࢭ࣮ࣝࣟࢫ࢔ࢭࢸ࣮ࢺࡢ࢔ࢭࢺࣥ⁐ゎᛶ
Study of the structure and functions of cellulose and its related molecules and macromolecules
using molecular dynamics and quantum chemical calculations: Solubility of cellulose acetate in acetone.
‫⩏୍ ⏣ୖۑ‬㸦ᶓ὾ᅜ❧኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲㝔㸧

1◊✲┠ⓗࠊෆᐜ
ࢭ࣮ࣝࣟࢫࡣᆅ⌫ୖ࡟᭱ࡶ㇏ᐩ࡟Ꮡᅾࡍࡿ㧗ศᏊࡢ୍ࡘ࡛࠶ࡾࠊ࢚ࢿࣝࢠ࣮ࡸᮦᩱศ㔝࡬ከࡃࡢᛂ
⏝◊✲ࡀάⓎ࡟⾜ࢃࢀ࡚࠸ࡿࠋࡑࡢ୍᪉࡛ࠊࢭ࣮ࣝࣟࢫ㛵㐃ศᏊࡢᇶ♏≀ᛶ࡟ࡣ࠸ࡲࡔ୙᫂࡞Ⅼࡀከ࠸ࠋࡑࡢ୍ࡘࡀ⁐ゎᛶ࡛࠶ࡿࠋࡇࢀࡲ࡛ࠊᡃࠎࡣࠊࢭ࣮ࣝࣟࢫ࢜ࣜࢦ࣐࣮ࠊ࣓ࢳࣝࢭ࣮ࣝࣟࢫ࡞࡝ࡢỈ࡬ࡢ⁐ゎᛶࢆศᏊືຊᏛィ⟬ 0' ィ⟬ ࡜࢚ࢿࣝࢠ࣮⾲♧ἲ (5 ἲ ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬>@ࢆ⤌ࡳྜࢃࡏ᳨࡚ウࡋ࡚ࡁࡓࠋᮏᖺᗘࡣࠊࢭ࣮ࣝࣟࢫ㛵㐃ศᏊ࡜ࡋ࡚ࢭ࣮ࣝࣟࢫ࢔ࢭࢸ࣮ࢺ࡟ࡘ࠸࡚࢔ࢭࢺࣥ⁐፹࡬ࡢ⁐ゎᛶ࡟ࡘ࠸᳨࡚ウࡋࡓ⤖ᯝࢆ㏙࡭ࡿࠋࢭ࣮ࣝࣟࢫࢺࣜ࢔ࢭࢸ࣮ࢺ &7$ ࡣࠊᾮᬗࢹ࢕ࢫࣉࣞ࢖୰ࡢ೫ගಖㆤࣇ
࢕࣒ࣝ࡞࡝࡟ᗈࡃᕤᴗ฼⏝ࡉࢀ࡚࠸ࡿࢭ࣮ࣝࣟࢫㄏᑟయ࡛࠶ࡾࠊࡑࡢ⁐ゎᛶࡢྥୖࡀᕤᴗⓗ࡟㔜せ࡞ㄢ㢟࡜࡞ࡗ࡚࠸ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊศᏊືຊᏛ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜࢚ࢿࣝࢠ࣮⾲♧ (5 ἲࢆ⏝࠸࡚⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࠊ⁐ゎ⮬⏤࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡍࡿࡇ࡜࡟ࡼࡾࠊ&7$ ࢜ࣜࢦ࣐࣮ࡢ࢔ࢭࢺࣥ⁐፹࡟ᑐࡍࡿ⁐ゎᛶࡢ ᗘኚ໬࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋ2◊✲᪉ἲ࣭ィ⟬᪉ἲ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮⟬ฟࡢࡓࡵ࡟ &7$ 㔞యࢆ࢜ࣜࢦ࣐࣮ࣔࢹࣝ࡜ࡋ࡚⏝࠸ࠊࡑࢀࡒࢀࡢ୍ᮏ㙐ࡢ⁐㉁⣔, ࢔ࢭࢺࣥࡢࡳࡢ⁐፹⣔, ࠾ࡼࡧ࢜ࣜࢦ࣐࣮ࢆ࣎ࢵࢡࢫࡢ୰ᚰ࡟⨨࠸ࡓ࢔ࢭࢺࣥ⁐ᾮ⣔ࢆసᡂࡋࠊᅽຊ 1bar,ᗘ ̿. ࡢ᮲௳࡛ྛ⣔ࡑࢀࡒࢀ 100 ns, 100 ps, 10 ns ࡢ MD ィ⟬ࢆ⾜ࡗࡓࠋࡇࢀ࡟ࡼࡗ࡚

ᚓࡽࢀࡓ㌶㊧ࢹ࣮ࢱࢆ⏝࠸࡚ࠊER ἲ࡟ࡼࡾ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࡓࠋḟ࡟ࠊ⁐ゎ⮬⏤࢚ࢿࣝࢠ࣮ࢆ
⟬ฟࡍࡿࡓࡵࡢ⁐ゎࢧ࢖ࢡࣝࢆ⪃࠼ࠊǼ* ⁐ゎ Ǽ* ⁐፹࿴Ǽ* ゎ㞳࠿ࡽࠊゎ㞳⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋ࡚࿴ࢆྲྀࡿ
ࡇ࡜࡛⁐ゎࡢ⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋ&7$ ศᏊࡀ &7$ ࢔ࣔࣝࣇ࢓ࢫ୰࡟ᤄධࡉࢀࡿ㐣⛬ࡢ㏫ࡀゎ㞳㐣⛬࡛࠶ࡿࡇ࡜࠿ࡽࠊᤄධ㐣⛬ࢆ⁐፹࿴ࡢ㐣⛬࡜ࡳ࡞ࡍࡇ࡜࡛ࠊඛ࡯࡝࡜ྠᵝࡢᡭἲ࡛ゎ㞳㐣⛬ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࡓࠋࡉࡽ࡟ࠊࡇࡇ࡛ᚓࡽࢀࡓ್࡜ᅛ┦࠿ࡽẼ┦࡬ࡢ୪㐍࠾ࡼࡧᅇ㌿࢚ࣥࢺࣟࣆ࣮ኚ໬
ࢆຍ࠼࡚ゎ㞳⮬⏤࢚ࢿࣝࢠ࣮࡜ࡋࡓࠋࡇࡢ್࡟ࠊ
ୖグࡢ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࢆ㊊ࡋྜࢃࡏࡿࡇ
࡜࡟ࡼࡗ࡚⁐ゎ⮬⏤࢚ࢿࣝࢠ࣮ࢆᚓࡓࠋ࡞࠾ࠊィ⟬ࢯࣇࢺ࡟ࡣ MD ィ⟬࡟ GROMACS-4.5.5 ࢆࠊER

ᗘ[K]300.15273.15253.15233.15213.15193.15⾲䠍㻌 ⁐፹࿴⮬⏤䜶䝛䝹䜼䞊⁐፹࿴⮬⏤䜶䝛䝹䜼䞊[kcal mol-1]-135.9-151.0-165.4-180.9-198.2-215.2ἲ࡟ࡼࡿィ⟬࡟ ERmod-0.3.4 ࢆࠊຊሙࣃ࣓࣮ࣛࢱ
࣮࡟ࡣࢭ࣮ࣝࣟࢫ࢔ࢭࢸ࣮ࢺ࢜ࣜࢦ࣐࣮࡜࢔ࢭࢺࣥ࡟ charmm36 ຊሙࢆ⏝࠸ࡓࠋ- 122 -

3◊✲ᡂᯝ(5 ἲ࡟ࡼࡗ࡚⟬ฟࡉࢀࡓ &7$ 㔞యࡢ࢔ࢭࢺ
ࣥ⁐፹࡬ࡢ⁐፹࿴⮬⏤࢚ࢿࣝࢠ್࣮ࢆ⾲㸯࡟♧ࡍࠋప ࡯࡝⁐፹࿴⮬⏤࢚ࢿࣝࢠ್࣮ࡣ㈇࡟
኱ࡁࡃ࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓǼ+ ⁐፹࿴ࠊǼ6ࡀ ᗘ࡟ᑐࡋ୍࡚ᐃ࡛࠶ࡿ࡜௬ᐃࡋࠊ௒ᅇ

⁐፹࿴ᚓࡽࢀࡓ್ࢆǼ*㸻Ǽ+7Ǽ6 ࡢᘧ࡟௦ධࡍࡿ࡜ࠊ
Ǽ6 ⁐፹࿴ NFDO.PROࠊǼ+ ⁐፹࿴ 

ᗘ[K]300.15273.15253.15233.15213.15193.15⾲䠎㻌 ⁐ゎ⮬⏤䜶䝛䝹䜼䞊⁐ゎ⮬⏤䜶䝛䝹䜼䞊[kcal mol-1]
18.2
12.2
4.9
-3.5
-16.0
-22.4

NFDOPRO ࡜࡞ࡗࡓࠋ ḟ࡟ࠊ⟬ฟࡉࢀࡓ⁐ゎ⮬⏤࢚ࢿࣝࢠ್࣮ࢆ⾲㸰࡟♧ࡍࠋ Ǽ* ⁐ゎࡣ ᗘࡢపୗ࡟కࡗ࡚ῶᑡࡋ࡚࠸ࡃࡇ࡜ࡼࡾࠊప ࡯࡝ &7$ࡣ࢔ࢭࢺࣥ⁐፹࡬⁐ゎࡋࡸࡍࡃ࡞ࡿ࡜ุ᫂ࡋࡓࠋࡲࡓࠊ. ௨ୗ࡛⁐ゎ⮬⏤࢚ࢿࣝࢠ࣮ࡣṇࡢ್࠿ࡽ㈇ࡢ್࡬࡜ኚ໬ࡋ࡚࠾ࡾࠊ&7$ 㔞యࡣࡇࡢ ᗘ௜㏆࡛࢔ࢭࢺࣥ⁐፹࡬࡜⁐ゎࡍࡿࡇ࡜ࡀィ⟬࠿ࡽ᥎ ࡉࢀࡓࠋ ᐇ㦂࡟࠾࠸࡚ࡶ &7$ ࡣప ࡯࡝࢔ࢭࢺࣥ࡟⁐ゎࡋࡸࡍ࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡀࠊヨᩱࡢศᏊ㔞ศᩓᛶࠊ࢔ࢭࢳࣝ⨨᥮ᗘศᕸࡢᏑᅾ➼ࡢࡓࡵࠊ≀ᛶࡢᐃᛶⓗ⪃ᐹࡀᐜ࡛᫆࡞࠸ࠋ௒ᅇࠊィ⟬࡟ࡼࡾ⁐ゎᛶࡢ᳨ウࡀྍ⬟࡟࡞ࡗࡓࡇ࡜ࡣ௒ᚋࡢᐃ㔞ⓗ࡞≀ᛶᢕᥱ࡟᭷⏝࡞▱ぢࢆ୚࠼ࡿࡇ࡜ࡀฟ᮶ࡿࡶࡢ࡜ᛮࢃࢀ
ࡿࠋ௒ᚋࡣ⁐ゎࡢᶵᵓࢆ⇕ຊᏛⓗㅖ㔞࡜ࡢ㛵㐃ᛶ࡟ࡘ࠸᳨࡚ウࡍࡿࠋ

4 ཧ⪃ᩥ⊩1) Matubayasi, N., et al. J. Chem. Phys., 2000, 113, 6070.

5 Ⓨ⾲ࠊฟ∧ᐇ⦼ࡲࡓࡣணᐃ
(1) ‫"ۻ‬A E-Diketiminato-based pincer-type nickel(II) complex, Ni-NNP: synthesis andits catalytic performance for cross-coupling reaction of aryl fluorides with aryl Grignard
reagents”Nobutaka Kurisu, Yuki Hatayama, Erika Asano, Toru Hashimoto, Youji
Kurihara, Kei Funatsu, Kazuyoshi Ueda, and Yoshitaka Yamaguchi, European Journalof Inorganic Chemistry. 126-133 (2019) 10.1002/ejic.201801179.
(2) "DFT study of the influence of acetyl groups of cellulose acetate on its intrinsic
birefringence and wavelength dependence.” Daichi Hayakawa, Hiroaki Gouda, Shuichi
Hirono, and Kazuyoshi Ueda, Carbohydr. Polym. 207, 122-130 (2019).
https://doi.org/10.1016/j.carbpol.2018.11.074(3) "Development of PolyParGen Software to Facilitate the Determination of
Molecular Dynamics Simulation Parameters for Polymers. Makoto Yabe, Kazuki Mori,
Kazuyoshi Ueda, and Minoru Takeda, J. Comput. Chem. Jpn., 5, 2018-0034 (2019).
https://doi.org/10.2477/jccjie.2018-0034(4) ‫"ۻ‬A comparative study of interactions of antimicrobial peptide of L- andD-phenylseptin with 1,2-dimyristoyl-sn-glycero-3-phosphocholine” Batsaikhan
Mijiddorj, Yuta Matsuo, Hisako Sato, Kazuyoshi Ueda, and Izuru Kawamura, Applied
Sciences, 9, 2601, (2019) https://doi.org/10.3390/app9132601.

- 123 -



Structures and Properties of Molecular Nanocarbons
Ã ÀÒĄ~ùÊ_JST ERATOą

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1.$4ÕHOMO-LUMO#¡"/3.30 eV (1), 2.88 eV (2), 2.80 eV (3a), 2.62

eV (3b) Úp1TD-DFT#-0S0-S1ôÖ;JY=`+}¹$r/nπ-π*ôÖ#10{/.#ål÷{-&ål#1ÇÙ'%3b$ålíâ

Ée$x|Æ-/ă" 0
LWATCY6RKM:IYá 01%HOMO$ðòþjb6X`Y#qqoþäqüÈ¦õqÏ#b

.10ëÚ#-/¢.1ªwf$k%1.
0Õ10- 124 -

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Figure 1. Photophysical properties of WNG derivatives. (a) UV/Vis absorption (solid lines) spectra, fluorescence (dottedlines) spectra, absolute fluorescence quantum yields, and photographs of dichloromethane solutions of 1, 2, 3a, and 3brecorded under illumination with either ambient or UV light (254 nm). (b) Frontier molecular orbitals and energy levelsof 1, 2, 3a, and 3b calculated at the B3LYP/6-31G(d) level of theory.

4ÎçpÅß)%c

Six-fold C–H Borylation of Hexa-peri-hexabenzocoronene
Mai Nagase, Kenta Kato, Akiko Yagi, Yasutomo Segawa,* and Kenichiro Itami*
Beilstein J. Org. Chem. 2020, 16, 391–397.
Selective Transformation of Strychnine and 1,2-Disubstituted Benzenes by C–H Borylation
Yutaro Saito, Kotono Yamanoue, Yasutomo Segawa,* and Kenichiro Itami*
Chem 2020, 6, 985-993.
 Synthesis and Structure of [9]Cycloparaphenylene Catenane: An All-benzene Catenane Consisting of
Small Rings
Yasutomo Segawa,* Motonobu Kuwayama, and Kenichiro Itami*
Org. Lett. 2020, 22, 1067-1070.
Two-step Synthesis of a Red-emissive Warped Nanographene Derivative via a Ten-fold C–H Borylation
Kenta Kato, Hsing-An Lin, Motonobu Kuwayama, Mai Nagase, Yasutomo Segawa,* Lawrence T. Scott,and Kenichiro Itami*
Chem. Sci. 2019, 10, 9038-9041.
Topological Molecular Nanocarbons: All-benzene Catenane and Trefoil Knot
Yasutomo Segawa,* Motonobu Kuwayama, Yuh Hijikata, Masako Fushimi, Taishi Nishihara, Jenny Pirillo,
Junya Shirasaki, Natsumi Kubota, and Kenichiro Itami*
Science 2019, 365, 272-276.

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㔞Ꮚ໬Ꮫ࡜⤫ィຊᏛ࡟ᇶ࡙ࡃ」㞧໬Ꮫ⣔ࡢ⌮ㄽⓗ◊✲Theoretical studies on complex chemical systems based on quantum
chemistry and statistical mechanics‫ۑ‬బ⸨ၨᩥࠊᮾ㞞኱ࠊ୰㎰ᾈྐࠊྜྷ⏣ᝆ୍㑻ࠊ▮ᮌᬛ❶ࠊ⏤ᮏ⨾㤶ࠊ㧗ᶫ೺ࠊ௒ᮧὯ㍜ࠊ኱す⯙㤶ࠊᢲᮌ῟ࠊṊ㔝ഔ㸦ி㒔኱Ꮫ㸧ࠊᒣෆ┿᲍Ụࠊ಴ዟ኱ᶞࠊẚ჆ᮍ㤶Ꮚ㸦⌰⌫኱Ꮫ㸧

1◊✲┠ⓗࠊෆᐜ
⌧௦໬Ꮫࡢᑐ㇟ࡣ┈ࠎ」㞧໬ࡋ࡚࠸ࡿࠋࡑࡢ᰿ᖿ࡛࠶ࡿ⣲㐣⛬ࡣ㔞ᏊຊᏛ࡟ᨭ㓄ࡉࢀ࡚࠸ࡿࡀࠊศᏊ㞟ᅋ࡜ࡋ࡚ࡢ≉ᛶࡣ⤫ィຊᏛⓗ࡟⌮ゎࡉࢀࡿᚲせࡀ࠶ࡿࠋᚑࡗ࡚ࠊ໬Ꮫ⌧㇟ࢆศᏊ⛉Ꮫⓗ࡞❧ሙ࠿ࡽグ㏙ࡍࡿࡓࡵ࡟ࡣࠊ㔞Ꮚ໬Ꮫ࠾ࡼࡧ⤫ィຊᏛࡀᚲ㡲࡜࡞ࡿࠋࡇࡢᚑ᮶࠿ࡽࡢ஧ࡘࡢどⅬ࡟ຍ࠼࡚ࠊࡑࢀࡽࢆ⼥ྜࡋࡓ᪂ࡋ࠸ᡭἲࢆ㛤Ⓨ࣭㥑౑ࡍࡿࡇ࡜࡛ࠊᚑ๓࠿ࡽᮏ◊✲ㄢ㢟࡛ࡣ໬Ꮫ⌧㇟ࡢ୍⯡ほࡢᵓ⠏ࢆ┠ᣦࡋ࡚ࡁࡓࠋᮏᖺ
ᗘࡢ୺࡞◊✲ෆᐜࢆ௨ୗ࡟♧ࡍࠋ
1.1 ᇶ┙ⓗ࡞໬Ꮫ㐣⛬࡟ᑐࡍࡿ᪉ἲㄽ㛤Ⓨ࡜ࡑࡢⓎᒎ㔞Ꮚ໬Ꮫ࠶ࡿ࠸ࡣ⤫ィຊᏛ࡟ᇶ࡙࠸ࡓ᪂つᡭἲࡢ㛤Ⓨࢆ⾜࠺࡜࡜ࡶ࡟ࠊࡇࢀࡽࢆ㥑౑ࡋࡓィ⟬ࢆ㏻ࡌ࡚඾
ᆺⓗ࡞᭷ᶵ໬Ꮫ཯ᛂࡸࠊ㑄⛣㔠ᒓඖ⣲ࢆྵࡴ」ྜ⣔ࠊ⏕య㛵㐃ศᏊ࡟⮳ࡿࡲ࡛ࠊ໬Ꮫⓗ࡟⯆࿡ࡀ࠶ࡿᖜᗈ࠸
⣔ࢆᑐ㇟࡜ࡋࡓ⌧ᐇࡢ⌧㇟ࡢ⌮ゎࢆ῝ࡵࡿࡇ࡜ࢆ┠ⓗ࡟◊✲ࢆ⾜ࡗࡓࠋ௒ᖺᗘࡣ㸦㸯㸧㑄⛣㔠ᒓࢆྵࡴ⣔ࡢࡓࡵࡢ᪉ἲㄽ㛤Ⓨࠊ࡜ࡾࢃࡅ」ᩘࡢ㑄⛣㔠ᒓࢆྵࡴ኱つᶍ⮬ᕫ㞟ྜ⣔ࢆᢅ࠺ࡓࡵࡢ㔞Ꮚ໬Ꮫ᭷ຠࣔࢹࣝࣁ࣑
ࣝࢺࢽ࢔ࣥἲࡢ㛤Ⓨ࡜ᛂ⏝ࠊ㸦㸰㸧ከཎᏊศᏊ⣔ࡢ⌮ㄽ໬Ꮫࠊࡼࡾලయⓗ࡟ࡣࢼࣀ࣮࢟ࣗࣈࡢ⮬ᕫ㞟ྜ㐣⛬ࡢゎᯒ࡜ࠊ㑄⛣㔠ᒓࢆྵࡴᆒ୍ゐ፹⣔ࡢᵓ㐀᥈⣴࡟㛵ࡍࡿ◊✲ࢆ㐍ࡵࡓࠋࡲࡓ㸦㸱㸧จ⦰⣔ศᏊࡢ NMR ໬Ꮫࢩࣇࢺࢆィ⟬ࡍࡿ᪂ࡋ࠸ᡭἲࢆ㛤Ⓨࡋࡓࠋ
1.2 ගྜᡂ཯ᛂ୰ᚰ࡟࠾ࡅࡿึᮇ㟁Ⲵศ㞳㐣⛬ࡢศᏊㄽⓗᶵᵓゎ᫂⥳Ⰽ᳜≀ࡢග໬Ꮫ⣔ II (PSII) ࡣࠊ⏕≀⏺࡛၏୍Ỉศゎ࣭㓟⣲Ⓨ⏕ࢆ⾜࠺Ⰽ⣲࣭ࢱࣥࣃࢡ㉁㉸」ྜయ࡛࠶ࡿࠋ
㏆ᖺࡢᐇ㦂◊✲࡟ࡼࡾࠊ㓟⣲㠀Ⓨ⏕ᆺࡢ⣚Ⰽ⣽⳦ࡢ཯ᛂ୰ᚰ࡜ẚ㍑ࡋ࡚ࠊ⥳Ⰽ᳜≀ࡢ PSII ཯ᛂ୰ᚰࡣࠊึᮇ
㟁Ⲵศ㞳㐣⛬ࢆ཯ᛂ㛤ጞሙᡤ࡜㏿ᗘࡢ୧᪉ࢆࡼࡾ᭱㐺໬ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡿࠋࡇࡢึᮇ㟁Ⲵศ㞳ࡢ᭱㐺໬ࡣࠊࢱࣥࣃࢡ㉁ࡢᵓ㐀ࡸᦂࡽࡂ࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽࢀ࡚࠸ࡿࡀࠊලయⓗ࡞ᶵᵓࡣ඲ࡃ᫂ࡽ࠿࡟࡞ࡗ
࡚࠸࡞࠸ࠋࡇࡢࡼ࠺࡞ึᮇ㟁Ⲵศ㞳㐣⛬࡟࠾ࡅࡿࢱࣥࣃࢡ㉁ࡢᙺ๭ࢆศᏊ࡛ࣞ࣋ࣝゎ᫂ࡍࡿࡓࡵ࡟ࡣࠊྛⰍ
⣲ࡢບ㉳≧ែࡸ㟁Ⲵศ㞳≧ែࡢ࢚ࢿࣝࢠ࣮ࡢ኱ࡁࡉ࡜ᦂࡽࡂࡢ୧᪉ࢆゎᯒࡍࡿᚲせࡀ࠶ࡿࠋࡋ࠿ࡋࠊⰍ⣲ࡢ࢚ࢿࣝࢠ࣮ࡢ኱ࡁࡉࡸᦂࡽࡂࢆᚑ᮶ࡢᡭἲ࡛㧗⢭ᗘ࡟ゎᯒࡍࡿࡓࡵ࡟ࡣࠊࢧࣥࣉࣜࣥࢢィ⟬࡟⭾኱࡞ᩘࡢ㧗⢭ᗘ࣭㧗ࢥࢫࢺ࡞㔞Ꮚ໬Ꮫィ⟬ࢆせồࡉࢀࡿࡓࡵࠊ᭱ඛ➃ࡢࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࢆ⏝࠸࡚ࡶ஦ᐇୖィ⟬୙ྍ⬟࡛࠶ࡿࠋࡇࡢ⌧≧ࢆᡴ㛤ࡍ࡭ࡃࠊᡃࠎࡣศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜㔞Ꮚ໬Ꮫィ⟬ࢆຠ⋡ⓗ࡟⤖ࡧࡘࡅࡿ⊂⮬ࡢᡭἲࢆ㛤Ⓨࡋࠊᚑ᮶ࡢᡭἲ࡛ࡣゎᯒࡀ୙ྍ⬟࡞จ⦰┦ࡢ໬Ꮫ཯ᛂࢲ࢖ࢼ࣑ࢡࢫࡢゎ᫂࡟ྲྀࡾ⤌ࢇ࡛ࡁࡓࠋ
ᮏᖺᗘࡣࠊࡇࢀࡲ࡛࡟ᡃࠎࡀ㛤Ⓨࡋ࡚ࡁࡓᡭἲࢆ⏝࠸࡚⥳Ⰽ᳜≀ࡢ PSII ཯ᛂ୰ᚰ࡟ྵࡲࢀࡿ 6 ࡘࡢࢡࣟࣟࣇ
࢕ࣝⰍ⣲ࡢ㟁Ꮚ≧ែࡢゎᯒࢆ⾜ࡗࡓࠋ
1.3 ࢱࣥࣃࢡ㉁-ᇶ㉁㛫┦஫స⏝࡜᣺ືࢫ࣌ࢡࢺࣝࡢ┦㛵ࡢゎ᫂⭷ࢱࣥࣃࢡ㉁࡜ᇶ㉁ࡸ࢖࢜ࣥ࡜ࡢ┦஫స⏝ࢆ⌮ゎࡍࡿୖ࡛ࠊ඲཯ᑕ㉥እศගἲࡣ㠀ᖖ࡟ᙉຊ࡞ᡭἲ࡛࠶ࡿࠋ

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ࡋ࠿ࡋࠊ᣺ືࢫ࣌ࢡࢺࣝࡢኚ໬ࡢศᏊㄽⓗ㉳※ࢆ⌮ゎࡍࡿࡇ࡜ࡣࠊᐇ㦂◊✲ࡔࡅ࡛ࡣᅔ㞴࡛࠶ࡾࠊศᏊࢩ࣑
࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿゎᯒࡀᚲせ࡜ࡉࢀ࡚࠸ࡿࠋࡇࢀࡲ࡛ᡃࠎࡣࠊ࢖࢜ࣥࢳࣕࢿࣝࡢ᣺ືࢫ࣌ࢡࢺࣝࡢゎᯒࢆ⾜࠸ࠊ᣺ືࢫ࣌ࢡࢺࣝࡢኚ໬ࡢ㉳※ࢆ᫂ࡽ࠿࡟ࡋ࡚ࡁࡓࠋᮏᖺᗘࡣࠊ࢔ࢹࣀࢩࣥ 2A ཷᐜయ A2AR ෆࡢ࢔ࢹࣀ
ࢩࣥࡢ᣺ືࢫ࣌ࢡࢺࣝࡢゎᯒࢆ⾜ࡗࡓࠋ
1.4 ΰྜ⁐፹୰࡟࠾ࡅࡿࣁ࢖ࣈࣜࢵࢻゐ፹཯ᛂࡢศᏊㄽⓗᶵᵓゎ᫂」ᩘࡢゐ፹ࡀᶵ⬟ࡍࡿࣁ࢖ࣈࣜࢵࢻゐ፹཯ᛂ࡛ࡣࠊ⁐፹ࡢ㑅ᢥࡶࡼࡾ㔜せ࡜࡞ࡿࠋࡑࡢ㑅ᢥࡣ༢୍⁐፹ࡔࡅ࡛࡞ࡃΰྜ⁐፹࡟ࡶཬࡧࠊ㏆ᖺࠊỈࢆ୍ᐃ㔞ῧຍࡍࡿ࡜኱ᖜ࡟཯ᛂᛶࡀྥୖࡍࡿࣁ࢖ࣈࣜࢵࢻゐ፹཯ᛂࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊῧຍࡋࡓỈࡢᙺ๭࡟ࡘ࠸࡚ࡣࡼࡃศ࠿ࡗ࡚࠸࡞࠸ࠋࡇࢀࡲ࡛ᡃࠎࡣࠊ୺࡟㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸࡚ࣁ࢖ࣈࣜࢵࢻゐ፹཯ᛂ࡟࠾ࡅࡿỈࡢῧຍຠᯝࡢゎᯒࢆ⾜ࡗ࡚ࡁࡓࠋᮏᖺᗘࡣࠊMacMillan ᩍᤵ㸦ࣉࣜࣥࢫࢺࣥ኱㸧ࡢࢢ࣮ࣝࣉ࡟ࡼࡾ㛤Ⓨࡉࢀࡓࠊ3 ࡘࡢゐ፹࡟ࡼࡾ≉ᐃࡢ C-H ⤖ྜࢆ࢔࣮ࣜࣝ໬ࡍࡿࣁ
࢖ࣈࣜࢵࢻゐ፹཯ᛂ࡟࠾ࡅࡿỈࡢῧຍຠᯝࢆゎᯒࡋࡓࠋ
1.5 ࣅ࣮ࣝࡢⱞࡳᡂศࡢ⏕ᡂᶵᵓࡢゎᯒࣅ࣮ࣝࡢ୺࡞ⱞࡳᡂศࡣࠊ࣍ࢵࣉ࡟ྵࡲࢀࡿȘ㓟ࡀ㔊㐀㐣⛬࡛␗ᛶ໬ࡋࡓ࢖ࢯȘ㓟࡛࠶ࡿࠋ࢖ࢯȘ㓟ࡣࢩࢫయ࡜ࢺࣛࣥࢫయࡀᏑᅾࡍࡿࡀࠊࡇࢀࡲ࡛ࡢᐇ㦂◊✲࡟ࡼࡾࠊࢺࣛࣥࢫయࡢ᪉ࡀ⏕ᡂࡋࡸࡍ࠸ࡀ୙Ᏻᐃ࡛࠶
ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡑࡢศᏊㄽⓗᶵᵓࡣ୙࡛᫂࠶ࡗࡓࠋࡇࢀࡲ࡛ᡃࠎࡣࠊࡇࡢ␗ᛶ໬཯ᛂࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾゎᯒࡋࠊࢺࣛࣥࢫయࡀ⏕ᡂࡋࡸࡍ࠸ࡢࡣࠊࢩࢫయ࡟⮳ࡿ㑄⛣≧ែࡀ❧య㞀ᐖ࡟ࡼࡾ୙Ᏻᐃ
࡞ࡓࡵ࡜᫂ࡽ࠿࡟ࡋࡓࠋᮏᖺᗘࡣࡉࡽ࡟◊✲ࢆ㐍ࡵࠊ㔠ᒓ࢖࢜ࣥࡀࡇࡢ␗ᛶ໬཯ᛂ࡟୚࠼ࡿᙳ㡪ࢆゎᯒࡋࡓࠋ2◊✲ᡂᯝ
2.1 ᇶ┙ⓗ࡞໬Ꮫ㐣⛬࡟ᑐࡍࡿ᪉ἲㄽ㛤Ⓨ࡜ࡑࡢⓎᒎᙜヱㄢ㢟࡟㛵㐃ࡋࡓ௒ᖺᗘᚓࡽࢀࡓᡂᯝࡢ୍㒊ࡣḟࡢ㏻ࡾせ⣙ࡉࢀࡿࠋ㸦㸯㸧ᮾி኱Ꮫࡢ⸨⏣ࡽࡀ㛤Ⓨࡋࡓ㑄⛣㔠ᒓࢆྵࡴ⮬ᕫ㞟ྜ⣔ >3Gn/m@2n+㸦ࡓࡔࡋ n,m          ࡛࠶ࡿ㸧ࢆᑐ㇟࡜ࡋࡓィ⟬ࢆ⾜ࡗࡓࠋ஭ෆࡽࡀ㛤Ⓨࡋࡓ㔞Ꮚ໬Ꮫ᭷ຠࣔࢹࣝ
ࣁ࣑ࣝࢺࢽ࢔ࣥࡢᯟ⤌ࡳࢆ⏝࠸࡚ 03 ィ⟬ࢆ⢭ᗘࡼࡃ෌⌧ࡍࡿࣃ࣓࣮ࣛࢱ࣮ࢭࢵࢺࢆ㛤Ⓨࡋࡓࠋ⁐፹࿴ຠᯝࡣ୍⯡໬࣎ࣝࣥἲࢆ⏝࠸࡚ホ౯ࡋࠊ࢚ࢿࣝࢠ࣮໙㓄ἲࡢ㛤Ⓨࡶేࡏ࡚⾜ࡗࡓࠋ୍㐃ࡢ㔠ᒓ㘒యࡣࢧ࢖ࢬࡀ኱ࡁࡃ࡞ࡿ࡜㟁Ⲵ཯Ⓨࡀ኱ࡁࡃ࡞ࡾ୙Ᏻᐃᛶࡀቑࡍࡀࠊྠ᫬࡟ࡼࡾᙉࡃ⁐፹࿴ࡉࢀࡿࠋࡍ࡞ࢃࡕ୧⪅ࡀ⿵ൾⓗ࡟ാࡁࠊࡑࡢࣂࣛࣥࢫࡢ⤖ᯝ࡜ࡋ࡚኱ࡁ࡞ࢧ࢖ࢬࡢ㔠ᒓ㘒యࡀᙉࡃᏳ
ᐃ໬ࡉࢀࡿࡇ࡜ࢆぢฟࡋࡓࠋࡲࡓ n  ࡟ࡘ࠸࡚㑄⛣㔠ᒓࡢ㟁Ꮚ≧ែࢆㄪ࡭ࡿ࡜ࠊ≉ᐃࡢ㟁Ꮚ㓄⨨ࡀ㸷๭㏆ࡃࢆ༨ࡵ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
㸦㸰㸧ᮾி኱Ꮫࡢᖹᒸࡽࡣ㸴ࡘࡢṑ㌴≧୧ぶ፹ᛶศᏊࡀ㞟ྜࡋ࡚ࢼࣀ࣮࢟ࣗࣈ࡜࿧ࡤࢀࡿ❧᪉య≧ࡢศᏊ࢝ࣉࢭࣝࡀ⮬Ⓨⓗ࡟⏕ᡂࡉࢀࡿࡇ࡜ࢆሗ࿌ࡋ࡚࠸ࡿࠋࡇࡢ⣔࡟ࡘ࠸࡚ࡣࡇࢀࡲ࡛࡟⡆౽࡞ࣔࢹࣝ
ศᏊ⣔ࡢ࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡸ⁐፹ࢆྵࡴ඲ཎᏊ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࡁࡓࡀࠊ
⮬ᕫ㞟ྜ⤒㊰࡟ࡘ࠸࡚ࡣ୙᫂ࡢࡲࡲ࡛࠶ࡗࡓࠋᮏㄢ㢟࡛ࡣ඲ཎᏊ 0' ࡢ⤖ᯝࢆ෌⌧ࡍࡿ⢒ど໬ࣔࢹࣝࢆ᪂ࡓ࡟㛤Ⓨࡋ 0' ィ⟬ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓᵓ㐀ኚ໬ࣃࢱ࣮ࣥࢆࢡࣛࢫࢱ࣮ศᯒࡢᡭἲࢆ฼
⏝ࡋ࡚㢮ఝᗘࡢ㧗࠸ࢢ࣮ࣝࣉ࡟ศ㢮ࡋ㸪ࡑࡢ㛫ࡢ㑄⛣ࢆゎᯒࡍࡿࡇ࡜࡛཯ᛂ⤒㊰ࡢࢿࢵࢺ࣮࣡ࢡᵓ
㐀ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࣆࣥࢧ࣮ᆺ㓄఩Ꮚࢆᣢࡘࣝࢸࢽ࣒࢘㘒య࡟ࡼࡿỈࡢศゎ཯ᛂࢆᑐ㇟࡜ࡋ࡚ࠊ
ᗈᇦᵓ㐀᥈⣴࡟ࡼࡗ࡚ᚓࡽࢀࡓከᩘࡢᏳᐃᵓ㐀ࢆ GLVFRQQHFWLYLW\ JUDSK ࡟ᇶ࡙࠸࡚ᩚ⌮ࡋࠊ཯ᛂ㐣- 127 -

⛬ࢆゎᯒࡋࡓࠋ
㸦㸱㸧NMR ໬ᏛࢩࣇࢺࡣศᏊࡢྠᐃ࡟ᖜᗈࡃ⏝࠸ࡽࢀ࡚࠸ࡿࠋࡲࡓ⁐ᾮෆศᏊࡢ㟁Ꮚ≧ែࢆ┤᥋ⓗ࡟ほࡍࡿ᪉ἲ࡜ࡋ࡚ࡢព⩏ࡶ࠶ࡿࠋࡑࡇ࡛ᾮయࡢ✚ศ᪉⛬ᘧ⌮ㄽ㸦RISM㸧࡜㔞Ꮚ໬Ꮫィ⟬ࡢࣁ࢖ࣈࣜࢵࢻἲ࡛࠶ࡿ RISM-SCF-SEDD ἲࢆᇶ࡟ࡋࡓ NMR 㐽ⶸᐃᩘࢆィ⟬ࡍࡿ᪉ἲࢆ㛤ⓎࡋࡓࠋỈࠊ࣓ࢱࣀ࣮ࣝࠊ࢔ࢭࢺࣥ୰ࡢࣆࣜࢲࢪࣥࡢ N ໬Ꮫࢩࣇࢺࡢィ⟬ࡣࠊ᪤ ࡢᐇ㦂⤖ᯝࢆ⢭ᗘⰋࡃ෌⌧ࡋࡓࠋࡲࡓ໬Ꮫࢩࣇࢺࡢ

ᗘኚ໬࡟ࡘ࠸࡚ࡶㄪ࡭ࡓࠋ

2.2 ගྜᡂ཯ᛂ୰ᚰ࡟࠾ࡅࡿึᮇ㟁Ⲵศ㞳㐣⛬ࡢศᏊㄽⓗᶵᵓゎ᫂ᡃࠎࡀ㛤Ⓨࡋࡓจ⦰⣔୰ࡢศᏊࡢ࣏ࢸࣥࢩࣕࣝ㠃ࢆຠ⋡ⓗ࡟グ㏙ྍ⬟࡞ MMSIC ἲࢆ⏝࠸࡚ࠊ⥳Ⰽ᳜≀ࡢ཯ᛂ୰ᚰ࡟ྵࡲࢀࡿ 6 ࡘࡢࢡࣟࣟࣇ࢕ࣝⰍ⣲ࡢບ㉳࢚ࢿࣝࢠ࣮ࡢ኱ࡁࡉ࡜ᦂࡽࡂࢆゎᯒࡋࡓࠋཧ↷࡜ࡍࡿ㔞Ꮚ໬Ꮫィ⟬ᡭἲ࡜ࡋ࡚ࠊ㐣ཤࡢ◊✲࡛⁐ᾮ୰ࡢࢡࣟࣟࣇ࢕ࣝⰍ⣲ࡢບ㉳࢚ࢿࣝࢠ࣮ࢆ෌⌧ࡍࡿࡼ࠺࡟ࣃ࣓ࣛ
࣮ࢱࢆㄪᩚࡋࡓ CAM-B3LYP ᐦᗘỗ㛵ᩘࢆ⏝࠸ࡓࠋMMSIC ἲ࡟ࡼࡾࠊྛⰍ⣲ࡢᇶᗏ≧ែ࡜ບ㉳≧ែࡢ࣏ࢸࣥ
ࢩࣕࣝ㛵ᩘࢆ㐣ཤࡢ◊✲࡜ྠ⛬ᗘࡢ⢭ᗘ㸦ᖹᆒㄗᕪ ~1 kcal/mol㸧࡛సᡂࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡋ࠿ࡋࠊࡑࡢ࣏
ࢸࣥࢩࣕࣝ㛵ᩘ࡟ࡼࡾᚓࡽࢀࡓྛⰍ⣲ࡢບ㉳࢚ࢿࣝࢠ࣮ࡣࠊᐇ㦂⤖ᯝ࠿ࡽணࡉࢀࡿࡶࡢ࡜኱ࡁࡃ␗࡞ࡗࡓࠋ

ᚓࡽࢀࡓ⤖ᯝࢆゎᯒࡋࡓ࡜ࡇࢁࠊࢡࣟࣟࣇ࢕ࣝⰍ⣲ࡢഃ㙐ࡢࣅࢽࣝᇶࡢࡡࡌࢀᗘྜ࠸ࡀບ㉳࢚ࢿࣝࢠ࣮࡟኱
ࡁ࡞ᙳ㡪ࡀ࠶ࡿࡇ࡜ࡀุ᫂ࡋࠊࡇࢀࡲ࡛ࡼࡾࡶ㧗⢭ᗘ࡞࣏ࢸࣥࢩࣕࣝ㛵ᩘࡀᚲせ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ
ࡓࠋࡲࡓࠊ୰ኸࡢ Mg ࡟㓄఩Ꮚࡀ⤖ྜࡍࡿࢡࣟࣟࣇ࢕ࣝ࡜ Mg ࡀ࡞࠸ࣇ࢕࢜ࣇ࢕ࢳ࡛ࣥບ㉳࢚ࢿࣝࢠ࣮ࡢᕪ
ࡀᐇ㦂⤖ᯝ࠿ࡽண

ࡉࢀࡿࡶࡢࡼࡾ㐶࠿࡟኱ࡁࡃࠊ࣏ࢸࣥࢩࣕࣝ㛵ᩘࡢᇶ࡜࡞ࡿ㔞Ꮚ໬Ꮫィ⟬ࡶࡉࡽ࡟ὀព

῝࠸ྲྀࡾᢅ࠸ࡀᚲせ࡛࠶ࡿࡇ࡜ࡶ᫂ࡽ࠿࡟࡞ࡗࡓࠋᘬࡁ⥆ࡁヲ⣽࡞ゎᯒࢆ㐍ࡵ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ
2.3 ࢱࣥࣃࢡ㉁-ᇶ㉁㛫┦஫స⏝࡜᣺ືࢫ࣌ࢡࢺࣝࡢ┦㛵ࡢゎ᫂࢔ࢹࣀࢩࣥ 2A ཷᐜయ A2AR ෆࡢ࢔ࢹࣀࢩࣥࡢ᣺ືࢫ࣌ࢡࢺࣝࡣࠊỈ⁐ᾮ୰ࡢ࢔ࢹࣀࢩࣥࡢ᣺ືࢫ࣌ࢡࢺࣝ
࡜ẚ㍑ࡋ࡚ࠊ᣺ືᩘࡀኚ໬ࡍࡿࣆ࣮ࢡ࡜ኚ໬ࡋ࡞࠸ࣆ࣮ࢡࡀ⌧ࢀࡿࡇ࡜ࡀᐇ㦂ⓗ࡟᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࡀࠊ
ࡑࡢ⌮⏤ࡣศ࠿ࡗ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊQM/MM ᇶ‽᣺ືゎᯒࢆ⏝࠸࡚ཷᐜయ୰࡜Ỉ⁐ᾮ୰ࡢ࢔ࢹࣀࢩࣥࡢ᣺
ືࢫ࣌ࢡࢺࣝࢆゎᯒࡋࡓࠋ᣺ືᩘࡀኚ໬ࡋ࡞࠸ࣆ࣮ࢡ࡟ࡘ࠸࡚ࡣࠊᐇ㦂࡜୍⮴ࡋࡓ⤖ᯝࡀᚓࡽࢀࠊ࢔ࢹࢽࣥ
㒊ศࡢ㦵᱁᣺ື࡟⏤᮶ࡍࡿࡶࡢ࡜ศ࠿ࡗࡓࠋ୍᪉ࠊ᣺ືᩘࡀኚ໬ࡍࡿࣆ࣮ࢡ࡟ࡘ࠸࡚ࡣࠊỈ⁐ᾮ୰ࡢ࢔ࢹࣀ
ࢩࣥࡢ❧య㓄ᗙ࡟ࡼࡾ኱ࡁࡃኚ໬ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋỈ⁐ᾮ୰࡛࢔ࢹࣀࢩࣥࡣᵝࠎ࡞❧య㓄ᗙࢆྲྀࡾᚓࡿࡇ࡜ࡀศ࠿ࡗࡓࡓࡵࠊᘬࡁ⥆ࡁࠊ࡝ࡢ❧య㓄ᗙࡀᏳᐃ࡛࠶ࡿ࠿ゎᯒ୰࡛࠶ࡿࠋ
2.4 ΰྜ⁐፹୰࡟࠾ࡅࡿࣁ࢖ࣈࣜࢵࢻゐ፹཯ᛂࡢศᏊㄽⓗᶵᵓゎ᫂
MacMillan ᩍᤵࡢࢢ࣮ࣝࣉ࡟ࡼࡾ㛤Ⓨࡉࢀࡓࣁ࢖ࣈࣜࢵࢻゐ፹཯ᛂࡣࠊDMSO ⁐ᾮ୰࡟ 40 ᙜ㔞ࡢỈࢆຍ࠼ࡿࡇ࡜࡛཰⋡ࡀ๻ⓗ࡟ྥୖࡍࡿࡀࠊࡑࡢ⌮⏤ࡣ୙࡛᫂࠶ࡗࡓࠋࡑࡇ࡛ࠊ㔞Ꮚ໬Ꮫィ⟬࡜ศᴟ㐃⥆యࣔࢹࣝࢆ
⏝࠸࡚ࠊࡇࡢࣁ࢖ࣈࣜࢵࢻゐ፹཯ᛂࡢ DMSO ⁐ᾮ୰࡜Ỉ⁐ᾮ୰࡟࠾ࡅࡿ཯ᛂ⤒㊰ࢆゎᯒࡋࡓࠋࡑࡢ⤖ᯝࠊ⮬⏤࢚ࢿࣝࢠ࣮ⓗ࡟ጇᙜ࡞཯ᛂ⤒㊰ࢆᚓࡿࡇ࡜࡟ᡂຌࡋࠊ཯ᛂࡢᚊ㏿ẁ㝵ࡣ Ni ゐ፹ୖ࡛ C-C ⤖ྜࡀ⏕ᡂࡍࡿࢫࢸࢵࣉ࡜᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊỈ⁐፹࡟ࡼࡾᚊ㏿ẁ㝵ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀῶᑡࡍࡿࡇ࡜ࡶ᫂ࡽ࠿࡟࡞ࡾࠊ
ᐇ㦂࡜୍⮴ࡋࡓ⤖ᯝࡀᚓࡽࢀࡓࠋ⌧ᅾࠊࡉࡽ࡟ヲ⣽࡞ゎᯒࢆ㐍ࡵ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ
2.5 ࣅ࣮ࣝࡢⱞࡳᡂศࡢ⏕ᡂᶵᵓࡢゎᯒࡇࢀࡲ࡛ࡢᐇ㦂◊✲࡛ࠊMg2+࢖࢜ࣥࡸ Fe3+࢖࢜ࣥࢆῧຍࡍࡿࡇ࡜࡛࢖ࢯȘ㓟ࡢ཰⋡ࡀ኱ᖜ࡟ୖ᪼ࡍࡿࡇ࡜
ࡀ▱ࡽࢀ࡚࠸ࡓࡀࠊࡑࡢ⌮⏤ࡣ୙࡛᫂࠶ࡗࡓࠋࡑࡇ࡛ࠊ㔞Ꮚ໬Ꮫィ⟬࡜ศᴟ㐃⥆యࣔࢹࣝࢆ⏝࠸࡚ Mg2+࢖࢜
ࣥᏑᅾୗ࡛ࡢȘ㓟␗ᛶ໬཯ᛂࢆゎᯒࡋࡓࠋࡑࡢ⤖ᯝࠊȘ㓟࡜ Mg2+࢖࢜ࣥࡀ㘒యࢆᙧᡂࡍࡿࡇ࡜࡛ࠊάᛶ໬⮬- 128 -

⏤࢚ࢿࣝࢠ࣮ࡸ཯ᛂ⮬⏤࢚ࢿࣝࢠ࣮ࡀୗࡀࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡉࡽ࡟ࠊάᛶ໬⮬⏤࢚ࢿࣝࢠ࣮ࢆ 3 ࡘࡢᐤ୚࡟ศ๭ࡋࠊάᛶ໬⮬⏤࢚ࢿࣝࢠ࣮ࡀୗࡀࡿ୺せᅉࡀ཯ᛂ≀࡜㑄⛣≧ែࡢỈ࿴࢚ࢿࣝࢠ࣮ࡢᕪ࡛࠶ࡿࡇ࡜
ࡶ᫂ࡽ࠿࡟ࡋࡓࠋ୍᪉ࠊ᭱㏆ࡢ⣸እྍど྾཰ࢫ࣌ࢡࢺࣝࢆ⏝࠸ࡓᐇ㦂◊✲࡛ࠊȘ㓟࡜ Mg2+࢖࢜ࣥࡢΰྜ≀࡛྾཰ࢫ࣌ࢡࢺࣝࡢኚ໬ࡀ㉳ࡁ࡞࠸ࡇ࡜࠿ࡽ㘒యࢆᙧᡂࡋ࡞࠸ࡇ࡜ࡀ♧၀ࡉࢀ࡚࠸ࡿࠋࡇࢀ࡟ᑐࡍࡿ཯ㄽ࡜ࡋ
࡚ࠊ⣸እྍど྾཰ࢫ࣌ࢡࢺࣝࡢゎᯒࡶ⾜࠸ࠊȘ㓟࡜࣐ࢢࢿࢩ࣒࢘ࡀ㘒యࢆᙧᡂࡋ࡚ࡶࠊ᭱㧗⿕༨㌶㐨ࡸ᭱ప
✵㌶㐨ࡢ㌶㐨࢚ࢿࣝࢠ࣮ࡣ࡯ࡰኚ໬ࡋ࡞࠸ࡓࡵࢫ࣌ࢡࢺࣝࡣ࡯࡜ࢇ࡝ኚ໬ࡏࡎࠊ⣸እྍど྾཰ࢫ࣌ࢡࢺࣝࡔ
ࡅ࡛ࡣ㘒యᙧᡂࡢ᭷↓ࢆド࡛᫂ࡁ࡞࠸ࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

3Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬Hirofumi Sato, “Theoretical chemistry for a group of molecules: electronic structure of solvated molecules andself-assembly,” Taiwan-Japan Workshop on Theoretical Chemistry, Taipei, Taiwan, December 2019.
‫ۻ‬Hirofumi Sato, “Understanding the self-assembly processes: A global and local approach,” 9th Conference of the
Asia-Pacific Association of Theoretical and Computational Chemists, Sydney, Australia, September-October 2019.
‫ۻ‬ᮾ 㞞኱㸪ࠕගྜᡂࢱࣥࣃࢡ㉁」ྜయࡢᶵ⬟ゎ᫂ࢆ┠ᣦࡋ࡚ࠖ㸪QIQB ࢭ࣑ࢼ࣮ࠕ㔞Ꮚ໬Ꮫ࡜㔞Ꮚ᝟ሗ࣭㔞Ꮚ⏕࿨ࡢ᥋Ⅼࠖ㸪㇏୰㸪኱㜰㸪2019 ᖺ 12 ᭶.
‫ۻ‬Masahiro Higashi, “Theoretical study on excitation energy transfer in photosynthetic proteins,” The 10th Conferenceof the Asian Consortium on Computational Materials Science, Hong Kong, China, July 2019.

4ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬Kosuke Imamura, Takeshi Yamazaki, Daisuke Yokogawa, Higashi Masahiro, and Hirofumi Sato³Nuclear magnetic
shielding of molecule in solution based on reference interaction site model self-consistent field with spatial electron
density distribution´J. Chem. Phys.2020 SDJHV ‫ۻ‬Kaho Nakatani, Hirofumi Sato, and Ryoichi Fukuda ³Pseudo-Jahn-Teller effect on the lowest triplet state ofpara-benzoquinone involving inequivalent carbonyl bonds´Chem. Phys. Lett.2020 SDJHV ‫ۻ‬Kosuke Imamura, Takeshi Yamamoto, and Hirofumi Sato ³Coarse-grained modeling of nanocube self-assembly
system and transition network analyses´Chem. Phys. Lett.2020 SDJHV ‫ۻ‬7DWVX\D,LRND6DWRVKL7DNDKDVKL<XLFKLUR<RVKLGD<RVKLKLUR0DWVXPXUD6KXLFKL+LUDRNDDQG+LURIXPL6DWR³$
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DSSURDFK´J. Comput. Chem.2019 ‫ۻ‬6KRKHL.RPLQH6DWRVKL7DNDKDVKL7DWVXR.RMLPD+LURIXPL6DWRDQG6KXLFKL+LUDRND³6HOI$VVHPEO\3URFHVVHVRI2FWDKHGURQ6KDSHG3G´J. Am. Chem. Soc.2019
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4XDQWXP)UHH(QHUJ\6XUIDFHIRUD3URWRQ7UDQVIHU5HDFWLRQ´J. Chem. Theory Comput.2019 ‫ۻ‬6KLQML 6DLWR 0DVDKLUR +LJDVKL DQG *UDKDP 5 )OHPLQJ ³6LWHGHSHQGHQW IOXFWXDWLRQV RSWLPL]H HOHFWURQLF HQHUJ\WUDQVIHULQWKH)HQQDí0DWWKHZVí2OVRQSURWHLQ´J. Phys. Chem. B,2019123 FRUUHFWLRQ ‫'ۻ‬DLNL.XUDRNX7VXQDNL<RQDPLQH*HQWD.RMD1RULR<RVKLGD6DWRUX$ULPLWVXDQG0DVDKLUR+LJDVKL³(IIHFWVRIZDWHUDGGLWLRQRQDFDWDO\WLFIOXRULQDWLRQRIGLHQDPLQH´Molecules,201924 SDJHV - 129 -

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Theoretical studies on synthesis and reactivity of heterocyclic
compounds.
‫ۑ‬㔠㔝 ኱ຓࠊబࠎᮌ ⩏❶ࠊྜྷỌ ᭷భ㸦㧗▱኱㝔⥲ྜ㸧

1◊✲┠ⓗࠊෆᐜ
㟁Ꮚồᘬᛶᇶࢆ᭷ࡍࡿ」⣲⎔ᘧ໬ྜ≀ࡣ㸪ศᏊෆ࡟㟁Ꮚ౪୚ᛶ㒊఩࡜㟁Ꮚཷᐜᛶ㒊఩ࡢ୧᪉ࢆేࡏᣢࡘࡓ

ࡵ㸪᭷ᶵᮦᩱ࡜ࡋ࡚ࡢ᭷⏝ᛶࡀ㧗࠸ࠋࡋ࠿ࡋ」⣲⎔ᘧⰾ㤶᪘໬ྜ≀࡬ࡢ⨨᥮཯ᛂ࡟ࡼࡿ㟁Ꮚồᘬᇶᑟධ࡟࠾
ࡅࡿ఩⨨㑅ᢥᛶࡸ཯ᛂ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࡣᮍ▱࡞㒊ศࡀከࡃ㸪ࡑࢀࡽࡢຠ⋡ⓗྜᡂࡢጉࡆ࡜࡞ࡗ࡚࠸ࡿࠋ
ᮏ◊✲࡛ࡣ㸪ᡃࠎࡀࡇࢀࡲ࡛⾜ࡗ࡚ࡁࡓ㸪ࣆ࣮ࣟࣝ㢮ࡢࢺࣜࢩ࢔ࣀࣅࢽࣝ໬཯ᛂ㸦Scheme 1㸧࡟ࡘ࠸࡚㸪N
ୖࡢ⨨᥮ᇶࡸ⁐፹✀ࡀ఩⨨㑅ᢥᛶ࡟୚࠼ࡿᙳ㡪ࡢ㉳※࡟ࡘ࠸࡚㸪ᐇ㦂࠾ࡼࡧ⌮ㄽィ⟬ࡢ୧ᡭἲࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡗ࡚ゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋScheme 1. Tricyanoethenylation of pyrroles.

2◊✲᪉ἲࠊィ⟬᪉ἲࡇࢀࡲ࡛ࡢ◊✲࡟ࡼࡾ㸪ࢸࢺࣛࢩ࢔ࣀ࢚ࢳࣞࣥ࡟ࡼࡿࣆ࣮ࣟࣝ㢮ࡢ⨨᥮཯ᛂ࡛ࡣ㸪❅⣲ཎᏊୖࡢ⨨᥮ᇶࡢ✀㢮ࡸ㸪⏝࠸ࡿ⁐፹✀࡟ࡼࡗ࡚ࢺࣜࢩ࢔ࣀࣅࢽࣝ໬ࡉࢀࡿ఩⨨ࡀ኱ࡁࡃ␗࡞ࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋࡑࡇ࡛
ᮏ◊✲࡛ࡣ㸪ࢺࣜࢩ࢔ࣀࣅࢽࣝ໬཯ᛂ࡛ࡣ㏻ᖖ⏝࠸ࡽࢀ࡞࠸ࣉࣟࢺࣥᛶ⁐፹ࡸⰾ㤶᪘⣔ࡢ⁐፹ࢆ࠶࠼࡚⏝࠸ࡿࡇ࡜࡛㸪཯ᛂᛶࡸ఩⨨㑅ᢥᛶ࡟࡝ࡢࡼ࠺࡞ኚ໬ࡀ㉳ࡇࡿ࠿࡟ࡘ࠸࡚㸪ᐇ㦂࡟ࡼࡾ☜ㄆࡍࡿࡇ࡜࡜ࡋࡓࠋ୍
᪉⌮ㄽ◊✲࡜ࡋ࡚㸪ᇶᗏ≧ែࡸ཯ᛂึᮇࡢẁ㝵࡛ᇶ㉁࡜ヨ⸆㸪ࡉࡽ࡟⁐፹ࡀ」ྜయࢆᙧᡂࡋࡓ≧ែ㸦ึᮇ㘒య㸧ࡸ཯ᛂ୰㛫య㸪࠾ࡼࡧ㑄⛣≧ែ࡟ࡘ࠸࡚ศᏊ㌶㐨ィ⟬࡟ࡼࡾᵓ㐀᭱㐺໬ࡋ࡚ồࡵ㸪ྛᵓ㐀㸪ྛẁ㝵ࡢ࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡍࡿࡇ࡜࡛㸪཯ᛂ㐍⾜࡟క࠺ᵓ㐀ኚ⛣ࢆ᳨ドࡋࡓࠋࡲࡓ㸪ᚓࡽࢀࡓྛ᭱㐺໬ᵓ㐀࡟⁐፹ຠᯝィ⟬ࢆ㐺⏝ࡍࡿࡇ࡜࡛㸪⁐፹✀ࡢ㐪࠸࡟ࡼࡿ㑅ᢥᛶࡢኚ໬࡟ࡘ࠸࡚ࡶ᳨ウࢆ⾜࡞ࡗࡓࠋศᏊ㌶㐨ィ⟬࡟ࡣ
gaussian16 ࢆ⏝࠸㸪ྛᵓ㐀ࡢ᭱㐺໬࡟ࡣ cam-B3LYP/6-31+G(d)㸪M06-2X/6-31+G(d,p)࠾ࡼࡧ apfd/6-311+g(2d,p)ࡢྛࣞ࣋ࣝィ⟬ࢆ⏝࠸㸪࢚ࢿࣝࢠ࣮ィ⟬࡟ࡣྠࣞ࣋ࣝ࠾ࡼࡧ MP2/6-311++G(d,p)ࢆ㸪ࡲࡓ⁐፹ຠᯝィ⟬࡟ࡣ
CPCM ἲ࠾ࡼࡧ SMD ἲࢆ⏝࠸ࡓࠋ- 130 -

3◊✲ᡂᯝࡇࢀࡲ࡛ࡢᐇ㦂⤖ᯝ࡟ࡼࡾ㸪ࡇࡢ཯ᛂࡣ༢⣧࡞ồ㟁Ꮚ⨨᥮཯ᛂ࡛ࡣ࡞ࡃ㸪ẚ㍑ⓗᏳᐃ࡞ࢸࢺࣛࢩ࢔ࣀ࢚ࢳ

ࣝ୰㛫యࢆ⤒⏤ࡋ࡚཯ᛂࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ࡚࠸ࡿࠋࡇࡢᐇ㦂᝟ሗ࡟ᇶ࡙࠸࡚㸪ྛ୰㛫య࠾ࡼࡧ㑄⛣≧ែࢆồࡵࡓ࡜ࡇࢁ㸪ࣆ࣮ࣟࣝ⎔࠿ࡽ࢚ࢳࣝᮎ➃࡬ࡢỈ⣲㌿఩ẁ㝵࡜㸪ࢩ࢔ࣥ໬Ỉ⣲ࡢ⬺㞳ẁ㝵ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡀ࡜ࡶ࡟ 100 kJ/mol ௨ୖ࡜࡞ࡾ㸪ᐊ

࡛㏿ࡸ࠿࡟཯ᛂࡋ࡚࠸ࡿᐇ㦂஦ᐇ࡜␗࡞ࡿ⤖ᯝ࡜࡞ࡗࡓࠋ

ࡑࡇ࡛㸪཯ᛂ⣔୰࡟ᚤ㔞࡟ΰᅾࡋ࡚࠸ࡿỈࡀゐ፹ⓗᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼㸪ྛ㑄⛣≧ែ࡟ࡘ࠸࡚ỈศᏊࢆ፹௓࡜ࡋࡓᵓ㐀࡟ࡘ࠸࡚ࡶィ⟬ࡋࡓ࡜ࡇࢁ㸪࠸ࡎࢀࡢẁ㝵࡟࠾࠸࡚ࡶ㸪ỈศᏊࡢᏑᅾ࡟ࡼࡾ
άᛶ໬࢚ࢿࣝࢠ࣮ࡀ 20 kJ/mol ௨ୖపୗࡍࡿྍ⬟ᛶࡀ♧ࡉࢀࡓ㸦Figure 1㸧ࠋࡋࡓࡀࡗ࡚ࡇࡢ⣔࡛ࡣ㸪ᚤ㔞࡟ΰᅾࡋ࡚࠸ࡿỈࡢᏑᅾࡀ㔜せ࡛࠶ࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ

  
2-TS2

2-TS3

Figure 1. Transition state structures of proton transfer (2-TS2) and HCN elimination (2-TS3) step on
tricyanovinylation of 1H-pyrrole optimized at cam-B3LYP/6-31+G(d,p) level.

ࡲࡓ㸪N ୖ࡟ࣇ࢙ࢽࣝᇶࢆᑟධࡋࡓሙྜ㸪཯ᛂ㏿ᗘࡀⴭࡋࡃపୗࡍࡿࡇ࡜ࡀᐇ㦂࡟ࡼࡾ♧ࡉࢀ࡚࠸ࡓࡀ㸪ࡇࡢ⣔࡛ࡣ㸪TCNE ࡀࣆ࣮ࣟࣝ⎔ࢆồ㟁Ꮚᨷᧁࡍࡿ㝿㸪ࣇ࢙ࢽࣝᇶࡀ❧య㞀ᐖ࡜࡞ࡿࡓࡵ࡟㑄⛣≧ែᵓ㐀࡟኱ࡁ࡞ṍࡳࡀ⏕ࡌ࡚࠾ࡾ㸪ࡑࡢ⤖ᯝ㸪άᛶ໬࢚ࢿࣝࢠ࣮ࡀቑ኱ࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ۻ‬D. Kaneno, S. Tomoda, 14th International Conference on the Chemistry of Selenium and Tellurium, June 5,

2019, Cagliari, Italy[2] ‫ྜྷۻ‬Ọ㸪㔠㔝㸪➨ 46 ᅇ᭷ᶵ඾ᆺඖ⣲໬Ꮫウㄽ఍㸪2019 ᖺ 12 ᭶ 6 ᪥㸪ᯇᒣ[3] ‫ۻ‬బࠎᮌ㸪㧗ᶫ㸪᭷⃝㸪㇂㸪㔠㔝㸪➨ 46 ᅇ᭷ᶵ඾ᆺඖ⣲໬Ꮫウㄽ఍㸪2019 ᖺ 12 ᭶ 6 ᪥㸪ᯇᒣ[4] ‫ྜྷۻ‬Ọ㸪㔠㔝㸪➨ 30 ᅇᇶ♏᭷ᶵ໬Ꮫウㄽ఍㸪2019 ᖺ 9 ᭶ 26 ᪥㸪኱㜰[5] ‫ྜྷۻ‬Ọ㸪㔠㔝㸪2019 ᖺ᭷ᶵ཯ᛂᶵᵓ◊✲఍㸪2019 ᖺ 8 ᭶ 30 ᪥㸪ὠ
[6] ‫⏣ۻ‬㷂㸪㔠㔝㸪2019 ᖺ᭷ᶵ཯ᛂᶵᵓ◊✲఍㸪2019 ᖺ 8 ᭶ 30 ᪥㸪ὠ
[7] ‫▼ۻ‬ᘓ㸪㔠㔝㸪2019 ᖺ᭷ᶵ཯ᛂᶵᵓ◊✲఍㸪2019 ᖺ 8 ᭶ 30 ᪥㸪ὠ
[8] ‫ۻ‬బࠎᮌ㸪㔠㔝㸪2019 ᖺ᭷ᶵ཯ᛂᶵᵓ◊✲఍㸪2019 ᖺ 8 ᭶ 30 ᪥㸪ὠ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋ- 131 -





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In silico molecular design of transmembrane peptide induces lipid
flipping
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1 
Z´³Æ8,>H15Ò¹Q³ÆDL:EÏd 'Þ³ÆDL:E³ÆWÒy´RSyÕ)³Æbo È¥O¥d'Ïd&Ý($&³Æ´#RSy '³Æ®Ûbo¦#bot|Ü me'Þ(%´Ìme³Æw±ÛF41MÜ}#ÝF41M
­±´·hÛ-N=3,<P45Ü)q'Ò¹jo&Ý­±a³Æ#GE9=O7NC1
ÆÉÊZ²{  Ò¹Q'Þ³ÆDL:EË{ÝbÛminuteÜ#ÕÛhourÜ.P8PÇ'Ø{Îbo8,>H15'Ý´ÅËÛTMÜGE9=v_$Ý³ÆDL:E ]Í('(Y [Biochemistry 2001, 40, 10500]ÝrÚOÄ`n 

M. A. Kol ©$ºÖ 'Þ  %ÝTM GE

9=$'³ÆDL:E¢§rÚ»× %gb¢§ (&Ý³ÆDL:EÁÇboJ/?6I¼p¸°n Þ Ý=K:2;LBLP~('³Æ
F41MÝ³Æ´)'bo®#}Û³ÆÜ ²q!Ò¹jo'ÞTM GE
9=(%¹¬)ÃÝq'!bo~( &Ý³ÆDL:E)]Í' TM G
E9=bo¾½¸£¨µpOfbÓ "Ò¹ÂÙ'Þ kauznpUx©
D+L:E nTM GE9=Ô#*HAÑl)m'$Ý³Æ]Í(')¶^-@M0P¥dÛFRETÜ#Uo VrÚ)¤[J. Phys.

Chem. B 2018, 122, 43184324]ÞUx©$'ÝGE9=bo#´adÌ#¡X[ ³Æ
DL:E]Í!Ò¹jo'('Þ(%¹¬$³ÆDL:E]ÍsT' ßiª'!Ý«¯*HAÑlÐc)m TM GE9=)hÝÌ#¡X[Ý³ÆDL:E²À­)»O¿\'¹ ' ÝFRET #Uo VrÚ Ý(%GE9=´adÌ#¡X[À­)% '×Þ |¸¢§bo4HP4N¸)Ò-'$(%ÂÙ)¼ÝTM GE9=
$'³ÆDL:EÁÇboJ/?6I)¼'Þ³ÆDL:E)ÁÇ'GE9=#³ÆdÌ#¡X[Ý³ÆDL:E²)bo4HP4N)5Z% 'Þ  TM GE9=
Ô#*HAÑÐc)«¯me«4HP4N¼)rwÝj%(½ ;P7)Ö
O¼'$³ÆDL:E)ÁÇ'GE9=ubo¾½qÆ)T'Þ|¸¢§LN³ÆDL:E)ÁÇ'´ÅËGE9=½ bo¾½)¯Þ¢§ ½pvÛbo;LN2Obod8p4HP4NOª-@M0P½ Ü)Ý³ÆDL:E)ÁÇ'´ÅË(TM)GE9=bo¾½)¯Þ5ZÝ1. Ô#Ðc)m TM GE9=
)LN³Æ´r_ MD ½ )¯Ý´a TM GE9=dÌ#¡X[À­¼)¯Þ Ý2. ÓÁOÓ¡|ª-@M0P½ )ÈÝTM GE9=K½³ÆDL:EÇ&- 132 -

#)qÄ¿\'½ ¸)£¨'ÞrOÕÖcÕÝR´×¢§ÂÙ½ rObo¢nP"c½ )-¯Û£ CPU Ù25 !ÜÞ½ 2O½ r¯O¼Õ 9y)$q &Ý&Ø yÄt© !)¯ÞYSÝE¢§ÂÙÀ­¿'Þ(1) TM GE9= MD 4HP4NÌO¡X[¼
Ux©rÚ$'ÝTM GE9=³Æ´ÔH5:9#Ý²*HAÑlv_$&³ÆDL:E² me' %('[J. Phys. Chem. B 2018, 122, 43184324]Þ|ÂÙ«¯*HAÑÐc)m TM GE9=;LN2# MD 4HP4N)rwÝE« ' TM
GE9=Ì#ÝK½³Æ#bo¡X[À­)% 'Þ5ZYS×ÂÙA&® Ý($&³ÆDL:EsT'Ì#¡X[)5Z% 'ÞOTM GE9=Ô) 19% 31 l mÝ³Æ´e¬ÇÐQÌ:9N2)«¯me« MD 4HP4N)¯ÞTM GE9=+Ôme\' TM GE9=#´ÌmeÀ­)% 'ÞOTM GE9=²*HAÑl)d v_« MD 4HP4N)rw'Þv_'²*HAÑls#¦ÑÝ,¦)«¯meTh TM GE9=Ì#ÝK½³Æbo#bo¢hfÀ­)% 'Þ(2) ³ÆDL:E!ª-@M0P½ oÈ³ÆDL:E\'ª-@M0Pme)ÓÁOÓ¡|¿\'oO½ E2KI)ÈÝTM
GE9=K½³ÆDL:EÇ&#)qÄ¿\'½ ¸)£¨'Þ|¸¢§S
k# Èª-@M0P½ ÛLogMFD Ü)'ÞS È½ E2KI)³Æ´«½ pgO_ÈÝ³ÆDL:E\'«ª-@M0Pme)¿\'Þ5Z5<«µ½ Ý½ ¡|#5MPE:<¿\ÝTM GE9=v_<À­µ)¯ÞYSrw'¢§Ï )´ÙO'±«' POPC ´³ÆDL:Eª-@M0P½ )¯Þi½ 
ÛUmbrella SamplingÜ» %Ý½ ¡|O5MPE:<)µ'Þ
O³ÆDL:E)]Í' TM GE9=ÛUÓ©rÚ$£·("Ü)I  POPC ´ª-@M0P½ )¯ÞrÚ»µ"¯ÝTM GE9=v_$'³ÆDL:E²me)5Z% 'Þ

2 

Y! POPC ) 128 /Ýbo) 8192 / POPC ³ÆWÒy´)[Ý()?«h³Æ´ POPC bo' &5PM(CHOL)ÝKH=(CER)Ý*M2LPM(DAG)Ý5
D+NH-LN(PSM)):[bo|3 20 mol%MD 4HP4N3qOqN}(S(T=303K, P=1atm)r¯³Æ8T CHARm36 )[2]Ý;M TIP3 )PMF ½ *N3NELN2ÛUSÜ[3] LogMFD[4]×¦Ñv)¿\@me  z ºÛ´=vHÜÝPOPC ³Æ P >o)´aUlvH¥dTh PMF )´ÀÂ
(Flip-flop)ª-@M0P¥Ý´XvH¥dTh PFM ) POPC ´ %Ë©(desorption)-@
M0P¥q°½ )¯MD ½  GROMACS 5.2.1  Plumed v2.5 [5])

- 133 -

3 
± 1  MD ½

%j%(E« '´ÌCKJP7Û´ÍÝ´=Ý.P8PCKJP7ÝlÐHÜ¢)¤3« bo:$&´Í ]Ý´= V:'¢)j(* POPC *4MÇÐH"V:'¢ ¤((%¢ %bo:$'´
6Ö< PSM < DAG < CER < CHOL ' ¤((%6Ö<Ã:boÌ#¡X[ÃÛbo7ÝlnwÝ¬¢hsÃÜ$'§%('
M 1  PMF ½ $&j%(E« ' POPC ´=vH\'ª-@M0P¥¢)¤ª-@M0P¥w POPC  P >o´a 'b°,¦Û $ z = 20&¾Ü\m'z = 0 ´aUl,¦\m' PMF 1ÛFlip-flop ª-@M0PÊWÜ&Ýz = 40YÉBM1ÐQ&ÝPMF 1 POPC ´« %©Ë (desorption)-@M0P1\m'M¤$*NK3NELN2ÛUSÜ¿\ PMFÛÌ¥Ü LogMFD ¿\ PMFÛ¹O¤¥ÜØ{­ Q«'¢ ¤(LogMFD "¡|­ ³Æ´ÀÂª-@M0P¥ ¿\(' ¤(  PMF ¥ j%(' £½ 5:Es) US  LogMFD »
LogMFD v$ 1.8 0|½ < ­ ¤(hx5PMÝKH=Ý*M2LPMÝ5D+NH-LN)I « PMF ¢"SJ'

Table1. Membrane structural parameters for mixed
POPC bilayers

4 



1.  “bod8p4HP4N)>H=Ñ´aÌ|.Z”, epH?P4
NDN+* 6 L4È4N I 2019, 2019 c 12 y 9 xÛyÜÚ10 x (), nm°Unp
xFNC5, Ô®nD
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 c 11 y 3 x~6 x Î
kOa, 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”

CBI p) 2019 cn), 2019 c 10 y 22 x()Õ24 x({)~%O¬R, Hiroaki Saito, Takao Otsuka, Noriaki Okimoto, Makoto Taiji
4.  “LogMFD $'³Æbo´ÀÂª-@M0P¥”, bop³Ä) 2019, 2019 c 9 y 17 x
ÛÜ
Ú20 xÛÅÜ,GC^np, Ô®nSk#- 134 -

5 



1.  “Structural Feature of Lipid Scrambling Model Transmembrane Peptides: Same-Side Positioning ofHydrophilic Residues and Their Deeper Position”. The journal of physical chemistry letters, 1662 – 1667, Hiroyuki
Nakao, Yuta Sugimoto, Keisuke Ikeda, Hiroaki Saito, Minoru Nakano
2.  “zep¨½

ep¨;"%LN=-B[ZÕ=:N24HP 4N$'bo¾½9' ”, bo4HP4Np)¶ "*N3NM", 21, 196-203, Rr, Ó`¼,
Ô®n

- 135 -

ࢭ࣮ࣝࣟࢫᮦᩱ࠾ࡼࡧ㛵㐃ࢱࣥࣃࢡ㉁ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ◊✲Molecular dynamics study of cellulose fiber and carbohydrate-related enzymes‫‮ۑ‬஭ ᩄᩥ㸦ᐑᓮ኱ᏛᕤᏛ㒊㸧ࠊᏱ㒔 ༟ஓ㸦ᐑᓮ኱Ꮫࢸࢽࣗ࢔ࢺࣛࢵࢡ᥎㐍ᶵᵓ㸧
1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࣉࣟࢪ࢙ࢡࢺࡣࠊࢭ࣮ࣝࣟࢫ࣭࢟ࢳࣥ࡜࠸ࡗࡓᵓ㐀ከ⢾ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㏻ࡋ࡚ࠊ⤖ᬗᵓ㐀≉ᛶࡸ⁐ゎᣲືࠊ⢾㉁㛵㐃ࢱࣥࣃࢡ㉁࡜ࡢ┦஫స⏝ࠊศゎ㓝⣲࡞࡝࡟ࡼࡿ཯ᛂᶵᵓࡢゎᯒ࡟ྲྀ⤌ࢇ࡛ࡁࡓࠋ
ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࢆ฼⏝ࡋࡓᡂᯝ࡜ࡋ࡚ࠊ┤㏆ 2 ᖺ࡛ཎⴭㄽᩥ 10 ሗ࠾ࡼࡧ⥲ㄝ 3 ሗࢆฟ∧ࡋࠊᏛ఍Ⓨ⾲ࢆ 25 ௳⾜ࡗࡓࠋ2019 ᖺᗘ࡛ࡣࠊ௨ୗ࡟ᣲࡆࡿ 2 ࡘࡢ◊✲ࢸ࣮࣐ࢆ㔜Ⅼⓗ࡟ྲྀ⤌ࢇࡔࠋ
2010 ᖺ௨㝆ࠊࢭ࣮ࣝࣟࢫ⏕ྜᡂ࡟㛵ࢃࡿࢱࣥࣃࢡ㉁ࡢ⤖ᬗᵓ㐀ゎᯒࢹ࣮ࢱࡀḟࠎ࡜ሗ࿌ࡉࢀ࡚࠸ࡿࠋ㓑㓟⳦㸦Komagataeibacter
hansenii㸧ࡀ⏕⏘ࡍࡿࣂࢡࢸࣜ࢔ࢭ࣮ࣝࣟࢫࡢྜᡂᶵᵓ࡜ࡋ࡚ࠊࢭ
࣮ࣝࣟࢫྜᡂ㓝⣲ࢧࣈࣘࢽࢵࢺ⩌㸦CesA-CesD㸧࡛ᵓᡂࡉࢀࡿྜ
ᡂ㓝⣲」ྜయ㸦TC㸧ࡀᥦ᱌ࡉࢀ࡚࠸ࡿࠋࡇࡢ࠺ࡕࠊCesD ࡢ N ᮎ➃Ḟᦆᰴ࡛ࡣࠊࢭ࣮ࣝࣟࢫ⏕⏘⬟ࡀ኱ࡁࡃపୗࡍࡿࡇ࡜ࡀ▱ࡽࢀࡿࠋCesD ❧యᵓ㐀ࡣ 4 ࢝ᡤࡢ⢾㙐⤒㊰ࢆ᭷ࡍࡿ෇ᰕ≧ࡢ࣍ࣔ 8

ᅗ 1. CesD 䝩䝰 8 㔞య䛾❧యᵓ㐀䛸ᴫ␎ᅗ㔞య࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗ࡚࠾ࡾࠊ⢾㙐⤒㊰ࡣ⳦యෆ࡛ྜᡂࡉࢀࡓࢭ࣮ࣝࣟࢫ㙐ࡢࣛࣥࢲ࣒࡞఍ྜࢆ㜵ࡂࠊຠ⋡ⓗ࡞ྜᡂ࠾ࡼࡧ᤼ฟ࡟ᐤ୚ࡋ࡚࠸ࡿྍ⬟ᛶࡀ♧၀ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡇࡢ⢾㙐⤒㊰ෆ࡟࡝ࡢࡼ࠺
࡟ࢭ࣮ࣝࣟࢫศᏊ㙐ࡀ㓄⨨ࡋ࡚࠸ࡿ࠿࡟ࡘ࠸࡚ࡣ୙᫂░࡞ࡲࡲ࡛࠶ࡿࠋᮏ◊✲ࢢ࣮ࣝࣉࡣࠊCesD ࡢ⤖ᬗᵓ㐀ࢹ࣮ࢱ㸦Hu, et al., Proc. Natl. Acad. Sci. USA 107, 17957–17961, 2010㸧ࢆ⏝࠸࡚ 4 ᮏࡢࢭ࣮ࣝࣟࢫศᏊ㙐㸦DP=12㸧
࡜ࡢ」ྜయࣔࢹࣝࢆศᏊࢢࣛࣇ࢕ࢵࢡࢫ࡟ࡼࡗ࡚ᵓ⠏ࡋࠊMD ィ⟬࠾ࡼࡧ QM/MM-MD ィ⟬ࢆᐇ᪋ࡋࡓࠋ
ḟ࡟ࠊ⢾⤖ྜᛶࢱࣥࣃࢡ㉁࡟ࡼࡿ⢾㙐ㄆ㆑ᶵᵓࡢゎ᫂ࢆ┠ⓗ࡜ࡋࡓࢻࢵ࢟ࣥࢢィ⟬ࢆᐇ᪋ࡋࡓࠋ࣊࣋࢖ࣥ
ࡣࣃࣛࢦ࣒ࣀ࢟㸦Hevea brasiliensis㸧⏤᮶ࡢ࣌ࣉࢳࢻ࡛࠶ࡾࠊ᳜≀࡟ᐤ⏕ࡍࡿ࢝ࣅ࡞࡝ࡢ⣽⬊ቨᡂศ࡛࠶ࡿ࢟
ࢳࣥ࡜⤖ྜࡍࡿࠋ࣊࣋࢖ࣥᵝ㡿ᇦࢆᣢࡘ࣌ࣉࢳࢻࡣከᵝ࡞ᢠ⳦ᛶ㸦≉࡟ᢠ┿⳦άᛶ㸧ࢆ♧ࡍࠋᮏ◊✲࡛ࡣࠊ࢟ࢺࢺ࣮ࣜ࢜ࢫ㸦GlcNAc3㸧ࢆ⢾㙐ᇶ㉁࡜ࡋ࡚ࠊ࣊࣋࢖ࣥࢆᑐ㇟࡜ࡋࡓࢻࢵ࢟ࣥࢢィ⟬ࢆ⾜࠸ࠊࡍ࡛࡟ሗ࿌ࡉ
ࢀ࡚࠸ࡿ NMR 」ྜయᵓ㐀㸦N. Aboitiz, et al., ChemBioChem 5, 1245–1255, 2004㸧࡜ࡢẚ㍑ࢆヨࡳࡓࠋࡉࡽ࡟ࠊ9✀㢮ࡢኚ␗࣊࣋࢖ࣥ࡟ᑐࡍࡿྠᵝࡢࢻࢵ࢟ࣥࢢィ⟬ࢆᐇ᪋ࡋࠊኚ␗ᑟධ࡟ࡼࡿᇶ㉁ㄆ㆑⬟ࡢኚ໬ࢆゎᯒࡋࡓࠋ

2

◊✲᪉ἲ

2㸫1㸬㓑㓟⳦⏤᮶ࢭ࣮ࣝࣟࢫྜᡂ㓝⣲ࢧࣈࣘࢽࢵࢺ D㸫⢾㙐」ྜయࣔࢹࣝࡢ MD ィ⟬㔝⏕ᆺ࠾ࡼࡧ N ᮎ➃Ḟᦆኚ␗ CesD ࡢ⢾㙐」ྜయࣔࢹࣝࡣࠊCesD ⤖ᬗᵓ㐀ࢹ࣮ࢱ㸦PDB: 3AJ2 ࠾ࡼࡧ 3A8E㸧
ࢆฟⓎᵓ㐀࡟ࡋ࡚ࠊ࣐ࢽࣗ࢔ࣝࣔࢹࣜࣥࢢ࡛సᡂࡋࡓࠋᚓࡽࢀࡓ CesD ࡜ G12 ࡢ」ྜయࣔࢹࣝ㸦CesD-G12㸧
࠿ࡽࠊN ᮎ➃࣌ࣉࢳࢻ㙐ࢆ Met1~Lys6 ࡲ࡛Ḟᦆࡉࡏࡓ CesD'N6 ࡢ」ྜయࣔࢹࣝ㸦CesD'N6-G12㸧ࡶᵓ⠏ࡋࠊ୧⪅ࢆ MD ィ⟬ࡢᑐ㇟࡜ࡋࡓࠋMD ィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣ Amber16 ࢆ౑⏝ࡋࠊ⢾࡜ࢱࣥࣃࢡ㉁ࣃ࣓࣮ࣛࢱ࡟ࡣࠊ
ࡑࢀࡒࢀࠊGlycam06 ࡜ ff14SB ࢆ㐺⏝ࡋࡓࠋᐃ

300 Kࠊᐃᅽ 1 bar ࡢ MD ィ⟬ࢆ 200 ns ᐇ᪋ࡋࡓࠋ ࡉࡽ࡟ࠊCesD-G12 ࡢࡼࡾ⢭ᐦ࡞⌮ㄽ࡟ᇶ࡙࠸ࡓࢻࢵ࢟ࣥࢢᵓ㐀ࢆ᳨ウࡍࡿࡓࡵ࡟ࠊQM/MM-MD ィ⟬ࢆྠᵝࡢ᮲௳࡛ 50 ns ᐇ᪋ࡋࡓࠋQM ィ⟬࡟ࡣࠊSCC-DFTB ἲ࡛ Slater-Koster ࣃ࣓࣮ࣛࢱࡣ mio-1-1 ࢆ౑⏝ࡋࡓࠋ
G12 ࡢ୰ኸ 8 ṧᇶࢆ QM 㡿ᇦ࡜ࡋࠊCesD-G12 ࡢṧࡾࡢ㒊ศ࡜ỈศᏊࠊ࢖࢜ࣥ࡟ࡘ࠸࡚ࡣ MM 㡿ᇦ࡜ࡋࡓࠋ

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2㸫2㸬ࣃࣛࢦ࣒ࣀ࢟⏤᮶ࡢᢠ⳦ᛶ࣌ࣉࢳࢻ࡟ᑐࡍࡿ⢾㙐ࢻࢵ࢟ࣥࢢィ⟬㔝⏕ᆺ࣊࣋࢖ࣥapoయࡢ❧యᵓ㐀ࢹ࣮ࢱ㸦PDB: 4WP4㸧ࢆࡶ࡜࡟ࠊ࢟ࢺࢺ࣮ࣜ࢜ࢫ㸦GlcNAc3㸧1ศᏊࢆ࣊࣋
࢖ࣥኚ␗య࿘㎶࡟௵ព࡟㓄⨨ࡋࡓึᮇᵓ㐀ࣔࢹࣝࢆ6㏻ࡾసᡂࡋࠊࡇࡢィ⟬ࣔࢹࣝ࡟ᑐࡋ࡚GlcNAc3ࡀ࣊࣋࢖
ࣥᇶ㉁ㄆ㆑㒊఩࡟୙ྍ㏫ⓗ࡟⤖ྜࡍࡿࡲ࡛᭱኱2 μsࡢ⁐፹࿴MDィ⟬ࢆᐇ᪋ࡋࡓࠋࡍ࡭࡚ࡢMDィ⟬ࡣࠊỈศᏊ5,000ಶࢆ㓄⨨ࡋࡓ⁐፹࿴᮲௳ୗ࡛ᐃ 㸦300 K㸧ࠊᐃᅽ㸦1 bar㸧࡛⾜ࢃࢀࡓࠋMDィ⟬ࣉࣟࢢ࣒ࣛ࡟ࡣAmber18
ࢆ౑⏝ࡋࡓࠋࢱࣥࣃࢡ㉁ࣃ࣓࣮ࣛࢱࡣff14SBࠊ⢾ศᏊࣃ࣓࣮ࣛࢱ࡟Glycam06ࢆ㐺⏝ࡋࡓࠋ

3.

◊✲ᡂᯝ

3㸫1㸬㓑㓟⳦⏤᮶ࢭ࣮ࣝࣟࢫྜᡂ㓝⣲ࢧࣈࣘࢽࢵࢺ D㸫ࢭ࣮ࣝࣟࢫ」ྜయࡢࢲ࢖ࢼ࣑ࢡࢫᣲື
㔝⏕ᆺ CesD ࡜ࢭ࣮ࣝࣟࢫศᏊ㙐 G12 ࡢ」ྜయ㸦 CeSD-G12 㸧 ࡜ N ᮎ ➃ ࣌ ࣉ ࢳ ࢻ 㙐 ࢆ Ḟ ᦆ ࡉ ࡏ ࡓ
CesD-G12 」ྜయ㸦CesD'N6-G12㸧ࡢึᮇᵓ㐀ࢆᅗ 2 ࡟♧ࡍࠋCeSD-G12 ࡟ẚ࡭࡚ࠊCesD'N6-G12 ࡣෆ⭍㒊ࡢ┤ᚄࡀᣑ኱ࡋࡓࠋCesD-G12 」ྜయࡢึᮇᵓ㐀࡟࠾ࡅࡿ⢾㙐⤒㊰ෆࡢࢭ࣮ࣝࣟࢫศᏊ㙐ࡢ⤖ྜ≧ែࢆᅗ 3 ࡟♧ࡍࠋ
CesD ୰ᚰ㒊࠿ࡽ㑏ඖᮎ➃᪉ྥࢆ+ࠊ㠀㑏ඖᮎ➃᪉ྥࢆ࡜ࡋ࡚⢾ṧᇶ఩⨨ࢆᐃ⩏ࡋࡓࠋs2~3 ࡛⢾ṧᇶࡀ⢾㙐⤒㊰ࡢᢡࢀ᭤ࡀࡿ㒊ศ࡟㓄⨨ࡋࡓࠋ⁐፹࿴ MD ィ⟬࡟࠾

ᅗ 2. 㔝⏕ᆺ䛚䜘䜃 N ᮎ➃Ḟᦆኚ␗ CesD 䛾⢾㙐䠄G12䠅」ྜయ䝰䝕䝹䛾ึᮇᵓ㐀࠸࡚ࠊࡇࡢᒅ᭤ࡋࡓࢭ࣮ࣝࣟࢫศᏊ㙐ᙧែࢆ⥔ᣢࡋࡓࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ࡞࠾ࠊS Ꮠ≧ᒅ᭤㒊ศࡢ⢾ṧᇶࣆࣛࣀ࣮ࢫ⎔࡟࠾࠸࡚ 4C1
࢖ࢫᆺ㓄ᗙ࠿ࡽ⯚ᆺ㓄ᗙ࡬ࡢ୙ྍ㏫ⓗ࡞㓄ᗙኚ᥮ࡀⓎ⏕ࡋࡓࠋࢢࣝࢥ࣮ࢫṧᇶࡢຊሙࣃ࣓࣮ࣛࢱ㸦Glycam06㸧ࡣࠊ4C1 ࢖ࢫᆺ㓄ᗙࡢࣆࣛࣀ࣮ࢫ㦵᱁࡟ᇶ࡙࠸࡚㛤Ⓨࡉࢀ࡚࠾ࡾࠊࡇ࠺ࡋࡓ㓄ᗙኚ᥮ࡣ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࡀ㐺ษ࡟ホ౯࡛ࡁ࡞࠸ᜍࢀࡀ࠶ࡿࠋ
ࡑࡇ࡛ࠊ⢾ࣆࣛࣀ࣮ࢫ⎔ࡀ 4C1 ࢖ࢫᆺ㓄ᗙࢆ⥔ᣢࡍࡿࡼ࠺࡟ࠊࡡ
ࡌࢀᅇ㌿ゅ㸦O5-C1-C2-C3/C3-C4-C5-O5㸧ࡢ᮰⦡᮲௳ࢆタᐃࡋࡓࠋCesD ࡢ N ᮎ➃࣏ࣜ࣌ࣉࢳࢻ㙐ࢆᵓᡂࡍᅗ 3. CesD-G12 」ྜయ࡟࠾ࡅࡿ⢾㙐⤒㊰ෆࡢࢭ࣮ࣝࣟࢫศᏊ㙐ࡢ⤖ྜ≧ែࡿ࢔࣑ࣀ㓟ṧᇶ࡟ᑐࡍࡿࢭ࣮ࣝࣟࢫศᏊ㙐࡜ࡢ⤖ྜ࢚ࢿࣝࢠ࣮㸦'Ebind㸧ࢆᅗ 7 ࡟♧ࡍࠋ
CesD-G12 ࡛ࠊLys6ࠊLys7 ࠾ࡼࡧ Asp9 ࡛኱ࡁ࡞┦஫స⏝ࡀㄆࡵࡽࢀࡓࠋCesD'N6-G12 ࡟࠾࠸࡚ࡶ㢮ఝࡢࣉࣟࣇ࢓࢖ࣝࢆ♧ࡋࡓࠋḟ࡟ࠊCesD-G12 」ྜయࡢ࣍ࢵࢺࢫ࣏ࢵࢺ
ࢆศ๭┦஫స⏝࢚ࢿࣝࢠ࣮࡜ṧᇶ㛫㊥㞳㸦ࢥࣥࢱࢡࢺ࣐ࢵࣉ㸧࡟ᇶ࡙࠸࡚ᢳฟࡋࡓࠋ
ࢭ࣮ࣝࣟࢫศᏊ㙐ࡢᒅ᭤㒊࡟࠾࠸࡚ࠊN ᮎ➃࣏ࣜ࣌ࣉࢳࢻ㙐㸦Met1–Leu12㸧ࡔࡅ࡛࡞ࡃࠊ
Į1㸦Thr11–Val25㸧࠾ࡼࡧ Į3㸦Val53–Ile67㸧ࡢ Į-࣊ࣜࢵࢡࢫᮎ➃࡜᥋ゐࡋ࡚࠸ࡓࠋ

ᅗ 4. CesD ࢱࣥࣃࢡ㉁ࡢ N ᮎ➃࢔࣑ࣀ㓟ṧᇶ࡟ᑐࡍࡿࢭࣝࣟ
࣮ࢫศᏊ㙐࡜ࡢ⤖ྜ࢚ࢿࣝࢠ࣮㸦'Ebind㸧- 137 -

ࢭ࣮ࣝࣟࢫࡢᒅ᭤㒊࡟࠾࠸࡚ࠊࣆࣛࣀ࣮ࢫ⎔ࡢ㓄ᗙኚ᥮ࡀⓎ⏕ࡍࡿ࠿࡝࠺࠿ࢆ㧗⢭ᗘ࡞ QM/MM-MD ィ⟬࡟ࡼࡗ᳨࡚ドࡋࡓࠋ
CesD-G12 」ྜయࡢ QM/MM-MD ィ⟬ࡢ⤖ᯝࠊࢭ࣮ࣝࣟࢫศᏊ㙐ࡣS Ꮠ≧ᒅ᭤㒊㸦s2~3㸧࡛ CesD ࡢ Į-࣊ࣜࢵࢡࢫ㸦Į1/Į3㸧ᮎ➃࡜᥋
ゐࡋࠊࣆࣛࣀ࣮ࢫ⎔ࡢྍ㏫ⓗ࡞㓄ᗙኚ᥮ࡀⓎ⏕ࡋࡓ㸦ᅗ 5㸧ࠋࢭ࣮ࣝࣟࢫࡢ㔜ྜ࡟㛵୚ࡍࡿ CesA-CesB ࡣࠊࣛࢳ࢙ࢵࢺᶵᵓ࡟
ࡼࡗ࡚ࢭ࣮ࣝࣟࢫఙ㛗࣭㍺㏦ࢆไᚚࡍࡿ㸦J. L. W. Morgan, et al.,Nature 531, 329–334, 2016㸧ࠋᐇ㝿࡟ࡣࠊࢭ࣮ࣝࣟࢫศᏊ㙐ࡣ CesDࡢ⢾㙐⤒㊰ࢆ㐃⥆ⓗ࡟⛣ືࡍࡿࡇ࡜ࡀ᝿ᐃࡉࢀࡿࠋCesD ࡟࠾࠸࡚ࡶྠᵝ࡟ࠊࡇࡢࡼ࠺࡞཯᚟ⓗ࡞ศᏊ㐠ືࡀࢭ࣮ࣝࣟࢫ㙐ࢆ୙㐃⥆࡟ື࠿ࡋࠊࢭ࣮ࣝࣟࢫࡢ⛣ື㏿ᗘࢆ୍ᐃ࡟ไᚚࡋᚓࡿ࡜⤖ㄽ࡙ࡅࡓࠋ

ᅗ 5. CesD-G12 ࣔࢹࣝࡢ QM/MM-MDィ⟬࡛ほᐹࡉࢀࡓ⢾ࣆࣛࣀ࣮ࢫ㦵᱁ࡢ
ྍ㏫ⓗ࡞㓄ᗙኚ໬

3㸫2㸬ࣃࣛࢦ࣒ࣀ࢟⏤᮶ࡢᢠ⳦ᛶ࣌ࣉࢳࢻ࡟ࡼࡿ⢾㙐ㄆ㆑㔝⏕ᆺ࣊࣋࢖ࣥ–⢾㙐㸦GlcNAc3㸧」ྜయ NMR ᵓ㐀㸦PDB㸸IT0W㸧ࢆᅗ 6 ࡟♧ࡍࠋW23 ࡜ W21 ࡀࡑࢀࡒࢀࠊᇶ㉁⤖ྜࢧࣈࢧ࢖ࢺ+1 ࡜+2 ࡟┦ᙜࡋࠊ⢾㙐ࡣ+1 ࡟㠀㑏ඖᮎ➃ṧᇶࡀ㓄⨨ࡋࡓ㓄ྥ࡜࡞ࡿࠋᅗ 6 ࡟ࠊNMRᵓ㐀ࢆᇶ‽࡜ࡋࡓࣜ࢞ࣥࢻ఩⨨ࡢ೫ᕪ㸦RMSd㸧࡟ᑐࡍࡿ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮㸦'Gbind㸧್ࢆ MD ㌶㊧ 1 ns ࡈ࡜࡟ࣉࣟࢵࢺࡋࡓ㸰ḟඖ࣐ࢵࣉࢆ♧ࡍࠋࣜ࢞ࣥࢻࡀࢧࣈࢧ࢖ࢺ+1~+3 ࡟⤖ྜࡍࡿ NMR ᵓ㐀㸦a㸧࡛ࡣ'Gbind
್ࡀ-24 kcal/mol ࿘㎶࡟ศᕸࡋࡓࠋ6 ಶࡢࢻࢵ࢟ࣥࢢᵓ㐀ࡢ࠺ࡕࠊ5 ಶࡣࢧࣈࢧ࢖ࢺ-1㹼+3㸦b㸧ࠊṧࡾࡢ 1 ಶࡣࢧࣈࢧ࢖ࢺ-2㹼+1㸦c㸧࡟ࣜ࢞ࣥࢻࡀ⤖ྜࡋࠊ'Gbind ್ࡀࠊࡑࢀ

+3 W21(+2)

W23(+1)

S19

Y30

-1

ࡒࢀࠊ-32 kcal/mol ࡜-31 kcal/mol ࿘㎶࡟ศᕸࡋࡓࠋ࠸ࡎࢀࡢࢻࢵ࢟
ࣥࢢᵓ㐀࡟࠾࠸࡚ࡶࠊNMR ᵓ㐀࡜ࣜ࢞ࣥࢻࡢ⤖ྜ᪉ྥࡀ୍⮴ࡋࡓࠋࣜ࢞ࣥࢻ⤖ྜᣲືࢆほᐹࡋࡓ⤖ᯝࠊY30 ࡢⰾ㤶᪘⎔ഃ㙐࡜ࢧࣈࢧ
࢖ࢺ+1 ࡟⤖ྜࡍࡿ⢾ṧᇶࡢ N-࢔ࢭࢳࣝ࢔࣑ࣀᇶ㛫ࡢ┦஫స⏝ࢆ௓ࡋ࡚ࣜ࢞ࣥࢻࡢ⤖ྜ᪉ྥࡀไᚚࡉࢀࡿᇶ㉁ㄆ㆑ᶵᵓࡀ᥎ᐃࡉࢀࡓࠋ
⾲ 1 ࡟ 9 ✀ࡢኚ␗࣊࣋࢖ࣥ࡜㔝⏕ᆺࡢࢻࢵ࢟ࣥࢢᵓ㐀ࡢ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡍࡿࠋb ࣔࢹࣝࡀࡍ࡭࡚ࡢኚ␗య࣊࣋࢖ࣥ࡟࠾
࠸࡚᭱Ᏻᐃࡢ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࢆ♧ࡋࡓࠋNMR ᵓ㐀࡟┦ᙜࡍࡿa ࣔࢹࣝࡀ W21F ࢆ㝖ࡃࡍ࡭࡚ࡢኚ␗య࡛ᚓࡽࢀࡓࠋ඲యⓗ࡟ኚ␗⾲ 1. ࣊࣋࢖ࣥ࡟ᑐࡍࡿ⢾㙐ࡢᖹᆒ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮'Gbind (kcal/mol)ᑟධ࡟ࡼࡾ⤖ྜ࢚ࢿࣝࢠ࣮㔞ࡣῶᑡࡋࡓ

࣑ࣀ㓟㸦W21ࠊW23ࠊ
Y30㸧࡟ᑐࡍࡿ␗࡞
ࡿⰾ㤶᪘࢔࣑ࣀ㓟ࡢᑟධࡣኚ␗యࡢᇶ㉁ㄆ㆑࡟㢧ⴭ࡞ᙳ㡪ࢆ୚࠼࡞࠿ࡗࡓࠋࡍ࡭

ࡣ⢾㙐ࡢ⤖ྜ᪉ྥࡀ

docking structure typea (NMR)
b
c
wt
-24
-32
-30
W21F
n.d.*
-30
-30
W21Y
-22
-30
n.d.*
W23F
-25
-30
-28
W23Y
-24
-30
n.d.*
Y30F
-21
-28
-27
S19T
-19
-26
-19
Y30T
-18
-24
n.d.*
Y30A
-18~-20
-23
n.d.*
S19A
-19
-26
n.d.*
*ࢻࢵ࢟ࣥࢢᵓ㐀ࡀ⏕ࡌ࡞࠿ࡗࡓࡓࡵ
model

ࡀࠊ3 ࡘࡢⰾ㤶᪘࢔࡚ࡢࢻࢵ࢟ࣥࢢᵓ㐀ᅗ 6㸬࣊࣋࢖ࣥ-GlcNAc3 」ྜయࡢ❧యᵓ㐀ࠊᇶ㉁ㄆ㆑࢔࣑ࣀ㓟࡜ࢧࣈࢧ࢖ࢺ

ᅗ 7㸬ࢻࢵ࢟ࣥࢢ㐣⛬࡟࠾ࡅࡿ⢾㙐఩⨨࡜⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࡢ 2 ḟඖศᕸ- 138 -NMR ᵓ㐀࡜୍⮴ࡋࠊࢧࣈࢧ࢖ࢺ+3 ࠿ࡽ-1 ᪉ྥ࡟⢾㙐ࡀ㑏ඖᮎ➃࠿ࡽ㠀㑏ඖ᪉ྥ࡟⤖ྜࡋࡓࠋ

4. Ⓨ⾲ᐇ⦼
1. մT. Yui and T. Uto, Desorption behavior of guest molecule from cellulose I–EDA complex crystals, 255th ACS
National Meeting & Exposition, New Orleans, LA, USA (March 2018)
2. մT. Uto, K. Yamamoto and J. Kadokawa, Cellulose dissolution in ionic liquids: A theoretical study, The Fiber
Society’s Spring 2018 Conference, Tokyo, Japan (June 2018)
3. մT. Uto, K. Yamamoto and J. Kadokawa, Dissolution simulation of chitin in imidazolium-based ionic liquids,
MACRO18 World Polymer Congress, Cairns, QLD, Australia (July 2018)
4. մT. Uto, K. Yamamoto and J. Kadokawa, Understanding the dissolution processes of chitin in ionic liquids: A
theoretical study, 256th ACS National Meeting & Exposition, Boston, MA, USA (August 2018)
5. մT. Yui, R. Otoshi and T. Uto, Carbohydrate recognition by chitin binding proteins: A molecular dynamics study,
14th International Chitin and Chitosan Conference, Osaka, Japan (August 2018)6. մᏱ㒔༟ஓ, ‫‮‬஭ᩄᩥ, ᒣඖ࿴ဢ, 㛛ᕝ῟୍ࠕ࢝ࢳ࢜ࣥᛶ࡜࢔ࢽ࢜ࣥᛶࡢ࢔࣑࣮ࣟࢫ࢔ࢼࣟࢢ࢔࣑ࣀከ⢾࠿ࡽࡢ㘒యᙧᡂࠖ᪥ᮏ໬Ꮫ఍➨ 98 ᫓Ꮨᖺ఍, ⯪ᶫᕷ㸦2018 ᖺ 3 ᭶㸧
7. մᏱ㒔༟ஓ, ᒣඖ࿴ဢ, 㛛ᕝ῟୍ࠕ࢖࢜ࣥᾮయ୰࡟࠾ࡅࡿ࢟ࢳࣥࡢ⁐ゎࢩ࣑࣮ࣗࣞࢩࣙࣥࠖ➨ 67 ᅇ㧗ศᏊᏛ఍ᖺḟ኱఍, ྡྂᒇ㸦2018 ᖺ 5 ᭶㸧
8. մᏱ㒔༟ஓࠕᵓ㐀ከ⢾ᮦᩱࡢ⤖ᬗᵓ㐀≉ᛶ࡜⁐ゎᶵᵓ࡟㛵ࡍࡿィ⟬໬Ꮫ◊✲ࠖ2019 ᖺᗘ⧄⥔Ꮫ఍ᖺḟ኱఍, ᮾி㒔Ụᡞᕝ༊㸦2019 ᖺ 6 ᭶㸧
9. մྜྷᕝ⥈, Ᏹ㒔༟ஓ, ‫‮‬஭ᩄᩥࠕኳ↛Ϩᆺࢭ࣮ࣝࣟࢫ⤖ᬗ⾲㠃࠿ࡽࡢศᏊ㙐๤㞳ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ
◊✲ࠖ➨ 56 ᅇ໬Ꮫ㛵㐃ᨭ㒊ྜྠ஑ᕞ኱఍, ໭஑ᕞᕷ㸦2019 ᖺ 7 ᭶㸧
10. մᇽᅬᫀᘯ, Ᏹ㒔༟ஓ, ‫‮‬஭ᩄᩥࠕࢭ࣮ࣝࣟࢫϨᆺ̽࢔࣑ࣥ」ྜయ⤖ᬗ࠿ࡽࡢࢤࢫࢺศᏊ⬺㞳ᣲືࠖ➨ 56
ᅇ໬Ꮫ㛵㐃ᨭ㒊ྜྠ஑ᕞ኱఍, ໭஑ᕞᕷ㸦2019 ᖺ 7 ᭶㸧
11. մᒸ⏣⨾Ἃᕼ, 㧗ᶫࡉࡃࡽ, Ᏹ㒔༟ஓ, ‫‮‬஭ᩄᩥࠕ࢟ࢳࣥ⤖ྜᛶࢱࣥࣃࢡ㉁࣊࣋࢖ࣥ࡟ࡼࡿ⢾㙐ㄆ㆑ࠖ➨
26 ᅇࢭ࣮ࣝࣟࢫᏛ఍㸪⚟ᒸᕷ㸦2019 ᖺ 7 ᭶㸧
12. մᏱ㒔༟ஓ, ୕㇂ுᶞ, ‫‮‬஭ᩄᩥࠕQM/MM ἲ࡟ࡼࡿࢽ࣡ࢺࣜ༸ⓑࣜࢰࢳ࣮࣒ࡢ⢾ຍỈศゎ཯ᛂࢩ࣑ࣗࣞ
࣮ࢩࣙࣥࠖ➨ 57 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, ᐑᓮᕷ㸦2019 ᖺ 9 ᭶㸧
13. մᏱ㒔༟ஓ, ኱すᏕ࿴, 㯮⏣ᾈ௓ࠕ୧ᛶ࢖࢜ࣥᾮయ࡟ࡼࡿࢭ࣮ࣝࣟࢫ⁐ゎࢩ࣑࣮ࣗࣞࢩࣙࣥࠖ➨ 10 ᅇ࢖࢜ࣥᾮయウㄽ఍, ㇏୰ᕷ㸦2019 ᖺ 11 ᭶㸧

5. ฟ∧ᐇ⦼
1. մT. Uto, Y. Kodama, T. Miyata and T. Yui, Molecular dynamics simulations of theoretical cellulose nanotube
models, Carbohydrate Polymers 190, 331-338 (2018)
2. մT. Yui, T. Uto, T. Nakauchida, K. Yamamoto and J. Kadokawa, Double helix formation from non-natural
amylose analog polysaccharides, Carbohydrate Polymers 189, 184-189 (2018)
3. մᏱ㒔༟ஓ, ⡿಴ດ, ‫‮‬஭ᩄᩥࠕࢭ࣮ࣝࣟࢫࢸࢡࣀࣟࢪ࣮㸸ศᏊ㙐ࢩ࣮ࢺࡢ❧యᵓ㐀Ᏻᐃᛶ࡟ᇶ࡙࠸ࡓࢭ
࣮ࣝࣟࢫ⤖ᬗከᙧࡢᵓ㐀≉ᛶゎᯒࠖCellulose Communications 25, 20–23 (2018)4. մᏱ㒔༟ஓ, ‫‮‬஭ᩄᩥࠕィ⟬໬Ꮫ࡟ࡼࡗ࡚ண ࡉࢀࡓࢭ࣮ࣝࣟࢫࡢ㧗ḟᵓ㐀㸸ࢩࢡࣟ࣊࢟ࢧࣥ࡜㓑㓟࢚ࢳࣝ୰࡟࠾ࡅࡿࢭ࣮ࣝࣟࢫࢼࣀࢳ࣮ࣗࣈࠖJournal of Fiber Science and Technology 74, 171–176 (2018)
5. մT. Uto, K. Yamamoto and J. Kadokawa, Cellulose crystal dissolution in imidazolium-based ionic liquids: A
theoretical study, The Journal of Physical Chemistry B 122, 258-266 (2018)
6. մT. Uto, S. Idenoue, K. Yamamoto and J. Kadokawa, Understanding dissolution process of chitin crystal in ionicliquids: Theoretical study, Physical Chemistry Chemical Physics 20, 8050–8058 (2018)
7. մT. Uto and T. Yui, DFT optimization of isolated molecular chain sheet models constituting native cellulose
crystal structures, ACS Omega 3, 8050–8058 (DOI: 10.1021/acsomega.8b00834) (2018)
8. մT. Uto, M. Minamizaki and T. Yui, Molecular dynamics simulation of cellulose I–ethylenediamine complex
crystal models, The Journal of Physical Chemistry B 124, 134–143 (2019)9. մᏱ㒔༟ஓࠕᵓ㐀ከ⢾ᮦᩱࡢ⤖ᬗᵓ㐀≉ᛶ࡜⁐ゎᶵᵓ࡟㛵ࡍࡿィ⟬໬Ꮫ◊✲ࠖJournal of The Society ofFiber Science and Technology 75, 497–500 (2019)10. մᏱ㒔༟ஓ, ‫‮‬஭ᩄᩥࠕࢭ࣮ࣝࣟࢫࡢᐇ㦂࡜ゎᯒἲ㸸ศᏊຊᏛィ⟬࡟࠾ࡅࡿ⿵᏶ຊሙࣃ࣓࣮ࣛࢱࡢసᡂࠖ
Cellulose Communications 27, 28–33 (2020)11. մT. Uto, S. Nakamura, K. Yamamoto and J. Kadokawa, Evaluation of artificial crystalline structure from amylose
analog polysaccharide without hydroxy groups at C-2 position, Carbohydrate Polymers 240, 116347-116352 (2020)12. մT. Yui and T. Uto, Docking and molecular dynamics study of the carbohydrate binding module from Trichoderma
reesei Cel7A on the surfaces of the cellulose IIII crystal, Journal of Renewable Materials 8, in press (2020)- 139 -











Structure formation of molecular assemblies
and their related functions  "(+ 5+.73 0 4+ 2  1)8 %*0 #$ ,! -(& 3 '6          
/% 

1 
\lÖf«$Êx ²3.#0+#TÆ.Ý\l#ÓË0¢¨3¹"$PNÁ>LC# $¢¨3hd0 Tµ$\l_^nÀª1)#°¶¬±$¬±µ3V#$jasµ Zasµ$³Æ­311X2§Û$³ÆQÎsE?Hµ3rÅ \l_^n (MD) Àª3¹. ³Æ­#Ør¦3,³ÆQÎsµ$asµÒ0|$Ì , asµÒ$|$ Ó,-'o³Æ\l$Y[Öx~$pÕ

.#. , n#¸e1 0o³Æ§ (7I:>JLH) $µZ$Y[Ö -'×# $o -'5G:<L84;Wm|3.#(§$¿3¹".

 Ý\l$£i£i$\lÄÇ
Ý\l %Æ#-º3O .10 ´|)%u|

"0|Æ3¥½ 3

Ñ -'0MblIBH$¡¼Î» 09FHALÂÜ"!$C5J"pÜ.%
blIBH$}h3z0 " PMMA

PC %Ú¯#U21 0Ý\l  /PMMA

%´|3PC %u|3¥ ¡.1 01.$Ì 3.#0+#C5J"ÂÜ.Å3¿Í-Â*.1$®| -'.*c qt"!$C5J"Ï

Î»

0

Ã1)#©.1

PMMA

PC 3<L6=@#.#PMMA %k{^3È 0 void Ð0

%D5J"¾.´|

u|$Ì

3

£i#·/PC %ÔSyÉ`K¤`Ç0 £i#·0 3¥)/k{^ÞÔS{^ß$]y´| u|$Ì D5J#vÇ10 2".#´|3¥u|3¥\." ÙgÞk{^ÞÔS{^ßR]$Ùgß 0w|Ùg#PMMAPC # 0\l$Ì %¿1 " %R]$¢¨

z.1{^&*v$."0¿3¹>T#%z.1{^311$HL
.$Ç#\D)/®c ®c $\lZ 29$ZO !+?H*LH:^K5
LJ+^$\lÒ 29#\vg.10 #-0HLY` {^Y`3¥(1#r{0ÊY`$¿3¹

- 140 -

2  Tµ$\l_^nÀª 1 #%E?HQÎsµ$³Æ­¤¬3¥¶³Æ§ )J)+³Æ (PC, PE, PS-' PI), :!+D)+ (SM), ))+³Æ(l-PC, l-PS)-'7I:>JLH (CH) 3l¶)+³Æ^­$, -µMt -'1.$Dc# ,pÜ<3G#o¶¬±Zj$4+t (Na+, K+, Cl-) $Ì 3It ²¿Æ3¢0 ¬±ZjV3?
. ³Æ\l;%asµ / 256 ; , ³Æ^U# CHARMM36, \l^U# TIP3P, 4+§$^U% CHARMM36

G&L<!4H5_$,$3U³Æ\l$Y®3G+%#Y «3 3 ¨/k11#  t 310.15K, S^ 1 atm y6N 1$ MD Àª3¹.
Lennard-Jones

293Fh 12Å (force switching Ó3 8-12 Å #¬) =@!0,, ³² 29% particle mesh Ewald #-/ÀªMD Àª%!@ MODYLAS 3U¹Table 1. Lipid composition of model bilayers of outer and inner leaflets of hepatocyte plasma membranes / mol%.
Outer

Inner

PC

SM

l-PC

CH

Tail composition*

23

20

7

50

65/16/19

PE

PS

PI

l-PS

CH

Tail composition*

36

24

7

3

30

47/6/47

PC: Phosphatidylcholine, SM: Sphingomyelin, PE: Phosphatidyl- ethanolamine, PS: Phosphatydylserine, PI:
Phosphatidylinositol,l-PC:

lyso-PC,l-PS:

lyso-PS.,CH:

cholesterol.

*Mole

fractionofsaturated/mono-unsaturated /poly-unsaturated acyl tails of PLs.

 Ý\l$£i£i$\lÄÇ´|$ PMMA H'u|$ PC 3rÅ#p#c¦1 0Ý\l 3XÀª«39
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[1] T. Nagai, S. Tsurumaki, R. Urano,

K. Fujimoto, W. Shinoda, S. Okazaki, “Novel method to evaluate

position-dependent diffusion constant of small molecules in heterogeneous systems”, the 36th International
Conference on Solution Chemistry (ICSC2019), PR[c, 2019 f 8 w 4 q»8 q[2] T. Taddese, M. Kitabata, S. Okazaki, “Molecular dynamics study of thermodynamic stability of a polymer
solution;non-solvent induced phase separation of PVDF/NMP/water”, Joint EMLG/JMLG conference 2019,
GASK(Kutna Hora,Czech Republic), 2019 f 9 w 8 q»13 q[3] x MX /0`a ª, ØuÝ\l$º£i#Ó0\lÄ¢¨,  68 OÝ\l¡Ä7,
3kno4F+ :, 2019 f 9 w 25 q»27 q- 142 -

[4] x MX /0`a ª, ØuÝ\l$º£i#Ó0\lÄ¢¨,  68 OÝ\l¡Ä7,
3kno4F+ :, 2019 f 9 w 25 q»27 q[5]  /0x MX `a ª, ØuÝ\l$º£i#Ó0\lÄ¢¨:D5J$¾# 0ÔSÅ$¿,  68 OÝ\l¡Ä7, 3kno4F+ :, 2019 f 9 w 25 q»27 q[6] W. Shinoda, S. Seo, K. Funahashi, “Coarse-Grained Molecular Dynamics Study of Lipid-Protein Complex”, The
5th International Conference on Molecular Simulation, Lotte Hotel Jeju(Korea), 2019 f 11 w 3 q»6 q
[7]

5 





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_Ñ#WÑ'Į"ıĵĲToshihide Horikawa and Do D.D.: Water Adsorption

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Mechanism on Porous Carbon Materials, EMN Meeting on Porous Materials 2019, Dubrovnik, Croatia, Oct. 2019.
ıĶĲK. Yoshida, M. Nakahara: Self-diffusion of water and cyclohexane in supercritical mixture studied by NMR
and MD, Joint Conference of EMLG/JMLG Meeting 2018 and 41st Symposium on Solution Chemistry of Japan, Nagoya,Nov. 2018.

5räĄ-(^ıĴĲK. Yoshida, M. Nakahara; Self-diffusion of water–cyclohexane mixtures in supercritical conditions as studied

by NMR and molecular dynamics simulation, J. Chem. Phys. Vol. 150, 174505 (2019).
ıĵĲì l: êú¤ċ 2020, --- åê/zğ 520527 ĭãz ĳ532535 ĭĪÕzTâÜz âĒ¥ĩâ'âĒ¥û---, ]rä Ì¦dù, Éa, 2019 ¤ 11 Å.

ıĶĲAyaka Kuroki, Megumi Hiroto, Yoshitomo Urushihara, Toshihide Horikawa, Ken-Ichiro Sotowa and Jesus
Rafael Alcantara Avila: Adsorption mechanism of metal ions on activated carbon, Adsorption, Vol. 25, No. 6, 1251-1258,
2019.
ıķĲLuisa Prasetyo, Toshihide Horikawa, Naoki Takashima, D.D. Do and D. Nicholson : On the Transition from
Partial Wetting to Complete Wetting of Methanol on Graphite, Physical Chemistry Chemical Physics, Vol. 21, No. 47,
26219-26231, 2019.
ıĸĲK. Yoshida, M. Nakahara, Handbook of Scientific Tables, Maruzen Publishing Co., Ltd., Tokyo and World
Scientific Publishing Co, Singapore, in press.

- 145 -

ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ࢞ࣛࢫ≧ែࡢᙎᛶ࡜ረᛶࡢ◊✲Simulation study on the elasticity and plasticity of the glassy states‫ۑ‬ụ⏣ ᫀྖࠊỈ㔝 ⱥዴࠊᓥ⏣ ┿ᡂࠊⓑ▼ ⸅ᖹࠊཎ 㞝௓㸦ᮾ኱⥲ྜᩥ໬㸧

1◊✲┠ⓗࠊෆᐜ
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࠸ࡃ࡜ࠊ࠶ࡿᐦᗘ࡟࠾࠸࡚๛ᛶࡀⓎ⌧ࡍࡿ㌿⛣࡛࠶ࡿࠋࡇࢀࡲ࡛༢ᡂศ⣔ࡢࢪ࣑ࣕࣥࢢ㌿⛣ࡣࠊ⌮ㄽ࣭ᐇ㦂࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ῝ࡃ⌮ゎࡉࢀ࡚ࡁࡓࠋࢪ࣑ࣕࣥࢢ㌿⛣㏆ഐ࡛ࡣࠊᙎᛶ⋡ࡀ⮫⏺ࢫࢣ࣮ࣜࣥࢢ࡟ᚑ࠺
ࡇ࡜ࡸࠊ≉␗࡞ࢯࣇࢺ࣮ࣔࢻࡀฟ⌧ࡍࡿࡇ࡜ࡀศ࠿ࡗ࡚ࡁ࡚࠸ࡿࠋࡋ࠿ࡋ⌧ᅾࡢࢪ࣑ࣕࣥࢢ㌿⛣ࡢ⌮ゎࡣࠊ㸦࡯ࡰ㸧༢ᡂศࡢ⌫≧⢏Ꮚ⣔࡟㝈ࡽࢀ࡚࠸ࡿࠋ⌧ᐇࡢ࢞ࣛࢫࡣࡶࡗ࡜ከᙬ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ௨ୗࡢ஧ࡘ
ࡢሙྜ࡟ὀ┠ࡋࠊࢪ࣑ࣕࣥࢢ㌿⛣ࡢ⌮ゎࢆࡼࡾᗈ࠸ࢡࣛࢫࡢ⣔࡬࡜ᢲࡋᗈࡆࡿࠋ
(1) ࣐ࣚࢿ࣮ࢬࡸ࣮࣌ࢫࢺ࡞࡝ࠊ⌧ᐇⓗ࡞࢞ࣛࢫ⣔ࡣᵝࠎ࡞኱ࡁࡉࡢ⢏Ꮚ࠿ࡽ࡞ࡿከศᩓ⣔࡛࠶ࡾࠊ༢ศᩓ
⣔࡜ࡣ࠿ࡅ㞳ࢀ࡚࠸ࡿࠋከศᩓ⣔ࡢ୰࡛᭱ࡶࢩࣥࣉࣝ࡞ࣔࢹࣝࡣࠊࢧ࢖ࢬ஋㞳ࡢ኱ࡁ࠸஧ศᩓ⣔࡛࠶ࡿࠋࡇ
ࢀࡲ࡛ࡢᐇ㦂◊✲࡛ࡣࠊ஧✀㢮ࡢ࢞ࣛࢫ┦ࡢฟ⌧ࡸࠊ≉␗࡞ຊᏛᛂ⟅࡞࡝ࠊ༢ศᩓ⣔࡟ࡣ࡞࠸」㞧࡞⌧㇟ࡀほࡉࢀ࡚࠸ࡿࠋࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ◊✲ࡶᏑᅾࡍࡿࡀࠊࡇ࠺ࡋࡓ⌧㇟ࡢ⌮ゎࡣ༑ศ࡛ࡣ࡞࠸ࠋᮏ◊✲࡛ࡣࠊࢧ࢖ࢬ஋㞳ࡢ࠶ࡿ஧ศᩓ⣔ࡢࢪ࣑ࣕࣥࢢ㌿⛣ࢆ◊✲ࡋࡓࠋࡑࡢ⤖ᯝࠊࡇࡢ⣔࡛ࡣ༢ᡂศ⣔࡛ࡣぢࡽࢀ࡞࠸ࠊ᪂つ࡞┦㌿⛣ࡀ㉳ࡇࡿࡇ࡜ࢆぢฟࡋࡓࠋ(2) ᐇ㝿ࡢ࢞ࣛࢫ࡛ࡣࠊᵓᡂ⢏Ꮚࡀ␗᪉ᛶࢆᣢࡘሙྜࡶከ࠸ࠋࡋ࠿ࡋࠊ␗᪉ⓗ࡞⢏Ꮚࡢ࢞ࣛࢫ≧ែࡢ≀ᛶ࡟ࡘ࠸࡚⌮ゎࡉࢀ࡚࠸ࡿࡇ࡜ࡣᴟࡵ࡚ᑡ࡞࠸ࡢࡀ⌧≧࡛࠶ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ⌫ᙧ⢏Ꮚࢆ஧ࡘࡘ࡞ࡆࡓࢲ
࢖࣐࣮ᆺ⢏Ꮚ࡟ὀ┠ࡋࠊࡑࡢࢪ࣑ࣕࣥࢢ㌿⛣ࡸࢪ࣒ࣕ┦࡛ࡢ≀ᛶࢆ᫂ࡽ࠿࡟ࡍࡿࠋ᫖ᖺᗘࡣࡇࡢࣉࣟࢢ࣒ࣛ
ࢆ஧ḟඖ⣔࡛⾜࠸ࠊ⌫ᙧ⢏Ꮚࡢሙྜ࡜ࡢ㐪࠸ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ௒ᖺᗘࡣࡇࡢ◊✲ࢆࠊࡼࡾᐇ㦂ⓗ࡟㔜せ࡞୕ḟඖ⣔࡬࡜ᣑᙇࡋࡓࠋ
(3) (1,2)ࡢ◊✲࡟ຍ࠼࡚ࠊ࢞ࣛࢫ⣔࡟࠾ࡅࡿ㠀ㄪ࿴ᛶࡢ◊✲ࢆ⾜ࡗࡓࠋ㏆ᖺࡢ◊✲࠿ࡽࠊ࢞ࣛࢫ≧ែ࡟࠾ࡅࡿ᣺ືࡢ≉␗ᛶࡢ⌮ゎࡀ῝ࡲࡗ࡚ࡁࡓࠋࡋ࠿ࡋࡑࡢ୍᪉࡛ࠊ࢞ࣛࢫ⣔ࡢ㠀⥺ᙧ࡞ᛂ⟅࡟ࡘ࠸࡚ࡣࠊࡑࡢ⌮ゎࡣⴌⱆⓗ࡞ẁ㝵࡟࠶ࡿࠋᮏ◊✲࡛ࡣࠊྛ᣺ື࣮ࣔࢻࡢ㠀ㄪ࿴ᛶ࡜࠸࠺ほⅬ࠿ࡽࠊ࢞ࣛࢫ⣔ࡢ㠀⥺ᙧ࡞ᛂ⟅ࢆヲࡋࡃㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
(1,2,3)ࡢࡍ࡭࡚࡟ࡘ࠸࡚ࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ (1)࡛ࡣࠊ⢏Ꮚࢫࢣ࣮ࣝࡢ➇ྜࡢຠᯝࢆ

ྲྀࡾ㎸ࢇࡔ᭱ࡶ༢⣧࡞ࣔࢹࣝ࡜ࡋ࡚ࠊࢧ࢖ࢬẚ 5 ࡢ஧ᡂศ᩺ຊ⢏Ꮚ⣔㸦ㄪ࿴┦஫స⏝㸧࡟ࡘ࠸࡚ࠊࡑࡢࢪ࣑ࣕࣥࢢ㌿⛣ࡸ≀ᛶࢆㄪ࡭ࡓࠋ(2)࡛ࡣࠊ␗᪉ᛶࢆྲྀࡾ㎸ࢇࡔࡶࡗ࡜ࡶ༢⣧࡞ࣔࢹࣝ࡜ࡋ࡚ࠊ⌫ᙧ⢏Ꮚࢆ஧ࡘࡘ
࡞ࡆࡓࢲ࢖࣐࣮ᆺ⢏Ꮚ࡟ࡘ࠸࡚ࠊࡑࡢࢪ࣑ࣕࣥࢢ㌿⛣ࡸ≀ᛶࢆㄪ࡭ࡓࠋ(3)࡛ࡣࠊㄪ࿴┦஫స⏝࠿ࡽ࡞ࡿ⢏Ꮚ⣔࡜ Lennard-Jones ⢏Ꮚ⣔࡟ࡘ࠸࡚ࠊ᣺ື࣮ࣔࢻࢆᙉࡃບ㉳ࡋࡓሙྜࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ- 146 -

3◊✲ᡂᯝ(1) ஧ศᩓ⣔ࡢࢪ࣒ࣕ┦ࡢ≧ែࡣࠊ඲⢏Ꮚ୰ࡢᑠ⢏Ꮚࡢ๭ྜ (XS) ࡜ࠊ⣔ࡢᅽຊ (P) ࡟ࡼࡗ࡚ᣦᐃࡉࢀࡿࠋ

ᮏ◊✲࡛ࡣࠊXs-P ࡢ┦ᅗ୰ࡢྛⅬ࡛ከᩘࡢ࢞ࣛࢫ㓄⨨ࢆసᡂࡋࠊࢪ࣒ࣕ┦ࡢ๛ᛶ࡟ᐤ୚ࡍࡿᑠ⢏Ꮚࡢ๭ྜ RS
ࢆ

ᐃࡋࠊRs ࡢ☜⋡ศᕸࢆồࡵࡓࠋRs ࡣᑠ⢏Ꮚࡀࢪ࣒ࣕࡍࡿ࠿ྰ࠿ࢆ༊ูࡍࡿ࣮࢜ࢲ࣮ࣃ࣓ࣛࢱ࡛࠶ࡿࠋࡇ

ࢀ࡟ࡼࡾࠊ኱⢏Ꮚࡢࡳࡀࢪ࣒ࣕࡍࡿ┦ (L ┦) ࡜ࠊ኱ᑠ⢏Ꮚࡢ୧᪉ࡀࢪ࣒ࣕࡍࡿ┦ (LS ┦) ࡀ┦ᅗ୰࡟Ꮡᅾ
ࡍࡿࡇ࡜ࠊࡑࡋ࡚ࡇࡢ஧✀㢮ࡢࢪ࣒ࣕ┦ࡢ㛫ࡢኚ໬ࡀ୍ḟ┦㌿⛣࡛࠶ࡿࡇ࡜ࢆぢฟࡋࡓࠋࡲࡓࠊࡇࡢ୍ḟ┦㌿⛣ࡣపᅽ≧ែ࡟ࡋ࠿Ꮡᅾࡏࡎࠊࡼࡾ㧗ᅽ≧ែ࡛ࡣ୍ḟ㌿⛣ࡣ⮫⏺Ⅼ࡜࡞ࡾࠊࡉࡽ࡟㧗ᅽ࡛ࡣࢡࣟࢫ࣮࢜ࣂ
࣮࡟࡞ࡿࡇ࡜ࢆぢฟࡋࡓ ࠋࡇࡢ┦ᅗࡣࠊẼᾮࡢ┦ᅗ࡟㓞ఝࡋ࡚࠸ࡿࠋࡋ࠿ࡋࠊࡑࡢ୍ḟ┦㌿⛣ࡢ⇕ຊᏛⓗᛶ㉁ࡣࠊẼᾮ㌿⛣࡜኱ࡁࡃ㐪ࡗ࡚࠸ࡓࠋලయⓗ࡟ࡣࠊ⇕ຊᏛᴟ㝈࡟࠾࠸࡚ࡣࠊ㌿⛣Ⅼ࡛ RS ࡢᖹᆒ್ࡢഴࡁࡀ
ⓎᩓࡍࡿࡀࠊࡇࡢഴࡁࡢⓎᩓࡀ⣔ࡢ⢏Ꮚᩘ N ࡟ẚ౛ࡏࡎࠊN1/2 ࡟ẚ౛ࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡇࢀࡣ㏻ᖖࡢ୍ḟ┦㌿⛣࡛ࡣ࡞ࡃࠊࣛࣥࢲ࣒☢ሙ࢖ࢪࣥࢢᶍᆺ࡞࡝ࡢ୍ḟ┦㌿⛣࡜㓞ఝࡋ࡚࠸ࡿࠋࡍ࡞ࢃࡕࠊᑠ⢏Ꮚࡀࢪ࣒ࣕࡍࡿ࠿ྰ࠿ࡢ㌿⛣ࡣࠊࣛࣥࢲ࣒ࢿࢫࡢᙳ㡪ࢆṧࡋࡓ୍ḟ┦㌿⛣࡛࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
(2) ୕ḟඖࢲ࢖࣐࣮⣔ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊࡑࡢࢪ࣑ࣕࣥࢢ㌿⛣ࢆヲࡋࡃㄪ࡭ࡓࠋ᫖ᖺᗘࠊ஧ḟඖ⣔ࢲ࢖࣐࣮⣔࡛ࡣࠊRrotational rattler ࡜࿧ࡤࢀࡿ⢏Ꮚࡀ⏕ᡂࡋࠊ᥋ゐᩘࡀ isostatic ᩘࡼࡾࡶ୙㊊ࡍࡿࡇ࡜ࢆぢฟࡋ࡚࠸ࡓࠋᮏ◊✲࡛ࡣࡲࡎࠊࡇࡢᛶ㉁ࡀ୕ḟඖ⣔࡛ࡶᏑᅾࡍࡿࡇ࡜ࢆ♧ࡋࠊࡑࡢᅇ㌿⮬⏤ᗘࢆ㝖ࡃ࡜㌿⛣Ⅼୖ࡛ isostaticity ࡀᅇ᚟ࡍࡿࡇ࡜ࢆ♧ࡋࡓࠋḟ࡟ࠊ᫖ᖺᗘࡣ᳨ウࡋ࡚࠸࡞࠿ࡗࡓࠊᅽຊ࡜ᙎᛶ⋡ࡢ⮫⏺ᣲືࢆㄪ࡭ࡓࠋࡑࡢ⤖ᯝࠊ஧ḟඖ⣔࣭୕ḟඖ⣔ࡢ཮᪉࡛ࠊ⮫⏺ᣦᩘࡀ➼᪉⢏Ꮚ⣔࡜➼ࡋ࠸ࡇ࡜ࢆ♧ࡋࡓࠋ᭱ᚋ࡟ࠊ
ࢲ࢖࣐࣮⣔ࡢ᣺ື≧ែᐦᗘࢆィ⟬ࡋࡓࠋ஧ḟඖ⣔ࡢሙྜ࡜ྠᵝ࡟ࠊࣆ࣮ࢡ࡜ప࿘Ἴᩘࡢࣉࣛࢺ࣮ࡣᅇ㌿㐠ືࡀᨭ㓄ⓗ࡞࣮ࣔࢻ࠿ࡽᵓᡂࡉࢀ࡚࠸ࡿࡇ࡜ࢆぢฟࡋࡓࠋࡍ࡞ࢃࡕࢲ࢖࣐࣮࢞ࣛࢫࡢప࿘Ἴ᣺ືࡣࠊᅇ㌿㐠ື࡟ࡼࡗ࡚≉ᚩ࡙ࡅࡽࢀࡿࠋ௨ୖ࡟ࡼࡾࠊ᫖ᖺᗘ☜❧ࡋࡓ஧ḟඖࢲ࢖࣐࣮⣔ࡢࢪ࣑ࣕࣥࢢ㌿⛣ࡢ⌮ゎࡀࠊᐇ㦂ⓗ࡟ࡼࡾ㔜せ࡞୕ḟඖ⣔࡟ᣑᙇࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋ
(3) ࡇࢀࡲ࡛ࡢ◊✲࡟ࡼࡾࠊ࢞ࣛࢫ⣔ࡣ≉␗࡞ᒁᅾ᣺ື࣮ࣔࢻࢆᣢࡘࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋࡇࢀࡽࡢ᣺ືࣔ
࣮ࢻ࡜ࣇ࢛ࣀࣥ࡟㏆࠸࣮ࣔࢻࢆࠊࡑࢀࡒࢀᙉࡃບ㉳ࡋࠊࡑࡢᚋࡢኚ఩ࢆほᐹࡋࡓࠋࡑࡢ⤖ᯝࠊࡇࢀࡽࡢບ㉳࡟ࡼࡾࠊ⢏Ꮚࡢ෌㓄⨨ࡀ㉳ࡇࡾࠊ᪂ࡋ࠸࢞ࣛࢫ≧ែ࡬ࡢ㌿⛣ࡀ㉳ࡇࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡉࡽ࡟ࣇ࢛ࣀࣥࡽࡋ
࠸࣮ࣔࢻ࡜ᒁᅾ࣮ࣔࢻࡢ࡝ࡕࡽࡶࡀࠊᐜ᫆࡟ࡇࡢ㌿⛣ࢆ㉳ࡇࡍࡇ࡜ࡀࢃ࠿ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

᪥ᮏ≀⌮Ꮫ఍ 2020 ᫓Ꮨ኱఍㸸(1)ཱྀ㢌Ⓨ⾲ࠊ᪥ᮏ≀⌮Ꮫ఍ 2019 ⛅Ꮨ኱఍㸸(2)ཱྀ㢌Ⓨ⾲

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
(3)ࡢㄽᩥࡣࡍ࡛࡟ฟ∧῭ࡳ࡛࠶ࡿ㸸”Anharmonic properties of vibrational excitations in amorphous solids”

Mizuno et al. Phys. Rev. Research 2, 013215 (2020). (2)ࡢㄽᩥ࡟ࡘ࠸࡚ࡣࠊJ. Phys. Soc. Jpn.ㄅ࡟ᢞ✏῭ࡳ࡛࠶ࡿࠋ
(1)ࡢㄽᩥࡣ⌧ᅾᇳ➹୰࡛࠶ࡾࠊᇳ➹᏶஢ࡋࡔ࠸ᢞ✏ࡍࡿࠋࡲࡓࠊ᫖ᖺᗘᢞ✏ࡋ࡚࠸ࡓୗグࡢィ⟬⛉Ꮫ◊✲ࢭࣥࢱࡢィ⟬ᶵ࡟ࡼࡿ◊✲ᡂᯝࡀฟ∧ࡉࢀ࡚࠸ࡿ㸸”Universal relaxation dynamics of sphere packings below
jamming”, Ikeda et al., Phys. Rev. Lett. 124, 058001-1-6 (2020).; “Vibrational properties of two-dimensional dimer
packings near the jamming transition”, Shiraishi et al., Phys. Rev. E 100, 012606 (2019).

- 147 -

OZ ⌮ㄽ࠿ࡽồࡲࡿ஧ཎᏊศᏊ⁐㉁ࡢ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮⿵ṇ࡟㛵ࡍࡿ◊✲㸸ࢡ࣮ࣟࣥ┦஫స⏝ࢆ⪃៖ࡍࡿሙྜ
A study on the correction of solvation free energy of diatomic solute
molecule based on OZ integral equation theory: the case including the
coulomb potential‫ۑ‬ᐑ⏣ ❳ᙪ㸦ឡ፾኱㝔⌮ᕤ㸧

1◊✲┠ⓗࠊෆᐜ
ศᏊ㛫┦஫స⏝ࡀ LJ ࣏ࢸࣥࢩ࡛ࣕࣝグ㏙ࡉࢀࡿ⁐ᾮ࡛ࡣࠊHNC ㏆ఝࡸ KH ㏆ఝࡣ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮

ࢆ㐣኱ホ౯ࡍࡿࠋࡇࢀࡣࠊ⁐㉁ࡀ༢ཎᏊศᏊ࠾ࡼࡧ஧ཎᏊศᏊࡢሙྜ࡟ඹ㏻࡟ぢࡽࢀࡿࠋ⏦ㄳ⪅ࡣࡇࢀࢆ⿵
ṇࡍࡿ᪉ἲ࡜ࡋ࡚ࣈࣜࢵࢪ⿵ṇࡢ୍✀࡛࠶ࡿ SEB ⿵ṇἲࢆᥦ᱌ࡋࠊ༢ཎᏊ⁐㉁࠾ࡼࡧ஧ཎᏊ⁐㉁ࡢሙྜ࡟ࡑ
ࡢ᭷ຠᛶࢆ♧ࡋ࡚ࡁࡓࠋᮏᖺᗘࡣࠊLJ ࣏ࢸࣥࢩࣕࣝ࡟ࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࡀ㔜ࡡྜࢃࡉࢀࡓሙྜ࡟ࡘ࠸࡚
᳨ウࡋࡓࠋ

2

◊✲᪉ἲࠊィ⟬᪉ἲ⁐㉁࡜ࡋ࡚஧ཎᏊศᏊࢆ⪃࠼ࡓࠋ⁐፹ࡣ࢝ࢳ࢜ࣥࠊ࢔ࢽ࢜ࣥࡢ஧ᡂศΰྜ⣔࡜ࡋࡓࠋ⁐㉁ࡢྛཎᏊୖ࡟ṇ㈇ࡢ㟁Ⲵࢆ㓄⨨ࡋࠊLJ+ࢡ࣮࣏ࣟࣥࢸࣥࢩ࡛ࣕࣝ┦஫స⏝ࢆグ㏙ࡋࡓࠋࡇࡢሙྜࠊMolecular Ornstein-Zernike㸦MOZ㸧⌮ㄽ࡬෇⟄ᗙᶆࢆ㐺⏝ࡋࡓ 2D-OZ ⌮ㄽࡀ฼⏝࡛ࡁࡿࠋẚ㍑ࡢࡓࡵࠊྠ⁐㉁࡟ᑐࡍࡿ 2 ḟඖศᕸ㛵ᩘࢆ MD ἲ࡛ồࡵࡓࠋࡲࡓࠊ⁐㉁-⁐፹㛫ࡢ┦㛵㛵ᩘࡢグ㏙࡟ RISM ⌮ㄽࢆ⏝࠸ࡓሙྜࡶ᳨ウࡋࡓࠋィ⟬࡟ࡣࡍ࡭࡚⮬సࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ3◊✲ᡂᯝ⁐㉁ࡢ∦᪉ࡢཎᏊࡢ LJ ࣏ࢸࣥࢩࣕࣝࡀࢮ࡛ࣟ࠶ࡾࠊ࠿ࡘ௚᪉ࡢཎᏊ࡟ᇙࡶࢀ࡚࠸ࡿሙྜࡢ⤖ᯝࢆ୰ᚰⓗ࡟㏙࡭ࡿࠋࡇࡢሙྜࠊRISM/HNCࠊRISM/KH ⌮ㄽࡣ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࢆ㢧ⴭ࡟㐣ᑠホ౯ࡋࡓࠋࡇࢀࡣࠊศ
Ꮚෆ࡛ཎᏊྠኈࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜࡟ࡼࡿ᤼㝖య✚ຠᯝࢆ RISM ⌮ㄽ࡛ࡣ༑ศ࡟グ㏙ࡋษࢀ࡚࠸࡞࠸ࡇ࡜࡟
ࡼࡿࡶࡢ࡛࠶ࡿࠋࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࡢ࡞࠸ࣔࢹ࡛ࣝ࠶ࢀࡤࠊࡇࡢࡇ࡜ࡣ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮࡬㢧ⴭ࡟ᙳ㡪ࡋ࡞࠸ࡀࠊࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࢆྵࡴ⣔࡛ࡣỴᐃⓗ࡟㔜せ࡜࡞ࡿࠋ2D-OZ/HNCࠊ2D-OZ/KH ⌮ㄽ࡛ࡣ㏫࡟㐣኱ホ౯࡜࡞ࡗࡓࠋ2D-OZ ⌮ㄽࡢ⤖ᯝࡣỈ୰࡛ࡢ୰ᛶ⁐㉁ࡢ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮࡟㛵ࡍࡿ 3D-RISM ⌮ㄽࡢ⤖ᯝ࡜ࡶᐃᛶⓗ࡟ྜ⮴ࡋ࡚࠸ࡿࠋRISM ⌮ㄽࢆಟṇࡍࡿ┠ⓗ࡛ࠊAAOZ ⌮ㄽࡢᥦ᱌ࡶ⾜࡞ࡗࡓࠋ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ۻ‬ᐑ⏣❳ᙪ, ᆏᮏⴌ, బࠎᮌᗣ, "RISM ⌮ㄽ࡟࠾ࡅࡿ஧ཎᏊศᏊὶయࡢ⇕ຊᏛ㔞ࡢ⢭ᗘ࡟㛵ࡍࡿ◊✲",2019 ᖺ 10 ᭶, ➨ 42 ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘㸪ᮾ໭኱Ꮫ㸦ᐑᇛ㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ۻ‬T. Miyata, Y. Ogasawara, T. Fujii, D. Yano, and Y. Ebato, J. Molec. Liquids, 290 (2019) 111167.

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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 IIࠐᒣཱྀ ඙ࠊỿ ᘓோ(ᒸᒣ኱Ꮫ)ࠊ୰㇂ ࿴ᙪ(኱㜰኱Ꮫ)ࠊ
ᗉྖ ග⏨(⟃Ἴ኱Ꮫ)ࠊ⚄㇂ ಙኵ(኱㜰ᕷ❧኱Ꮫ)ࠊ☾㒊 ᐶ(ᒸᒣ኱Ꮫ)1◊✲┠ⓗࠊෆᐜ
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
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 ≧ែ࡛᪂ࡋࡃᤄධࡉࢀ
ࡿỈศᏊ⏤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࠶ࡿࠋ2017 ᖺࡢⳢࡽࡢ S3 ≧ែ࡛ࡢ O(5)-O(6)㛫㊥㞳ࡣ 1.5 Å ࡛

ᅗ1

Kok ࢧ࢖ࢡࣝ

࠶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࡟Ⳣࡽࡀ
ሗ࿌ࡋࡓ S3 ≧ែ࡛ࡢ O(5)-O(6)㛫㊥㞳ࡣ 1.9 Å ࡛࠶ࡾࠊoxyl-oxo ࢱ࢖ࣉࡢࡶࡢ࡛࠶ࡿ࡜࠸࠺⤖ᯝ࡛࠶ࡗࡓ[12]ࠋ
ࡲࡓࠊIbrahim 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୙☜ᐃᛶࡢࡓࡵࠊ
ᚤጁ࡞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ⓗ࡟ྫྷ࿡ୖ࡛ࡣ༑ศ࡛ࡣ࡞ࡃࠊ౛࠼ࡤࠊS3 ≧ែࡢࣁ࢖ࣈࣜࢵࢻ 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୰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࠶ࡿ- 149 -DLPNO-CC ἲ[6]ࢆ⏝࠸ࡓᵓ㐀␗ᛶయ㛫ࡢ┦ᑐ࢚ࢿࣝࢠ࣮ཝᐦ࡞ẚ㍑ࢆ⾜࠸ࠊᚑ᮶⾜ࡗ࡚࠸ࡓ DFT ࡟ࡼࡿ⤖ᯝ࡜ࡢẚ㍑᳨ウࡶ┠ⓗ࡜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໬ࡣᚑ᮶࠿ࡽ⏝࠸࡚࠸ࡿ NWChem ࢆ⏝࠸ࠊQM ィ⟬ࢆᐇ⾜ࡋࡓࠋᵓ㐀᭱㐺໬ࡢᡭἲ࡟ࡣ UB3LYP
࡟ Grimme ࡢ D3 ࢱ࢖ࣉࡢศᩓ⿵ṇࢆຍ࠼ࡓࡶࡢࢆ⏝࠸ࠊᇶᗏ㛵ᩘ࡟ࡣ Mn ࡜ Ca ཎᏊ࡟ LanL2TZ(f)ࠊṧࡾࡢ
ཎᏊ࡟ 6-311+G**ࢆ⏝࠸ࡓ(⣙ 1300 ᇶᗏ)ࠋࡲࡓ⎔ቃຠᯝ࡜ࡋ࡚ 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=7)࡛ᇶᗏ㛵ᩘ࡟ࡣ
Def2-TZVP ࢆ⏝࠸࡚ィ⟬ࢆ⾜࠸(⣙ 2000 ᇶᗏ)ࠊ⎔ቃຠᯝ࡟ࡣ COSMO ࡲࡓࡣ CPCM ࢆ⏝࠸ࡓࠋHDFT ࡟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౯ࡋࡓࠋDFT ࡢィ⟬࡟ࡣ NWChem ࢆ⏝࠸ࠊ(D)LPNO-CC ἲ࡟ࡣ ORCA4
ࡢࣉࣟࢢ࣒ࣛࢆ OpenMPI3 ࡛୪ิฎ⌮ࡉࡏࡿࡼ࠺࡟ࡋ࡚౑⏝ࡋࡓࠋDLPNO-CC ィ⟬࡟ࡣከᩘࡢ࣓ࣔࣜ࡜ࢫࢡ
ࣛࢵࢳࣇ࢓࢖ࣝࡢ㧗㏿࡞ㄞࡳ᭩ࡁࡀᚲせ࡜࡞ࡿࡓࡵࠊ኱ᐜ㔞ࡢ࣓ࣔࣜࢆ✚ࢇࡔ 110Rh-1 ࡢ౑⏝࡟ࡼࡾ㧗㏿࡞ィ⟬ࡀྍ⬟࡛࠶ࡗࡓࠋᅗ2(ᕥ) 㧗ゎീᗘ࠿ࡽᚓࡽࢀࡓ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࠊ(ྑ) (A)PSII ࡢ OEC ࡢ S1 ≧ែࡢάᛶࢧ࢖ࢺࡢィ⟬ࣔࢹࣝࠊ(B)ྑഃࡢ✵࠸ࡓ S1 ᵓ㐀ࡢࣔࢹࣝࠊ(C)ᕥഃࡢ✵࠸ࡓ S1 ᵓ㐀ࡢࣔࢹࣝ3◊✲ᡂᯝ࣐ࣥ࢞ࣥࡢ㓟໬≧ែࡣ High-valent ࡞㓟໬≧ែࢆ௬ᐃࡋࠊ(III, III, IV, IV)ࡢࡶࡢ࡛࠶ࡿ࡜ࡋࡓࠋS1 ≧ែࡢᵓ㐀㛫ࡢ࢚ࢿࣝࢠ࣮ࡢẚ㍑ࢆ⾜࠺๓࡟⌮ㄽⓗ࡟ྍ⬟࡞ 6 ✀㢮ࡢ୰㛫యࢆồࡵࡓࠋᅗ 3 ࡟ᚓࡽࢀࡓᵓ㐀࡟ࡘ࠸࡚ᅗ
♧ࡋࡓࠋᅗ 3 ࡢ(A)ࠊ(C)ࠊ(E)ࡣ(Mn1, Mn2, Mn3, Mn4)= (III, IV, IV, III)ࡢࣂࣞࣥࢫࢆᣢࡘࡶࡢࠊ(B)ࠊ(D)ࠊ(F)ࡣ(Mn1,
Mn2, Mn3, Mn4)= (III, III, IV, IV)ࡢࣂࣞࣥࢫࡢࡶࡢ࡛࠶ࡿࠋࡇࡇ࡛ࠊO(5)=XࠊW2=YࠊW1=ZࠊO(4)=W ࡢࣉࣟࢺ- 150 -

ࣥ໬≧ែࢆ O2–=aࠊOH–=bࠊH2O=c ࡜グࡋ࡚ࠊྛ≧ែࢆ S1XYZW ࡜ࡍࡿ(ᅗ 2 ཧ↷)ࠋᅗ 3 ࡼࡾࠊS1acca(3443)ࡢᵓ
㐀ࡣ▮㔝ࡽࡢ EXAFS ࡢ⤖ᯝ࡜ᑐᛂࡍࡿࡶࡢ࡛࠶ࡿ࡜⌮ゎࡉࢀࡿࠋࡲࡓ S1bbca(3443)ࡢᵓ㐀ࡣ 2015 ᖺࡢⳢࡽࡢ
XEFL ࡢᵓ㐀࡟ᑐᛂࡋࠊ୍᪉ S1bbca(3343)ࡢᵓ㐀ࡣ Loll ࡽࡢ XRD ࡢᵓ㐀࡟㏆࠸ࡶࡢ࡛࠶ࡿ࡜⌮ゎࡉࢀࡿࠋࡲࡓࠊ
S1abcb(3443)ࡢᵓ㐀ࡣᩧ⸨ࡽ࡟ࡼࡿ QM/MM ࡟ࡼࡿ S0 ≧ែࡢᵓ㐀࡟㏆࠸ࡶࡢ࡜⌮ゎࡉࢀࡿࠋࡇࢀࡽࡢᵓ㐀࡟ࡘ࠸࡚┦ᑐ࢚ࢿࣝࢠ࣮ࢆ᳨ウࡋ࡚࠸ࡃࠋ
ᅗ 4 ࡣ S1bbca(3443)ࡢ࢚ࢿࣝࢠ࣮ࢆᇶ‽࡜ࡋ࡚ HDFTࠊB2PLYPࠊDLPNO-CCSDࠊDLPNO-CCSD(T0)ࡢᡭἲ࡟ࡼࡾẚ㍑ࡋࡓࡶࡢ࡛࠶ࡿࠋHDFT ࡢ⤖ᯝ࡛ࡣ S1bbca(3443)
࡜ S1bbca(3443)࡜ࡀ࢚ࢿࣝࢠ࣮ⓗ࡟㏆ࡋࡃ⦰㏥ࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀ࡚࠸ࡿࠋ୍᪉࡛ DLPNO-CCSD(T0)࡟ࡼࡿ
⤖ᯝ࡛ࡣࠊHDFT ࡢሙྜ࡜␗࡞ࡾࠊ(3443)ࡢࣂࣞࣥࢫࢆᣢࡘ S1accaࠊS1bbca ࡑࡋ࡚ S1abcb ࡀ࢚ࢿࣝࢠ࣮ⓗ࡟⦰㏥ࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢ⤖ᯝ࠿ࡽ DLPNO-CC ἲ࡛♧ࡉࢀ࡚࠸ࡿ 3 ࡘࡢ୰㛫యࡢᑠࡉ࡞࢚ࢿࣝࢠ࣮ᕪࡣ
CaMn4O5 ࢡࣛࢫࢱ࣮ࡢᵓ㐀ⓗ࠿ࡘ㟁Ꮚⓗ࡞ᰂ㌾ᛶࢆ♧၀ࡋ࡚࠾ࡾࠊS1 ≧ែࡢ PSII ࡢ OEC ࡢ⺮ⓑ㉁ࡢ⎔ቃ࡟ࡼࡾࡑࡢᰂ㌾ᛶࡀࢥࣥࢺ࣮ࣟࣝࡉࢀࡿྍ⬟ᛶࡶ⪃࠼ࡽࢀࡿࠋ

ᅗ3

S1 ≧ែ࡛ࡢ UB3LYP-D3/LanL2TZ(f)࡟ࡼࡿྍ⬟࡞୰㛫యࡢ᭱㐺໬ᵓ㐀ᚓࡽࢀࡓᵓ㐀࡜࢚ࢿࣝࢠ࣮ࡢ㛵ಀ࠿ࡽ S1 ≧ែࡢ୰㛫యࣔࢹࣝ࡟ࡘ࠸࡚⪃࠼ࡿ࡜ࠊ༢୍ࣔࢹࣝࡢሙྜࠊ᭱㐺໬ࡋࡓᵓ㐀ࡢ࡜ࡇࢁ࡛㆟ㄽࡋࡓࡼ࠺࡟ࠊ᭱㐺໬ࡋࡓᵓ㐀࡜ᐇ㦂ᵓ㐀࡜ࡢᑐᛂ࠿ࡽ⌮ゎࡉࢀࡿࡀ᭱㐺໬ࡋࡓᵓ㐀඲యࡀᐇ㦂⤖ᯝ࡜୍⮴ࡍࡿࡶࡢ࡛ࡣ࡞࠸ࠋ୍᪉ࠊከ㔜ࣔࢹࣝࢆ⪃࠼ࡓሙྜࠊ≉࡟ DLPNO-CCSD(T)ἲ࡟ࡼ
ࡾ࢚ࢿࣝࢠ࣮ⓗ࡟⦰㏥ࡋ࡚࠸ࡿࡢ(3443)ࡢࣂࣞࣥࢫࢆᣢࡘ S1accaࠊS1bbcaࠊS1abcb ࡟㛵ࡋ࡚ࡑࢀࡒࢀࡢᵓ㐀࡟㛵ࡋ
࡚ 0 ࠿ࡽ 1 ࡢ㛫ࡢᩘ್࡛㔜ࡳࢆࡘࡅ࡚ΰྜࡍࡿࡇ࡜࡛ࠊXFEL ࡸ௚ࡢᐇ㦂⤖ᯝࢆ⌮ゎ࡛ࡁࡿ⤖ᯝࡀᚓࡽࢀࡓ[7,8]ࠋᚑࡗ࡚ࠊS1 ≧ែࡢ DLPNO-CCSD(T0)࡟ࡼࡾ࢚ࢿࣝࢠ࣮ⓗ࡟⦰㏥ࡋ࡚࠸ࡿ࡜ᚓࡽࢀࡓ 3 ࡘࡢᵓ㐀࡟㛵ࡋ࡚ࡢືⓗ࡞ᖹ⾮ࣔࢹࣝࡀᐇ㦂⤖ᯝࡢྜ⌮ⓗ࡞ㄝ᫂ࢆ୚࠼ࡿࡶࡢ࡛࠶ࡗࡓࠋ
ࡋ࠿ࡋ࡞ࡀࡽࠊEPR ࡢᐇ㦂࡛♧ࡉࢀ࡚࠸ࡿࡼ࠺࡟ S1 ≧ែ࡛ࡣ୍㔜㡯(S=0)࡜⇕ⓗ࡟ບ㉳ࡉࢀࡓ୕㔜㡯(S=1)≧ែ࡜ࡀᏑᅾࡍࡿࠋࡇࢀࡽࡢ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢపࢫࣆࣥ࡜୰㛫ࢫࣆࣥ≧ែࡢᏳᐃᛶࢆヲ⣽࡟㆟ㄽࡍࡿࡓࡵ࡟ࡣࠊከཧ↷(MR) ࡢᡭἲ࡛࠶ࡿ MRCC ἲ(DLPNO-MkCC ἲ➼)ࡸ᏶඲άᛶ✵㛫(CAS) ἲ࡟ᇶ࡙࠸ࡓDMRG-NEVPT2 ἲ࡞࡝ࡀᚲせ࡜࡞ࡿࠋࡇࢀࡽࡢᡭἲࢆ⏝࠸ࡓヲ⣽࡞ゎᯒࢆ௒ᚋࡢㄢ㢟࡜ࡋࡓ࠸ࠋࡲࡓࠊ௒ᅇ

- 151 -

ࡢィ⟬⣔ࡣࠊS1 ≧ែࡢ⌮ㄽⓗ࡟⪃࠼ࡽࢀࡿᵓ㐀␗ᛶయ㛫ࡢ࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡍࡿࡓࡵ࡟ࠊCaMn4O5 ࢡࣛࢫࢱ࣮ࡢ㔠ᒓཎᏊ࡟㓄఩ࡍࡿṧᇶࢆ᭱ᑠ㝈࡟ྲྀࡾධࢀࡓࡶࡢ࡛࠶ࡗࡓࡓࡵࠊỈ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࢆ⪃៖ࡋࡓ኱ࡁ࡞⣔࡟ᑐࡍࡿ CC ἲࢆ⏝࠸࡚཯ᛂ㐣⛬ࡢゎᯒࢆ㐍ࡵ࡚࠸ࡁࡓ࠸ࠋ

ᅗ4

PSII ࡢ OEC ࡢ CaMn4O5 ࢡࣛࢫࢱ࣮ࡢ 6 ࡘࡢ␗࡞ࡿ S1 ࡢᵓ㐀࡟ᑐࡍࡿ HDFT ࡜ post DFTࡢィ⟬࡟ࡼࡿ┦ᑐ࢚ࢿࣝࢠ࣮ཧ⪃ᩥ⊩[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., PNAS, 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⦼ࡲࡓࡣணᐃ
T. Kawakami, K. Miyagawa, Y. Suzuki, H. Isobe, M. Shoji, S. Yamanaka, M. Okumura, K. Nakatani, T. Nakajima

and K. Yamaguchi, Domain-based local pair natural orbital CCSD(T) calculations of all different S2 structures ofoxygen evolving complex of photosystem II, 9th MQM (Molecular Quantum Mechanics conference), 2019.6.30-7.5,
Heidelberg, Germany (Poster).
K. Yamaguchi, K. Miyagawa, T. Kawakami, H. Isobe, M. Shoji and T. Nakajima, DLPNO-CCSD(T) calculation for
CaMn4O5 clusters in oxygen evolving complex of photosystem II, 9th MQM (Molecular Quantum Mechanics- 152 -

conference), 2019.6.30-7.5, Heidelberg, Germany (Poster).
ᕝୖ㈗㈨, ᐑᕝ᫭୍, 㕥ᮌ㞝ኴ, ☾㒊 ᐶ, ᗉྖග⏨, ᒣ୰⚽௓, ዟᮧග㝯, ୰ᔱ㝯ே, ᒣཱྀ඙, ගྜᡂ㓟⣲Ⓨ⏕㘒య(CaMn4O5 ࢡࣛࢫࢱ)ࡢ S1 ≧ែ࡛ࡢྛᵓ㐀࡜㟁Ꮚ≧ែࡢ LPNO-CC ἲ࡟ࡼࡿゎᯒ, ➨ 13 ᅇ ศᏊ⛉Ꮫウㄽ఍, 2019.9.17-9.20, ྡྂᒇ኱Ꮫᮾᒣ࢟ࣕࣥࣃࢫ, ྡྂᒇ (Poster).
Koichi Miyagawa, Takashi Kawakami, Hiroshi Isobe, Mitsuo Shoji, Shusuke Yamanaka, Kazuhiko Nakatani,
Mitsutaka Okumura, Takahito Nakajima, Kizashi Yamaguchi, DFT and DLPNO-CC calculation of the geometricalstructures and electronic states of the S2 state in the Kok cycle of the CaMn 4O5 cluster of the OEC of the PSII, 㘒య໬Ꮫ఍➨ 69 ᅇウㄽ఍, 2019.9.21-9.23, ྡྂᒇ኱Ꮫᮾᒣ࢟ࣕࣥࣃࢫ, ྡྂᒇ (Oral).
Koichi Miyagawa, Takashi Kawakami, Hiroshi Isobe, Mitsuo Shoji, Shusuke Yamanaka,Kazuhiko Nakatani,
Mitsutaka Okumura, Takahito Nakajima and Kizashi Yamaguchi, ගྜᡂ⣔ II ࡢ㓟⣲Ⓨ⏕୰ᚰࡢ S1 ≧ែ࡛ࡢ 12 ࡢᵓ㐀ࣔࢹࣝࡢ DLPNO-CCSD(T)ἲ࡟ࡼࡿィ⟬ DLPNO-CCSD(T) calculations of twelve structural models for the S1state of oxygen evolving complex of photosystem II, ⏕≀≀⌮Ꮫ఍➨ 57 ᅇᖺ఍, 2019.9.24-9.26, ᐑᓮࢩ࣮࢞࢖࢔,ᐑᓮ (Poster).
Mitsuo Shoji, Koichi Miyagawa, Hiroshi Isobe, Yasuteru Shigeta and Kizashi Yamaguchi, Role of Valine 185 in the
Oxygen-Evolving Complex of Photosystem II Revealed by QM/MM Calculations, ISF-3 Yong, 2019.11.19-11.20, JMS
Aster Plaza, Hiroshima (Poster).
Koichi Miyagawa, Takashi Kawakami, Hiroshi Isobe, Mitsuo Shoji, Kazuhiko Nakatani and Kizashi Yamaguchi,
Domain-Based Local Pair Natural Orbital Coupled Cluster Calculation for Ten Different S0 State Structures of the
Oxygen Evolving Complex of Photosystem II: Possibility of Valence Fluctuation, ISF-3 Yong, 2019.11.19-11.20, JMS
Aster Plaza, Hiroshima (Poster).
Takashi Kawakami, Koichi Miyagawa, Hiroshi Isobe, Mitsuo Shoji, Shusuke Yamanaka, Mitsutaka Okumura,
Takahito Nakajima and Kizashi Yamaguchi, Theoretical Evaluation of Relative Energy Difference between Fourteen
Different S2 Intermediates by High Accuracy DLPNO-CCSD(T) Methods, ISF-3/ICARP2019, 2019.11.20-11.24,
Hiroshima Convention Hall, Hiroshima (Poster).
Koichi Miyagawa, Takashi Kawakami, Hiroshi Isobe, Mitsuo Shoji, Shusuke Yamanaka, Kazuhiko Nakatani,
Mitsutaka Okumura, Takahito Nakajima and Kizashi Yamaguchi, Domain-Based Local Pair Natural Orbital Coupled
Cluster Calculation for Twelve Different S1 State Structures of The Oxygen Evolving Complex of Photosystem II,
ISF-3/ICARP2019, 2019.11.20-11.24, Hiroshima Convention Hall, Hiroshima (Poster).
Kizashi Yamaguchi, Takashi Kawakami, Koichi Miyagawa, Hiroshi Isobe, Mitsuo Shoji, Shusuke Yamanaka,
Mitsutaka Okumura and Takahito Nakajima, Theoretical Elucidation of Relative Energy Difference among Different S3Intermediates by Hybrid DFT and DLPNO-CCSD(T) Methods, ISF-3/ICARP2019, 2019.11.20-11.24, Hiroshima
Convention Hall, Hiroshima (Poster).
Hiroshi Isobe, Mitsuo Shoji, Takayoshi Suzuki, Jian-Ren Shen and Kizashi Yamaguchi, Theoretical Analysis of theElectronic and Spin Structures of the Oxygen-Evolving Complex, ISF-3/ICARP2019, 2019.11.20-11.24, Hiroshima
Convention Hall, Hiroshima (Oral).
Mitsuo Shoji, Koichi Miyagawa, Hiroshi Isobe, Yasuteru Shigeta and Kizashi Yamaguchi, Elucidation of the Entire
Kok Cycle of the Photosynthetic Water Oxydation Using QM/MM Calculations, ISF-3/ICARP2019, 2019.11.20-11.24,
Hiroshima Convention Hall, Hiroshima (Oral).
Takashi Kawakami, Koichi Miyagawa, Hiroshi Isobe, Mitsuo Shoji, Shusuke Yamanaka, Mitsutaka Okumura,- 153 -

Takahito Nakajima and Kizashi Yamaguchi, Electronic structures of CaMn4O5 cluster in oxygen evolving complex ofphotosystem II. Theoretical calculations by LPNO-CC methods in the S2 state of the Kok cycle, 60th Sanibel
Symposium, 2020.2.16-2.21, St. Simons Island, Goergia (Poster).

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫[ۻ‬6] M. Shoji, H. Isobe, J.-R. Shen, M. Suga, F. Akita, K. Miyagawa, Y. Shigeta and K. Yamaguchi, Elucidation of

the entire Kok cycle for photosynthetic water oxidation by the large-scale quantum mechanics/molecular mechanics
calculations: Comparison with the experimental results by the recent serial femtosecond crystallography, Chem. Phys.
Lett. 730, 416-425 (2019). DOI: 10.1016/j.cplett.2019.06.026.
‫[ۻ‬7] K. Miyagawa, T. Kawakami, Y. Suzuki, H. Isobe, M. Shoji, S. Yamanaka, M. Okumura, T. Nakajima, K.
Yamaguchi, 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 state of photosystem II, Mol. Phys.,1666171 (2019).
‫[ۻ‬8] K. Miyagawa, T. Kawakami, H. Isobe, M. Shoji, S. Yamanaka, K. Nakatani, M. Okumura, T. Nakajima, K.
Yamaguchi, Domain-based local pair natural orbital CCSD(T) calculations of six different S1 structures of oxygen
evolving complex of photosystem II. Proposal of multi-intermediate models for the S1 state, Chem. Phys. Lett., 732,
136660 (2019).
‫[ۻ‬9] K. Miyagawa, H. Isobe, T. Kawakami, M. Shoji, S. Yamanaka, M. Okumura, T. Nakajima, K. Yamaguchi,
Domain-based local pair natural orbital CCSD(T) calculations of fourteen different S2 intermediates for water oxidationin the Kok cycle of OEC of PSII. Re-visit to one LS-two HS model for the S2 state, Chem. Phys. Lett., 734, 136731(2019).
‫[ۻ‬10] K. Miyagawa, M. Shoji, H. Isobe, S. Yamanaka, T. Kawakami, M. Okumura and K. Yamaguchi, UNO(ULO)
active space for multireference calculations on classical and quantum computers. Revisit to the iron-sulfur complexes,
Chem. Phys. Lett. 746, 137252 (2020). DOI: 10.1016/j.cplett.2020.137252[11] K. Yamaguchi, S. Yamanaka, H. Isobe, M. Shoji, K. Miyagawa, T. Nakajima, T. Kawakami, M. Okumura,
Theoretical and computational investigations of geometrical, electronic and spin structures of the CaMn4OX (X=5, 6)
cluster in the Kok cycle Si (i=0-3) of oxygen evolving complex of photosystem II, Physiol. Plant., 166, 44-59 (2019).
[12] M. Suga, F. Akita, K. Yamashita, Y. Nakajima, G. Ueno, H. Li, T. Yamane, K. Hirata, Y. Umena, S. Yonekura,
L.-J. Yu, H. Murakami, T. Nomura, T. Kimura, M. Kubo, S. Baba, T. Kumasaka, K. Tono, M. Yabashi, H. Isobe, K.
Yamaguchi, M. Yamamoto, H. Ago and J.-R. Shen, An oxyl/oxo mechanism for oxygen-oxygen coupling in PSII
revealed by an x-ray free-electron laser, Science, 366, 334-338 (2019). DOI: 10.1126/science.aax6998.

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㠀ᖹ㠃ᆺࣃ࢖ඹᙺศᏊࡢᵓ㐀࡜≀ᛶStructure and Properties of non-planar S-conjugated molecules‫ۑ‬ὠ␃㷂 㝧኱㸦኱㜰ᗓ❧኱Ꮫ኱Ꮫ㝔⌮Ꮫ⣔◊✲⛉㸧1◊✲┠ⓗࠊෆᐜ
ࡽࡏࢇ୙ᩧࢆ᭷ࡍࡿ࣊ࣜࢭࣥࡣࠊ㠀ᖹ㠃ᆺከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲(PAH)ࡢ୍ࡘ࡛࠶ࡾࠊࡑࡢග
Ꮫⓗ࣭㟁Ẽⓗ≉ᛶࢆ཯ᫎࡋࡓᶵ⬟ᛶศᏊ࡬ࡢᛂ
⏝ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋࡈࡃ᭱㏆ࠊ࣊ࣜࢭࣥㄏᑟ
య 2 ࠿ࡽⓎ⏕ࡉࡏࡓ࣊ࣜࢭࢽࣝ࢔ࣛ࢖ࣥ࡜࢔
ࣝ࢟ࣥ 3a ࡜ࡢ஺ᕪ୕㔞໬཯ᛂ࡟ࡼࡾࠊศᏊෆ࡟  ࡘࡢ>@࣊ࣜࢭࣥ㒊఩ࢆ᭷ࡍࡿ୕㔜࣊ࣜࢭࣥ TH-1a ࡀᚓࡽࢀࡿࡇ࡜ࢆぢฟࡋࡓࠋࡉࡽ࡟ࠊ࢟ࣛࣝ㓄఩Ꮚ࡛࠶ࡿ 6 48,1$3 ࢆ⏝࠸ࡿ࡜ࠊ᭱㧗 HH ࡛ 030 యࡀᚓࡽࢀ
ࡓ 6FKHPH  ࠋࡇࡢ⏕ᡂ≀࡟࠾࠸࡚ࠊฟⓎᇶ㉁⏤᮶ࡢ>@࣊ࣜࢭࣥ㒊఩ࡣࡍ࡭࡚ 0 య࡬࡜ኚ᥮ࡉࢀ࡚࠸ࡿࡇ࡜
࠿ࡽࠊ㏿ᗘㄽⓗගᏛศ๭ .5 ࡶࡋࡃࡣືⓗ㏿ᗘㄽⓗගᏛศ๭ '.5 ࡟ࡼࡾ࢚ࢼࣥࢳ࢜㑅ᢥᛶࡀⓎ⌧ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋᐇ㦂⤖ᯝࡢࡳ࡛ࡣ࡝ࡕࡽ࡛࠶ࡿ࠿ࢆ᫂
☜࡟⤖ㄽ௜ࡅࡽࢀ࡞࠿ࡗࡓࡇ࡜࠿ࡽࠊィ⟬໬Ꮫࡢᡭἲ
ࢆ⏝࠸ࡓゎ᫂ࢆ᳨ウࡋࡓࠋࡲࡓࠊ'.5 ࡛࠶ࡿሙྜ࡟ࡣࠊ
࡝ࡢẁ㝵࡛>@࣊ࣜࢭࣥ㒊఩ࡢ཯㌿ࡀ⏕ࡌ࡚࠸ࡿ࠿ࠊࡉ
ࡽ࡟ᚓࡽࢀࡓ཯㌿㞀ቨࡀᐇ㦂᮲௳ᗘ ୗ࡛㐺ษ࡛࠶

ࡿ࠿ࡶ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡶ┠ᣦࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ*DXVVLDQ  ࠾ࡼࡧ *550 ࢆ฼⏝ࡋࡓࠋZ%;'* G ࣞ࣋ࣝࢆᇶᗏ㛵ᩘ࡜ࡋ࡚ࠊᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋࡲࡓࠊྛ཯ᛂ࡟࠾ࡅࡿ㑄⛣≧ែࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
ᚓࡽࢀࡓᵓ㐀࡟ࡘ࠸࡚ࡣࠊ᣺ືᩘィ⟬ࢆ⾜࠺ࡇ࡜࡛ࠊ
Ᏻᐃᵓ㐀ࡶࡋࡃࡣ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋࡲ
ࡓࠊ㑄⛣≧ែ࡟ࡘ࠸࡚ࡣ ,5& ィ⟬ࡶ⾜࠺ࡇ࡜࡛ࠊ஧ࡘ
ࡢᏳᐃᵓ㐀ࢆࡘ࡞ࡄ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࡶ☜ㄆࡋࡓࠋ

3◊✲ᡂᯝ᪤▱ࡢ཯ᛂᶵᵓࢆཧ⪃࡟ࡋ࡚(Figure 1)ࠊ᝿ᐃࡉࢀࡿ

୰㛫య࡛࠶ࡿ஬ဨ⎔ࣃࣛࢲࢧ࢖ࢡࣝ 5 ࡜ 6ࠊ࠾ࡼࡧ୐
ဨ⎔ࣃࣛࢲࢧ࢖ࢡࣝ 7 ࡢᵓ㐀᭱㐺໬ࢆᐇ᪋ࡋࡓ࡜ࡇࢁ
❧య␗ᛶయࡣࡑࢀࡒࢀࠊ8 ✀㢮ࠊ4 ✀㢮ࠊ20 ✀㢮Ꮡᅾ)ࠊ
(M,P,M)-5a, (P)-6b, (M,P,M)-7a ࡀࠊ᭱Ᏻᐃࡢ␗ᛶయ࡛࠶
ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋḟ࡟ࠊ࣊ࣜࢭࢽࣝ࢔ࣛ࢖ࣥ 4 ࠾ࡼ- 155 -

ࡧ࢔ࣝ࢟ࣥ 3a ࡀ  ศᏊ௜ຍࡋࡓࣃࣛࢪ࣒࢘㘒య 8 ࠾ࡼࡧ 9 ࠿ࡽ஬ဨ⎔ࣃࣛࢲࢧ࢖ࢡࣝ 5 ࡜ 6 ࡀᚓࡽࢀࡿ⤒㊰ࢆ᥈⣴ࡋࡓ࡜ࡇࢁ
(Figure 2)ࠊ࣊ࣜࢭࢽࣝ࢔ࣛ࢖ࣥࡀ஧ศᏊ௜ຍࡋࡓ 5a ࢆ୚࠼ࡿάᛶ
໬㞀ቨ(7.4 NFDOPROí)ࡢ࡯࠺ࡀࠊ6c ࢆ୚࠼ࡿሙྜ(15.6 NFDOPROí)ࡼ
ࡾࡶ༑ศ࡟ప࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓࠊ࢔ࣝ࢟ࣥ௜ຍయ 9 ࠿ࡽฟⓎࡋࡓሙྜ࡟࠾࠸࡚ࡶࠊ࢔ࣝ࢟ࣥ 3a ࡢ⬺㞳ࢆ⤒⏤ࡋ࡚ 9ĺ11 ĺ8)ࠊ5a ࡟⮳ࡿࡇ࡜ࡶศ࠿ࡗࡓࠋ
⥆࠸࡚ࠊ5a ࡟࠾ࡅࡿ[5]࣊ࣜࢭࣥ㒊఩ࡢ཯㌿ᣲື࡟ࡘ࠸᳨࡚ウࡋࡓ(Figure 3)ࠋ୧➃ࡢ[5]࣊ࣜࢭࣥ㒊఩ࡢ࢟ࣛࣜࢸ࢕࣮ࡀ␗࡞ࡿ 4 ࡘࡢ␗ᛶయ(PMM, MMP, PPM, MPP)࠿ࡽࠊ᭱Ᏻᐃ␗ᛶయ(MPM)࡟⮳ࡿάᛶ໬㞀ቨࡣ 22.8
ࡶࡋࡃࡣ 24.1 NFDOPROí ࡛࠶ࡾࠊྠࡌ࡛ࣞ࣋ࣝィ⟬ࡋࡓ[5]࣊ࣜࢭࣥࡢ್(25.7 NFDOPROí)ࡼࡾప࠸ࡇ࡜ࡀศ࠿ࡗ
ࡓࠋࡋࡓࡀࡗ࡚ࠊࡇࡢẁ㝵࡛[5]࣊ࣜࢭࣥ㒊఩ࡢ཯㌿ࡀ㐍⾜ࡋࡓࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡉ ࡽ ࡟ ࠊ (M,P,M)-5a ࠿ ࡽ ୐ ဨ ⎔ ࣃ ࣛ ࢲ ࢧ ࢖ ࢡ ࣝ(M,P,M)-7a ࡢᙧᡂࠊ⥆ࡃ㑏ඖⓗ⬺㞳࡟ࡼࡿ(M,P,M)-
TH-1a ࡢ⏕ᡂ࡟ᑐࡍࡿ཯ᛂ⤒㊰ࡶ᫂ࡽ࠿࡟ࡋࡓࠋ࢔ࣝ
࢟ࣥ 3a ࡢᤄධ࡟ࡼࡿ୐ဨ⎔ࣃࣛࢲࢧ࢖ࢡࣝᙧᡂࡢά
ᛶ໬㞀ቨࡀ⣔඲య࡛᭱ࡶ㧗ࡃ(25.4 NFDO PROí)ࠊࡇࡢẁ㝵ࡀ஺ᕪ୕㔞໬཯ᛂࡢᚊ㏿ẁ㝵࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

4ฟ∧ᐇ⦼‫ ۻ‬$<XEXWD7+RVRNDZD0*RQ.7DQDND<&KXMR$7VXUXVDNL..DPLNDZD³(QDQWLRVHOHFWLYH6\QWKHVLVRI7ULSOH+HOLFHQHVE\&URVV&\FORWULPHUL]DWLRQRID+HOLFHQ\O$U\QHDQG$ON\QHVYLD'\QDPLF.LQHWLF5HVROXWLRQ´-
$P&KHP6RFLQSUHVV '2, MDFVF ‫ ۻ‬$7VXUXVDNL58UD..DPLNDZD³*ROG , &RPSOH[ZLWK¶%LQDSKWK\O6XEVWLWXWHG'LSKRVSKHQH6\QWKHVLV6WUXFWXUHDQG&DWDO\WLF$SSOLFDWLRQWR,QWUDPROHFXODU+\GURDU\ODWLRQ5HDFWLRQ´2UJDQRPHWDOOLFV2020 - 156 -

ࢼࣀ࣮࣭࢝࣎ࣥ࢔࣑ࣀ㓟࣭ࢡࣛࢫࢱ࣮ࡢ཯ᛂືຊᏛࡢ㔞Ꮚ໬Ꮫⓗ◊✲Quantum Chemical Study on Reaction Dynamics of Nanocarbons,
Animo Acids and Clusters‫ۑ‬ᒣ໭ ెᏹࠊ㧗ᶫ ᾴࠊὸぢ 㝣ࠊ∦ᒸ ❳㤿ࠊᒣཱྀ ៞࿃㸦㟁㏻኱㝔᝟ሗ⌮ᕤ㸧1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࡢ┠ⓗࡣࠊḟࡢ㔞Ꮚ໬Ꮫⓗ◊✲࡛࠶ࡿࠋձከ⎔ⰾ㤶᪘Ⅳ໬Ỉ⣲㸦PAH㸧ࡢ He*(23S)࡜ࡢ 3 ḟඖ┦஫స⏝࣏ࢸࣥࢩࣕࣝ࠾ࡼࡧ࢖࢜ࣥ໬࢚ࢿࣝ
ࢠ࣮ࠊղศᏊෆᅇ㌿ࢆ᭷ࡍࡿ࢔࣑ࣀ㓟ࡸ࣋ࣥࢮࣥㄏᑟయࡢศᏊෆᅇ㌿࣏ࢸࣥࢩࣕࣝࠊճࣛࣥࢱࣀ࢖ࢻࡸ㑄⛣㔠ᒓ࡟ศᏊࡀ྾╔ࡋࡓࢡࣛࢫࢱ࣮ࡢᏳᐃᵓ㐀ࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲձ࡟ࡘ࠸࡚ࠊࢼࣇࢱࣞࣥ࡞࡝ࡢ PAH ࡟㛵ࡋ࡚➼౯እẆ࡛࠶ࡿ Li ࢆ⏝࠸࡚ࠊ┦஫స⏝࢚ࢿࣝࢠ࣮ࢆ MP2 ࡛ࣞ࣋ࣝ Counterpoise ἲࢆ౑ࡗ࡚ィ⟬ࡋࠊ࢖࢜ࣥ
໬࢚ࢿࣝࢠ࣮ࢆ OVGF ἲ࡛ィ⟬ࡋࡓࠋղ࡟ࡘ࠸࡚ࡣࠊࣇ࢙ࢽࣝ࢔ࣛࢽࣥࠊࢳ
ࣟࢩࣥࠊࢫࣞ࢜ࢽࣥ࡟ࡘ࠸࡚ࠊGRRM ἲࢆ⏝࠸࡚ᅇ㌿␗ᛶయ᥈⣴ࢆ⾜ࡗࡓࠋศᏊෆᅇ㌿࢚ࢿࣝࢠ࣮㞀ቨ࡟ࡘ࠸࡚ࡣࠊMolpro ࡛㟁Ꮚ┦㛵ࢆ⪃៖ࡋ CASSCF
࡜ NBO ࡢィ⟬ࢆ⾜ࡗࡓࠋճ࡟ࡘ࠸࡚ࡣࠊLa+࡟࢔ࢭࢺࣥࡀ 2㹼3 ศᏊ㓄఩ࡋࡓࢡࣛࢫࢱ࣮࢖࢜ࣥࡢ཯ᛂ⤒㊰᥈⣴ࢆ GRRM ࣉࣟࢢ࣒࡛ࣛ⾜ࡗࡓࠋ3◊✲ᡂᯝձ࡟ࡘ࠸࡚ࠊ࢔ࣥࢺࣛࢭࣥࡢ He*(23S)⾪✺࡟ࡼࡿ࣌ࢽࣥࢢ࢖࢜ࣥ໬཯ᛂ࡟

ࡘ࠸࡚ࠊ⾪✺࢚ࢿࣝࢠ࣮ศゎࡋࡓ཯ᛂ㐣⛬ࢆࢺࣛࢪ࢙ࢡࢺࣜィ⟬࡛᫂ࡽ࠿࡟
ࡋࡓ㸦ᅗ㸯㸧ࠋղ࡛ࡣࠊ࢔࣑ࣀ㓟ࡢ࣌ࢽࣥࢢ㟁Ꮚࢫ࣌ࢡࢺࣝ࡟⌧ࢀࡿ␗ᛶయ
⏤᮶ࡢࣂࣥࢻࢆᖐᒓࡋࠊ࢚ࣥࢺࣟࣆ࣮ࡢᐤ୚ࡀ㔜せ࡛࠶ࡿࡇ࡜ࢆ♧ࡋࠊ࢝ࣝࢥࢤࣀ࢔ࢽࢯ࣮ࣝࡢศᏊෆᅇ㌿࡟క࠺ n-S࠾ࡼࡧV-SᏳᐃ໬ᶵᵓࢆゎ᫂ࡋࡓࠋճ࡟࠾࠸࡚ࠊࣛࣥࢱࣀ࢖ࢻ࢖࢜ࣥ࡟ゐ፹ࡉࢀࡓ࢔ࣝࢻ࣮ࣝ཯ᛂ⤒㊰ࢆィ⟬ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ

4

ᅗ 1 He*(23S)࡟ࡼࡿࢼࣇࢱ
ࣞࣥࡢ࣌ࢽࣥࢢ࢖࢜ࣥ໬ࡢ
࢜ࣃࢩࢸ࢕㛵ᩘⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] ᒣཱྀ㸪ᒣ໭㸪኱㔝㸪᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍ (2019)㸪2E2-02㸬‫[ۻ‬2] 㧗ᶫ㸪ᒣ໭㸪➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ 2019 ྡྂᒇ㸪2P094㸬‫[ۻ‬3] ᒣ໭㸪⏥ᩫ㸪➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ 2019 ྡྂᒇ㸪1A04㸬[4] Y. Yamakita,
N. Yokoyama, B. Xue, N. Shiokawa, Y. Harabuchi, S. Maeda, T. Kobayashi, FEMTO14, 21㸬5ฟ∧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, in press. ‫[ۻ‬2] Y. Ishiguro, Y. Yamakita, and N. Hayashi, Chem. Phys. Lett., in press. ‫[ۻ‬3] Y.
Yamakita and N. Kai, Mol. Phys. 117, 3184 (2019). 10.1080/00268976.2019.1642525 [4] Y. Yamakita, N. Yokoyama, B.
Xue, N. Shiokawa, Y. Harabuchi, S. Maeda, and T. Kobayashi, Phys. Chem. Chem. Phys. 21(10), 5344-5358 (2019).
10.1039/C8CP06405A (2018 PCCP HOT Articles).

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ࢡࣛ࢘ࢹ࢕ࣥࢢศᏊࡢࢡࣛࢫࢱ࣮ᵓ㐀ࡀ᰾㓟ࡢᏳᐃᛶ࡟୚࠼ࡿᙳ㡪ࡢゎᯒ
7KHLQYHVWLJDWLRQIRUHIIHFWVRIFOXVWHUVWUXFWXUHVE\FURZGLQJPROHFXOHVRQVWDELOLW\RIQXFOHLFDFLGV˕ੁຌ ௜‫ހ‬ɼ୉ࢃ ୣ໷ɼ‫ ੶ݒ‬थࢮʤߗೈ୉ָ઎୼ਫ਼ໍ޽ָ‫ॶڂݜ‬ʥ‫ڂݜ‬໪దɼ಼༲ࡋ๖಼ͺνϱϏέ࣯Ώ֫࢐ɼେःࢊ෼͵ʹ͹෾ࢢ͗ࠠΊ߻ͮͪέϧΤυΡϱή‫͍Ͳڧ؂‬Ζ>@ɽ͞͹Γ͑͵‫ڧ؂‬ԾͲͺɼਫ਼ର߶෾ࢢ͹੓࣯Ώ‫ڏ‬ಊͺ‫س‬മ༻ӹ஦ͳͺҡ͵Ζ͞ͳ͗໎Δ͖Ͷ͵ͮͱ͏Ζɽྭ͓ͻɼ֫࢐ͺ್॑࠱ߑଆΝ‫ܙ‬੔ͤΖ͞ͳ͗߁͚எΔΗͱ͏Ζ͗ɼ෾ࢢέϧΤυΡϱή‫ڧ؂‬ԾͲͺࢀ॑࠱Ώ࢝॑࠱͵ʹ͹ඉඬ६ߑଆΝ‫ܙ‬੔͢ͱ͕Εɼ೦ྙָద͵҈ఈ੓΍್॑ΔͦΞߑଆ͹֫࢐Ͷർ΄ͱ߶͚͵Ζ>±@ɽࣰ‫Ͳݩ‬ͺɼ͞͹Γ͑͵‫ڏ‬ಊΝ؏଎ͤΖͪΌͶɼέϧΤυΡϱή‫ڧ؂‬ΝໝแͤΖέϧΤυΡϱή෾ࢢͳ͢ͱϛϨΦοϪϱήϨ
αʖϩ 3(*  ΏυΫηφϧϱ͵ʹΝՅ͓ͱਫ਼ର߶෾ࢢ͹‫ڏ‬ಊΝ؏଎ͤΖɽ ೧ౕͺɼϏϧϪϩ‫ܗ‬͹ '1$࢝॑࠱ΏϖΠϒϱ‫ܗ‬͹ '1$ ್॑ΔͦΞߑଆ  ͶϛϨΦοϪϱήϨαʖϩΏήϩαʖηɼλϩϑφʖϩΝέϧΤυΡϱή෾ࢢͳ͢ͱՅ͓ͪ‫ܧ‬Ͷͯ͏ͱ෾ࢢಊྙָ 0'  εϝϣϪʖεϥϱͳుࢢয়ସ‫ࢋܯ‬Ν༽͏ͱմੵ͢ɼ'1$ ͳέϧΤυΡϱή෾ࢢؔ͹૮‫༽ࡠޕ‬Ν໎Δ͖Ͷͪ͢ɽ͖͢͢͵͗Δɼ͞ΗΔ͹έϧΤυΡϱή෾ࢢ͹෾ࢢྖͺ୉͚͘ͱ΍਼ඨ JPRO ఖౕͲ͍Εɼࣰ‫Ͳݩ‬ͺ෾ࢢྖ͗ JPRO Ґ৏͹୉͘͏έϧΤυΡϱ
ή෾ࢢଚࡑԾͲͺɼ֫࢐͹೦ྙָద͵҈ఈ੓͗୉͚͘ҡ͵Ζ͞ͳ͗ࣖࠨ͠Ηͱ͏Ζɽ͠ΔͶɼըʓͺϏϧϪϩ‫࠱॑࢝ܗ‬Νඉඬ६ߑଆ֫࢐͹φϛϫζʖΝմੵଲেͳ͢ͱͪ͗͘ɼਫ਼ର಼Ͳͺ͞͹Ά͖ͶΠϱοϏϧϪϩ
‫ܗ‬ɼύ΢ϔϨρχ‫ܗ‬͹࢝॑࠱΍ଚࡑ͢ͱ͏Ζɽ͞ΗΔ͹͞ͳ͖Δɼըʓ͹εϝϣϪʖεϥϱͲͺɼέϧΤυΡϱή‫࢐֫͗ڧ؂‬Ͷ༫͓ΖӪ‫ڻ‬Νॉ෾Ͷ٠࿨Ͳ͘ͱ͏͵͏ͳ‫͓ݶ‬Ζɽ͞ΗΔ͹͞ͳ͖Δɼຌ‫Ͳڂݜ‬ͺɼΓΕ‫ܧ‬౹దͶմੵͤΖͪΌͶɼΠϱοϏϧϪϩ‫ܗ‬Ώύ΢ϔϨρχ
‫ܗ‬͹࢝॑࠱΍ '1$ ࢝॑࠱ͳ͢ͱմੵଲেͳ͢ɼ෾ࢢྖ͗
 J PRO ͹ 3(* Ώ 'H[WUDQ ΍έϧΤυΡϱή෾ࢢͳ͢ͱՅ͓ͪ‫ܧ‬Ν 0' εϝϣϪʖεϥϱɼుࢢয়ସ‫ࢋܯ‬Ν༽͏ͱմੵͪ͢ɽ͠ΔͶɼέϧΤυΡϱή෾ࢢ͹‫ڏ‬ಊΝৠΊࠒΊωϣʖϧϩϋρφϭʖέͶΓͮͱ෾ྪͪ͢ɽ

‫ڂݜ‬๏๑ɼ‫ࢋܯ‬๏๑
 '1$ ͹ߑଆͺɼϏϧϪ ϩ‫'  ܗ‬1$ ࢝॑࠱ 3'% ,'.) 4SDUDOOHO ɼύ΢ϔϨρχ‫' ܗ‬1$ ࢝॑࠱ '1$ 3'% ,'+< 4K\EULG ɼΠϱοϏϧϪϩ‫' ܗ‬1$ ࢝॑࠱ 3'% ,'
0%-4DQWLSDUDOOHO ɼϖΠϒϱ‫' ܗ‬1$ 3'%,'$&+3  Ν
3URWHLQ'DWD%DQN ͖Δखಚ͢ɼ͞ΗΔ͹ߑଆΝॵ‫ߑغ‬ଆͳ͢ͱ༽͏ͪ ਦ  ɽ͞ΗΔ͹ '1$ Ͷଲ͢ɼਭ෾ࢢ͹ΊɼΦοϪϱήϨαʖϩ (* ɼζΦοϪϱήϨαʖϩ (* ɼφϨΦοϪϱήϨαʖϩ (* ɼτφϧΦοϪϱήϨαʖϩ(* ɼΨένΦοϪϱήϨαʖϩ (* ɼ J PRO ͹

- 158 -

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- 160 -

F ɽ*TXDUWHW ͺ  ທ͹Ԛ‫͗خ‬ਭો݃߻Ν‫ܙ‬੔͢ɼ෵਼ທ͗ηνρΫϱή͢ͱ͏ΖͪΌɼԚ‫͗خ‬ൕ఺ͤΖ͞ͳ͵͚҈ఈͪ͢ &+ʞʌ ૮‫༽ࡠޕ‬Νң࣍Ͳ͘ΖɽҲ๏ɼୱର͖ϭφλϱʀέϨρέԚ‫خ‬ଲΝ‫ܙ‬੔͢ͱ͏ΖϩʖϕԚ‫خ‬ͺԚ‫͗خ‬ൕ఺͢Ώͤ͏ͪΌɼओ͏ &+ʞʌ ૮‫ܙ͖͢༽ࡠޕ‬੔Ͳ͘͵͏ɽࣰ‫Ͳݩ‬ɼέϧΤυΡϱ
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+LVDH 7DWHLVKL.DULPDWDɼ6KLJHQRUL 7DQDNDɼ1DRNL 6XJLPRWRɼ୊  յࠅࡏ֫࢐ԿָεϱϛζΤϞ ‫ٸ‬ஏֺ‫ح‬ϙʖϩ ɼϛηνʖɼ ೧  ݆  ೖड़൝ࣰ੹Ήͪͺ༩ఈຌ‫ڂݜ‬τʖϜͶͯ͏ͱ͹࿨ชΝࣧජ஦Ͳ͍Ζɽࢂߡช‫ݛ‬>@  5-(OOLV&XUU2SLQ6WUXFW%LRO±  >@  5-(OOLV7UHQGV%LRFKHP6FL±  >@  07UDMNRYVNL7(QGRK+7DWHLVKL.DULPDWD72K\DPD67DQDND-3ODYHF16XJLPRWR1XFOHLF$FLGV5HV±  >@  $.-DLVZDO56ULYDVWDYD33DQGH\3%DQG\RSDGK\D\3/2621(H  >@  01DNDQR+7DWHLVKL.DULPDWD67DQDND)7DPD20L\DVKLWD61DNDQR16XJLPRWR &KHP3K\V/HWW±  >@  01DNDQR+7DWHLVKL.DULPDWD67DQDND)7DPD20L\DVKLWD61DNDQR16XJLPRWR1XFOHLF$FLGV5HV±  - 161 -

࣑࢜ࢩࣥ VI ࡢ㛗㊥㞳ࢫࢸࢵࣉ㐠ືࢆ฼⏝ࡋࡓ㧗ຠ⋡࡞ືస࣓࢝ࢽࢬ࣒ࡢゎ᫂Elucidation of the efficient working mechanism of myosin VI using
long-distance stepping motion‫ۑ‬ᑎ⏣ ᬛᶞࠊ➲஭ ⌮⏕㸦ྡྂᒇ኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ
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 II ࡢ㢌㒊ࡢ࢔ࢡࢳࣥ
ࣇ࢕࣓ࣛࣥࢺࡢ࿘ᅖࡢࣈࣛ࢘ࣥ㐠ື࡟ࡘ࠸࡚ࠊᐇ㦂ⓗ࡟Ỵᐃࡉࢀࡓᵓ㐀ࢆ⏝࠸࡚⢒ど໬ࣔࢹࣝࢆᵓ⠏ࡋࠊࣛࣥࢪࣗࣂࣥືຊᏛィ⟬࡜ WHAM ἲࢆ⤌ࡳྜࢃࡏ࡚⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࢆィ⟬ࡍࡿᡭἲࢆ㛤Ⓨࡋࡓࠋࡇࡢᡭἲ࡟ࡶ࡜࡙ࡃィ⟬࡟ࡼࡾࠊ࣑࢜ࢩࣥ II ࡢ㢌㒊࡟࠾ࡅࡿ໬Ꮫኚ໬࡜࢝ࢵࣉࣝࡋࡓᵓ㐀ኚ໬࡟ࡼࡗ࡚ࠊ
ࣈࣛ࢘ࣥ㐠ືࡢ⮬⏤࢚ࢿࣝࢠ࣮᭱ᑠࡢ఩⨨ࡀ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺ࡟ἢࡗ࡚⛣ືࡋࠊࡇࡢຠᯝࡀ➽཰⦰࡟኱ࡁࡃᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ㸦Nie et al., Phys. Chem. Chem. Phys. (2014) ࠊNie et al., PLoS Comp.
Biol. (2014)ࠊᑎ⏣ᬛᶞ, ⏕≀≀⌮ (2015)㸧ࠋᮏ◊✲࡛ࡣࠊ⣽⬊ෆ≀㉁㍺㏦࡟࠿࠿ࢃࡿ࣑࢜ࢩࣥࣇ࢓࣑࣮ࣜࢱࣥࣃࢡ㉁࡛࠶ࡿ࣑࢜ࢩࣥ VI ࢆᑐ㇟࡜ࡋ࡚ࠊ
࣑࢜ࢩࣥ II ࡛☜❧ࡋࡓᡭἲࢆ⏝࠸࡚ࠊࣛࣥࢻࢫࢣ࣮ࣉ⌮ㄽࢆᒎ㛤ࡍࡿࠋ࣑࢜ࢩࣥ VI ࡣ 2 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 36 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 VI ࡢᶵ⬟Ⓨ⌧࡟࡜ࡗ࡚㔜せ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ
࣑࢜ࢩࣥ VI ࡢ 2 ࡘࡢ㢌㒊ࡀ࡝ࡢࡼ࠺࡟ࡋ࡚ࡘ࡞ࡀࡗ࡚࠸ࡿ࠿࡟ࡘ࠸࡚ࡣࠊᐇ㦂ⓗ࡞◊✲࠿ࡽ 2 ࡘࡢࣔࢹࣝ
ࡀᥦၐࡉࢀ࡚࠸ࡿࠋSpudich ࣔࢹࣝ࡟࠾࠸࡚ࡣࠊsingle alpha-helix domain ࡛ࡣࢥ࢖ࣝࢻࢥ࢖ࣝ㡿ᇦࢆᙧᡂࡏࡎࠊ
ࡼࡾ C ᮎ➃ഃࡢ cargo-binding domain ࡛ 2 ࡘࡢ㢌㒊ࡀ఍ྜࡍࡿ୍᪉ࠊ2 ࡘࡢ㢌㒊ࡑࢀࡒࢀࡢ three-helix bundleࡀࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸦Spink et al., Nat. Struct. Mol. Biol. (2008)㸧ࠋࡇࢀ࡟ᑐࡋ࡚ࠊ
Sweeney-Houdusse ࣔࢹࣝ࡟࠾࠸࡚ࡣࠊsingle alpha-helix domain ࡢ୍㒊ࡀࢥ࢖ࣝࢻࢥ࢖ࣝ㡿ᇦࢆᙧᡂࡍࡿࡇ࡜
࡟ࡼࡾ 2 ࡘࡢ㢌㒊ࡀ఍ྜࡍࡿ୍᪉ࠊ2 ࡘࡢ㢌㒊ࡑࢀࡒࢀࡢ three-helix bundle ࡀ࢔ࣥࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸦Mukherjea et al., Mol. Cell (2009)㸧
ࠋࡇࢀࡽ 2 ࡘࡢࣔࢹࣝࡣ࡜ࡶ࡟ࠊ36 ࢼࣀ࣓࣮ࢺࣝࢫࢸࢵࣉࢆྍ
⬟࡟ࡍࡿࡓࡵ࡟ࠊ࡝࠺ࡍࢀࡤ 2 ࡘࡢ㢌㒊ࡀ 36 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

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ࣥ II ࡟ᑐࡋ࡚㛤Ⓨ࣭㐺⏝ࡋ࡚ࡁࡓィ⟬ᡭἲࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊࡇࢀࡽ 2 ࡘࡢࣔࢹࣝ࡟㛵ಀࡍࡿᵝࠎ࡞᮲௳࡟ࡘ࠸࡚ࠊࣈࣛ࢘ࣥ㐠ືࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡢᙧ≧ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊ36 ࢼࣀ࣓࣮ࢺࣝࢫ
ࢸࢵࣉࢆྍ⬟࡟ࡍࡿ᮲௳ࢆ᥈ࡿ࡜࡜ࡶ࡟ࠊ࣑࢜ࢩࣥ VI ࡢࣈࣛ࢘ࣥ㐠ື࡟࠾ࡅࡿᵓ㐀࢔ࣥࢧࣥࣈࣝࡢ≉ᚩࢆ᫂ࡽ࠿࡟ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ࢔࣑ࣀ㓟 1 ṧᇶࢆ 1 ⢏Ꮚ࡜ࡋ࡚⾲⌧ࡍࡿ⢒ど໬ࣔࢹࣝࢆ⏝࠸࡚ࠊ࣑࢜ࢩࣥ VI ࡢ๓㊊࡜ᚋࢁ㊊࡟┦ᙜࡍࡿ 2ࡘࡢ㢌㒊࡜࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺࢆィ⟬ᶵୖ࡟⾲⌧ࡍࡿ࡜࡜ࡶ࡟ࠊࡇࢀࡽࡑࢀࡒࢀࡢෆ㒊ࡢ┦஫స⏝࡜ࡋ࡚ᙎᛶࢿࢵࢺ࣮࣡ࢡࣔࢹࣝࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊࡑࢀࡒࢀࡢᵓ㐀ࡀ᭱Ᏻᐃᵓ㐀ࢆ୰ᚰ࡜ࡋ࡚⇕ᦂࡽࡂࡍࡿᵝᏊࢆ⾲⌧ࡋࡓࠋࡲࡓࠊ2 ࡘࡢ࣑࢜ࢩࣥ㢌㒊ࡢ C ᮎ➃ഃ࡟ࡣ single alpha-helix domain ࡜ࡼࡤࢀࡿࠊȘ࣊ࣜࢵࢡࢫ
༢య࡛Ᏻᐃ࡟Ꮡᅾࡋ࡚࠸ࡿ㡿ᇦࡀ࠶ࡾࠊࡑࢀࡽࢆ௓ࡋ࡚ 2 ࡘࡢ㢌㒊ࡀ఍ྜࡋ࡚࠸ࡿࡀࠊࡇࢀࡽࡢ㡿ᇦࡢᵓ㐀ࢆ V Ꮠᆺ࡟⤖ྜࡋࡓ 2 ࡘࡢᙎᛶᱱ࡜ࡋ࡚࠶ࡽࢃࡋࠊࡇࢀࡽࡢᙎᛶኚᙧࡢ࢚ࢿࣝࢠ࣮ࢆ 2 ࡘࡢ㢌㒊ࡢ C ᮎ➃௜㏆ࡢᗙᶆࢆ⏝࠸࡚⾲ࡋࡓࠋࡉࡽ࡟ࠊᚋࢁ㊊࡟┦ᙜࡍࡿ࣑࢜ࢩࣥ㢌㒊ࡀ࣑࢜ࢩࣥ II ࡜ྠ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࡟ 8 ㏻ࡾࠊ୰ᚰ㍈ࡢ᪉ྥ࡟ 7 ㏻ࡾࠊ୰ᚰ㍈࠿ࡽࡢ㊥㞳ࡢ᪉ྥ࡟ 3 ㏻ࡾ࡛ྜィ 873
㸻168 ㏻ࡾࡢ࢔ࣥࣈ࣏ࣞࣛࢸࣥࢩࣕࣝࢆ࠿ࡅ࡚ࠊࣛࣥࢪࣗࣂࣥືຊᏛィ⟬࡟ࡼࡿࢧࣥࣉࣜࣥࢢࢆ⾜ࡗࡓࠋࡇࡢィ⟬࠿ࡽᚓࡽࢀࡓ࢔ࣥࢧࣥࣈࣝࢆ WHAM ἲ࡛⤌ࡳྜࢃࡏࡿࡇ࡜࡟ࡼࡾࠊ࣑࢜ࢩࣥ VI ࡢ๓㊊࡟┦ᙜࡍࡿ㢌㒊ࡢࣈࣛ࢘ࣥ㐠ືࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࢆィ⟬ࡋࡓࠋ3◊✲ᡂᯝᮏ◊✲࡛ࡣࠊࢃࢀࢃࢀࡀ࣑࢜ࢩࣥ II ࡟ᑐࡋ࡚㛤Ⓨ࣭㐺⏝ࡋ࡚ࡁࡓィ⟬ᡭἲࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊࡇࢀࡽ 2ࡘࡢࣔࢹࣝ࡟㛵ಀࡍࡿᵝࠎ࡞᮲௳࡟ࡘ࠸࡚ࠊࣈࣛ࢘ࣥ㐠ືࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡢᙧ≧ࢆẚ㍑ࡍ
ࡿࡇ࡜࡟ࡼࡾࠊ36 ࢼࣀ࣓࣮ࢺࣝࢫࢸࢵࣉࢆྍ⬟࡟ࡍࡿ᮲௳ࢆ᥈ࡗࡓࠋࡑࡢ⤖ᯝ࡜ࡋ࡚ࠊ(1) Houdusse-Sweeneyࣔࢹࣝࡼࡾࡶ Spudich ࣔࢹࣝࡢ᪉ࡀ኱ࡁ࡞ࢫࢸࢵࣉࢧ࢖ࢬ࡬ྥ࠿࠺ࣂ࢖࢔ࢫࢆㄝ᫂ࡋࡸࡍ࠸ࡇ࡜ࠊ(2) ๓㊊ࡢ࣑࢜ࢩࣥ㢌㒊ࡢᵓ㐀ࡀ prestroke ᵓ㐀࠿ࡽ poststroke ᵓ㐀࡟ኚ໬ࡍࡿࡇ࡜࡟ࡼࡾࠊ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ
࣮ࣉࡢࣂ࢖࢔ࢫࡀᙉࡲࡿࡇ࡜ࠊ(3) three-helix bundle ࡀ࢔ࣥࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿ࡜ࣂ࢖࢔ࢫࡀᙅࡲࡿࡇ࡜ࠊ(4) 2ࡘࡢ࣑࢜ࢩࣥ㢌㒊ࢆࡘ࡞ࡄ࣑࢜ࢩࣥᑿ㒊ࡢᣢ⥆㛗ࡢ್ࡀ኱ࡁ࠸࡯࡝⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉ࡟ᙉ࠸ࣂ
࢖࢔ࢫࡀࡶࡓࡽࡉࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ
ᖹᡂ 30 ᖺᗘࡢ⤊ࢃࡾࡢ᫬Ⅼ࡛ࠊ௨ୖࡢࡼ࠺࡞⤖ᯝࡀᚓࡽࢀ࡚࠸ࡓ୍᪉ࠊࡇࡇࡲ࡛࡟ᚓࡽࢀ࡚࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡣ஧ᅇᑐ⛠ᛶࢆᣢࡘ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺ࡟ἢࡗࡓ஧ᮏࡢ⁁ࡀ࡯ࡰ➼ࡋ࠸⮬⏤࢚ࢿࣝࢠ࣮ࢆᣢࡗ࡚࠾ࡾࠊࡇࡢⅬࡣࠊ࣑࢜ࢩࣥ VI ࡀ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺࡢ⿬ഃ࡟ᅇࡾ㎸ࡲࡎ࡟ᩘ࣐࢖ࢡ࣓࣮ࣟࢺ
ࣝ࡟ࢃࡓࡗ࡚┤⥺ⓗ࡟Ṍ⾜ࡍࡿ࡜࠸࠺ᐇ㦂஦ᐇ࡜ᩚྜࡋ࡚࠸࡞࠸ࡓࡵࠊࡇࢀࡲ࡛ࡢࣔࢹࣝ࡟㊊ࡾ࡞࠸㒊ศࡀ࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋ2 ࡘࡢ࣑࢜ࢩࣥ㢌㒊ࢆࡘ࡞ࡄ࣑࢜ࢩࣥᑿ㒊ࡢ࢔ࢡࢳࣥࣇ࢕࣓ࣛࣥࢺ࡜ࡢ⾪✺ࢆ⾲⌧ࡋࡓ࣏ࢸࣥࢩࣕࣝࢆ᪂ࡓ࡟⪃᱌࣭ᐇ⿦ࡋࡓࡀࠊࡇࡢ࣏ࢸࣥࢩࣕࣝࡀാ࠸࡚࠸࡚ࡶ࣑࢜ࢩࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡵ࡚ࡋࡲ࠺ࡓࡵࠊࡇࢀࡔࡅ࡛ࡣ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉࡢᙧ≧ࡣ࡯࡜ࢇ࡝ኚࢃࡽ࡞࠿ࡗࡓࠋ

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ᅗ㸯 ᵝࠎ࡞᮲௳࡟࠾࠸࡚ィ⟬ࡉࢀࡓࠊ๓㊊࡟┦ᙜࡍࡿ࣑࢜ࢩࣥ VI 㢌㒊ࡢ⮬⏤࢚ࢿࣝࢠ࣮
ࣛࣥࢻࢫࢣ࣮ࣉࠋ㸦ᕥୖ㸧Spudich ࣔࢹࣝ㸦single alpha-helix domain ࡢ㛗ࡉ 94.5ύࠊゅᗘ 160ᗘ㸧࡛ᣢ⥆㛗ࢆ 22.5 ࢼࣀ࣓࣮ࢺࣝ࡜ࡋࠊthree-helix bundle ࡀࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿሙྜࠋ
㸦ྑୖ㸧
Spudich ࣔࢹ࡛ࣝᣢ⥆㛗ࢆ 5 ࢼࣀ࣓࣮ࢺࣝ࡜ࡋࠊthree-helix bundle ࡀࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿሙྜࠋ
㸦ᕥୗ㸧Spudich ࣔࢹ࡛ࣝᣢ⥆㛗ࢆ 22.5 ࢼࣀ࣓࣮ࢺࣝ࡜ࡋࠊthree-helix bundle ࡀ࢔ࣥࣇ࢛࣮ࣝ
ࢻࡋ࡚࠸ࡿሙྜࠋ㸦ྑୗ㸧Sweeney-Houdusse ࣔࢹࣝ㸦single alpha-helix domain ࡢ㛗ࡉ 34.5ύࠊゅᗘ 20 ᗘ㸧࡛ᣢ⥆㛗ࢆ 22.5 ࢼࣀ࣓࣮ࢺࣝ࡜ࡋࠊthree-helix bundle ࡀ࢔ࣥࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿ
ሙྜࠋࡑࡇ࡛௧࿴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࡟ࠊ2 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
ࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡴࡉ࠸࡟ࡣࠊ᥋ྜ㒊ࡀ኱ࡁ࡞ゅᗘ࡛᭤ࡀࡿࡇ࡜࡟ࡼࡗ࡚Ᏻᐃ࡞┦஫స⏝ࡀᐇ⌧ࡉࢀ࡚- 164 -

ࡋࡲࡗ࡚࠸ࡓࡇ࡜ࢆព࿡ࡋ࡚࠸ࡿࠋࡇࡢ᮲௳ࡢࡶ࡜࡛ᚓࡽࢀࡓࣛࣥࢻࢫࢣ࣮ࣉࢆᅗ㸯࡟♧ࡍࠋThree-helix
bundle ࡀ࢔ࣥࣇ࢛࣮ࣝࢻࡋ࡚࠸ࡿሙྜࢆ㝖࠸࡚ࠊ࣑࢜ࢩࣥ㢌㒊ࡀ⿬ഃ࡟ᅇࡾ㎸ࡴ⌧㇟ࡀῶᑡࡋ࡚࠸ࡿ୍᪉ࠊ
(1)࠿ࡽ(4)ࡢ୺せ࡞⤖ㄽ࡟ࡣኚ᭦ࡀ࡞࠸ࡇ࡜ࡀࢃ࠿ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

(1) ‫ۻ‬T. P. Terada, Q.-M. Nie, M. Sasai, “A landscape-based view on the stepping movement of myosin VI”, Joint 12th
EBSA, 10th ICBP-IUPAP Biophysics Congress, Madrid ᕷ Spain㸦2019 ᖺ 7 ᭶㸧(2) ‫ۻ‬T. P. Terada, Q.-M. Nie, M. Sasai, “Effects of interhead connection on the stepping motion of myosin VI”, ➨ 57
ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, ᐑᓮᕷ㸦2019 ᖺ 9 ᭶㸧(3) K. Matsuda, M. Sasai, T. P. Terada, “Three-state model of muscle contraction with switched free energy landscapesfor myosin heads”, ➨ 57 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, ᐑᓮᕷ㸦2019 ᖺ 9 ᭶㸧(4) Ryota Mori, Masaki Sasai, Tomoki P. Terada, “Conformational transition of adenylate kinase studied with the
improved chameleon model”, ➨ 57 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, ᐑᓮᕷ㸦2019 ᖺ 9 ᭶㸧(5) ‫ۻ‬T. P. Terada, Q.-M. Nie, M. Sasai, “A landscape-based view on the stepping movement of myosin VI”, The
Biophysical Society Annual Meeting, San Diego ᕷ USA㸦2020 ᖺ 2 ᭶㸧(6) ᳃㑈ኴ, ➲஭⌮⏕, ᑎ⏣ᬛᶞ, “࣓࢝ࣞ࢜ࣥࣔࢹࣝ࡟ࡼࡿ࢔ࢹࢽࣝ㓟࢟ࢼ࣮ࢮࡢᵓ㐀㌿⛣࡜࢔ࣥࣇ࢛࣮ࣝࢹ࢕ࣥࢢ㌿⛣ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉゎᯒ”, ᪥ᮏ≀⌮Ꮫ఍➨ 75 ᅇᖺḟ኱఍, ྡྂᒇ኱Ꮫ㸦2020 ᖺ 3᭶㸧㸦᪂ᆺ⫵⅖ឤᰁ㜵Ṇࡢࡓࡵ୰Ṇ࡜࡞ࡗࡓࡀࠊⓎ⾲ࡣබᘧ࡟࡞ࡉࢀࡓࡶࡢ࡜ㄆᐃࡉࢀࡓ㸧(7) ‫ۻ‬ᑎ⏣ᬛᶞ, Q.-M. Nie, ➲஭⌮⏕, “࣑࢜ࢩࣥ VI ࡢṌ⾜࣓࢝ࢽࢬ࣒ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣛࣥࢻࢫࢣ࣮ࣉゎᯒ”,᪥ᮏ≀⌮Ꮫ఍➨ 75 ᅇᖺḟ኱఍, ྡྂᒇ኱Ꮫ㸦2020 ᖺ 3 ᭶㸧㸦᪂ᆺ⫵⅖ឤᰁ㜵Ṇࡢࡓࡵ୰Ṇ࡜࡞ࡗࡓࡀࠊⓎ⾲ࡣබᘧ࡟࡞ࡉࢀࡓࡶࡢ࡜ㄆᐃࡉࢀࡓ㸧௚ 14 ௳

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1) ‫ۻ‬Qing-Miao Nie, Masaki Sasai, Tomoki P. Terada, “Conformational flexibility of loops of myosin enhances theglobal bias in the actin-myosin interaction landscape”, Physical Chemistry Chemical Physics 16, 6441-6447㸦2014 ᖺ
1 ᭶㸧(2) ‫ۻ‬Qing-Miao Nie, Akio Togashi, Takeshi N. Sasaki, Mitsunori Takano, Masaki Sasai, Tomoki P. Terada, “Couplingof Lever Arm Swing and Biased Brownian Motion in Actomyosin”, PLoS Computational Biology 10(4): e1003552,
1-13㸦2014 ᖺ 4 ᭶㸧(3) S. S. Ashwin, Tadasu Nozaki, Kazuhiro Maeshima, Masaki Sasai, “Organization of fast and slow chromatin revealedby single-nucleosome dynamics”, Proceedings of the National Academy of Sciences USA 116, 19939̽19944㸦2019ᖺ 9 ᭶㸧

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ࢱࣥࣃࢡ㉁࡜ศᏊ㞟ྜయࡢศᏊᶵ⬟ࡢ⌮ㄽィ⟬
Theoretical calculations of molecular functions of proteins andmolecular assemblies‫ۑ‬ᯘ 㔜ᙪࠊ಴㔜 భ㍤ࠊ⏣ཱྀ ┿ᙪࠊᡂ ࢭ࢖ࠊᒣᮏ ⿱⏕ࠊᑠᒣ ⣊ࠊ໭ᮧ┤኱ࠊᯇᒣ ⥤ኟࠊすᑿ ᐀୍㑻ࠊ௒஭ࠊᯇ⃝ ඃኴࠊ㮵಴ ၨྐࠊ㧗ᶫ ᏹᘺ㸦ி㒔኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧
1◊✲┠ⓗࠊෆᐜ

ගࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮༢᰾㘒యࡸ༢ศᏊ☢▼ከ᰾㔠ᒓ㘒యࡢ㢧ⴭ࡞ศᏊᶵ⬟ࡢ࣓࢝ࢽࢬ࣒ࢆࠊከཧ↷㟁Ꮚ≧ែ⌮ㄽ࡟ࡼࡿ㟁Ꮚ≧ែィ⟬࡟ࡼࡾ᫂ࡽ࠿࡟ࡍࡿࠋࡲࡓࠊࢱࣥࣃࢡ㉁ࡸ⮬ᕫ⤌⧊໬ศᏊࡢ㐜࠸ࢲ࢖ࢼ࣑ࢡࢫ
ࢆ᭷ࡍࡿศᏊᶵ⬟࡟㛵ࡋ࡚ࠊࣁ࢖ࣈࣜࢵࢻ QM/MM ἲࠊཬࡧศᏊືຊᏛ㸦MD㸧ἲࢆ⏝࠸ࡓ◊✲ࢆ⾜࠺ࠋ
1.1 ከཧ↷㟁Ꮚ┦㛵⌮ㄽ࡟ࡼࡿ Fe 㘒యࡢ㧗㏿ࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮⌧㇟ࡢᶵᵓゎ᫂ග↷ᑕ࡟ࡼࡾ୍㔜㡯≧ែ࠿ࡽ஬㔜㡯≧ែ࡬࡜ᩘ༑ࣇ࢙࣒ࢺ⛊ࡢ㏿ࡉ࡛㧗㏿࡟ࢫ࢖ࢵࢳࡍࡿ Fe(bpy)3 㘒యࡢࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮⌧㇟࡟ࡘ࠸࡚ࠊࢫࣆࣥ⚗ไ࡞㡯㛫஺ᕪࢆ 2 ᅇ௨ୖࡢᚲせ࡜ࡍࡿᙜ཯ᛂࡀ࡝ࡢࡼ࠺࡞ᶵᵓ
࡛▷᫬㛫࡟ᐇ⌧ࡉࢀࡿ࠿㆟ㄽ࡜࡞ࡗ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊd 㟁Ꮚᵓ㐀ࡢᣦᩘ㛵ᩘⓗ࡞኱⮬⏤ᗘከ㓄⨨ᛶࡢྲྀࡾᢅ࠸ࢆྍ⬟࡟ࡍࡿᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ࢆᇶ┙࡜ࡍࡿከཧ↷㟁Ꮚ┦㛵⌮ㄽࢆ⏝࠸ࡓບ㉳≧ែࡢᏳᐃᵓ㐀᥈⣴࡜ከ≧ែ࢚ࢿࣝࢠ࣮࣏ࢸࣥࢩࣕࣝ᭤㠃ィ⟬࡟ࡼࡾࠊ୰㛫≧ែࡢ୕㔜㡯≧ែࡢྠᐃࢆ⾜࠸ග↷ᑕ┤ᚋࡢศᏊᵓ
㐀ኚ໬࡟ࡼࡾࢫࣆࣥ㌶㐨┦஫స⏝ࡀቑ኱ࡋ㧗㏿࡞㡯㛫஺ᕪࡀྍ⬟࡜࡞ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ
1.2 ከ᰾㔠ᒓ㘒యࡢࢮࣟ☢ሙศ⿣࡜༢ศᏊ☢▼࡬ࡢᛂ⏝㏆ᖺࡢࢫࣆࣥࢺࣟࢽࢡࢫ࡟௦⾲ࡉࢀࡿࡼ࠺࡟ࠊ㟁Ꮚࡢࢫࣆࣥ⮬⏤ᗘࢆไᚚࡋ฼⏝ࡍࡿࡇ࡜ࡣࠊศᏊ࡟᪂ࡓ࡞
ᶵ⬟࣭≀ᛶࢆ୚࠼ࡿࡶࡢ࡜ᮇᚅࡉࢀࡿࠋᮏ◊✲࡛ࡣࠊ」㞧࡞㟁Ꮚᵓ㐀ࡢグ㏙ࡀྍ⬟࡛࠶ࡿᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ἲࢆ┦ᑐㄽⓗࣁ࣑ࣝࢺࢽ࢔ࣥ࡟ᣑᙇࡍࡿࡇ࡜࡟ࡼࡾࠊ㟁Ꮚࢫࣆࣥࡢ୍㍈␗᪉ᛶࢆᣢࡘࡇ࡜࠿ࡽ୍ศᏊ࡛☢
▼ࡢࡼ࠺࡟᣺ࡿ⯙࠺༢ศᏊ☢▼ࠊ≉࡟ 2018 ᖺ࡟ྜᡂࡉࢀࡓ᭱㧗ࡢࣈࣟࢵ࢟ࣥࢢ
ࣟ☢ሙศ⿣ࡢ⌮ㄽணᗘࢆ♧ࡍ Co ᅄ᰾㘒యࡢࢮࢆ⾜࠺ࠋ1.3 ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜయࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜయࢱࣥࣃࢡ㉁ࡣࠊග㑇ఏᏛࡢ㔜せ࡞ࢶ࣮ࣝ࡜࡞ࡗ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊග↷ᑕ࡟ࡼࡿ⚄⤒⣽⬊ࡢᢚไ໬ࢆᘬࡁ㉳ࡇࡍගឤཷᛶ࢔ࢽ࢜ࣥࢳࣕࢿ࡛ࣝ࠶ࡿ ACR1 ࢱࣥࣃࢡ㉁ࡢ࢖࢜ࣥ㍺㏦ࡢศᏊ
ᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࠋ᭦࡟ࠊྠᵝࡢ⚄⤒⣽⬊ࡢᢚไ໬ࢆᘬࡁ㉳ࡇࡍග㥑ືᆺሷ⣲࢖࣏࢜ࣥࣥࣉ࡛࠶ࡿࣁࣟࣟ
ࢻࣉࢩࣥ㸦hR㸧ࡢගάᛶ໬㐣⛬ࡢゎᯒࢆ⾜࠺ࠋ
1.4 HIV ࣉࣟࢸ࢔࣮ࢮࡢ⸆๣⪏ᛶᶵᵓࡢゎᯒHIV ࣉࣟࢸ࢔࣮ࢮࡣ HIV ࢘࢖ࣝࢫឤᰁࢆ㜼ᐖࡍࡿ⸆๣㛤Ⓨࡢࢱ࣮ࢤࢵࢺ࡟࡞ࡗ࡚࠸ࡿࡀࠊ୍᪉࡛㧗࠸⸆๣⪏ᛶ⬟ࢆ᭷ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊQM/MM RWFE-SCF ἲࢆ⏝࠸࡚⸆๣⪏ᛶኚ␗࡟ࡼࡿ⸆๣
ศᏊ⤖ྜ≧ែࡢኚ໬ࢆゎᯒࡍࡿ࡜ඹ࡟ࠊኳ↛ᇶ㉁ศᏊࡢ㓝⣲཯ᛂᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡟ࡼࡾࠊ⸆๣⪏ᛶࡢศᏊᶵᵓ࡟㛵ࡍࡿ▱ぢࢆᚓࡿࠋ
1.5 ගྜᡂ⣔ II㸦PSII㸧㓟⣲Ⓨ⏕୰ᚰࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿゎᯒ
PSII ࡣග྾཰࡟క࠺㏲ḟⓗ࡞㓟໬ࢧ࢖ࢡࣝࡢ୰࡛ࠊ࣐ࣥ࢞ࣥࢡࣛࢫࢱ࣮ࢆ᭷ࡍࡿ཯ᛂάᛶ㒊఩࡟࠾࠸࡚Ỉ஧ศᏊࢆ㓟⣲ศᏊ࡟ኚ᥮ࡍࡿࠋᮏ◊✲࡛ࡣࠊ㓟⣲Ⓨ⏕཯ᛂࡢ⌮ゎ࡟ᚲせ࡛࠶ࡿ࣐ࣥ࢞ࣥࢡࣛࢫࢱ࣮ࡢࣉࣟࢺࣥ
໬≧ែ࡜ࡑࡢ㑄⛣ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊQM/MM RWFE-SCF ἲࢆ⏝࠸࡚ࣉࣟࢺࣥ໬ཬࡧ㓟໬≧ែࡀ␗࡞ࡿ

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」ᩘࡢ≧ែࡢ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࠊཬࡧ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜࠺ࠋ
1.6 ࣆࣞࣥⰍ⣲ࢆᣢࡘⓎගᛶᾮయࡢග≉ᛶ࡜ࣞ࢜ࣟࢪ࣮ࡢゎᯒࠊศᒱ࢔ࣝ࢟ࣝ㙐⨨᥮ᇶ࡟ࡼࡾศ㞳ࡉࢀࡓࣆࣞࣥⰍ⣲ࢆ᭷ࡍࡿⓎගᛶศᏊᾮయࡣࠊ⨨᥮ࡍࡿศᒱ࢔ࣝ࢟ࣝ㙐ࡢ㓄⨨ࢆኚ࠼ࡿࡇ࡜࡟ࡼࡾࠊⓎග≉ᛶࡸ⢓ᛶ࡞࡝ࡢࣞ࢜ࣟࢪ࣮ࡢไᚚࡀྍ⬟࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊࡇࡢⓎගᛶศᏊᾮయࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊᾮ≧ศᏊ୰࡛ࡢືຊᏛ≉ᛶ࡞࡝ࢆゎᯒࡍࡿࡇ࡜࡟ࡼࡾࠊࣞ࢜ࣟࢪ
࣮ไᚚࡢศᏊᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 ከཧ↷㟁Ꮚ┦㛵⌮ㄽ࡟ࡼࡿ Fe 㘒యࡢ㧗㏿ࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮⌧㇟ࡢᶵᵓゎ᫂ග↷ᑕ┤ᚋࡢࢫࣆࣥᑐ⛠ᛶኚ໬ࢆక࠺ࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮⌧㇟ࡢᶵᵓゎᯒࢆከཧ↷㟁Ꮚ┦㛵⌮ㄽ࡟ࡼࡾ⾜ࡗࡓࠋ㑄⛣㔠ᒓ㘒యࡢከᩘࡢపບ㉳≧ែࡢ࢚ࢿࣝࢠ࣮‽఩ࢆᐃ㔞ⓗ࡟⟬ฟࡍࡿࡓࡵ࡟ࠊ⌮ㄽ࡟ࡣ㠀⤒㦂ⓗᐦᗘ⾜ิࡃࡾࡇࡳ⩌ἲࢆ⏝࠸ࡓ኱つᶍ᏶඲άᛶ✵㛫⮬ᕫ↓᧐╔ሙ⌮ㄽ㸦DMRG-CASSCF ἲ㸧࡞࡝ࢆ୰ᚰ࡟⏝࠸ࡓࠋ㑄⛣㔠ᒓ㘒యࡢ౯㟁ᏊࡣࠊⅣ⣲ȧඹᙺ⣔࡞࡝ࡢపḟඖ⣔࡟ẚ࡭࡚ࠊࡼࡾ㧗ḟඖⓗ࡞㔞Ꮚ࢚ࣥࢱࣥࢢ࣓ࣝ
ࣥࢺࢆᢅ࠺ࡓࡵᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ἲ࡟ࡼࡿࣁ࣑ࣝࢺࢽ࢔ࣥࡢᑐゅ໬࡛ࡣࠊከࡃࡢάᛶ㌶㐨 (k) ࡜⧞ࡾ㎸ࡳከయᇶᗏ (M) ࢆᚲせ࡜ࡍࡿࠋᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ࡢィ⟬㔞ࡣ O(k2M3) ࡜ᛴ㏿࡟ቑ኱ࡍࡿࡓࡵ኱つᶍ࡞୪ิィ⟬ࢆ⏝࠸ࡓࠋᥦ᱌ࡋࡓ཯ᛂ⤒㊰ࡢ⿬௜ࡅ࡜ࡋ࡚ࢫࣆࣥᑐ⛠ᛶኚ໬ࢆྍ⬟࡟ࡍࡿࢫࣆࣥ㌶㐨┦஫స⏝ࢆ཯ᛂ⤒㊰࡟ἢࡗ࡚ィ⟬ࡋࡓࠋ
2.2 ከ᰾㔠ᒓ㘒యࡢࢮࣟ☢ሙศ⿣࡜༢ศᏊ☢▼࡬ࡢᛂ⏝ᇶᗏ≧ែࡢࢮࣟ☢ሙศ⿣ࢆ┦ᑐㄽⓗࣁ࣑ࣝࢺࢽ࢔ࣥࡢᑐゅ໬࡟ࡼࡾィ⟬ࡋࡓࠋከ᰾㔠ᒓ㘒యࡢィ⟬࡟ࡣᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌࡟ᇶ࡙ࡃከཧ↷㟁Ꮚ┦㛵⌮ㄽࢆ⏝࠸࡚ࠊࢮࣟ☢ሙศ⿣ࢆᘬࡁ㉳ࡇࡍ୺࡞せᅉ࡛࠶ࡿࢫࣆࣥ㌶
㐨┦஫స⏝ࢆぢ✚ࡶࡿࡓࡵ࡟ࠊᚑ᮶ࡢ Quasi-degenerate perturbation (QDPT) ἲ࡛ࡣ࡞ࡃࠊࡼࡾ኱ࡁ࡞✵㛫࡛࠶ࡿ᏶඲άᛶ✵㛫࡟࡚ࢫࣆࣥ㌶㐨┦஫స⏝ࣁ࣑ࣝࢺࢽ࢔ࣥࢆᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌࡟࡚ᑐゅ໬ࡍࡿᡭἲࢆ⏝࠸ࡓࠋᚓࡽࢀࡓࢮࣟ☢ሙศ⿣࡟ࡼࡿ࢚ࢿࣝࢠ࣮ࣞ࣋ࣝ࠿ࡽࠊࡑࢀࡽࡢᅛ᭷್ࢆ෌⌧ࡍࡿࡼ࠺࡟ᇶᗏ≧ែ࠿ࡽ⏕ᡂࡍࡿࢫࣆࣥᑕᙳ㔞Ꮚᩘࡢࡳ␗࡞ࡿ≧ែ࡟ᑕᙳࡋࡓ᭷ຠࣁ࣑ࣝࢺࢽ࢔ࣥࢆᵓ⠏ࡋࠊࢫࣆࣥ≀ᛶࢆグ㏙ࡍࡿࡓࡵࡢ
D ࢸࣥࢯࣝࣃ࣓࣮ࣛࢱࢆ⏝࠸ࡓ୍⯡ⓗ࡞ࣔࢹࣝࣁ࣑ࣝࢺࢽ࢔ࣥࡢᅛ᭷್࡜ࡢẚ㍑࠿ࡽ D ࢸࣥࢯࣝࣃ࣓࣮ࣛࢱ
ࢆỴᐃࡋࡓࠋD ࢸࣥࢯࣝࣃ࣓࣮ࣛࢱ࠿ࡽࡣᑐゅ໬࡟ࡼࡾ☢໬ᐜ᫆㍈ࡢᐇ✵㛫࡟࠾ࡅࡿ᪉ྥ࡜ࣀ࣒ࣝࢆᑟ࠸ࡓࠋ
2.3 ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜయࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ
ⓎⰍᅋศᏊ㒊ศ㸦56 ཎᏊ㸧ࢆ QM 㡿ᇦ࡜ࡋࠊQM/MM RWFE-SCF ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋࡇࡢ㝿ࠊQM 㡿ᇦࡢィ⟬ࡣ M06-2X/6-31G**㸦⣙ 500 ᇶᗏ㛵ᩘ㸧ࢆ⏝࠸ࠊMM 㡿ᇦࡣ ACR1 ࡀ⣙ 20 ୓ཎᏊࠊhR ࡀ⣙ 9 ୓ཎᏊ࡛ࠊAmber ཬࡧ CHARMM ศᏊຊሙࢆ⏝࠸࡚グ㏙ࡋࡓࠋ
2.4 HIV ࣉࣟࢸ࢔࣮ࢮࡢ⸆๣⪏ᛶᶵᵓࡢゎᯒ཯ᛂάᛶ㒊఩࡜⸆๣ศᏊ㸦Indinavir㸧ࢆྵࡴ 105 ཎᏊ㸦ᇶᗏ㛵ᩘᩘ 1,060㸧ࢆ QM 㡿ᇦ࡜ࡋ࡚ QM/MM
RWFE-SCF ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋኳ↛ᇶ㉁ศᏊࡢ཯ᛂゎᯒ࡟㛵ࡋ࡚ࡣࠊ཯ᛂ
άᛶ㒊఩ࡢ 59 ཎᏊࢆ QM 㡿ᇦ࡜ࡋࡓ㸦ᇶᗏ㛵ᩘᩘ 590㸧ࠋMM 㡿ᇦࡣ⣙ 76,000 ཎᏊ࡛ Amber ศᏊຊሙࢆ⏝࠸࡚グ㏙ࡋࡓࠋ≧ែ㛫ࡢ⮬⏤࢚ࢿࣝࢠ࣮ᕪࡣ⮬⏤࢚ࢿࣝࢠ࣮ᦤືἲ࡟ࡼࡾィ⟬ࡋࡓࠋ
2.5 ගྜᡂ⣔ II㸦PSII㸧㓟⣲Ⓨ⏕୰ᚰࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿゎᯒ࣐ࣥ࢞ࣥࢡࣛࢫࢱ࣮཯ᛂ୰ᚰ㒊఩ࢆ QM 㡿ᇦ࡜ࡋ࡚ QM/MM RWFE-SCF ἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ཬࡧ MD ἲ࡟ࡼࡿ⮬⏤࢚ࢿࣝࢠ࣮ᦤືィ⟬ࢆ⾜ࡗࡓࠋQM 㡿ᇦࡢィ⟬ࡣ B3LYP ἲ㸦⣙ 2,000 ᇶᗏ㛵ᩘᩘ㸧ࢆ⏝࠸࡚⾜ࡗࡓࠋMM 㡿ᇦࡣ⣙ 400,000 ཎᏊ࡛ࠊAmber ศᏊຊሙࢆ⏝࠸࡚グ㏙ࡋࡓࠋ

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2.6 ࣆࣞࣥⰍ⣲ࢆᣢࡘⓎගᛶᾮయࡢග≉ᛶ࡜ࣞ࢜ࣟࢪ࣮ࡢゎᯒ
4 ✀㢮ࡢⓎගᛶᾮయศᏊ࡟ᑐࡋ࡚ࠊࣘࢼ࢖ࢸࢵࢻཎᏊࣔࢹࣝࢆ⏝࠸࡚ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࢩ࣑
࣮ࣗࣞࢩࣙࣥ⣔ࡣ஧ࡘࡢ⣔࡟㛵ࡋ࡚ 11,200 ཎᏊࠊṧࡾࡢ஧ࡘ࡟㛵ࡋ࡚ࡣ 35,200 ཎᏊ࡛࠶ࡿࠋ

3

◊✲ᡂᯝ

3.1 ከཧ↷㟁Ꮚ┦㛵⌮ㄽ࡟ࡼࡿ Fe 㘒యࡢ㧗㏿ࢫࣆࣥࢡࣟࢫ࣮࢜ࣂ࣮⌧㇟ࡢᶵᵓゎ᫂ඛ⾜⌮ㄽ◊✲࡛ぢ✚ࡶࡽࢀࡓࣇࣛࣥࢡ̽ࢥࣥࢻࣥ㡿ᇦ࡛ࡢࢫࣆࣥ㌶㐨┦஫స⏝ࡣࠊ᫬㛫ศゎ㐣Ώ྾཰ศග࡟ࡼ
ࡾ♧၀ࡉࢀࡿ ~50 fs ࡢ▷᫬㛫࡛ࡢ≧ែ㛫㑄⛣ࢆྍ⬟࡟ࡍࡿ࡟ࡣᑠࡉࡍࡂࡿࡇ࡜ࡀᣦ᦬ࡉࢀ࡚࠸ࡓࡀࠊᮏ◊✲࡛ࡣࣇࣛࣥࢡ̽ࢥࣥࢻࣥ㡿ᇦࢆ㞳ࢀࠊᑐ⛠ᛶࢆᔂࡍࡼ࠺࡞ᵓ㐀⦆࿴࡟క࠸ࢫࣆࣥ㌶㐨┦஫స⏝ࡀቑ኱ࡋࠊ㧗㏿࡞㑄⛣ࢆྍ⬟࡟ࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ୍㔜㡯࠿ࡽ୕㔜㡯ࠊࡑࡋ࡚஬㔜㡯࡬࡜࠸࠺஧ᅇࡢࢫࣆࣥ཯㌿ࡢ཯ᛂ⤒㊰࡟ἢࡗ࡚␗࡞ࡿ඲࡚ࡢࢫࣆࣥ≧ែࢆྵࡵࡓ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤⥺ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡑࡇ࡛
࢚ࢿࣝࢠ࣮‽఩࡜ࢫࣆࣥ㌶㐨┦஫స⏝ࡢ኱ࡁࡉ࠿ࡽ㑄⛣㏿ᗘࡢぢ✚ࢆヨࡳࡓ࡜ࡇࢁࠊከཧ↷ᦤືἲ࡛⏝࠸ࡿࢮࣟḟࡢࣁ࣑ࣝࢺࢽ࢔ࣥࡢ௵ពᛶࡀ኱ࡁࡃᙳ㡪ࡋࡓࡇ࡜࠿ࡽࢮࣟḟἼື㛵ᩘࡢ᭦࡞ࡿᨵⰋࡀᚲせ࡛࠶ࡿࡇ࡜
ࡀ⪃࠼ࡽࢀࡿࠋࡼࡗ࡚⤖ᯝࡣᖜࢆᣢࡗࡓᩘ್࡜࡞ࡿࡀ༑ศᐇ㦂್ࢆྵࡴ⠊ᅖࢆணࡍࡿࡇ࡜ࡀฟ᮶ࡓࠋ

3.2 ከ᰾㔠ᒓ㘒యࡢࢮࣟ☢ሙศ⿣࡜༢ศᏊ☢▼࡬ࡢᛂ⏝Co ᅄ᰾㘒యࡢᇶᗏ≧ែࢆከ㓄⨨Ἴື㛵ᩘ⌮ㄽ࡟ࡼࡾỴᐃࡋࡓࠋྠᐃࡉࢀࡓᇶᗏ㟁Ꮚ≧ែ࡛ࡣࠊ୍ࡘࡢ Co ࢖࢜ࣥࡢࡳ 1 ౯㸦d7㸧ࡢᛶ㉁ࢆࡶࡕࠊࡑࡢ௚㸱ࡘࡢ Co ࢖࢜ࣥࡣ 2 ౯㸦d8㸧ࡢᛶ㉁ࢆ୺㓄⨨࡜ࡋ࡚ࡶࡘࠋ඲࡚ࡢ
Co ࢖࢜ࣥ 3d ㌶㐨࡜㓄఩Ꮚ㌶㐨ࢆྵࡴάᛶ✵㛫࡟࠾ࡅࡿ☢Ẽ␗᪉ᛶࡢィ⟬࡛ࡣࠊCo(I)࡜㞄᥋ࡍࡿ N ཎᏊࡢ⤖ྜ᪉ྥࡀ☢໬ᐜ᫆㍈࡜࡞ࡗࡓࠋࡲࡓࠊࡑࡢࢮࣟ☢ሙศ⿣ࣃ࣓࣮ࣛࢱࡣ 10 cmᙉ࡛࠶ࡾᐇ㦂್ 12.34 cm࡟㏆࠸್ࡀᚓࡽࢀࡓࠋCo ࢖࢜ࣥ 3d ㌶㐨ࡔࡅ࠿ࡽ࡞ࡿάᛶ✵㛫࡟࠾ࡅࡿ☢Ẽ␗᪉ᛶࡢィ⟬࡛ࡣࠊ㓄఩Ꮚ㌶㐨
ࢆྵࡴሙྜ࡜࠾࠾ࡴࡡྠࡌྥࡁࡢ☢໬ᐜ᫆㍈ࡀᚓࡽࢀࡓࡀࠊࡑࡢ୺್ࡢ኱ࡁࡉࡣ 1/2 ⛬ᗘ࡜࡞ࡗࡓࠋ඲࡚ࡢ
༙༨᭷ 3d ㌶㐨࡜ྛ Co ཎᏊࡢ஧㔜༨᭷㌶㐨࠿ࡽ࡞ࡿ 4 ✀㢮ࡢάᛶ✵㛫࡟࠾ࡅࡿ☢Ẽ␗᪉ᛶࡢィ⟬࡛ࡣࠊ၏୍
d7 㟁Ꮚ㓄⨨࡛࠶ࡿ Co(I)ࡣ Co-N ᪉ྥࢆ☢໬ᐜ᫆㍈࡜ࡍࡿ☢Ẽ␗᪉ᛶࢆ♧ࡋࡓ୍᪉ࠊd8 㟁Ꮚ㓄⨨࡛࠶ࡿ Co(II)ࡢ☢Ẽ␗᪉ᛶࡣᑠࡉ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ௨ୖࡢ⤖ᯝ࠿ࡽࠊCo(()ࡢ☢Ẽ␗᪉ᛶࡀ㘒య඲యࡢ☢Ẽ␗᪉ᛶࡢ୺せ࡞㉳※࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡉࡽ࡟ࠊ୍⯡ࡢ㑄⛣㔠ᒓ㘒య࡟ࡘ࠸࡚ࡢゎᯒᡭἲࢆ㐺⏝ࡍࡿࡇ࡜࡛ࠊ
Co(I)ࡀୖ㏙ࡢ☢Ẽ␗᪉ᛶࢆ♧ࡍ࣓࢝ࢽࢬ࣒ࢆ 3d ㌶㐨ࡢᛶ㉁࡟ᇶ࡙࠸࡚ㄝ࡛᫂ࡁࡿࡇ࡜ࢆ♧ࡋࠊࡑࡢ 3d ㌶㐨
ࡢᛶ㉁ࡀᮏ㘒యࡢ㓄఩ᵓ㐀࡟ࡼࡾࡶࡓࡽࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࡇ࡜ࢆ♧ࡋࡓ
3.3 ᚤ⏕≀ᆺࣟࢻࣉࢩࣥගཷᐜయࢱࣥࣃࢡ㉁ࡢගάᛶ໬ᶵᵓࡢゎᯒ
ACR1 ࡟㛵ࡋ࡚ࡣࠊⓎⰍᅋศᏊࡢࣞࢳࢼ࣮ࣝࣉࣟࢺࣥ໬ࢩࢵࣇሷᇶࡢ㏆ഐࡢ࢝ࣝ࣎ࣥ㓟ഃ㙐ࡢࣉࣟࢺࣥ໬≧ែࢆㄪ࡭ࡿࡓࡵ࡟ࠊࣉࣟࢺࣥ໬≧ែࢆኚ࠼ࡓ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࠊཬࡧ MD ィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ
⤖ᯝࠊ࢝ࣝ࣎ࣥ㓟ഃ㙐ࡀࣉࣟࢺࣥ໬ࡋ࡚࠸ࡿሙྜࡣࠊሷ⣲࢖࢜ࣥࡀࢳࣕࢿࣝෆ࡟౵ධࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ
ࡓࠋࡲࡓࠊhR ࡟㛵ࡋ࡚ࡣࠊᐇ㦂࡛▱ࡽࢀ࡚࠸ࡿ⣽⬊እഃࡢ࢝ࣝ࣎ࣥ㓟ࡢ⬺ࣉࣟࢺࣥ໬ࡢᙳ㡪ࢆㄪ࡭ࡿࡓࡵ࡟ࠊ
⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜ࡗࡓࠋ
3.4 HIV ࣉࣟࢸ࢔࣮ࢮࡢ⸆๣⪏ᛶᶵᵓࡢゎᯒ㔝⏕ᆺཬࡧ⸆๣⪏ᛶኚ␗యࡢ୧⪅࡟ᑐࡋ࡚ࠋゐ፹άᛶࢆࡶࡓࡽࡍ஧ࡘࡢ࢝ࣝ࣎ࣥ㓟ഃ㙐ࡢࣉࣟࢺࣥ໬≧ែࢆࠊ⮬⏤࢚ࢿࣝࢠ࣮ᵓ㐀᭱㐺໬ཬࡧ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡟ࡼࡾỴᐃࡋࡓࠋࡑࢀࡽࡢࣉࣟࢺࣥ໬≧ែࢆ⏝࠸࡚ࠊ⸆๣⪏ᛶኚ␗ᑟධ࡟క࠺⸆๣ศᏊ⤖ྜ࢚ࢿࣝࢠ࣮ኚ໬ࢆ alchemy ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡟ࡼࡾồࡵࡓࠋࡑࡢ⤖ᯝࠊኚ␗࡟క࠺␯Ỉᛶ┦஫స⏝ࡢኚ໬࡟ࡼࡾࠊኚ␗య࡛⤖ྜ࢚ࢿࣝࢠ࣮ࡀ኱ᖜ࡟ῶᑡࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
3.5 ගྜᡂ⣔ II㸦PSII㸧㓟⣲Ⓨ⏕୰ᚰࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿゎᯒ

- 168 -

4 ಶࡢ␗࡞ࡿࣉࣟࢺࣥ໬≧ែ࡜ࠊ㓟໬≧ែࡢ␗࡞ࡿ S1 ཬࡧ S2 ୰㛫≧ែ࡟ᑐࡋ࡚ࠊQM/MM ⮬⏤࢚ࢿࣝࢠ࣮
ᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠸ࠊ᭦࡟ࡑࡢ㛫ࡢ⮬⏤࢚ࢿࣝࢠ࣮ᕪ㸦ࡍ࡞ࢃࡕ㓟໬㑏ඖ㟁఩࡜ࣉࣟࢺࣥ໬⮬⏤࢚ࢿࣝࢠ࣮㸧ࢆィ⟬ࡋࡓࠋࡑࡢ⤖ᯝࠊS1 ≧ែࡣࡇࢀࡲ࡛࡟௬ᐃࡉࢀ࡚࠸ࡿࣔࢹࣝࡼࡾከࡃࣉࣟࢺࣥ໬ࡉࢀ࡚࠾ࡾࠊࡲ
ࡓ S2 ≧ែ㑄⛣࡟క࠸ࣉࣟࢺࣥࡢ୍ࡘࡀูࡢࣉࣟࢺࣥ໬ࢧ࢖ࢺ࡟⛣ືࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋ
3.6 ࣆࣞࣥⰍ⣲ࢆᣢࡘⓎගᛶᾮయࡢග≉ᛶ࡜ࣞ࢜ࣟࢪ࣮ࡢゎᯒ
4 ✀㢮ࡢ␗࡞ࡿഃ㙐ࢆ᭷ࡍࡿⓎගᛶᾮయศᏊ࡟ᑐࡋ࡚ࠊࡑࢀࡒࢀ 25 ~ 50 ࣐࢖ࢡࣟ⛊ࡢ MD ࢩ࣑࣮ࣗࣞࢩࣙ
ࣥࢆ⾜ࡗࡓ࡜ࡇࢁࠊᐇ㦂࡛▱ࡽࢀ࡚࠸ࡿ⢓ᛶࡢ㐪࠸ࢆᐃᛶⓗ࡟෌⌧ࡍࡿࡇ࡜࡟ᡂຌࡋࠊ␗࡞ࡿഃ㙐࡟ࡼࡿᒁᡤ⁐ᾮᵓ㐀ࡢ㐪࠸ࡀ⢓ᛶࡢ㐪࠸ࢆ୚࠼࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬ICoPP2019 (International Conference on Photocatalysis and Photoenergy 2019), Inchon Korea 2019 ᖺ 5 ᭶ 24
᪥ Y. Kurashige, ͆Theoretical investigation of spin conversion processes in molecular systems͇ 㸦ᣍᚅㅮ₇㸧‫ ۻ‬QRS2019 workshop (XV International workshop on quantum reactive scattering), Saitama Japan 2019 ᖺ 7 ᭶ 3
᪥ Y. Kurashige, ͆Excited-State Quantum Dynamics with Time-Dependent Matrix-Product States͇㸦ᣍᚅㅮ₇㸧‫ ۻ‬APATCC2019 (Asia-Pacific Association of Theoretical and Computational Chemists), Sydney Australia, 2019 ᖺ
10 ᭶ 1 ᪥ Y. Kurashige,͆Excited-State Quantum Dynamics with Time-Dependent Matrix-Product States͇㸦ᣍᚅㅮ₇㸧‫ ۻ‬Telluride Science Research Center Workshop on ͆Protein Dynamics͇ Telluride, USA, 2019 ᖺ 7 ᭶ 8 ᪥
Shigehiko Hayashi “Atomistically deciphering functional processes of transporter and redox proteins withmolecular simulations”㸦ᣍᚅㅮ₇㸧‫ ۻ‬Frontiers in Multiscale Modelling of Photoreceptor Proteins, Tel Aviv, Israel,2019 ᖺ 9 ᭶ 4 ᪥ ShigehikoHayashi “Atomistically deciphering functional processes of photoreceptor proteins with molecular simulations”
㸦ᣍᚅㅮ₇㸧‫ ۻ‬APATCC2019, Sydney, Australia, 2019 ᖺ 10 ᭶ 2 ᪥ Shigehiko Hayashi “Atomistically deciphering functional
processes of photoreceptor and redox proteins with molecular simulations” 㸦ᣍᚅㅮ₇㸧
‫ ۻ‬5th International Conference on Molecular Simulation (ICMS 2019), Jeju, Korea, 2019 ᖺ 11 ᭶ 5 ᪥ ShigehikoHayashi “Atomistically deciphering functional processes of transporter and redox proteins with molecularsimulations” 㸦ᣍᚅㅮ₇㸦࣮࢟ࣀ࣮ࢺㅮ₇㸧㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬Jastrow-type Decomposition in Quantum Chemistry for Low-Depth Quantum Circuits. Yuta Matsuzawa andYuki Kurashige, J. Chem. Theory Comput., 16, 944–052 (2020). DOI: 10.1021/acs.jctc.9b00963‫ ۻ‬Soft chromophore featured liquid porphyrins and their utilization toward liquid electret applications. Avijit
Ghosh, Manabu Yoshida, Kouji Suemori, Hiroaki Isago, Nagao Kobayashi, Yasuhisa Mizutani, Yuki Kurashige,
Izuru Kawamura, Masami Nirei, Osamu Yamamuro, Tomohisa Takaya, Koichi Iwata, Akinori Saeki, Kazuhiko
Nagura,Shinsuke

Ishihara,

TakashiNakanishi,Nat.

Commun,10,42101–9(2019).

DOI:

110.1038/s41467-019-12249-8‫ ۻ‬Rank-one basis made from matrix-product states for a low-rank approximation of molecular aggregates. Soichiro
Nishio and Yuki Kurashige, J. Chem. Phys., 151, 1084110 (2019). DOI: 10.1063/1.5093346- 169 -

⺮ⓑ㉁࡟ࡼࡿ DNA ຍỈศゎ࡟࠾ࡅࡿ⁐፹ࡢᙺ๭The role of solvent in DNA hydrolysis with a protein‫ۑ‬ධబ ṇᖾࠊ኱す ฿㸦஑ᕞᕤᴗ኱Ꮫ኱Ꮫ㝔᝟ሗᕤᏛ㝔㸧1◊✲┠ⓗࠊෆᐜ

II ᆺไ㝈㓝⣲ EcoRV ࡣ࣍ࣔࢲ࢖࣐࣮࡛࠶ࡾࠊDNA ࡢ≉ᐃࡢ㓄ิࢆ㑅ᢥⓗ࡟ㄆ㆑ࡋࠊ≉␗ⓗ࡟ DNA 㙐ࢆษ᩿ࡍࡿࠋࡇࡢຍỈศゎ཯ᛂ࡟ࡣ Mg2+ ࢖࢜ࣥࡀᚲ㡲࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ᫖ᖺᗘሗ࿌ࡋࡓࡼ࠺࡟ࠊ
3D-RISM ィ⟬ࡢ⤖ᯝ࡟ᇶ࡙࠸࡚ Mg2+ ࢆ EcoRV ࡟ 2 ಶ/(άᛶ㒊఩) ࡎࡘ㓄⨨ࡋศᏊືຊᏛࢆ⾜࠺࡜ࠊscissile ࣜࣥ㓟ᇶࡀࢶ࢖ࢫࢺࡋồ᰾ᨷᧁࡍࡿỈศᏊࡀ཯ᛂ࡟㐺ษ࡞఩⨨࡟㓄఩ࡋࠊάᛶ㒊఩ࡢᵓ㐀ࡀ㔠ᒓ࢖࢜ࣥࡢ఩⨨ࡶྵࡵ BamHI–DNA 」ྜయࡢ⤖ᬗᵓ㐀 (2bam) ࡟㠀ᖖ࡟ఝ㏻ࡗࡓᵓ㐀࡜࡞ࡗࡓ[1]ࠋࡇࡢ MD ࡛ᚓࡽࢀࡓᖹ⾮≧ែࡢ❧యᵓ㐀ࢆ௨㝆 Structure M ࡜࿧ࡧࠊࡇࡢᵓ㐀୰ࡢ Mg2+ ࡢ఩⨨ࢆ site A (=site I), B ࡜࿧ࡪࠋ௒ᅇࠊ᭦࡟ Structure M ࢆึᮇᵓ㐀࡜ࡋ࡚」ᩘࡢ᮲௳࡛ヲ⣽࡞㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗࡓ⤖ᯝࠊ EcoRV ࡢ
DNA ຍỈศゎࡢ཯ᛂ⤒㊰ࢆண

2ࡍࡿ㔜せ࡞⤖ᯝࡀᚓࡽࢀࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ཯ᛂ๓㥑యࡢึᮇᵓ㐀࡜ࡋ࡚ Structure M ࢆ௬ᐃࡋࠊ QM/MM ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫィ⟬ࢆ⾜ࡗࡓࠋQM ᡭἲ࡜ࡋ࡚ࡣ Amber ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ༙⤒㦂ⓗᡭἲ DFTB3/3OB ࢆ⏝࠸ࡓࠋ཯ᛂᗙᶆ࡜ࡋ࡚
ࡣ (1) scissile ࣜࣥ㓟ᇶࡢ P ࡜ồ᰾๣ࡢỈศᏊࡢ O ཎᏊ㛫ࡢ㊥㞳 (RC1) ࠾ࡼࡧ (2) ⿕ษ᩿⤖ྜ (scissile bond) ࡢ㛗ࡉ (RC2) ࢆ㑅ࡧ(ᅗ1)ࠊStructure M ࢆ཯ᛂጞ≧ែ࡜ࡋ࡚ QM/MM ࣓ࢱࢲ࢖ࢼ
࣑ࢡࢫィ⟬ࢆ⾜ࡇ࡜࡟ࡼࡾࠊ RC1 ࡜ RC2 ࡟ἢࡗࡓᖹᆒຊ࣏ࢸࣥ ᅗ 1: Structure M, an equilibrium active-site
structure obtained from MD trajectories in ourprevious study. Two reaction coordinates (RCs),
P–OW distance (RC1) and bond-length of thescissile-bond (RC2), are adopted to analyze theresults of QM/MM metadynamics.

ࢩࣕࣝ (PMF) ᭤㠃ࢆồࡵࡓ(ᅗ2)ࠋ

3

◊✲ᡂᯝ

ィ⟬ࡢ⤖ᯝࠊồ᰾๣࠾ࡼࡧᇶ㉁ࡢỈศᏊࡣᐇ㝿࡟Structure M ࡛ೃ⿵࡜ࡋ࡚ண

ࡋࡓỈศᏊ࡛࠶ࡿࡇ࡜ࡀศ

࠿ࡗࡓࠋ௨㝆ࡣࠊ࣍ࣔࢲ࢖࣐࣮ࡢ 1 ࡘࡢࢧࣈࣘࢽࢵࢺ࡛
࠶ࡿ A 㙐ࢆྵࡴࢧࣈࣘࢽࢵࢺࡢ⤖ᯝࡢࡳࢆㄝ᫂ࡍࡿࠋ௒
ᅇᚓࡓ PMF ᭤㠃 (ᅗ 2) ࢆゎᯒࡋࡓ⤖ᯝࠊゎ㞳ᛶ཯ᛂ⤒㊰ࡢ᪉ࡀ ఍ྜᛶ཯ᛂ⤒㊰ࡼࡾࡶ࢚ࢿࣝࢠ࣮ࣂࣜ࢔ࡀప
࠸࡜࠸࠺⤖ᯝࡀᚓࡽࢀࡓ (ᅗ 3)ࠋ࢚ࢿࣝࢠ࣮ࣂࣜ࢔ࡢ㧗ࡉࡣࡑࢀࡒࢀゎ㞳ᛶ཯ᛂ⤒㊰ࡀ⣙ 11 kcal/molࠊ఍ྜᛶ཯ᛂ ⤒ ㊰ ࡀ ⣙ 14 kcal/mol ࡔ ࡗ ࡓ ࠋ Imhof ࡽ ࡀ ⾜ ࡗ ࡓ
QM/MM ィ⟬࡛ࡣࠊᡃࠎ࡜ࡣ␗࡞ࡿ఩⨨࡟ Mg2+ ࢖࢜ࣥࢆ 2 ಶ/(άᛶ㒊఩) 㓄⨨ࡋࡓึᮇᵓ㐀ࢆ౑⏝ࡋ࡚࠾ࡾࠊ
࢚ࢿࣝࢠ࣮ࣂࣜ࢔ࡣ 22 kcal/mol ࡔࡗࡓࠋィ⟬⤖ᯝ࠿ࡽồ- 170 -

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ࡵࡓゎ㞳ᛶ཯ᛂ⤒㊰࡛ࡣࠊồ᰾๣࠾ࡼࡧᇶ㉁ࡢỈศᏊࡣࡑࢀࡒࢀ site A, B ࡢ Mg2+ ࢖࢜ࣥࡢ㓄఩Ꮚࡢ≧ែࢆ⥔ᣢࡋࡓࠋࡲࡓࠊゎ㞳ᛶ཯ᛂ⤒㊰ࡢᚊ㏿ẁ㝵 (state E, ᅗ 3) ࡣࠊᇶ㉁ࡢỈศᏊ࠿ࡽ᪂ࡓ࡟⏕ᡂࡉࢀࡿDNA ࡢ 3’ ᮎ➃ࡢO ࡬ࡢࣉࣟࢺࣥ⛣ືࡔࡗࡓࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊ site A࡜ B ࡢ 2 ࡘࡢ Mg2+ ࢖࢜ࣥࡀࡑࢀࡒࢀồ᰾๣࠾ࡼࡧ
ᇶ㉁࡜ࡋ࡚ࡢỈศᏊࡢ⬺ࣉࣟࢺࣥ໬ࢆ⿵ຓࡋ࡚࠸ࡿࡇ

ᅗ 3: PMFs of minimum energy pathways fordissociative pathway (solid line) and associative࡜ࡀ♧၀ࡉࢀࡓ(ᅗ 4)ࠋ
௒ᅇࠊ3D-RISM ⌮ㄽ࡛ண ࡋࡓồ᰾๣࡜ᇶ㉁ೃ⿵ࡢỈศᏊࡣࠊ㔞Ꮚ໬Ꮫィ⟬࡟࠾࠸࡚ࡶࠊᐇ㝿࡟ồ᰾๣ཬࡧᇶ㉁࡜ࡋ࡚ാ࠸࡚࠸ࡿࡇ࡜
ࢆ‵ࡍࡇ࡜ࡀ࡛ࡁࡓࠋ௒ᚋ 3D-RISM ⌮ㄽࢆࠊ௚ࡢຍỈศゎ㓝⣲࡟ᑐࡋ࡚ࡶࠊồ᰾๣࠾ࡼࡧᇶ㉁ೃ⿵ࡢỈศᏊࡢ఩⨨ࢆぢࡘࡅࡿᡭἲ࡜ࡋ
࡚᥇⏝࡛ࡁࡿྍ⬟ᛶࡀ㛤࠿ࢀࡓࠋ᭦࡟ࠊ㔞Ꮚ໬Ꮫィ⟬࠿ࡽᚓࡓ཯ᛂ⤊≧ែࡢ❧యᵓ㐀ࡣࠊ
EcoRV–DNA 」ྜయࡢ DNA ษ᩿ᚋࡢᵓ㐀࡟ᑐᛂࡍࡿࠊ㹖⥺⤖ᬗᵓ㐀 (1rvc) ࡜㦫ࡃ⛬୍⮴ࡋ࡚࠸ࡓࠋࡇࡢࡇ࡜ࡣࠊ௒ᅇࡢ㔞Ꮚ໬Ꮫィ⟬⤖ᯝࡣࠊEcoRV ࡢ DNA ษ᩿཯ᛂ࡛㉳ࡇࡾ࠺ࡿάᛶ㒊఩ࡢ㟁Ꮚ≧ែኚ໬ࢆ࠶ࡿ⛬ᗘṇࡋࡃ෌⌧࡛ࡁ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ

4

ᅗ 4: ồ᰾๣ࡀࣜࣥ࡟࢔ࢱࢵࢡࡍࡿࠋAsp90
ࢆ௓ࡋࡓࣉࣟࢺ࣮ࣥࣜࣞࡀ㉳ࡇࡾᇶ㉁ࡢ
OH- ࡀࣉࣟࢺࣥࢆࡶࡽࡗ࡚Ỉ࡟࡞ࡿࠋⓎ⾲ᐇ⦼ࡲࡓࡣணᐃ

Ⓨ⾲: ‫ ➨ۻ‬57 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, 2019 ᖺ 9 ᭶ 24 ᪥–26 ᪥, ᐑᓮ.
Ⓨ⾲: ‫ ➨ۻ‬42 ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘, 2019 ᖺ 10 ᭶ 30 ᪥ –11 ᭶ 1 ᪥, ௝ྎ.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

ฟ∧[1]: ‫ۻ‬Itaru Onishi, Shunya Sunaba, Norio Yoshida, Fumio Hirata, and Masayuki Irisa, “Role of Mg2+ Ions in
DNA Hydrolysis by EcoRV, Studied by the 3D-Reference Interaction Site Model and Molecular Dynamics”, J. Phys.
Chem. B, 122, 39, 9061-9075 (2018) DOI: 10.1021/acs.jpcb.7b12555- 171 -

┦㛵㟁Ꮚ⣔ࡢ≉␗࡞≀ᛶ࡟㛵ࡍࡿᩘ್ⓗ◊✲Computational Study on Anomalous Properties ofCorrelated Electron Systems‫ۑ‬ኴ⏣ᖾ๎ࠊす⏣ᑦኸࠊᒣཱྀక⣖ࠊ⸨ෆுࠊ⏣㎶ဴᐶࠊ஭ୖ㞞㧗ࠊ㧗ᶫㄹࠊᑠᯘ㣁ேࠊᒣᮏᓧ௓㸦༓ⴥ኱࣭⌮㸧

1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࡢ┠ⓗࡣࠊ㑄⛣㔠ᒓ໬ྜ≀ࠊ᭷ᶵᑟయࠊ㔜࠸㟁Ꮚ⣔໬ྜ≀࡞࡝࡟ࡼࡗ࡚௦⾲ࡉࢀࡿᙉࡃ┦஫స⏝ࡍࡿከ㟁Ꮚ⣔ࡢ㟁Ꮚ≧ែ࡜ࡑࡢప࢚ࢿࣝࢠ࣮ບ㉳ࢆࠊ┦㛵㟁Ꮚ⣔ࡢᇶᮏᶍᆺ࡛࠶ࡿࣁࣂ࣮ࢻᶍᆺࡸ㛵㐃ࡍࡿ✀ࠎࡢᶍᆺࡢ㔞Ꮚ໬Ꮫⓗ࡞࠸ࡋィ⟬≀⌮Ꮫⓗᡭἲࠊ≉࡟ᑡᩘ⣔ࡢᩘ್ⓗཝᐦᑐゅ໬(ED)ࠊኚศࢡࣛࢫࢱ࣮㏆
ఝ(VCA)[1]ࠊᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌(DMRG)ࡢᡭἲࠊ᫬㛫Ⓨᒎࣛࣥࢳࣙࢫἲ࡞࡝ࢆ⏝࠸࡚✲᫂ࡍࡿࡇ࡜࡛࠶ࡿࠋ
ᮏᖺᗘࡣࠊ୺࡟⇕ⓗ⣧⢋㔞Ꮚ≧ែ(TPQ state)[2]ࡢ᪉ἲࢆ⏝࠸ࡓኚศࢡࣛࢫࢱ࣮ἲ࡟ࡼࡿࣁࣂ࣮ࢻᶍᆺࡢ᭷
㝈ᗘ≀ᛶࡢゎ᫂ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲᚑ᮶ࡢ㔞Ꮚ⤫ィຊᏛ࡛ࡣࠊ᭷㝈ᗘࡢ≀⌮㔞ࡣ࢔ࣥࢧࣥࣈࣝᖹᆒࢆࡍࡿᚲせࡀ࠶ࡾࠊࡑࢀࢆཝᐦ࡟ᐇ⾜ࡍࡿࡓࡵ࡟ࣁ࣑ࣝࢺࢽ࢔ࣥࡢ඲ᅛ᭷್࣭඲ᅛ᭷࣋ࢡࢺࣝࢆồࡵࡿ᏶඲ᑐゅ໬ࡲࡓࡣ㒊ศᑐゅ໬ࢆᐇ⾜ࡍࡿᚲせࡀ࠶ࡿࠋࡇࡢሙྜࠊࣁ࣑ࣝࢺࢽ࢔ࣥࡢ⾜ิࢧ࢖ࢬࡣࢩࢫࢸ࣒ࢧ࢖ࢬࡀ኱ࡁࡃ࡞ࡿ࡟ࡘࢀ࡚ᛴ㏿࡟኱ࡁࡃ࡞ࡿ
ࡓࡵࠊィ⟬ࢥࢫࢺࡢ㠃࠿ࡽࢩࢫࢸ࣒ࢧ࢖ࢬࡀཝࡋࡃไ㝈ࡉࢀ࡚ࡋࡲ࠺ࠋࡇࢀ࡟ᑐࡋ࡚ࠊ㏆ᖺࡢ㔞Ꮚ⤫ィຊᏛ
ࡢⓎᒎ࡟ࡼࡾࠊࢩࢫࢸ࣒ࢧ࢖ࢬࡢ኱ࡁ࡞㔞Ꮚ⣔࡛ࡣࠊ༢୍ࡢἼື㛵ᩘࡢ⹫᫬㛫Ⓨᒎ࡟ࡼࡗ࡚ᚓࡽࢀࡓ඾ᆺⓗ࡞⣧⢋≧ែ(TPQ state)࡟ࡼࡗ࡚࢔ࣥࢧࣥࣈࣝᖹᆒࡀ⨨ࡁ᥮࠼ྍ⬟࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀ࡚࠸ࡿ[2]ࠋࡇࡢ⌮ㄽࡣ⤫ィຊᏛ࡟࠾࠸࡚ࠕ඾ᆺᛶ (typicality)ࠖ࡟ᇶ࠸࡚ᐃᘧ໬ࡉࢀࡓ⏬ᮇⓗ࡞⌮ㄽ࡛࠶ࡿࠋ඾ᆺᛶ࡜ࡣࠊࠕ㔞Ꮚከయ⣔ࡢ㔞Ꮚ⣧⢋≧ែࢆ௵ព࡟ 1 ࡘ㑅ࢇࡔ᫬ࠊࡑࡢ≀⌮㔞ࡢᮇᚅ್ࡣ㸦ᅽಽⓗ࡞☜⋡࡛㸧⇕ᖹ⾮≧ែ࡟࠾ࡅࡿ≀⌮㔞ࡢᮇᚅ್࡜㠀ᖖ࡟㏆࠸್ࢆ♧ࡍࡇ࡜ࠋ࡛ࠖ࠶ࡿࠋࡇࡢཎ⌮࠿ࡽࠊཝᐦᑐゅ໬ἲ࡛⏝࠸ࡽࢀ࡚ࡁࡓࣛࣥࢳࣙ
ࢫἲࡢ࢔ࣝࢦࣜࢬ࣒ࢆ᥇⏝ࡋ࡚⇕ⓗ⣧⢋㔞Ꮚ≧ែࢆᵓᡂࡍࡿࡇ࡜࡛ࠊᚑ᮶ࡣゎᯒࡀᅔ㞴ࡔࡗࡓࢩࢫࢸ࣒ࢧ࢖
ࢬࡲ࡛ཝᐦ࡞᭷㝈ᗘィ⟬ࡀᐇ⾜࡛ࡁࡿࡼ࠺࡟࡞ࡗࡓࠋࡓࡔ౫↛࡜ࡋ࡚ࢩࢫࢸ࣒ࢧ࢖ࢬࡢไ㝈ࡣṧࡗࡓࡲࡲ࡛࠶ࡿࠋࡇࢀ࡟ᑐࡋ࡚ࠊ⮬ᕫ࢚ࢿࣝࢠ࣮ỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃ㔞Ꮚࢡࣛࢫࢱ࣮㏆ఝࡣࠊ⇕ຊᏛⓗᴟ㝈ࢆᢅ࠼ࡿ᭷ຠ࡞ᡭἲ࡛࠶ࡿࠋ౛࠼ࡤࠊVCA ࡣᑡᩘࢡࣛࢫࢱ࣮ࡢࢢ࣮ࣜࣥ㛵ᩘ࠿ࡽ⇕ຊᏛⓗᴟ㝈࡟࠾ࡅࡿᙉ┦㛵㟁Ꮚ⣔ࡢ⇕ຊᏛ㛵ᩘ࡜୍⢏Ꮚບ㉳ࢫ࣌ࢡࢺࣝࡀồࡲࡾࠊ⮬Ⓨⓗ࡞ᑐ⛠ᛶࡢ◚ࢀࡀᏑᅾࡍࡿሙྜࡶᢅ࠼ࡿᡭἲ࡛࠶ࡿࠋ
ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ
TPQ ࢆᑡᩘࢧ࢖ࢺࢯࣝࣂ࣮࡟⏝࠸࡚᭷㝈
2 ḟඖṇ᪉᱁Ꮚࣁࣂ࣮ࢻᶍᆺࡢ᭷㝈ᗘ VCA ࡢ᪂ࡓ࡞ᩘ್ィ⟬ᡭἲࡢ㛤Ⓨࢆ⾜࠸ࠊᗘゎᯒ࡟㐺⏝ࡋࡓࠋ౑⏝ࡋࡓࣉࣟࢢ࣒ࣛ:ᑡᩘ⣔ࡢᩘ್ⓗཝᐦᑐゅ໬ἲࡢࣉࣟࢢ࣒ࣛࠊ⮬ᕫ࢚ࢿࣝࢠ࣮ỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃኚศ
ࢡࣛࢫࢱ࣮㏆ఝィ⟬ࡢࣉࣟࢢ࣒ࣛࠊ᫬㛫Ⓨᒎࣛࣥࢳࣙࢫἲࡢࣉࣟࢢ࣒ࣛࠋࡇࢀࡽࡣᡃࠎࡢࢢ࣮ࣝࣉࡀ⊂⮬࡟
㛤Ⓨࡋࡓࡶࡢ࡛࠶ࡿࠋ

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3◊✲ᡂᯝᮏᖺᗘࡣࠊィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢࣜࢯ࣮ࢫ฼⏝࡟ࡼࡾࠊ௨ୗࡢ 3 ࡘࡢᡂᯝࡀᚓࡽࢀࡓࠋy

TPQ state ࡟ࡼࡿࣛࣥࢲ࣒ࢧࣥࣉࣜࣥࢢᖹᆒ࡟ᑐ
ࡍࡿࢢ࣮ࣜࣥ㛵ᩘ࡜㟼ⓗ≀⌮㔞ࡢศᩓ࡜ᖹᆒ್
ࢆㄪᰝࡋࠊཝᐦゎ࡬ࡢ཰᮰⢭ᗘࢆ☜ㄆࡋࡓࠋ඾
ᆺᛶ࠿ࡽ TPQ state ࡣࢩࢫࢸ࣒ࢧ࢖ࢬࡀ኱ࡁ࠸࡯
࡝ᑡ࡞࠸ࢧࣥࣉࣝᩘ࡛⇕ᖹ⾮್ࢆ⋓ᚓ࡛ࡁࠊᖹ

ᅗ 1.

ᆒ್࡜ศᩓࡀ VCA ࡟ᚲせ࡞⢭ᗘࡲ࡛ᚓࡽࢀࡓ

CPT ࡟ࡼࡿ 1 ḟඖࣁࣂ࣮ࢻᶍᆺࡢ
୍⢏Ꮚບ㉳ࢫ࣌ࢡࢺࣝ(12site).

ࡇ࡜ࢆ☜ㄆࡋࡓࠋy1 ḟඖࣁࣂ࣮ࢻᶍᆺࡢࣔࢵࢺ㌿⛣ࡣࠊࢫࣆࣥ࡜㟁Ⲵࡢศ㞳࡟ࡼࡗ࡚ㄝ᫂ࡉࢀࠊࡑࡢ≉ᚩࡣ୍⢏Ꮚບ㉳ࢫ࣌ࢡࢺࣝ࡟⌧ࢀࡿࠋࡑࡇ࡛᭷㝈ᗘࡢ୍⢏Ꮚࢢ࣮ࣜࣥ㛵ᩘ࡟ CPT ࢆ㐺⏝ࡉࡏࠊᗘࡈ࡜ࡢ୍⢏Ꮚບ㉳ࢫ࣌ࢡࢺࣝࢆồࡵࠊ᫬㛫౫Ꮡᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌ἲ(tDMRG)࡟ࡼࡿඛ⾜◊✲[3]࡜ࡢ༑ศ࡞୍⮴ࢆ☜ㄆࡋࡓ㸦ᅗ㸯㸧ࠋy2 ḟඖṇ᪉᱁Ꮚࣁࣂ࣮ࢻᶍᆺࡢ᭷㝈ᗘ VCA ࡟ࡼࡿゎᯒࢆ⾜࠸ࠊ⇕ຊᏛᴟ㝈࡟࠾ࡅࡿࢢࣛࣥࢻ࣏ࢸࣥࢩࣕࣝࢆኚศཎ
⌮࡟ᇶ࡙࠸࡚᭱㐺໬ࡍࡿࡇ࡜࡛ࠊ཯ᙉ☢ᛶ┦࡜↓⛛ᗎ┦ࡢ㌿⛣ᗘࢆ᫂ࡽ࠿࡟ࡋࡓ㸦ᅗ㸰㸧ࠋࡉࡽ࡟⛛ᗎኚᩘࠊ⢏Ꮚᩘࠊ࢚ࣥࢺࣟࣆ࣮ࠊẚ⇕ࡢᗘ౫Ꮡᛶࢆ᫂ࡽ࠿࡟ࡋࡓࠋ



ᅗ 2. 2 ḟඖṇ᪉᱁Ꮚ(12site)ࡢ཯
ᙉ☢ᛶ Weiss ሙ࡟ᑐࡍࡿࢢࣛࣥࢻ࣏
ࢸࣥࢩࣕࣝࡢ ᗘ౫Ꮡᛶ. T/t = 0.2 ~
0.3 (0.01).

௒ᅇ㛤Ⓨࡋࡓᩘ್ィ⟬ᡭἲࡣࠊ㞳ᩓ㔞Ꮚ⣔࡜ࡋ࡚グ㏙࡛ࡁࡿ⣔࡛࠶ࢀࡤ௚࡟ไ㝈ࡣ୍ษ࡞ࡃࠊ࡝ࡢࡼ࠺࡞⣔࡛ࡶ㐺⏝ྍ⬟࡛࠶ࡿࠋ౛࠼ࡤࠊືⓗᖹᆒሙ⌮ㄽ(DMFT)࡛୙⣧≀ࢯࣝࣂ࣮࡜ࡋ࡚⏝࠸ࡿ㔞Ꮚࣔࣥࢸ࢝ࣝࣟ(QMC)ἲ࡛࣎ࢺࣝࢿࢵࢡ࡜࡞ࡗ࡚࠸ࡿ㈇➢ྕၥ㢟ࡣ⏕ࡌࡎࠊᐦᗘ⾜ิ⧞ࡾ㎸ࡳ⩌(DMRG)ἲࡢࡼ࠺࡟㧗ḟඖ⣔࡛ᛴ㏿࡟ィ⟬⢭ᗘࡀⴠࡕࡿ࡜࠸ࡗࡓၥ㢟ࡶ࡞࠸ࡓࡵࠊ2 ḟඖࣇࣛࢫࢺ
࣮ࣞࢩࣙࣥ⣔ࡸࣇ࢙࣑ࣝ࢜ࣥ⣔࡟ᛂ⏝ྍ⬟࡞ᡭἲ࡜࡞ࡿࠋࡋࡓࡀࡗ࡚ࠊᮏ◊✲࡛㛤Ⓨࡋࡓᡭἲࡀከ✀ከᵝ࡞㔞Ꮚᶍᆺ◊✲࡟㐺⏝ࡉࢀࡿ࡜ᮇᚅࡍࡿࠋ ཧ⪃ᩥ⊩[1] M. Potthoff, Eur. Phys. J. B 36, 335 (2003).
[2] S. Sugiura and A. Shimizu, Phys. Rev. Lett. 108, 240401 (2012).
[3] A. Nocera, F. H. L. Essler, and A. E. Feiguin, Phys. Rev. B 97, 045146 (2018).

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃす⏣௚ࠊ᪥ᮏ≀⌮Ꮫ఍㸦2020 ⛅, Ⓨ⾲ணᐃ㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫“ۻ‬Typicality-Based Variational Cluster Approach to Thermodynamic Properties of the Hubbard Model”,
Hisao Nishida, Ryo Fujiuchi, Koudai Sugimoto, and Yukinori Ohta, J. Phys. Soc. Jpn. 89, 023702 (2020).

- 173 -

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. 24 -

5

A9`D•p

T. Yagasaki, M. Matsumoto, and H. Tanaka, "Lennard-Jones Parameters Determined to Reproduce the

Solubility of NaCl and KCl in SPC/E, TIP3P, and TIP4P/2005 Water", J. Chem. Theory Comput. 16, 2460
(2020).
•



H. Tanaka, T. Yagasaki, and M. Matsumoto, "On the Role of Intermolecular Vibrational Motions for Ice

Polymorphs. II. Atomic Vibrational Amplitudes and Localization of Phonons in Ordered and Disordered
Ices", J. Chem. Phys. 152, 074501 (2020).
•

H. Tanaka, T. Yagasaki, and M. Matsumoto, "On the Role of Intermolecular Vibrational Motions for Ice

Polymorphs I: Volumetric Properties of Crystalline and Amorphous Ices", J. Chem. Phys. 151, 114501(2019).
•



T. Yagasaki, M. Yamasaki, M. Matsumoto, and H. Tanaka, "Formation of Hot Ice Caused by Carbon

Nanobrushes", J. Chem. Phys. 151, 064702 (2019).

- 177 -

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ᅗ 3+7 ศᏊࡢཎᏊᩘࢆኚ࠼ࡓ࡜ࡁࡢ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲࡢィ⟬᫬㛫 V  ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿ࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụࡢ᪂つṇᏍ㍺㏦ᮦᩱࡢศᏊ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࠸ࡿࡀ㸪ࡼࡾ㧗࠸࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆಖᣢࡋࡘࡘࡼࡾᏳ౯࡞ྜᡂࢥࢫࢺࡀ᥎ᐃࡉࢀࡿᮦᩱࡢ᥈⣴ࡀᚲせ࡛࠶ࡿ㸬ᮏ◊✲࡛ࡣ㸪ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜ᶵᲔᏛ⩦ࢆ⏝࠸࡚ṇᏍ㍺㏦ᮦᩱࢆຠ⋡ⓗ࡟᥈⣴ࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓ㸬᪤ᏑࡢṇᏍ㍺㏦ᮦᩱࡢศᏊᵓ㐀ࡢ⤌ྜࡏ࠿ࡽศᏊࢆ⏕ᡂࡋ㸪ࡑࡢ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆ᥎ࡍࡿᏛ⩦ࣔࢹࣝࢆᵓ⠏ࡋࡓ㸬Ꮫ⩦ࣔࢹࣝࡢカ⦎ࢹ࣮ࢱ࡟ࡣ㸪࣌ࣟࣇࢫ࢝࢖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✚㸪࢚ࢿࣝࢠ࣮
ኚ᥮ຠ⋡ࢆ᥇⏝ࡋࡓ㸬 ศᏊࡢṇᏍ㍺㏦ᮦᩱࢆ  ࡘࡢࣇࣛࢢ࣓ࣥࢺ࡟ศゎࡋ㸪ࡇࢀࡽࡢࣇࣛࢢ࣓ࣥࢺࡢ⤌ྜࡏ࠿ࡽೃ⿵ศᏊࢆᵓ⠏ࡋࡓ㸬0RUGUHG ࢆ⏝࠸࡚ࣇࣛࢢ࣓ࣥࢺẖ࡟ศᏊグ㏙Ꮚࢆィ⟬ࡋࡓ㸬㔞Ꮚ໬Ꮫィ⟬࠿ࡽᚓࡽࢀࡿグ㏙Ꮚ +202㸪/802㸪඲࢚ࢿࣝࢠ࣮㸪㟁Ꮚ࢚ࢿࣝࢠ࣮㸪⏕ᡂ⇕㸪ศᩓຊ࢚ࢿࣝࢠ࣮㸪཮ᴟᏊ࣮࣓ࣔࣥࢺ  ࡣ 17&KHP ࢆ౑ࡗ࡚ィ⟬ࡋࡓ㸬ࡇࢀࡽࡢ⤌ࡳྜࢃࡏࢆṇᏍ㍺㏦ᮦᩱࡢධຊࢹ࣮ࢱ࡜ࡋ㸪࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆ᥎ࡍࡿ῝ᒙࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡࢆᵓ⠏ࡋࡓ㸬඾ᆺⓗ࡞ᐇ㦂᮲௳ࡢࡶ࡜ೃ⿵ศᏊࢆ࢞࢘

ࢫ㐣⛬ᅇᖐࣔࢹࣝ࡟ࡼࡗ࡚㑅ᢥࡋࡓ㸬௬᝿ᐇ㦂࡜ࡋ࡚㸪῝ᒙࢽ࣮ࣗࣛࣝࢿࢵࢺ࣮࣡ࢡ᥎
Ꮚࡢ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆ᥎ࣔࢹࣝ࠿ࡽೃ⿵ศ

ࡋࡓ㸬௬᝿ᐇ㦂ࢆ⧞ࡾ㏉ࡍࡇ࡜࡛㸪࢞࢘ࢫ㐣⛬ᅇᖐࣔࢹࣝࢆᨵၿࡋ㸪᭱㐺࡞ೃ⿵ศᏊࢆ᥈⣴ࡋࡓ㸬ೃ⿵ศᏊࡢ⤌ྜࡏࡣ࠾ࡼࡑ  ㏻ࡾ࡜࡞ࡾ㸪ࡇࡢࢣ࣑࢝ࣝ✵㛫ࢆ⥙⨶ⓗ࡟᥈⣴ࡍࡿࡇ࡜ࡣᅔ㞴࡛࠶ࡿ㸬㞳ᩓ⢏Ꮚ⩌᭱㐺໬ࢆ᥇⏝ࡋ㸪⭾኱࡞ࢣ࣑࢝ࣝ✵㛫ࢆ᥈⣴ࡋࡓ㸬ࡇࡢ᥎ࣔࢹࣝࡀ୚࠼ࡿ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆ┠ⓗ㛵ᩘ࡜ࡋ࡚㞳ᩓ⢏Ꮚ⩌᭱㐺໬ἲࢆ㐺⏝ࡋࡓ㸬඾ᆺⓗ࡞ᐇ㦂᮲௳࡜ࡋ࡚ 7L2 㟁
Ꮚ㍺㏦ᒙ࡜ )$3E,  0$3E%U  άᛶᒙࢆ᥇⏝ࡋೃ⿵ศᏊࡢ᥈⣴ࢆ⾜ࡗࡓ㸬6$) 㦵᱁࠾ࡼࡧ 6); 㦵᱁ࢆ᭷ࡍࡿೃ⿵ศᏊࡢ࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࡀ㧗࠸ࡇ࡜ࡀ♧ࡉࢀࡓ㸬 ᭷ᶵⷧ⭷ኴ㝧㟁ụ࡟࠾ࡅࡿ㠀ࣇ࣮ࣛࣞࣥ⣔పศᏊ࢔ࢡࢭࣉࢱ࣮ࡢศᏊタィ᭷ᶵⷧ⭷ኴ㝧㟁ụࡣ᭷ᶵ༙ᑟయ࠿ࡽᵓᡂࡉࢀࡿ࢚ࢿࣝࢠ࣮ኚ᥮ࢹࣂ࢖ࢫ࡛࠶ࡿࡀ㸪ኚ᥮ຠ⋡ࡀప࠸ࡇ࡜ࡀ
ᐇ⏝໬ࡢㄢ㢟࡜࡞ࡗ࡚࠸ࡿ㸬ኴ㝧㟁ụࡢᛶ⬟ࢆྥୖࡉࡏࡿ᪉ἲ࡜ࡋ࡚ࡣ㸪ಟ㣭࡟ࡼࡿ≀ᛶไᚚࡸࢱࣥࢹ࣒໬
ࡀᣲࡆࡽࢀࡿ㸬ᚑ᮶ࡣ࢔ࢡࢭࣉࢱ࣮࡟ࣇ࣮ࣛࣞࣥㄏᑟయࡀ⏝࠸ࡽࢀ࡚ࡁࡓࡀ㸪/802 ไᚚࡢほⅬ࠿ࡽ㠀ࣇࣛ- 179 -

࣮ࣞࣥ⣔పศᏊࡀὀ┠ࡉࢀ࡚࠸ࡿ㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪ಟ㣭ࡋࡓ௵ពࡢ໬ྜ≀ࢆᐇ㦂ⓗ࡟ྜᡂࡋ㸪ࢻࢼ࣮࣭࢔ࢡ
ࢭࣉࢱ࣮㸪࡞ࡽࡧ࡟ࡑࢀࡽࡢࢱࣥࢹ࣒࡟ࡘ࠸࡚㸪࠶ࡽࡺࡿ⤌ࡳྜࢃࡏࢆ᳨ドࡍࡿࡢࡣ㠀⌧ᐇⓗ࡛࠶ࡿ㸬ࡲࡓ㸬ࡇࢀࡲ࡛ࡢ⌮ㄽ◊✲࡛ᢅࢃࢀࡓ⤌ࡳྜࢃࡏࡶࡈࡃഹ࠿࡛㸪᮲௳ࢆᥞ࠼ࡓࢹ࣮ࢱࡀᚲせ࡛࠶ࡿ㸬ࡑࡇ࡛㸪ィ⟬໬Ꮫ࡟ࡼࡾ᭷ᶵⷧ⭷ኴ㝧㟁ụࡢᛶ⬟ࢆホ౯ࡋ㸪᭱㐺໬ᣦ㔪ࢆ♧ࡍࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬㔞Ꮚ໬Ꮫィ⟬࡟ࡣ
17&KHP ࢆ⏝࠸ࡓ㸬᭷ᶵⷧ⭷ኴ㝧㟁ụೃ⿵ᮦᩱࡢ㔞Ꮚ໬Ꮫィ⟬ࢆ %/<3GHI693 ࡛ࣞ࣋ࣝ⾜ࡗࡓ㸬ࢻࢼ࣮࡟ࡣ 3+7 ࠾ࡼࡧ 37%㸪࢔ࢡࢭࣉࢱ࣮࡟ࡣᩥ⊩>&<DQHWDO1DW5HY0DWHU  @࡟グ㍕ࡉࢀ࡚࠸ࡿࡶ
ࡢࢆ୰ᚰ࡟㸪LQGDFHQRGLWKLRSKHQH ㄏᑟయࢆ㑅ࢇࡔ㸬LQGDFHQRGLWKLRSKHQH ㄏᑟయࡢ≀ᛶࡣ L  ࢥ࢔ࡢ⦰⎔⣔ࡢ኱ࡁࡉ㸪 LL  ᮎ➃ᇶࡢ㟁Ꮚồᘬᛶ㸪 LLL  ഃ㙐ࡢ❧య㞀ᐖ࡟ࡼࡾỴᐃࡉࢀࡿ㸬ࡇࢀࡽࡢ⤌ࡳྜࢃࡏ࡟ࡘ࠸࡚㸪
60,/(6 ࡟ࡼࡾ࢖ࣥࣉࢵࢺࢆ⏕ᡂࡍࡿࢫࢡࣜࣉࢺࢆᐇ⿦ࡋ㸪ィ⟬ࢆ⾜ࡗࡓ㸬࢔ࢡࢭࣉࢱ࣮ࡢ୰࡛᭱ࡶ /802ࡀప࠿ࡗࡓࡢࡣᮎ➃ᇶ࡟ࣇࢵ⣲ࢆᑟධࡋࡓ⣔࡛࠶ࡿ ᅗ  㸬ᮎ➃ᇶࡢ㟁Ꮚồᘬᛶ࡟ࡼࡾ /802 ࢆไᚚ࡛ࡁࡿ
ࡇ࡜ࢆ☜ㄆࡋࡓ㸬௒ᚋࡣ⛣ືᗘ࡞࡝ࡢ≀ᛶࡶྵࡵ㸪௚ࡢ㠀ࣇ࣮ࣛࣞࣥ࢔ࢡࢭࣉࢱ࣮࡟ࡘ࠸࡚ࡶィ⟬ࢆ⾜࠺㸬ࡲࡓ㸪'\QDPLF0RQWH&DUOR ἲ࡟ࡼࡾኴ㝧㟁ụࡢᛶ⬟ࢆホ౯ࡍࡿணᐃ࡛࠶ࡿ㸬ᅗ  ࢻࢼ࣮ 㟷  ࠾ࡼࡧ࢔ࢡࢭࣉࢱ࣮ ㉥  ࡢ +202㸪/802 ‽఩ ࢫࣆࣥ཯㌿ᆺ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲ࡟ࡼࡿ㠀᩿⇕ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
㧗࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡ࢆࡶࡘኴ㝧㟁ụᮦᩱศᏊࡢ⌮ㄽタィࢆ⾜ࡗࡓ㸬ග྾཰࡟ࡼࡾ⏕ᡂࡍࡿṇᏍ࣭㟁Ꮚᑐບ㉳Ꮚ  ࡢࢲ࢖ࢼ࣑ࢡࢫࢆィ⟬ᶵࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾ⌮ゎࡍࡿ㸬≉࡟㸪ࢻࢼ࣮࣭࢔ࢡࢭࣉࢱ࣮㛫ࡢ㟁Ⲵ⛣ື≧ែ࠿ࡽ㟁Ꮚᇶᗏ≧ែ࡬ࡢኻά㐣⛬ 㟁Ⲵ෌⤖ྜ࡟ࡼࡿᦆኻ  ࡣኚ᥮ຠ⋡ࢆᕥྑࡍࡿࡓࡵ㸪㐺ษ࡞ィ⟬ᡭἲࢆᑟධࡋゎᯒࡍࡿᚲせࡀ࠶ࡿ㸬ࡑࡢࡓࡵ࡟㸪ࢫࣆࣥ཯㌿ᆺ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲࢆศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔ࠕ17&KHPࠖ࡟ᐇ⿦ࡋࡓ㸬ࡇࡢ᪉ἲࡢ㛗ᡤࡣ㸪᭱ప㟁Ꮚບ㉳≧ែ࠿ࡽ㟁Ꮚᇶᗏ≧ែ࡬ࡢ㑄⛣ࢆ⮬↛࡟
グ㏙࡛ࡁࡿⅬ࡛࠶ࡿ㸬ࡉࡽ࡟㸪7XOO\ ࡟ࡼࡿ㠀᩿⇕ศᏊືຊᏛ࢔ࣝࢦࣜࢬ࣒ >-&7XOO\-&KHP3K\V
 @ ࢆ᥇⏝ࡋ㸪㠀᩿⇕ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⌧ࡋࡓ㸬࠸ࡃࡘ࠿ࡢศᏊ࡛ࢸࢫࢺィ⟬ࢆ⾜࠸㸪᪉ἲㄽ࡜ࡋ࡚ࡢ᭷⏝ᛶࢆ☜ㄆࡋ㸪ᡂᯝࢆㄽᩥ࡜ࡋ࡚Ⓨ⾲ࡋࡓ㸬ᐇ㝿ࡢศᏊ⣔࡛ࡣ㸪ศᏊ㛫┦஫స⏝ࡀࢲ࢖ࢼ࣑ࢡࢫ࡟ᙳ㡪ࡍࡿ㸬ࡑࡇ࡛㸪ὀ┠ࡍࡿศᏊࢆ㔞Ꮚ໬Ꮫィ⟬ 40 㸪࿘ᅖࡢศᏊࢆྂ඾ⓗ࡞ศᏊຊሙ 00  ࡜ࡍࡿ 4000 ἲࢆ᥇⏝ࡋࡓ㸬ࢸࢫࢺィ⟬࡜ࡋ࡚㸪⥳Ⰽ⺯ගࢱࣥࣃࢡ㉁ࡢⓎⰍᅋࡢ㠀᩿⇕ศᏊືຊᏛࢩ࣑ࣗࣞ
࣮ࢩࣙࣥࢆ⾜ࡗࡓ㸬ࡇࡢศᏊࡣỈ⁐ᾮ୰࡛ࡣ⺯ග཰⋡ࡀⴭࡋࡃῶᑡࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾ㸪㠀᩿⇕㑄⛣࡟ࡼࡿᇶᗏ≧ែ࡬ࡢ⦆࿴ࡀᥦ᱌ࡉࢀ࡚࠸ࡿ㸬ᐇ㝿ࡢィ⟬࡛ࡣ㸪ᇶᗏ≧ែ࡬⣙  IV ࡛⦆࿴ࡍࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ ᅗ  㸬ࡲࡓ㸪཯ᛂᗙᶆ࡜ࡋ࡚  ဨ⎔ഃࡢ && ⤖ྜࡢࡡࡌࢀࡀ㔜せ࡛࠶ࡾ㸪㐺ᙜ࡞⨨᥮ᇶࡸ࢔࣑ࣀ㓟ṧᇶࢆᑟධࡍࡿࡇ࡜࡛཯ᛂࢆไᚚ࡛ࡁࡿྍ⬟ᛶࢆ♧ࡋࡓ㸬ࡇࡢᡂᯝࡶㄽᩥ࡜ࡋ࡚Ⓨ⾲ࡋࡓ㸬ࢫࣆࣥ཯㌿ᆺࡢ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲࢆᑟධࡍࡿࡇ࡜࡛㸪ᇶᗏ≧ែ࡬ࡢ⦆࿴ࢲ࢖ࢼ࣑ࢡࢫࢆ⮬↛࡞ᙧ࡛グ㏙࡛ࡁࡿࡼ࠺࡟࡞ࡗࡓ㸬
4000 ἲ࡬࡜ᣑᙇࡍࡿࡇ࡜࡛㸪ᐇ㝿ࡢศᏊ⣔ࢆᶍࡋࡓ㠀᩿⇕ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࡀྍ⬟࡛࠶ࡿ㸬- 180 -

௒ᚋࡢㄢ㢟࡜ࡋ࡚㸪ᐇ㝿ࡢኴ㝧㟁ụ࡛⏝࠸ࡽࢀ࡚࠸ࡿࡼ࠺࡞ࢻࢼ࣮࣭࢔ࢡࢭࣉࢱ࣮」ྜศᏊ⣔࡟ᑐࡋ࡚㐺⏝ࢆ᳨ウࡋ࡚࠸ࡿ㸬ᅗ  ⓎⰍᅋศᏊࡢࢺࣛࢪ࢙ࢡࢺ࣮ࣜ౛
 Ⓨ⾲࣭ฟ∧ᐇ⦼‫ @>ۻ‬୰ᔱ㝯ே㸪͇ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࢆ฼⏝ࡋࡓศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿ᪂ᮦ
ᩱタィ͇㸪͆$, ࡜᭷ᶵྜᡂ໬Ꮫ͇ ➨  ᅇබ㛤ㅮ₇఍㸪᪩✄⏣㸪 ᖺ  ᭶  ᪥㸬‫ @>ۻ‬୰ᔱ㝯ே㸪͇㦫ࡃ࡭ࡁࢫࣃࢥࣥࡢୡ⏺̽ࡑࡢά⏝࡜ᮍ᮶ᒎᮃ̽͆㸪㔞Ꮚ⛉Ꮫᢏ⾡◊✲㛤ⓎᶵᵓᏛ⾡᝟ሗὶ
㏻ㅮᗙ㸪✄ẟ㸪 ᖺ  ᭶  ᪥㸬
‫ @>ۻ‬୰ᔱ㝯ே㸪͆ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫࡢ⼥ྜ࡟ࡼࡿ᪂ᮦᩱタィ ̽ᐩᓅ࡟ྥࡅ࡚͇̽㸪➨ ᅇ࢟ࣕࢱࣜࢫࢺ࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫࢩ࣏ࣥࢪ࣒࢘㸪ᮾி㸪 ᖺ  ᭶  ᪥㸬‫ @>ۻ‬୰ᔱ㝯ே㸪͆ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࢆ฼⏝ࡋࡓ➨୍ཎ⌮ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ᪂ᮦᩱタィ͇㸪᪂໬Ꮫᢏ⾡᥎㐍༠఍ඛ➃໬Ꮫ࣭ᮦᩱᢏ⾡㒊఍ㅮ₇఍㸪ᮾி㸪 ᖺ  ᭶  ᪥㸬‫ @>ۻ‬1 0LQH]DZD 7 1DNDMLPD ³4XDQWXP PHFKDQLFDOPROHFXODU PHFKDQLFDO WUDMHFWRU\ VXUIDFH KRSSLQJ PROHFXODUG\QDPLFVVLPXODWLRQE\VSLQIOLSWLPHGHSHQGHQWGHQVLW\IXQFWLRQDOWKHRU\´-&KHP3K\V   
‫@>ۻ‬7<RQHKDUD71DNDMLPD ³(OHFWURQG\QDPLFVPHWKRGXVLQJDORFDOO\SURMHFWHGJURXSGLDEDWLF)RFNPDWUL[IRU
PROHFXOHVDQGDJJUHJDWHV´&KHP3K\V   
‫ @>ۻ‬: 8HPXUD 7 1DNDMLPD ³5HTXLUHG QXPEHU RI VWDWHV LQFUHDVHV RQO\ PRGHUDWHO\ ZLWK WKH SUREOHP VL]H IRUDQWLV\PPHWUL]HGJHPLQDOSRZHUV´DU;LY  ‫ @> ۻ‬1 0LQH]DZD 7 1DNDMLPD ³7UDMHFWRU\ VXUIDFH KRSSLQJ PROHFXODU G\QDPLFV VLPXODWLRQ E\ VSLQIOLSWLPHGHSHQGHQWGHQVLW\IXQFWLRQDOWKHRU\´-&KHP3K\V  ‫@>ۻ‬:8HPXUD71DNDMLPD³$QWLV\PPHWUL]HGJHPLQDOSRZHUVZLWKODUJHUFKHPLFDOEDVLVVHWV´3K\V5HY$
  ‫@>ۻ‬7<RQHKDUD10LQH]DZD71DNDMLPD³([FLWHG6WDWH'\QDPLFVLQ17&KHP´LQ0ROHFXODU6SHFWURVFRS\$
4XDQWXP&KHPLVWU\$SSURDFKHGLWHGE\<2]DNL0-:RMFLN-3RSS :LOOH\ ±  >@ : 'DZVRQ ⃝⏣ၨ௓ ⚄㇂᐀᫂ ୰ᔱ㝯ே ³ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࠕᐩᓅࠖ࡟ྥࡅࡓศᏊ⛉Ꮫィ⟬ࢯࣇࢺ࢙࢘࢔ࠕ17&KHPࠖࡢ㛤Ⓨ´ ࢩ࣑࣮ࣗࣞࢩࣙࣥ±  >@ ୰ᔱ㝯ே ᯇᒸ㈗ⱥ ³ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿ࣌ࣟࣈࢫ࢝࢖ࢺᮦᩱࡢೃ⿵᥈⣴´ගᏛ±  - 181 -

⏕యศᏊࡢ࣐ࣝࢳࢥࣆ࣮࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ
0XOWLFRS\DQGPXOWLVFDOHVLPXODWLRQRIELRPROHFXOHV‫ۑ‬᳃ḟ ᆂ㸦ᶓ὾ᕷ኱㝔㸧 ◊✲┠ⓗࠊෆᐜ◊✲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
࢙࢔ࠕPOLEࠖࡢ㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓ KWWSZZZFVUSULNHQMSDSSOLFDWLRQBMKWPO ࠋࡲࡓࠊࡑࡢ࢔ࣉࣜࢣ࣮ࢩࣙࣥ࡜
ࡋ࡚ࠊ⮬⏤࢚ࢿࣝࢠ࣮᭱ᑠ⤒㊰᥈⣴ἲ㸦ࢫࢺࣜࣥࢢἲ㸧࡜ᵓ㐀᥈⣴ἲ㸦06(6 ἲ㸧ࡢ◊✲㛤Ⓨࢆ⾜ࡗࡓࠋࢫࢺࣜࣥࢢἲ࡛ࡣࠊ඲ཎᏊࣔࢹࣝ࡜ప⮬⏤ᗘࡢ㞟ᅋᗙᶆ㸦FROOHFWLYHYDULDEOHV&9V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
◊✲࡛ࡣࠊከ๣᤼ฟ $%& ࢺࣛࣥࢫ࣏࣮ࢱ࣮㸦$%&%㸧࡟ᮏᡭἲࢆ㐺⏝ࡋࠊ⸆๣㠀⤖ྜ࠾ࡼࡧ⸆๣⤖ྜ≧ែ࡟࠾ࡅࡿᵓ㐀ኚ໬ࣃࢫ࡜ࡑࡢ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆィ⟬ࡋࡓࠋ ◊✲᪉ἲࠊィ⟬᪉ἲࢫࢺࣜࣥࢢἲࡢィ⟬ᑐ㇟࡜ࡋ࡚ࡣࠊ⸆๣䛾యෆືែ䛻㛵䜟䜛 $%&䠄$73ELQGLQJFDVVHWWH䠅ከ๣᤼ฟ䝖䝷䞁䝇䝫䞊䝍䞊䛾୍䛴䛷䛒䜛 &P$%&% ࢆ㑅ࢇࡔࠋ⤖ᬗᵓ㐀ゎᯒ࡛ᚓࡽࢀࡓ &P$%&% ࡢෆྥᆺࠊእྥᆺࡢ  ࡘࡢ≧ែ࡛ࡢ❧యᵓ㐀᝟ሗࢆ⏝࠸ࠊ0' ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥ౑⏝ࡍࡿࣔࢹࣝࡢసᡂࢆ⾜࡞ࡗࡓࠋ⬡㉁ศᏊ 323& ಶ࣭ỈศᏊ 7,3 ࣔࢹࣝ⣙  ୓ಶࢆ⏝࠸࡚సᡂࡋࡓ⬡㉁஧㔜⭷ࡢ㔜ᚰ࡟ࢱࣥࣃࢡ㉁⤖ᬗᵓ㐀ࡢ⭷㈏㏻㒊఩ࡢ㔜ᚰࢆ㔜ࡡྜࢃࡏࡿࡇ࡜࡛ࢱࣥࣃࢡ㉁ࢆᇙࡵ㎸ࢇࡔࠋࡑࡢ㝿ࠊእྥᆺࡢ⤖ᬗᵓ㐀࡛ࡣ⤖ᬗ໬Ᏻᐃࡢࡓࡵኚ␗ࢆ࠿ࡅ
࡚࠸ࡓࡢ࡛㸦4$7$㸧㔝⏕ᆺ࡟ᡠࡋࡓࠋ⁐ᾮࡢሷ⃰ᗘࡀ  P0 ࡜࡞ࡿࡼ࠺࡟ࢼࢺ࣒ࣜ࢘࢖࢜ࣥ࠾ࡼ
ࡧሷ⣲࢖࢜ࣥࢆຍ࠼ࠊྜィ⣙  ୓ཎᏊ࠿ࡽ࡞ࡿ⣔ࢆᵓ⠏ࡋࡓࠋ⸆๣࡜ࡋ࡚ࡣࠊ⸆๣⃰ᗘ࡟ᑐࡋ࡚ $73 άᛶࡢୖ᪼ࢆ♧ࡍᐇ㦂⤖ᯝࡀ࠶ࡿ 5KRGDPLQH * ࢆ㑅ᢥࡋࠊࢻࢵ࢟ࣥࢢࢩ࣑࣮ࣗࣞࢩࣙࣥࢯࣇࢺ *2/' ࢆ⏝࠸࡚ྛ⤖ᬗᵓ㐀࡟⤖ྜࡋࡓᵓ㐀ࣔࢹࣝࢆᵓ⠏ࡋࡓࠋຊሙ࡜ࡋ࡚ࡣ &+$500ࠊ㟼㟁ⓗ┦஫స⏝ࡢィ⟬࡟ࡣ 3DUWLFOH
PHVK(ZDOG ἲࢆ⏝࠸ࠊ137 ࢔ࣥࢧࣥࣈ࡛ࣝ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋࡲࡎጞࡵ࡟ࠊෆྥᆺ࠿ࡽእྥᆺᵓ㐀ࢆࡘ࡞ࡄࡼ࠺࡞㠀ᖹ⾮ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦7DUJHWHG0'㸧ࢆᐇ⾜ࡋࠊ᭱㐺໬ࡍ࡭ࡁึᮇࣃࢫࢆᵓ⠏ࡋࡓࠋࡤࡡᐃᩘ࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫ࡢࣃ࣓ࣛࢱࢆኚ࠼࡞ࡀࡽࠊẁ㝵ࡈ࡜࡟ศ๭ࡋࡓᡭἲ࡞࡝ࡶྵࡵ࡚ᵝࠎ࡞ࢸࢫࢺィ⟬ࢆヨࡳࡓࠋ᭱㐺࡛࠶ࡿ࡜ࡉࢀࡓࢺࣛࢪ࢙ࢡࢺࣜࢆࢫࢺࣜࣥࢢἲࡢ
ึᮇࣃࢫ࡜ࡋ࡚ࠊ⸆๣㠀⤖ྜ≧ែ࠾ࡼࡧ 5KRGDPLQH* ࡀ⤖ྜࡋࡓ≧ែ࡟ࡘ࠸࡚ࠊ᭱ᑠ⮬⏤࢚ࢿࣝࢠ࣮⤒㊰᥈⣴ࢆᐇ⾜ࡋࡓࠋᚓࡽࢀࡓึᮇࣃࢫୖ࡛➼㛫㝸࡟࡞ࡿࡼ࠺࡟  ಶࡢ࢖࣓࣮ࢪࢆ㑅ᢥࡋࠊ QV ࡟ࢃࡓࡗ࡚༑ศ
࡟ึᮇࣃࢫᖹ⾮໬ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ༑ศ࡟ࣃࢫୖࡢᵓ㐀ࡀ⦆࿴ࡋࡓࡇ࡜ࢆ☜ㄆࡋࡓᚋࠊ ḟᵓ㐀ࢆᙧᡂࡍࡿṧᇶࡢ &DཎᏊᗙᶆ㸦 ಶ㸧ࢆ཯ᛂᗙᶆ &9V ࡜ࡋ࡚ࢫࢺࣜࣥࢢἲࢆ  ࢫࢸࢵࣉ SV[VWHSV QV ᐇ⾜ࡋࠊᵓ㐀ኚ໬ࣃࢫࡢ᭱㐺໬ࢆ⾜ࡗࡓࠋ᭱ᚋ࡟ࠊྛ࢖࣓࣮ࢪࢆᖹ⾮఩⨨࡜ࡍࡿࣁ࣮ࣔࢽࢵࢡ࣏

- 182 -

ࢸࣥࢩࣕࣝࢆ࠿ࡅࡓ QV ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊPXOWLVWDWH%HQQHWWDFFHSWDQFHUDWLR 0%$5 ἲࢆ⏝࠸࡚⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆィ⟬ࡋࡓࠋィ⟬࡟ࡣࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࣉࣟࢢ࣒ࣛ *(1(6,6 ࢆ⏝࠸ࡓࠋ ◊✲ᡂᯝ
࣭ࢫࢫࢺࣜࣥࢢἲ࡟ࡼࡿ $%&% ࡢᵓ㐀ኚ໬ࣃࢫィ⟬
$73ELQGLQJFDVVHWWH $%&  ࢺࣛࣥࢫ࣏࣮ࢱ࣮ࡣࠊ⃰ᗘ໙㓄࡟㏫ࡽ࠸⣽⬊⭷ࢆ㏻ࡋ࡚ࠊᵝࠎ࡞ᇶ㉁㸦⬡㉁ࠊ
⸆๣ࠊ࢖࢜ࣥࠊ࣌ࣉࢳࢻ࡞࡝㸧ࢆ㍺㏦ࡍࡿ⭷ࢱࣥࣃࢡ㉁࡛࠶ࡿࠋከࡃࡢ $%& ࢺࣛࣥࢫ࣏࣮ࢱ࣮࡟ࡘ࠸࡚ࠊᇶ㉁㍺㏦࡟ࡘ࡞ࡀࡿᵓ㐀ኚ໬࣓࢝ࢽࢬ࣒ࡀ◊✲ࡉࢀ࡚ࡁࡓࡀࠊᮏ◊✲࡛ࡣࠊᵝࠎ࡞⸆๣㸦ከ๣㸧ࢆ⣽⬊እ࡟᤼ฟࡍࡿከ๣᤼ฟ $%& ࢺࣛࣥࢫ࣏࣮ࢱ࣮$%&% ࢆ◊✲ᑐ㇟࡜ࡋࡓࠋෆྥᆺ࠾ࡼࡧእྥᆺࡢ  ᵓ㐀ࡀ⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡾゎ࠿ࢀ࡚࠾ࡾࠊ$73 ⤖ྜ࡟ࡼࡾ᰾㓟⤖ྜࢻ࣓࢖ࣥ 1%' ࡀ⤖ྜࡋࠊࡑࡢ㥑ືຊ࡟ࡼࡾ⭷㈏㏻ࢻ࣓
࢖ࣥ 70' ࡀෆྥᆺ࠿ࡽእྥᆺ࡬ࡢ኱ࡁ࡞ᵓ㐀ኚ໬ࡍࡿࡇ࡜ࠊࡲࡓࠊࡑࡢ኱ࡁ࡞ᵓ㐀ኚ໬࡜ඹᙺࡋ࡚⸆๣ࡀ
⣽⬊ෆ࠿ࡽእ࡟㍺㏦ࡉࢀࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋ࠶ࡿ✀ࡢ⸆๣㸦5KRGDPLQH*㸧࡟ࡘ࠸࡚⸆๣⃰ᗘ࡟ᑐࡋ࡚ $73
άᛶࡢୖ᪼ࢆ♧ࡍᐇ㦂⤖ᯝࡶ࠶ࡾࠊ⸆๣┦஫స⏝࡟ࡼࡾୖグࡢᵓ㐀ኚ໬ࡀಁ㐍ࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࠋ
ᮏ◊✲࡛ࡣࡲࡎࠊࢫࢺࣜࣥࢢἲࢆ㐺⏝ࡍࡿ࠺࠼࡛ࡢၥ㢟Ⅼ࡛࠶ࡿࠊࠕ᭱㐺໬ࡍ࡭ࡁึᮇࣃࢫࢆ࡝࠺タᐃࡍࡿ࠿ࠖࠊ࡟ྲྀࡾ⤌ࢇࡔࠋෆྥᆺ࠿ࡽእྥᆺᵓ㐀ࢆࡘ࡞ࡄࡼ࠺࡞㠀ᖹ⾮ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦7DUJHWHG 0'㸧ࢆࠊࢱ࣮ࢤࢵࢺ࡜࡞ࡿᵓ㐀㸦඲య࠿ 1%' ࢻ࣓࢖ࣥࡢࡳ࠿࡞࡝㸧ࡸࠊࡤࡡᐃᩘ࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫࡞࡝ࡢࣃ࣓ࣛ
ࢱࢆኚ࠼࡞ࡀࡽᐇ⾜ࡋࠊ␗࡞ࡿึᮇࣃࢫ⏕ᡂࢆࡓࡃࡉࢇヨࡳࡓࠋࡑࡢ⤖ᯝ࡜ࡋ࡚ࠊ1%' ࢻ࣓࢖ࣥࡀ㛢ࡌ࡚࠿
ࡽ 70' ࢻ࣓࢖ࣥࡀ㛤ࡃࣃࢫࡀ㸦⸆๣ࡀ࠺ࡲࡃ㍺㏦ࡉࢀࡿ࠿࡜࠸࠺Ⅼ࡟࠾࠸࡚ࡶ㸧᭱㐺࡛࠶ࡿࡇ࡜ࠊࡲࡓࠊ
୧➃࡛ࡶࣜࣛࢵࢡࢫࡋࡓᵓ㐀ࣃࢫࢆຠ⋡ⓗ࡟ᚓࡿࡓࡵࠊෆྥᆺ࡜እྥᆺᵓ㐀୧➃࠿ࡽጞࡵࡓࣃࢫࢆ࢚ࢿࣝࢠ
࣮ࡢ㑄⛣≧ែ௜㏆࡛ࡘ࡞ࡂྜࢃࡏࡓࣃࢫࡀࢫࢺࣜࣥࢢἲࡢึᮇࣃࢫ࡜ࡋ࡚ࡣ㐺ษ࡛࠶ࡿࡇ࡜ࢆぢฟࡋࡓࠋ
ḟ࡟ࠊୖグ࡛᭱㐺࡛࠶ࡿ࡜ࡉࢀࡓࢺࣛࢪ࢙ࢡࢺࣜࢆࢫࢺࣜࣥࢢἲࡢึᮇࣃࢫ࡜ࡋ࡚ࠊ⸆๣㠀⤖ྜ≧ែ࠾ࡼ
ࡧ 5KRGDPLQH* ࡀ⤖ྜࡋࡓ≧ែ࡟ࡘ࠸࡚᭱ᑠ⮬⏤࢚ࢿࣝࢠ࣮⤒㊰᥈⣴ࢆᐇ⾜ࡋࡓࠋ༑ศ࡟ึᮇࣃࢫୖࡢᵓ㐀ࡀ⦆࿴ࡋࡓࡇ࡜ࢆ☜ㄆࡋࡓᚋࠊࢫࢺࣜࣥࢢἲࢆ  ࢫࢸࢵࣉィ⟬ࡋࡓ࡜ࡇࢁࠊᵓ㐀ኚ໬ࣃࢫࡢ཰᮰ࡀ☜ㄆ࡛ࡁࡓ㸦ᅗ 㸧ࠋᅗ  ⸆๣㠀⤖ྜ≧ែ࡛ࡢ $%&% ࢫࢺࣜࣥࢢἲࣃࢫ᭱㐺໬ࡢ཰᮰ᛶࠋ ᕥ  ྛ࢖࣓࣮ࢪ࡛ࡢึᮇࣃࢫ࠿ࡽࡢ 506'ࠋ㸦ྑ㸧⭷㈏㏻ࢻ࣓࢖ࣥ 70' ⦪㍈ ࡜᰾㓟⤖ྜࢻ࣓࢖ࣥ 1%' ᶓ㍈ ࡢ㐠ື࠿ࡽぢࡓᵓ㐀ኚ໬ࣃࢫࡢ᭦᪂ࠋ

- 183 -ᅗ  ࡟ 0%$5 ࡟ࡼࡾィ⟬ࡉࢀࡓ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࢆ♧ࡍࠋ࢖࣓࣮ࢪ  ࠿ࡽ  ࡛ࡣࠊ1%' ࢻ࣓࢖ࣥࡀ㛢ࡌࡘࡘ 70' ࢻ࣓࢖ࣥࡀෆྥᆺᵓ㐀ࢆಖࡗ࡚࠸ࡿࠋࡑࡢࡼ࠺࡞ 2FFOXGHG ࡞ᵓ㐀࡟㏆࡙ࡃ࡟ࡘࢀ࡚⮬⏤࢚ࢿࣝࢠ࣮ࡀୖ᪼ࡍࡿࡇ࡜࠿ࡽࠊ2FFOXGHG ࡞ᵓ㐀ࡣᵓ㐀ኚ໬ࣃࢫୖ࡛㑄⛣ⓗ࡞୙Ᏻᐃ≧ែ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡿࠋ⸆
๣㠀⤖ྜ≧ែ DSR ࡛ࡣࠊ2FFOXGHG ᵓ㐀ࢆ㉸࠼ࡿ࡜⮬⏤࢚ࢿࣝࢠ࣮ࡀୗࡀࡾእྥᆺᵓ㐀࡟⮳ࡿࡢ࡟ᑐࡋࠊ⸆๣
⤖ྜ≧ែ KROR ࡛ࡣࠊ⸆๣㍺㏦࡟㛵ࢃࡿᵓ㐀ࡦࡎࡳ࡟ࡼࡾࡉࡽ࡟⮬⏤࢚ࢿࣝࢠ࣮ࡀୖ᪼ࡋࡓࡢࡕ࡟እྥᆺᵓ㐀࡟฿㐩ࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋᅗ  $%&% ࢫࢺࣜࣥࢢἲ࡟ࡼࡾᚓࡽࢀࡓ⸆๣㠀⤖ྜ≧ែ㸦㟷㸧ࠊཬࡧࠊ5KRGDPLQH* ⤖ྜ≧ែ㸦㉥㸧࡛ࡢ⮬⏤࢚ࢿࣝࢠ࣮ᆅᙧࠋ
 ᭱ᚋ࡟ࠊࢫࢺࣜࣥࢢἲ࡟ࡼࡾ᭦᪂ࡉࢀࡓ᭱ᑠ⮬⏤࢚ࢿࣝࢠ࣮ࣃࢫࡢゎᯒࢆ⾜ࡗࡓࠋ 㔞యࡍࡿ 1%' ࢻ࣓࢖ࣥࡢ㔜ᚰ㛫㊥㞳࡟ᑐࡋࠊ」㞧࡟࣊ࣜࢵࢡࢫࡀ஺ᕪࡍࡿ 70' ࢻ࣓࢖ࣥࡢᵓ㐀ኚ໬ ෆྥᆺᵓ㐀࠿ࡽࡢ 506'
ࢆࣉࣟࢵࢺࡋࡓ࡜ࡇࢁࠊ⸆๣㠀⤖ྜ≧ែ࡜⸆๣⤖ྜ≧ែ࡛ࣃࢫࡢ㐪࠸ࡀぢฟࡉࢀࡓ㸦ᅗ 㸧ࠋࡑࡢ㐪࠸ࡣࠊ
2FFOXGHG ᵓ㐀࡟⮳ࡿࡲ࡛ࡣ⸆๣࡟ࡼࡾ  㔞యᵓ㐀ࡀࡺࡿࡴࡇ࡜ࠊࡲࡓࠊ2FFOXGHG ᵓ㐀࠿ࡽእྥᆺᵓ㐀࡛ࡣࠊ⊃ࡲࡗࡓ✵㛫࡛ࡢ⸆๣┦஫స⏝࡟ࡼࡾᵓ㐀ࡀࡦࡎࡴࡇ࡜ࢆ♧ࡋ࡚࠾ࡾࠊᅗ  ࡛ᚓࡽࢀࡓ⮬⏤࢚ࢿࣝࢠ࣮ࡢ㐪࠸࡟┤⤖ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
௒ᖺᗘࡢィ⟬࡛ࡣࢫࢺࣜࣥࢢἲࡢᐇ⾜࡟␃ࡲࡗࡓࡀࠊ௒ᚋࡣྛ࢖࣓࣮ࢪ࡛ࡢ㏣ຍࡢィ⟬ࡸࡼࡾヲ⣽࡞඲ཎᏊᵓ㐀ࡢゎᯒࢆ㐍ࡵࠊ⸆๣㍺㏦࡜ඹᙺࡋࡓ❧యᵓ㐀ኚ໬ࡢ඲ㇺࢆ᫂ࡽ࠿࡟ࡍࡿணᐃ࡛࠶ࡿࠋࡲࡓࠊ௚ࡢ⸆๣
ศᏊࡢ㍺㏦㐣⛬࡟ࡶࢫࢺࣜࣥࢢἲࢆ㐺⏝ࡍࡿࡇ࡜࡟ࡼࡾࠊከ๣᤼ฟᛶࡀ࡝ࡢࡼ࠺࡞ศᏊ࣓࢝ࢽࢬ࣒࡛ྍ⬟࡟࡞ࡿ࠿ࢆ⌮ゎࡋ࡚࠸ࡁࡓ࠸ࠋ
- 184 -ᅗ  $%&% ࢫࢺࣜࣥࢢἲ࡟ࡼࡾᚓࡽࢀࡓ⸆๣㠀⤖ྜ≧ែ㸦㟷㸧ࠊཬࡧࠊ5KRGDPLQH* ⤖ྜ≧ែ㸦㉥㸧࡛ࡢ᭱㐺໬ࣃࢫࠋ⭷㈏㏻ࢻ࣓࢖ࣥ 70' ⦪㍈ ࡜᰾㓟⤖ྜࢻ࣓࢖ࣥ 1%' ᶓ㍈ ࡢ㐠ື࠿ࡽぢࡓᵓ㐀ኚ໬ࣃࢫࠋ Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ  ᮌᑎ ペ⣖ ᳃ḟ ᆂ す㔝 ᆂᙪ
͆,QWHUOREHPRWLRQRI(*)5NLQDVH'HWHUPLQDQWVRIVWUXFWXUDOYDULDWLRQLQWKHFU\VWDOVWUXFWXUHV͇ &%, Ꮫ఍  ᖺ኱఍ࠊᮾிࠊ ᖺ  ᭶‫  ۻ‬᳃ḟ ᆂ ᒣᮏ ඾ྐ ⡿⃝ ᗣ⁠ ᴙ ┿୍ ⸨ᓮ ᘯኈࠕ㔜ࡳ௜ࡁ࢔ࣥࢧࣥࣈࣝἲ࡟ࡼࡿ 3LQ ␗ᛶ໬ࡢࣃࢫࢧࣥࣉࣜࣥࢢࠖ
᪥ᮏ≀⌮Ꮫ఍➨  ᅇᖺḟ኱఍ࠊྡྂᒇࠊ ᖺ  ᭶ ฟ∧ᐇ⦼ࡲࡓࡣணᐃ  .HL0RULWVXJX7VXEDVD,WRDQG$NLQRUL.LGHUD$OORVWHULFUHVSRQVHWROLJDQGELQGLQJ0ROHFXODUG\QDPLFVVWXG\
RIWKH1WHUPLQDOGRPDLQVLQ,3UHFHSWRU%LRSK\VLFVDQG3K\VLFRELRORJ\  ‫  ۻ‬.HL0RULWVXJX+DNX.RDQG$NLQRUL.LGHUD³1XFOHRWLGHH[FKDQJHRQ626LVKLJKO\UHJXODWHGE\5DVVWUXFWXUDOG\QDPLFV´LQSUHSDUDWLRQ- 185 -

Ⓨගᛶ㔠ᒓ㘒య࠾ࡼࡧ㞟ྜయࡢ㟁Ꮚ≧ែ࡟㛵ࡍࡿィ⟬໬Ꮫⓗ࢔ࣉ࣮ࣟࢳ
7KHRUHWLFDODSSURDFKRQHOHFWURQLFVWDWHVRIOXPLQHVFHQWPHWDOFRPSOH[HVDQGWKHLUDVVHPEOHGV\VWHPV‫ۑ‬ຍ⸨ ᫀᏊ㸪㰻⸨ ኱ᑗ㸪ᮌᮧ ┿⌮㸪㏆⸨ ᪩⍛㸪ྜྷ⏣ ᑗᕫ㸪ᑠᯘ ཌᚿ㸦໭ᾏ㐨኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲㝔໬Ꮫ㒊㛛㸧 ◊✲┠ⓗࠊෆᐜⓎගᛶ㔠ᒓ㘒య࠾ࡼࡧࢡࣛࢫࢱ࣮ࡣࠊ᭷ᶵ (/ ⣲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 ◊✲᪉ἲࠊィ⟬᪉ἲィ⟬ᑐ㇟࡜ࡍࡿ㘒యࡣࠊᮏ◊✲ࢢ࣮ࣝࣉ࡛㛤ⓎࡋࡓⓎගᛶⓑ㔠 ,, 㘒యࡸ㖡 , 㘒య➼࡛࠶ࡿࠋึࡵ࡟ࠊึᮇ
ᵓ㐀ࡢᵓ⠏ࡣࠊ; ⥺ᵓ㐀ゎᯒ࡟ࡼࡾỴᐃࡋࡓᗙᶆࢆ⏝࠸࡚⾜࠸ࠊᵓ㐀᭱㐺໬ࡋࡓࠋᐦᗘỗ㛵ᩘἲ ')7 ࢆ⏝࠸࡚ᇶᗏ≧ែࢆィ⟬ࡋࡓࠋḟ࡟ࠊ᫬㛫౫Ꮡᐦᗘỗ㛵ᩘἲ 7'')7 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 ')7 ࠾ࡼࡧ 7'')7 ィ⟬࡟ࡣ *DXVVLDQࡲࡓࡣ *DXVVLDQ ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ ◊✲ᡂᯝ
 ᙉⓎගᛶ 1࣊ࢸࣟ⎔≧࢝ࣝ࣋ࣥⓑ㔠 ,, 㘒యࡢⓎග≉ᛶ࣭ⓎගⰍไᚚ
ᙜ◊✲ᐊ࡛㛤ⓎࡋࡓᙉⓎගᛶࡢ 1࣊ࢸࣟ⎔≧࢝ࣝ࣋ࣥⓑ㔠 ,, 㘒య⩌࡟ࡘ࠸࡚ࠊࡑ
ࡢⓎග≉ᛶࡢヲ⣽࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋ≉࡟ࠊྑᅗࡢⓑ㔠 ,, 㘒య㸦ྑᅗ㸧ࡢ⤖ᬗ࡟࠾࠸࡚ࠊ⨨᥮ᇶࡢᔞ㧗ࡉ࡟ࡼࡗ࡚㘒య㛫ࡢ✚ᒙࡀኚ໬ࡋࠊⓎගⰍࡀ㉥Ⰽ࠿ࡽ㟷Ⰽࡲ࡛ᖜᗈࡃࢳ࣮ࣗࢽࣥࢢྍ⬟࡛࠶ࡿࡇ࡜ࢆぢฟࡋࡓࠋࡑࡇ࡛ບ㉳≧ែ࡟ࡘ࠸࡚ศගᏛⓗᐇ㦂࡜࡜ࡶ࡟⌮ㄽィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊࡇࢀࡽࡢ㘒యࡣࠊ༢ศᏊ≧ែ࡟࠾࠸࡚ࡣࠊ
᭱పບ㉳୕㔜㡯≧ែࡣ⨨᥮ᇶࡢᙳ㡪ࢆཷࡅ࡞࠸ࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡇࢀࡣ⁐ᾮ୰࡟࠾ࡅࡿᐇ㦂⤖ᯝࢆࡼࡃ෌⌧ࡋ࡚࠸ࡿ୍᪉࡛ࠊ⤖ᬗ≧ែ࡟࠾ࡅࡿⓎගⰍ࡜ࡣ኱ࡁࡃ␗
࡞ࡿ⤖ᯝ࡜࡞ࡗࡓࡇ࡜࠿ࡽࠊࡇࡢ⤖ᬗ୰ࡢⓎගⰍࢳ࣮ࣗࢽࣥࢢࡀ⨨᥮ᇶࡢ㟁Ꮚⓗຠᯝ࡛ࡣ࡞ࡃ㘒య㛫ࡢ✚ᒙࡢኚ໬࡟⏤᮶ࡍࡿࡇ࡜ࡀ❧ドࡉࢀࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ㧗ຠ⋡᭷ᶵ (/ ⣲Ꮚࢆ㛤Ⓨࡍࡿࡓࡵࡢ㔜せ࡞ᣦ㔪ࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋ
 ᙉⓎගᛶࢩࢡ࣓ࣟࢱ࣮ࣞࢺᆺⓑ㔠 ,, 㘒యࡢⓎග≉ᛶ࡜ኻά㐣⛬ࡢᢚไᙜ◊✲ᐊ࡛㛤ⓎࡋࡓᙉⓎගᛶࡢࢩࢡ࣓ࣟࢱ࣮ࣞࢺᆺⓑ㔠 ,, 㘒య⩌࡟ࡘ࠸࡚ࠊࡑࡢⓎග≉ᛶࡢヲ⣽࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋ≉࡟ࠊⓑ㔠 ,, ࣅࣇ࢙ࢽࣝ㘒య⩌㸦ḟ㡫ᅗ㸧࡟࠾࠸࡚ࠊࡑࡢⓎග⏤᮶ࡣᑟධࡍࡿ⨨᥮ᇶࡢᙳ㡪- 186 -

ࢆ኱ࡁࡃཷࡅ࡞࠸࡟ࡶ࠿࠿ࢃࡽࡎࠊⓎග㔞Ꮚ཰⋡ࡀ኱ࡁࡃ␗࡞ࡿࡇ࡜ࢆぢฟࡋࡓࠋࡑࡇ࡛ࠊࡲࡎບ㉳≧ែࡢ㟁Ꮚ≧ែ࡟ࡘ࠸࡚⌮ㄽィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊࡇࢀࡽࡢ
㘒యࡣ࠸ࡎࢀࡶ㠀ᖖ࡟㢮ఝࡋࡓ᭱ప୕㔜㡯ບ㉳≧ែࢆ࡜ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡾࠊᐇ
㦂⤖ᯝࢆࡼࡃ෌⌧ࡋ࡚࠸ࡓࠋ୍᪉ࠊ᭱Ᏻᐃᵓ㐀࡟ࡘ࠸࡚⌮ㄽィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁࠊ
⁐ᾮ୰࡛ࡣ࠸ࡎࢀࡢ㘒యࡶ㧗࠸ᖹ㠃ᛶࢆಖࡗ࡚࠸ࡓࡢ࡟ᑐࡋࠊ⤖ᬗ≧ែ࡟࠾ࡅࡿ᭱
Ᏻᐃᵓ㐀ࡣⓎගᛶࡢప࠸㘒యࡢሙྜ࡟኱ࡁࡃᖹ㠃࠿ࡽṍࢇ࡛࠾ࡾࠊࡇࢀࡣ⤖ᬗᵓ㐀ゎᯒ࠾ࡼࡧศගᏛⓗᐇ㦂࡜ࡶ୍⮴ࡍࡿ⤖ᯝ࡜࡞ࡗࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊᙉⓎගᮦᩱࡢኻά㐣⛬ࢆᢚไࡍࡿࡓࡵࡢ㔜せ࡞ᣦ㔪ࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋ

 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
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glycan by theoretical methods” 25th International Symposium on Glycoconjugate, Milan, Italy, (Aug. 2019)
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㌾ ; ⥺ග໬Ꮫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Studies on soft X-ray Photochemical Phenomena‫ۑ‬㧗ᶫಟ㸪ᒣᮧᾴ௓㸪⛅ᘅ೺ᩯ㸪஧ཪᮃ㸦ᗈᓥ኱㝔⌮㸧㸯㸬◊✲┠ⓗ㸪ෆᐜᮏㄢ㢟࡛⾜ࡗࡓ◊✲ࡢ୰࠿ࡽ௨ୗࡢࢸ࣮࣐࡟ࡘ࠸࡚ࡑࡢ⤖ᯝࢆ⡆༢࡟㏙࡭ࡿࠋ
(1) Ỉࡢ㌾ X ⥺Ⓨගศග㸰㸬◊✲᪉ἲ㸪ィ⟬᪉ἲ㸪◊✲ᡂᯝ(1) Ỉࡢ㌾ X ⥺ⓎගศගX ⥺ศගἲࡣඖ⣲㑅ᢥⓗ࡞ບ㉳ࡀྍ⬟࡛࠶ࡾ㸪ບ㉳ཎᏊ࿘㎶ࡢᒁᡤᵓ㐀ࢆㄪ࡭ࡿᡭἲ࡜ࡋ࡚ᴟࡵ࡚᭷
ຊ࡛࠶ࡿࠋࡇࡢ≉ᚩࢆά࠿ࡋ㸪㏆ᖺᾮయ≧ែࡢᵓ㐀◊✲࡟ᗈࡃ฼⏝ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋỈࡢ X ⥺ศගࡢࢫ࣌ࢡࢺࣝゎ㔘ࡣ࠸ࡲࡔỴ╔ࡀࡘ࠸࡚࠸࡞࠸ࠋ≉࡟ၥ㢟࡞ࡢࡣ㸪㌾ X ⥺Ⓨගศග(XES)࡟࠾࠸࡚ᐇ㦂ࢫ࣌ࢡࢺࣝࡣ࡯ࡰྠᵝ࡛࠶ࡿ࡟ࡶ࠿࠿ࢃࡽࡎ㸪⌮ㄽゎ㔘ࡀ」ᩘᏑᅾࡋ㸪ΰ஘ࡀ⥆࠸࡚࠸ࡿࡇ࡜࡛࠶ࡿࠋXES࡛ࡣ㸰ࡘࡢ 1b1 ≧ែࡀᚓࡽࢀࡿࠋࡇࡢゎ㔘࡟㸪ᐦᗘࡢ␗࡞ࡿ஧ࡘࡢ≧ែ࡛ゎ㔘ࡍࡿ஧≧ែࣔࢹࣝ࡟ࡼࡿ
ゎ㔘㸪ෆẆṇᏍ≧ែ࡟ࡼࡗ࡚ㄏⓎࡉࢀࡿࢲ࢖ࢼ࣑ࢡࢫࢆ཯ᫎࡋࡓࡶࡢ㸪ࡢ 2 ㏻ࡾ࠶ࡾ㸪ࡉࡽ࡟Ỉࡢࣔࢹࣝ࡜ࡋ࡚㸪࠸ࢁࢇ࡞Ỉ⣲⤖ྜᵝᘧࡢΰࡊࡗࡓࣔࢹࣝ㸪࡟ࡼࡗ࡚ゎ㔘ࡍࡿ 3 ࡘ࡟኱ูࡉࢀࡿࠋࡈࡃ᭱㏆
Zhovtobriukh ࡽࡣ㸪࠿࡞ࡾ኱つᶍ࡞⌮ㄽィ⟬࡟ࡼࡾỈࡢ XES ࢫ࣌ࢡࢺࣝࡢゎ㔘ࢆ⾜ࡗࡓࡀ㸪ᐇ㦂ࡢ XES
ࢫ࣌ࢡࢺࣝ࡟ᚓࡽࢀࡿ 1b1 ≧ែࡢศ⿣ࡣ᜛ពⓗ࡞ࢧࣥࣉࣜࣥࢢࢆ⾜࠺ࡇ࡜࡟ࡼࡗ࡚ㄝ᫂ࡋ㸪 ᐃ࡟࠿࠿
ࡿ 2 ࡘࡢࣆ࣮ࢡࡣࡑࢀࡒࢀ 2 ✀㢮ࡢỈ⣲⤖ྜᵝᘧ࡟ᖐᒓࡋ࡚࠸ࡿࠋࡇࡢᗘᡃࠎࡣࣔࢹࣝᵓ⠏࠿ࡽ᳨ウࡋ㸪Ỉࡢ XES ࢫ࣌ࢡࢺࣝࢆᵓ⠏ࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋ⏝࠸ࡓࣔࢹࣝᵓ㐀ࡼࡾỈࡢᥥീ࡟ࡘ࠸࡚⪃ᐹࡍࡿࠋᵓ㐀ࣔࢹࣝࡢᵓ⠏ࡣศᏊືຊᏛἲ(MD)ࢥ࣮ࢻ Gromacs ࢆ⏝࠸ࡓࠋ1000 ศᏊࡢỈࢆࢩ࣑࣮ࣗࣞࢩࣙࣥ
࣎ࢵࢡࢫ࡟ධࢀ㸪TIP4P/ew ຊሙࢆ⏝࠸࡚㸪NPT ࢔ࣥࢧࣥࣈࣝ࡟ࡼࡗ࡚ᵓ㐀ࢆỴᐃࡋࡓࠋ ᗘࡣ 240, 270,
300, 330, 360 K ࡢࡶࡢࢆࡑࢀࡒࢀᚓࡓࠋࢫ࣌ࢡࢺࣝィ⟬ࡣᐦᗘỗ㛵ᩘἲ(DFT)ࢥ࣮ࢻ deMon2k ࢆ⏝࠸ࡓࠋMD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ᚓࡽࢀࡓࢫࢼࢵࣉࢩࣙࢵࢺࡼࡾ㸪㸯㸵ศᏊࢡࣛࢫࢱࢆࣛࣥࢲ࣒࡟ྜィ࡛
㸰㸮㸮㏻ࡾࡢึᮇᵓ㐀ࢆᚓࡓࠋࢧࣥࣉࣜࣥࢢࡋࡓࢡࣛࢫࢱࡢ୰ᚰศᏊ࡟ᑐࡋ㸪㸰ࡘࡢỈ⣲ཎᏊࡢ఩⨨ࡢࡳࢆᵓ㐀᭱㐺໬ࡋ㸪ࡉࡽ࡟᣺ືᩘィ⟬ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ᝟ሗࡼࡾ㔞ᏊຊᏛⓗ࡞఩┦✵㛫ࢧࣥࣉࣜࣥࢢ
ࢆ㸯ࡘࡢ᣺ື࣮ࣔࢻ࡟ᑐࡋ࡚఩⨨࡟ᑐࡋ࡚㸰ࡘ㸪㐠ື㔞࡟ᑐࡋ࡚㸲ࡘ⾜ࡗࡓࠋ࡞࠾㸪᣺ື࣮ࣔࢻࡣ㸰ࡘࡢ OH ఙ⦰࣮ࣔࢻࡢࡳ⪃៖ࡋࡓࠋᚓࡽࢀࡓึᮇ᮲௳࡟ᑐࡋ㸪ෆẆṇᏍࢲ࢖ࢼ࣑ࢡࢫィ⟬ࢆ 0.25 fs 㛫㝸࡛40 fs ᫬㛫Ⓨᒎࡉࡏࡓࠋᚓࡽࢀࡓ㌶㊧࡟ᑐࡋ࡚౯㟁Ꮚ㌶㐨࡜ O1s ㌶㐨㛫ࡢ㑄⛣࣮࣓ࣔࣥࢺࢆィ⟬ࡋࡓࠋ௨ୖࡢ᝟ሗࢆ඲࡚࠶ࢃࡏ㸪Kramers-Heisenberg ศᩓᘧ࡟ᚑࡗ࡚ XES ࢫ࣌ࢡࢺࣝィ⟬ࢆ⾜ࡗࡓࠋଶ‫݂ۦ‬ȁࡰᇱȁ݊ۧ‫݊ۦ‬ȁࡰȁ݅ۧ߱ᇱߪሺ߱Ԣǡ ߱ሻ ൌ  ෍ อ෍อ ߜሺ߱Ԣ െ ߱ ൅ ‫ܧ‬௙௜ ሻ߱ െ ‫ܧ‬௡௙ ൅ ݅Ȟ߱௙௡࡞࠾㸪ᮏ◊✲ࡣ㠀ඹ㬆ບ㉳࡟ࡼࡿ XES ࢫ࣌ࢡࢺࣝࡢࡳࢆྲྀࡾᢅࡗࡓࠋ
ᅗ㸯࡟㸪300, 330, 360 K ࡟࠾ࡅࡿ H2O, D2O ࡢ XES ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋᡃࠎࡢィ⟬ࢫ࣌ࢡࢺࣝࡢ≉ᚩ
ࢆ㏙࡭ࡿࠋᡃࠎࡢィ⟬ࢫ࣌ࢡࢺࣝࡣ᜛ពⓗ࡞ࢧࣥࣉࣜࣥࢢࢆ⾜࠺ࡇ࡜࡞ࡋ࡟㸪1b1 ࡢ㸰ࡘࡢࣆ࣮ࢡࢆ෌
⌧ࡋ࡚࠸ࡿࠋࣆ࣮ࢡᖜࡣ 300 K ࡟࠾࠸࡚㸯eV ࡛࠶ࡾ㸪ᐇ㦂ࢫ࣌ࢡࢺࣝ(0.7-0.9eV)ࡼࡾࢃࡎ࠿࡟ᖜᗈ࠸ࠋ
㸰ࡘࡢ 1b1 ≧ែࡣ ᗘࡀୖ᪼ࡍࡿ࡟ࡘࢀ࡚ప࢚ࢿࣝࢠ࣮ഃ(1b1’)ࡣ఩⨨ࢆኚ࠼ࡎᙉᗘࡀῶᑡࡋ㸪୍᪉㧗࢚ࢿࣝࢠ࣮ഃ(1b1”)ࡣࣆ࣮ࢡ఩⨨ࡀࢃࡎ࠿࡟㧗࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡋ㸪ࡉࡽ࡟ᙉᗘࡣቑຍࡍࡿࠋࡲࡓྛ

- 189 -

ᗘ࡜ࡶ H2O ࡢ 1b1’ࡢᙉᗘࡣ 1b1”ࡼࡾࡶ┦ᑐⓗ࡟኱ࡁ࠸ࠋࡇࢀࡽࡢഴྥࡣᩥ⊩࡟࠾࠸࡚ሗ࿌ࡉࢀ࡚࠸ࡿࡶ
ࡢࢆ᏶඲࡟෌⌧ࡋ࡚࠸ࡿࠋᅗ 2 ࡟ 300 K ࡟࠾ࡅࡿᵝࠎ࡞Ỉ⣲⤖ྜᵝᘧࡢ XES/RIXS ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ࡞࠾㸪ࢧࣥࣉࣜࣥࢢࡉࢀࡓᵓ㐀ࡢᩘࡣ D1A1, D2A2, D2A1 (DnAm ࡣỈ⣲ࢻࢼ࣮n ಶࠊỈ⣲࢔ࢡࢭࣉࢱ࣮m ಶࡢỈ⣲⤖ྜ≧ែࢆ⾲ࡍ)ࡀᨭ㓄ⓗ࡛࠶ࡿࡇ࡜ࢆグࡋ࡚࠾ࡃࠋ࡝ࡢࢣ࣮ࢫࡶ 1b1’, 1b1”ࡀࡳࡽࢀࡿࡀ㸪Ỉ⣲⤖ྜࡢᩘࡀቑ࠼ࡿ࡟ࡋࡓࡀࡗ࡚ 1b1’ࡢࣆ࣮ࢡࡀᨭ㓄ⓗ࡟࡞ࡗ࡚࠸ࡿࠋࡘࡲࡾ㸪ị࡟ఝࡓᵓ㐀(D2A2,
D2A1)࡛ࡣ 1b1’ࡀ୺࡛࠶ࡾ㸪ࡺࡀࢇࡔᵓ㐀(D1A1)࡛ࡣ 1b1”ࡀ୺࡛࠶ࡿᚑ᮶ࡢゎ㔘࡟୍⮴ࡍࡿࠋ

Fig.2: XES spectra of water at 300 K for various typesof hydrogen bonds. “DmAn” means number of hydrogen
donors and acceptors, respectively.

Fig.1: XES spectra of water at different temperature. Solidand dashed lines indicate those for H2O and D2O.

㸱㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
⛅ᘅࡽ㸪WK6\PSRVLXPRQ&KHPLFDONLQHWLFVDQG'\QDPLFV ᖺ  ᭶㸪ᮾᗈᓥ஧ཪࡽ㸪WK6\PSRVLXPRQ&KHPLFDONLQHWLFVDQG'\QDPLFV ᖺ  ᭶㸪ᮾᗈᓥᒣᮧࡽ㸪WK6\PSRVLXPRQ&KHPLFDONLQHWLFVDQG'\QDPLFV ᖺ  ᭶㸪ᮾᗈᓥ㧗ᶫࡽ㸪ศᏊ⛉Ꮫウㄽ఍㸪㻞㻜㻝㻥 ᖺ 㻥 ᭶㸪ྡྂᒇ㧗ᶫࡽ㸪ᨺᑕග⛉Ꮫྜྠࢩ࣏ࣥࢪ࣒࢘㸪 ᖺ  ᭶㸪ྡྂᒇᒣᮧࡽ㸪ᨺᑕග⛉Ꮫྜྠࢩ࣏ࣥࢪ࣒࢘㸪 ᖺ  ᭶㸪ྡྂᒇ㸲㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
N. Yoshimura et al, J. Phys. Chem. B, 123, 1332-1339 (2019).
R. Puettner et al, Phys. Chem. Chem. Phys., 21, 8827-8836 (2019).

- 190 -

໬Ꮫ཯ᛂࡢ㔞Ꮚࢲ࢖ࢼ࣑ࢡࢫ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Study on the Quantum Dynamics Processes of Chemical
Reactions‫ۑ‬ᒣୗ᫭୍㸪㔠Ꮚṇᚨ㸦ி኱ ESICB㸧㸪୕ᔱㅬ஧㸦⟃Ἴ኱㸧㸪ᕝᔱⱥభ㸦⌮◊⚄ᡞ㸧

1◊✲┠ⓗࠊෆᐜ

1.1

㓟໬ࢱࣥࢢࢫࢸࣥගゐ፹ࡢ㟁Ꮚ-ࣇ࢛ࣀࣥ┦஫స⏝ኴ㝧ග࡟ࡼࡾỈࢆỈ⣲ࡸ㓟⣲࡬ศゎࡍࡿỈศゎගゐ፹ࡣ㸪ࢡ࣮࡛ࣜࣥ෌⏕ྍ⬟࡞ḟୡ௦ࡢ࢚ࢿࣝࢠ࣮࡜ࡋ
࡚ὀ┠ࡉࢀࡿỈ⣲ࡢ〇㐀ᡭẁ࡜ࡋ࡚ᮇᚅࡉࢀ࡚࠸ࡿ㸬ኴ㝧ග࢚ࢿࣝࢠ࣮ࡢ኱㒊ศࢆྍどග㡿ᇦࡀ༨ࡵ࡚࠸ࡿ
ࡓࡵ㸪ࡇࢀࢆ฼⏝࡛ࡁࡿྍどගᛂ⟅ᆺගゐ፹ᮦᩱ࡜ࡋ࡚㓟໬ࢱࣥࢢࢫࢸࣥࡣὀ┠ࡉࢀ࡚࠸ࡿ㸬ගゐ፹཯ᛂࡣ㸪ࡲࡎග࡟ࡼࡾ౯㟁Ꮚᖏࡢ㟁Ꮚࡀఏᑟᖏ࡟ບ㉳ࡉࢀ㸪ບ㉳ࡉࢀࡓ㟁Ꮚ࡜⏕ࡌࡓ࣮࣍ࣝ㸦ග࢟ࣕࣜ࢔㸧ࡀศ㞳ࡋ㸪≀㉁୰ࢆ⛣ືࡋ࡚⾲㠃࡬฿㐩ࡍࡿࡇ࡜࡛཯ᛂࡀ㉳ࡇࡿ㸬㓟໬ࢱࣥࢢࢫࢸࣥࡢගບ㉳≧ែࡣ┒ࢇ࡟◊✲ࡉࢀ࡚࠾ࡾ㸪㠀ᖖ࡟㛗ᑑ࿨࡞ග࢟ࣕࣜ࢔ࡀගゐ፹཯ᛂ࡛㔜せ࡞≉ᛶࢆ᭷ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸬ୖᮧࡽࡣ㸪XAFS
ἲࢆ WO3 ࡢග྾཰㐣⛬࡟㐺⏝ࡋ㸪ග྾཰࡟క࠺㟁Ꮚ≧ែኚ໬࡜ᵓ㐀ኚ໬ࢆㄪ࡭ࡿࡇ࡜࡛㸪ග࢟ࣕࣜ࢔ࡢ㟁ᏊࡀࢱࣥࢢࢫࢸࣥཎᏊ࡟࡜࡝ࡲࡾ㸪ࢱࣥࢢࢫࢸࣥཎᏊࡀ 6 ౯࠿ࡽ 5 ౯࡬㑏ඖࡉࢀ㸪ᒁᡤᵓ㐀ࡀኚ໬ࡋ࠸࡚࠸ࡃ
ࡇ࡜ࢆ☜ㄆࡋࡓ[1,2]㸬ࡋ࠿ࡋ㸪ᐇ㝿࡟࡝ࡢࡼ࠺࡟ᵓ㐀ࡀኚ໬ࡋ࡚࠸ࡃࡢ࠿࡟ࡘ࠸࡚ࡣ࡯࡜ࢇ࡝ศ࠿ࡗ࡚࠸࡞
࠸㸬ࡑࡇ࡛ᮏ◊✲࡛ࡣ㸪㟁Ꮚ࡟ࡼࡾ⏕ࡌࡿ᱁Ꮚࡢṍࡳ࡟ࡘ࠸࡚㆟ㄽࡍࡿࡓࡵ㸪ᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃ➨୍ཎ⌮ィ⟬࡟ࡼࡾ㸪㓟໬ࢱࣥࢢࢫࢸࣥࡢ㟁Ꮚ-ࣇ࢛ࣀࣥ┦஫స⏝ࡢィ⟬ࢆ⾜ࡗࡓ㸬ࡇࢀ࡟ࡼࡾ㸪㟁Ꮚ-ࣇ࢛ࣀࣥ┦஫స⏝ࡀ኱ࡁ࡞ࣇ࢛ࣀ࣮ࣥࣔࢻࢆ᫂ࡽ࠿࡟ࡋࡓ㸬

1.2ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ᭷ᶵ↓ᶵࣁ࢖ࣈࣜࢵࢻᆺࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺࡢゎᯒ㏆ᖺ㸪࣌ࣟࣈࢫ࢝࢖ࢺ⤖ᬗᵓ㐀ࢆࡶࡘ᭷ᶵ↓ᶵࣁ࢖ࣈࣜࢵࢻᆺࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺࡣḟୡ௦ኴ㝧㟁ụࡢ᭷ᮃ࡞ᮦᩱ࡜ࡋ࡚ὀ┠ࢆ㞟ࡵ࡚࠸ࡿ㸬ࣁ࢖ࣈࣜࢵࢻᆺࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụࡣ㸪⣸እ࣭ྍど㡿ᇦ࡛ࡢ኱ࡁ࡞྾཰ಀᩘ㸪㧗࠸࢟ࣕࣜ࢔ఏᑟᛶ㸪㛗࠸㟁Ꮚ-࣮࣍ࣝᣑᩓ㛗㸪┤᥋㑄⛣ᆺࣂࣥࢻࢠࣕࢵࣉ࡜࠸ࡗࡓ
ඃࢀࡓ≉ᛶࢆࡶࡗ࡚࠸ࡿ㸬௦⾲ⓗ࡞ࣁ࢖ࣈࣜࢵࢻᆺࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺࡣ໬Ꮫᘧ APbX3 ࡛⾲ࡉࢀࡿࣁࣟ
ࢤࣥ໬㖄࣌ࣟࣈࢫ࢝࢖ࢺ࡛࠶ࡿ㸬ࡇࡇ࡛ࡣ㸪A ࢧ࢖ࢺ࢝ࢳ࢜ࣥ࡟㸪MA = CH3NH3㸪FA = HC(NH2)2 ࡜࠸ࡗࡓ᭷
ᶵศᏊ㸪X ࢧ࢖ࢺ࡟ࡣࣁࣟࢤࣥ㸦I, Br, Cl㸧ࡀྵࡲࢀ࡚࠸ࡿ㸬ࡇࡢࡼ࠺࡞໬ྜ≀ࡣపࢥࢫࢺ࡛⏕ᡂࡀᐜ࡛᫆࠶
ࡿ୍᪉㸪㖄ࢆྵ᭷ࡋ࡚࠸ࡿࡓࡵẘᛶࡢၥ㢟ࡀᣲࡆࡽࢀࡿ㸬ࡑࡢࡓࡵ㠀ẘᛶඖ⣲ࢆ⏝࠸ࡓ㠀㖄໬࣌ࣟࣈࢫ࢝࢖
ࢺᮦᩱࡢ㛤Ⓨࡀồࡵࡽࢀ࡚࠸ࡿ㸬Nakajima ࡽࡣ㸪ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࠕிࠖࢆ฼⏝ࡋࡓඖ⣲ᡓ␎ⓗ࡞ࣁ࢖ࢫ࣮ࣝࣉࢵࢺ࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ᇶ࡙࠸ࡓ࣐ࢸࣜ࢔ࣝࢬ࣭ࢫࢡ࣮ࣜࢽࣥࢢἲ࡟ࡼࡾ㸪㠀㖄໬࣌ࣟࣈࢫ࢝࢖
ࢺኴ㝧㟁ụࡢ᪂ࡋ࠸ᮦᩱࡢ᥈⣴ࢆ⾜࠸㸪ࢫࢡ࣮ࣜࢽࣥࢢ᫬࡟ィ⟬ࡉࢀࡓࢹ࣮ࢱࢭࢵࢺࢆබ㛤ࡋ࡚࠸ࡿ[3]㸬ᮏ◊✲࡛ࡣ㸪ࡇࡢࢹ࣮ࢱࢭࢵࢺ࡟ᑐࡋ࡚⤫ィࡸᶵᲔᏛ⩦ࡢᡭẁࢆ⏝࠸࡚㸪ኴ㝧㟁ụࡢᮦᩱ࡟㔜せ࡞≀ᛶ࡛࠶ࡿࣂࣥࢻࢠࣕࢵࣉࡸ㟁Ꮚ࣭࣮࣍ࣝࡢ᭷ຠ㉁㔞ࢆணࡋ㸪ࡑࡢせᅉࢆゎᯒࡋࡓ㸬- 191 -

2◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 㓟໬ࢱࣥࢢࢫࢸࣥගゐ፹ࡢ㟁Ꮚ-ࣇ࢛ࣀࣥ┦஫స⏝ ᐦᗘỗ㛵ᩘ⌮ㄽ(DFT)࡟ᇶ࡙ࡃ➨୍ཎ⌮ィ⟬ࣃࢵࢣ࣮ࢪࡢ QUANTUM ESPRESSO 6.3 ࠾ࡼࡧከయၥ㢟ࡢ➨୍ཎ⌮ィ⟬ࢆ⾜࠺࢔ࣉࣜࢣ࣮ࢩࣙࣥࡢ Yambo 4.2.4 ࢆ⏝࠸࡚㸪❧᪉ᬗࡢ WO3 ࡢᵓ㐀࡟ᑐࡋ࡚ィ⟬ࢆ⾜ࡗࡓ㸬
DFT ィ⟬࡛ࡣ㸪஺᥮┦㛵ỗ㛵ᩘ࡟ GGA-PBE㸪k Ⅼ࣓ࢵࢩࣗ࡟ 6×6×6 ࢆ⏝࠸㸪ࣀ࣒ࣝಖᏑᆺᨃ࣏ࢸࣥࢩࣕࣝࡢ
ࡶ࡜࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮ 80 Ry ࡢᖹ㠃Ἴᇶᗏࢆ⏝࠸ࡓ㸬 Generalized Eliashberg 㛵ᩘࢆィ⟬ࡋ㸪㟁Ꮚ࡜ᙉࡃ┦஫స⏝ࡍࡿࣇ࢛ࣀ࣮ࣥࣔࢻࡢ≉ᐃࢆ⾜ࡗࡓ㸬Generalized Eliashberg 㛵ᩘࡢィ⟬࡟ࡣࣛࣥࢲ࣒࡟సᡂࡋࡓ 500
Ⅼࡢ q Ⅼࢆ฼⏝ࡋࡓ㸬

2.2 ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ᭷ᶵ↓ᶵࣁ࢖ࣈࣜࢵࢻᆺࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺࡢゎᯒ
Python ࡢ࣮࢜ࣉࣥࢯ࣮ࢫᶵᲔᏛ⩦ࣛ࢖ࣈࣛࣜࡢ scikit-learn 0.21.2 ࢆ⏝࠸࡚ᶵᲔᏛ⩦ࢆ⾜ࡗࡓ㸬ᶵᲔᏛ⩦࢔ࣝࢦࣜࢬ࣒࡜ࡋ࡚㸪⥺ᙧᅇᖐ㸪Lasso ᅇᖐ㸪Ridge ᅇᖐ㸪ࣛࣥࢲ࣒ࣇ࢛ࣞࢫࢺ㸪ࢧ࣏࣮ࢺ࣋ࢡࢱ࣮࣐ࢩࣥࢆ฼
⏝ࡋ㸪ࡑࡢ୰࡛ࡶ⢭ᗘࡢⰋ࠿ࡗࡓࣛࣥࢲ࣒ࣇ࢛ࣞࢫࢺࢆ୺࡟⏝࠸࡚ணࡸゎᯒࢆ⾜ࡗࡓ㸬Nakajima ࡽࡀࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱࠕிࠖࢆ⏝࠸࡚⾜ࡗࡓࣁ࢖ࢫ࣮ࣝࣉࢵࢺ࣭ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜኱つᶍ࡞࣐ࢸࣜ࢔ࣝࢫࢡࣜ
࣮ࢽࣥࢢἲ࡟ࡼࡾసᡂࡉࢀࡓࢹ࣮ࢱࢭࢵࢺࢆ⏝࠸ࡓ㸬ࡇࡢࢹ࣮ࢱࢭࢵࢺ୰࡟ࡣ㸪࣌ࣟࣈࢫ࢝࢖ࢺ ABX3㸪ࢲࣈࣝ࣌ࣟࣈࢫ࢝࢖ࢺ A2BB’X6 ࡟ᑐࡋ࡚➨୍ཎ⌮ィ⟬ࢆᐇ᪋ࡋᚓࡽࢀࡓ 11,025 ௳ࡢࢹ࣮ࢱࡀ࠶ࡾ㸪⤖ᬗᵓ㐀㸪ࣂࣥࢻࢠࣕࢵࣉ㸪࣮࣭࣍ࣝ㟁Ꮚࡢ᭷ຠ㉁㔞࡞࡝ࡀྵࡲࢀ࡚࠸ࡿ㸬≀ᛶࢆࢹ࣮ࢱ࣐࢖ࢽࣥࢢࡍࡿࡓࡵࡢ Python ࣛ࢖ࣈࣛࣜ matminer 0.5.7 ࢆ⏝࠸࡚㸪ྛࢹ࣮ࢱࡢ⤌ᡂᘧ࠿ࡽ A ࢧ࢖ࢺ㸪B ࢧ࢖ࢺ㸪X ࢧ࢖ࢺẖ࡟㸪ඖ⣲ࡢ≀ᛶ㸦༢యࡢ⼥Ⅼࡸ౯㟁Ꮚࡢᩘ࡞࡝㸧ࡢᖹᆒ್ࡸᖹᆒ⤯ᑐ೫ᕪࢆィ⟬ࡋ㸪435 ಶࡢㄝ᫂ኚᩘࢆసᡂࡋࡓ㸬ࡇࢀࡽࡢㄝ᫂ኚᩘ࡟ࡼࡾࣂࣥࢻࢠࣕࢵࣉࡸ࣮࣭࣍ࣝ㟁Ꮚࡢ᭷ຠ㉁㔞ࢆணࡋࡓ㸬ㄝ᫂ኚᩘࡢᩘࢆ๐ῶࡍࡿࡓࡵ㸪RFE㸦෌ᖐⓗ≉ᚩᾘཤἲ㸧ࢆ⏝࠸࡚㸪ࣛࣥࢲ࣒ࣇ࢛ࣞࢫࢺ࡟࠾ࡅࡿ Feature Importance ࡢ᭱ᑠ࡞ࡶࡢࢆ෌ᖐⓗ࡟ᾘཤࡋࡓ㸬ᛶ⬟ࡢホ౯࡟ࡣ㸪࣮࣍ࣝࢻ࢔࢘ࢺἲࢆ౑࠸㸪ࢸࢫࢺࢹ࣮ࢱࢆ 30%㸪Ꮫ⩦⏝ࢹ࣮ࢱࢆ 70%࡜ࡋࡓ㸬

3

◊✲ᡂᯝ

3.1 㓟໬ࢱࣥࢢࢫࢸࣥගゐ፹ࡢ㟁Ꮚ-ࣇ࢛ࣀࣥ┦஫స⏝ᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃ㟁Ꮚ≧ែィ⟬ࢆ⾜࠸㸪WO3 ࡣ W6+࢖࢜ࣥࡀ d0 ࡢ㟁Ꮚ≧ែࢆ࡜ࡾ㸪ఏᑟᖏࡀ W ཎᏊࡢ d ㌶㐨㸪౯㟁Ꮚᖏࡀ O ཎᏊࡢ p ㌶㐨ࡼࡾᡂࡿࣂࣥࢻᵓ㐀ࢆ࡜ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ࣂࣥࢻࢠࣕࢵࣉࡣ
㛫᥋㑄⛣࡛⣙ 2 eV 㸪┤᥋㑄⛣࡛⣙ 3 eV ࡜࡞ࡗ࡚࠾ࡾ㸪㛫᥋㑄⛣ࡢ᪉ࡀᑠࡉࡃ᭷฼ࡔ࡜⪃࠼ࡽࢀ㸪࢟ࣕࣜ࢔ࡢ෌⤖ྜࡀᢚไࡉࢀ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿ㸬ࣇ࢛ࣀࣥ DOS ࡢィ⟬ࢆ⾜ࡗࡓ࡜ࡇࢁ㸪≉ᚩⓗ࡞㸱ࡘࡢ≧ែᐦᗘࡀ࠶ࡽࢃࢀ㸪ప࢚ࢿࣝࢠ࣮ഃ࠿ࡽࡑࢀࡒࢀࢱࣥࢢࢫࢸ
ࣥ࡜㓟⣲, 㓟⣲, 㓟⣲ ࡢᐤ୚࡟ࡼࡗ࡚⌧ࢀ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ㸦ᅗ 1㸧㸬ࣇ࢛ࣀࣥ DOS ࢆᵓᡂࡍࡿྛ࣮ࣔࢻ࡟ศゎࡍࡿ࡜㸪㓟⣲࡟ࡼࡿ᣺ືᩘࡢ㧗࠸㸱ࡘࡢ࣮ࣔࢻ࡜ 㸪ࢱࣥࢢࢫࢸࣥ࡜㓟⣲ࡢ୧᪉ࡀᐤ୚ࡍࡿ᣺ືᩘࡢప࠸㸷ࡘࡢ࣮ࣔࢻ
ࡀ⌧ࢀࡓ㸬
ᅗ 1.

- 192 -

WO3 ᵓ㐀ࡢࣇ࢛ࣀࣥ DOSḟ࡟㸪㟁Ꮚ࡜ᙉࡃ┦஫స⏝ࡍࡿࣇ࢛ࣀࣥࡢ᣺ືᩘࢆ⾲ࡍ㛵ᩘ࡛࠶ࡿ Eliashberg 㛵ᩘࢆィ⟬ࡋࡓ࡜ࡇࢁ㸪ࡇࡕࡽࡶࣇ࢛ࣀࣥ DOS ࡜ᑐᛂࡍࡿከᩘࡢ≉ᚩⓗ࡞ࣆ࣮ࢡࡀᏑᅾࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ㸬≉࡟㸪᣺ືᩘࡢẚ
㍑ⓗప࠸ࢱࣥࢢࢫࢸࣥ࡜㓟⣲୧᪉࡟⏤᮶ࡍࡿࣇ࢛ࣀ࣮ࣥࣔࢻࡀఏᑟᖏୗ➃ࡢ㟁Ꮚ࡜ᙉࡃ┦஫స⏝ࡋ࡚࠸ࡿࡇ
࡜ࡀࢃ࠿ࡗࡓ㸬
Eliashberg 㛵ᩘ࡬ࡢᐤ୚ࡢ኱ࡁ࡞ࣇ࢛ࣀࣥࡢ᣺ື᪉ྥ࡬ཎᏊ఩⨨ࢆࡎࡽࡋࡓᵓ㐀㸦ᅗ 2㸧࡟ࡘ࠸࡚㸪㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺࢆィ⟬ࡋࡓ㸬ఏᑟᖏୗ➃ࡢ㟁Ꮚ࡜ᙉࡃ┦஫స⏝ࡍࡿࣇ࢛ࣀ࣮ࣥࣔࢻࡢ᪉ྥ࡬ཎᏊࡀኚ఩ࡋࡓ
࡜ࡁ㸪㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺࡀᑠࡉࡃ࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ఏᑟᖏୗ➃ࡢ㟁Ꮚ࡜ᙉࡃ࢝ࢵࣉࣜࣥࢢࡍࡿࣇ࢛
ࣀࣥࡢ᪉ྥ࡟ཎᏊࡀࡎࢀࡿࡇ࡜࡛㸪౯㟁Ꮚᖏ࡜ࡢ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺࡀᑠࡉࡃ࡞ࡾ㸪࢟ࣕࣜ࢔ࡢ෌⤖ྜࡀᢚไࡉࢀࡿྍ⬟ᛶࡀ࠶ࡿ㸬ᅗ 2.

Eliashberg 㛵ᩘ࡬ࡢᐤ୚ࡢ኱ࡁ࡞ࣇ࢛ࣀࣥࡢ᣺ື᪉ྥ࡬ཎᏊ఩⨨ࢆࡎࡽࡋࡓ WO3 ࡢᵓ㐀

3.2 ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ᭷ᶵ↓ᶵࣁ࢖ࣈࣜࢵࢻᆺࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺࡢゎᯒࣂࣥࢻࢠࣕࢵࣉࡢண
࡟Ⰻࡃணࢆ⾜࠸㸪R2 ್ࡀᏛ⩦࣭ࢸࢫࢺ⏝ࡢ࡝ࡕࡽࡢࢹ࣮ࢱࢭࢵࢺ࡟࠾࠸࡚ࡶ 0.9 ࢆ㉸࠼㠀ᖖ࡛ࡁࡓ㸬ྠᵝ࡟㸪౯㟁Ꮚᖏୖ➃࡟࠾ࡅࡿ࣮࣍ࣝࡢ᭷ຠ㉁㔞࡜ఏᑟᖏୗ➃࡟࠾ࡅࡿ㟁Ꮚࡢ᭷ຠ㉁㔞

ࡀ 1.0 ᮍ‶࡛࠶ࡿ࠿࡟ࡘ࠸࡚ࡶணࢆ⾜࠸㸪࣮࣭࣍ࣝ㟁Ꮚࡢ᭷ຠ㉁㔞ࡀ 1.0 ᮍ‶࡛࠶ࡿࡶࡢࢆᏛ⩦࣭ࢸࢫࢺ⏝ࡢ࡝ࡕࡽࡢࢹ࣮ࢱࢭࢵࢺ࡟࠾࠸࡚ࡶ 88.1%௨ୖࡢṇゎ⋡࡛Ⰻࡃண
ࡇࢀࡽࡢண

࡛ࡁࡓ㸬

࡟㔜せ࡞ㄝ᫂ኚᩘࢆྠᐃࡍࡿࡓࡵ࡟ࡣ㸪Feature Importance ࡢ኱ࡁ࡞ㄝ᫂ኚᩘࢆồࡵࡓ㸬ࡑࡢ⤖ᯝ㸪ࣂࣥࢻࢠࣕࢵࣉࢆỴᐃ࡙ࡅࡿ୺࡞ㄝ᫂ኚᩘࡣ㸪ᙳ㡪ࡢ኱ࡁ࠸㡰࡟ B ࢧ࢖ࢺ࢝ࢳ࢜ࣥࡢ㟁Ꮚ≧ែ࡟㛵ࢃࡿ≀ᛶ㸪B ࢧ࢖ࢺ࢝ࢳ࢜ࣥࡢ⤖ᬗᵓ㐀࡟㛵ࢃࡿ≀ᛶ㸪X ࢧ࢖ࢺ࢔ࢽ࢜ࣥࡢ✀㢮㸪A ࢧ࢖ࢺ࢝ࢳ࢜ࣥࡢ✀㢮࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬࠸ࡃࡘ࠿ࡢ୺せ࡞ᵓ㐀࡟ࡘ࠸࡚➨୍ཎ⌮ィ⟬࡟ࡼࡾ PDOS ࢆィ⟬ࡋࡓ࡜ࡇࢁ㸪A ࢧ࢖ࢺ࢝ࢳ࢜ࣥࡣࣂࣥࢻᵓ㐀ࡢఏᑟᖏୗ➃㸪౯㟁Ꮚᖏୖ➃࡟㛵୚ࡋ࡚࠸࡞࠿ࡗࡓ㸬A ࢧ࢖ࢺ࢝ࢳ࢜ࣥࡢ㔜せᗘࡀప࠸ࡢࡣ㸪ࡇࡢࡓࡵࡔ࡜⪃࠼ࡽࢀࡿ㸬ࡋ࠿ࡋ㸪RFE ࡟ࡼࡾ㸯ࡘࡎࡘኚᩘࢆ๐ῶࡋ࡚࠸ࡃ࡜㸪A ࢧ࢖ࢺ࢝ࢳ࢜
ࣥࡢㄝ᫂ኚᩘࢆ㸯ࡘࡶྵࡲ࡞࠸࡜ࡁ࡟ࡣ㸪R2 ್ࡀ኱ࡁࡃపୗࡋ࡚ࡋࡲ࠺ࡇ࡜ࡀࢃ࠿ࡾ㸪A ࢧ࢖ࢺ࢝ࢳ࢜ࣥࡢ
✀㢮ࡶࣂࣥࢻࢠࣕࢵࣉࢆ⢭ᗘⰋࡃண

4ࡍࡿࡓࡵ࡟ࡣ㔜せ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

4.1 ཱྀ㢌Ⓨ⾲
[1]մ㔠Ꮚṇᚨ㸪ᒣୗ᫭୍[2]

Saeid ARABNEJAD, Megumi KOJIMA, Koichi YAMASHITA, International Conference on Material᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ⛅Ꮨᖺ఍㸦ᗈᓥ㸧

Strength and Applied Mechanics (MSAM 2019) Kiev (Ukraine)- 193 -

[3]Saeid ARABNEJAD, Megumi KOJIMA, Koichi YAMASHITA, EMN Amsterdam Meeting 2019㸸Energy
Storage Materials[4]

Koichi Yamashita, 2019 MRS Spring Meeting & Exhibit Symposium ES15: Fundamental Understanding of
the Multifaceted Optoelectronic Properties of Halide Perovskites, Phoenix, Arizona[5]

Koichi Yamashita, The 24th International Workshop on QUANTUM SYSTEMS IN CHEMISTRY, PHYSICS,
AND BIOLOGY(QSCP-XXIV)(Odessa, Ukraine)[6]

մKoichi Yamashita, Hiroki Iriguchi, Masanori Kaneko, 5th EMN Meeting on Computation and Theory,
Mauritius[7]

մKoichi Yamashita, Hiroki Iriguchi, Masanori Kaneko, 3rd International Solar Fuels Conference(ISF-3)International Conference on Artificial Photosynthesis-2019 (ICARP2019) 㸦ᶓ὾㸧

4.2 ࣏ࢫࢱ࣮Ⓨ⾲5[1]մ㔠Ꮚṇᚨ㸪ᒣୗ᫭୍[2]

Koichi Yamashita, Faraday Discussion㸸 Ultrafast Photoinduced Energy and Charge Transfer (Ventura, USA)

[3]

YAMASHITA Koichi, KOJIMA Megumi, ARABNEJAD Saeid, MRM2019㸦ᶓ὾㸧[4]

մH. Hatanaka, M. Kaneko, A. Muraoka, K. Yamashita, NIPHO20㸦ࢭࣅࣜ࢔ࠊࢫ࣌࢖ࣥ㸧᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ⛅Ꮨᖺ఍ 㸦ᗈᓥ㸧ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1]

մE. Kawashima, M. Fujii, and K. Yamashita: Chem. Lett. 48 (2019) 513–516.

[2]

I. Masumoto, N. Washida, S. Inomata, A. Muraoka, and K. Yamashita: J. Chem. Phys. 150 (2019) 174302.

[3]

G. Giorgi, K. Yamashita, M. Palummo, and S. Fabris: Curr. Opin. Green. Sustain. Chem. 17 (2019) A1–A4.

[4]

մE. Kawashima, M. Fujii, and K. Yamashita: J. Photochem. Photobiol. A: Chem. 382 (2019) 111875.

[5]

K. Mishima, K. Yamashita: ACS Omega 4 (2019) 10396–10404.

[6]

K. Mishima, M. Kaneko, J.-W. Song, H. Kawai, K. Yamashita, and K. Hirao: J. Chem. Phys. 152 (2020)
104105.

ཧ⪃ᩥ⊩[1]

Y. Uemura, H. Uehara, Y. Niwa, S. Nozawa, T. Sato, S. Adachi, B. Ohtani, S. Takakusagi, K. Asakura, Chem.
Lett. 43 (2014) 977.

[2]

Y. Uemura, D. Kido, Y. Wakisaka, H. Uehara, T. Ohba, Y. Niwa, S. Nozawa, T. Sato, K. Ichiyanagi, R.
Fukaya, S. Adachi, T. Katayama, T. Togashi, S. Owada, K. Ogawa, M. Yabashi, K. Hatada, S. Takakusa, Y.
Yokoyama, B. Ohtani, K. Asakura, Angew. Chem. Int. Ed. 55 (2016) 1364.

[3]

T. Nakajima, K.Sawada, J.Phys.Chem.Lett. 8 (2017) 4826-4831.

- 194 -

ศᏊ㌶㐨ィ⟬࡟ࡼࡿ᭷ᶵ཯ᛂ࠾ࡼࡧ᭷ᶵศᏊᵓ㐀ࡢタィ࡜ゎᯒ

Design and Analysis of Organic Reactions and Molecular Structures Based on
Theoretical Calculations䕿኱࿴⏣ᬛᙪ䚸ᑿ㇂ඃᏊ䚸బᒣ⨾⣪䚸䝄䜲㻌䝹䞊䝝䞁䚸⸽ዠ⃝䚸኱ሯ㝣ே䚸㝞㟢⍧䚸䜴㻌䝭䜰䞁䚸㻌㻌㻌㻌Ᏽ⯎⦋䚸ᑀᱜ၈䚸ᮔ☒㍤䚸➟ཎᙲ཭㻌䠄ᮾி኱Ꮫ኱Ꮫ㝔⸆Ꮫ⣔◊✲⛉䠅㻌㻌1◊✲┠ⓗࠊෆᐜ

ᮏ◊✲ࡣࠊ᭷ᶵ໬Ꮫ࠾ࡼࡧ๰⸆໬Ꮫ࡟࠾࠸࡚㔜せ࡞᭷ᶵ໬ྜ≀ࡢᵓ㐀≉ᛶࢆ㔞Ꮚ໬Ꮫィ⟬࠾ࡼࡧศᏊື
ຊᏛィ⟬ࢆ⏝࠸࡚ゎᯒࡍࡿ࡜࡜ࡶ࡟ࠊ᪂つศᏊࡢᵓ㐀タィࢆ┠ⓗ࡜ࡋࡓࠋ ஧⎔ᛶș࢔࣑ࣀ㓟ࢪ࣌ࣉࢳࢻࡢᵓ㐀≉ᛶኳ↛ࡢȘ࢔࣑ࣀ㓟ࡢ௦᭰࡜ࡋ࡚ேᕤࡢș࢔࣑ࣀ㓟ࡢ฼⏝ࡣࠊ࣌ࣉࢳࢻࡢ≀⌮໬Ꮫⓗᛶ㉁ࢆኚ໬ࡉࡏࠊ⏕⌮άᛶᵓ㐀ࡢᏳᐃ໬ࡸ㓝⣲ᾘ໬࡟ᑐࡍࡿᏳᐃᛶࢆቑ኱ࡍࡿࡇ࡜ࡀᮇᚅࡉࢀࠊ≉࡟ࠊࢥ࣓࣮ࣥ࣍ࢩࣙࣥไ㝈⬟ࡀ㢧ⴭ࡟㧗࠸⎔㦵᱁ࢆᣢࡘș࢔࣑ࣀ㓟ࡣ௒ᚋࡢᛂ⏝ࡀᮇᚅࡉࢀࡿࠋᮏ◊✲࡛ࡣࠊᅗ㸯࡟♧ࡍࡼ࠺࡞ᵝࠎ࡞ࣉࣟࣜࣥᆺࡢ஧⎔ᛶș࢔࣑ࣀ㓟ࠊࡍ࡞ࢃࡕᶫ࠿ࡅ❅⣲ᵓ㐀ࢆᣢࡕ஧⣭࢔࣑ࣀᇶࢆ᭷ࡍࡿேᕤș࢔࣑ࣀ㓟࡟╔┠ࡋࠊࡑࡢ࣌ࣉࢳࢻ㙐୰࡛ࡢᵓ㐀≉ᛶࢆ⌮ゎࡍࡿୖ࡛᭱ᑠ༢఩࡛࠶ࡿࢪ࣌ࣉࢳࢻ㸦&+&2;1+&+ ; ஧⎔ᛶ࢔࣑ࣀ㓟㸧ࡢᵓ㐀≉ᛶࢆศᏊືຊᏛィ⟬࡜ ')7 ィ⟬ࢆ⏝࠸࡚ㄪᰝࡋࡓࠋ⎔ࡦࡎࡳࡢ኱ࡁ࠸࢔࣑ࣀ㓟࡛࠶ࡿ㸯Ѹ㸱ࢆ㝖ࡃ඲࡚ࡢྜᡂἲࡀ☜❧ࡉࢀ࡚࠸ࡿࠋࡇࡢ࠺ࡕ㸵ࡣᮏ◊✲ࢢ࣮ࣝࣉ࡛ྜᡂࡉࢀࠊ㸵ࡢㄏᑟయࢆ㐃⤖ࡉࡏࡓ࢜ࣜࢦ࣐࣮ࡣ ṧᇶ࠿ࡽ ṧᇶࡲ࡛Ỉ⣲⤖ྜ࡟ࡼࡽ࡞࠸㠀ኳ↛ᆺࡢ࣊ࣜࢵࢡࢫᵓ㐀ࢆ࡜ࡿࠋᮏ◊✲࡛ࡣࠊ୍㐃ࡢ஧⎔ᛶș࢔࣑ࣀ㓟ࢪ࣌ࣉࢳࢻࡢࢥ࣓࣮ࣥ࣍ࢩࣙࣥࣉࣟࣇ࢓࢖ࣝࢆㄪᰝࡋࠊࢥ࣓࣮ࣥ࣍ࢩࣙࣥไᚚศᏊࡢࢹ
ࢨ࢖ࣥ࡟ᛂ⏝ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ


Bicyclo[1.1.1]pentane
H
N

Bicyclo[2.1.1]hexane

H
N

COOH

HOOC

Bicyclo[2.2.1]heptane
COOH

HOOC

H
N 7

H
N

7

COOH

HN

COOH

1

2

N
H

HN

3

4

Bicyclo[2.2.2]octane

2

5

6

Bicyclo[3.2.1]octane
H
N

㻌

H
N

COOH

9

HOOC

H
N

COOH

11

7

8

HN

COOH
COOH

COOH

10

COOH

Monocyclic

H
N
H

COOH

COOH

N 2
H

12

13

14

ᅗ䠍㻌᳨ウ䛻⏝䛔䛯஧⎔ᛶ䃑㻙䜰䝭䝜㓟䚹୺㙐䜢㉥䛷♧䛩䚹㻌- 195 -

15

2◊✲᪉ἲࠊィ⟬᪉ἲࢪ࣌ࣉࢳࢻ&+&2;1+&+ ; ஧⎔ᛶ࢔࣑ࣀ㓟 ࡢࢥ࣓࣮ࣥ࣍ࢩࣙࣥศᕸࢆaccelerated molecular dynamics
simulation ࡢ୍✀࡛࠶ࡿreplica exchange with solute tempering (REST) ࡟ࡼࡾィ⟬ࡋࡓࠋOPLS3e ຊሙࢆ⏝࠸࡚ィ⟬ࡋࡓࠋREST ィ⟬ࡣ࣓ࢱࣀ࣮ࣝ࠾ࡼࡧࢡ࣒ࣟࣟ࣍ࣝ⁐፹୰࡛⾜࡞ࡗࡓࠋࡲࡓࠊ஧⎔ᛶș-࢔࣑ࣀ㓟ࡢ❅⣲ୖࡢ࢔࣑ࢻ⤖ྜࡣࠊ஧⎔ᛶ㦵᱁ࡢ⎔ࡦࡎࡳ࡟ࡼࡾ❅⣲ࡀsp3 ᛶࢆᖏࡧࡿࡓࡵ㠀ᖹ㠃໬ࡍࡿࠋREST࡛ᚓࡽࢀࡓ࢚ࢿࣝࢠ࣮ᴟᑠᵓ㐀ࢆࡉࡽ࡟ᐦᗘỗ㛵ᩘἲࢆ⏝࠸࡚ᵓ㐀᭱㐺໬ࢆ⾜࠸ࠊ࣌ࣉࢳࢻศᏊࡢྛࢥ
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N

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N
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O

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CH3

- 196 -7c (trans)

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O

N

CH3

N

O

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H

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‫ۑ‬㝞㟢⍧ࠊబࢃ⨾⣪ࠊᑿ୫ඃࢢࠊୖਭ᫂἞ࠊ஭ୖඊ௙ࠊ੪໨῟㈼ࠊ୉࿴ీᬛᙪ㸦ᮾ୉㝔⸆ࠊᮾ໭୉㝔⸆㸧
/\VR36ཷᐜయ3<ࣜ࢞ࣥࢻࡢ⤖ྜࣔࢹࣝࡢᥦၐ࡜᳨ドࠊ➨ᅇᵓ㐀άᛶ┦㛵ࢩ࣏ࣥࢪ࣒࢘㸦⇃ᮏᕷ຿఍㤋࣭⇃ᮏ㸧㸰㸮㸯㸷ᖺ㸯㸰݆޳㢌Ⓨ⾲‫ۑ‬0LDQ:Xࠊబࢃ⨾⣪ࠊబ⸨⸅ࠊ߶ᶫ⳹ዉࢢࠊᑿ୫ඃࢢࠊ୉࿴ీᬛᙪ㸦ᮾ୉㝔⸆ࠊᅜཱི⾨◊㸧ෆᅾᛶ⬡⫫㓟࡜⬡⫫㓟࢔ࢼ࣮ࣟࢢࡢཱིయ㓄ᗙࡢർ㍑ࠊ➨ᅇᵓ㐀άᛶ┦㛵ࢩ࣏ࣥࢪ࣒࢘㸦⇃ᮏᕷ຿఍㤋࣭⇃ᮏ㸧㸰㸮㸯㸷ᖺ㸯㸰݆޳㢌Ⓨ⾲‫ۑ‬బࢃ⨾⣪ࠊୖਭ᫂἞ࠊ஭ୖඊ௙ࠊ੪໨῟㈼ࠊᑿ୫ඃࢢࠊ୉࿴ీᬛᙪ㸦ᮾ୉㝔⸆ࠊᮾ໭୉㝔⸆㸧ࢱࣥࣃࢡ㉁ඹᙺᆺཷᐜయ࡟ᑐࡍࡿ୧ぶ፹ᛶ࢔ࢦࢽࢫࢺࠊࣜࢰ࣍ࢫࣇ࢓ࢳࢪࣝࢭࣜࣥㄏᑟయࡢ࢔ࣥࢱࢦࢽࢫࢺ
໬ࠊ➨ᅇ࣓ࢹ࢕ࢩࢼࣝࢣ࣑ࢫࢺ࣮ࣜࢩ࣏ࣥࢪ࣒࢘㸦࠸ࡕࡻ࠺࣮࣍ࣝ ൂ⋤ࢢࠊᮾி㸧 㸰㸮㸯㸷ᖺ㸯㸯݆ ࣏ࢫࢱ࣮Ⓨ⾲‫ۑ‬㝞㟢⍧ࠊబࢃ⨾⣪ࠊᑿ୫ඃࢢࠊୖਭ᫂἞ࠊ஭ୖඊ௙ࠊ੪໨῟㈼ࠊ୉࿴ీᬛᙪ㸦ᮾ୉㝔⸆ࠊᮾ໭୉㝔⸆㸧/\VR36ཷᐜయ3<ࣜ࢞ࣥࢻࡢ⤖ྜࣔࢹࣝࡢᥦၐ࡜᳨ドࠊ➨㸴㸱ᅇೖᮏ⸆Ꮫ఍㛵ᮾࢩ㒊୉఍㸦໭཮୉Ꮫ⸆Ꮫ㒊࣭ᮾி㸧㸰㸮㸯㸷ᖺ㸷݆޳㢌Ⓨ⾲‫➟ۑۻ‬ཎᙲ཭ࠊᑿ୫ඃࢢ  ࠊ୉࿴ీᬛᙪ㸦ᮾ୉㝔⸆㸧⎔໬ࢺࣜࣉࢺࣇ࢓ࣥ୕⣭࢔࣑ࢻࡢFLVWUDQVᖹ⾮ไᚚࠊ➨㸴㸱ᅇೖᮏ⸆Ꮫ఍㛵ᮾࢩ㒊୉఍㸦໭཮୉Ꮫ⸆Ꮫ㒊࣭ᮾி㸧㸰㸮㸯㸷ᖺ㸷݆޳㢌Ⓨ⾲‫⸽ۑ‬ዟ⃝ࠊ⋤ᛮ㐲ࠊబీ࠶࠿ࡡࠊᑿ୫ඃࢢࠊ୉໨⌮ᜨࢢࠊ୉࿴ీᬛᙪ㸦ᮾ୉㝔⸆ࠊᅜཱིࡀࢇ◊✲ࢭࣥࢱ࣮◊✲ᡤ㸧ࠊS0'00'0;㛫┦஫స༽ࢆ㜼ᐖࡍࡿඉኳ↛࣊ࣜࢵࢡࢫศࢢࡢ๰〇ࠊ➨㸴㸱ᅇೖᮏ⸆Ꮫ఍
㛵ᮾࢩ㒊୉఍㸦໭཮୉Ꮫ⸆Ꮫ㒊࣭ᮾி㸧㸰㸮㸯㸷ᖺ㸷݆޳㢌Ⓨ⾲‫ۑۻ‬0LDQ:Xࠊబࢃ⨾⣪ࠊᑿ୫ඃࢢ  ࠊ୉࿴ీᬛᙪ㸦ᮾ୉㝔⸆㸧ࠊෆᅾᛶ⬡⫫㓟࡜᭷ᶵྜᡂࡋࡓ࢔ࢼࣟ࣮
ࢢࡢཱིయ㓄ᗙࡢർ㍑ࠊ➨㸴㸱ᅇೖᮏ⸆Ꮫ఍㛵ᮾࢩ㒊୉఍㸦໭཮୉Ꮫ⸆Ꮫ㒊࣭ᮾி㸧㸰㸮㸯㸷ᖺ㸷݆޳㢌Ⓨ⾲‫ۑۻ‬Ᏽ⯎⚣ࠊ‫ࠊ⹒ۆ‮‬ᑿ୫ඃࢢࠊụీ༤㝯ࠊࢃ޳೺ኴ㑻ࠊ✄ᇉ㒔࢞ࠊ୉࿴ీᬛᙪ㸦ᮾ୉㝔⸆ࠊᚨᓥช⌮୉ߵᕝ⸆㸧ࠊࢳ࢜࢔ࢭࢺ࢔ࢽࣜࢻࡢࢩࢫࢺࣛࣥࢫ␗ᛶ໬࡟࠾ࡅࡿ⨨᥮ᇶຠᯝࠊ➨㸴㸱ᅇೖᮏ⸆Ꮫ఍㛵ᮾࢩ㒊୉఍㸦໭཮୉Ꮫ⸆Ꮫ㒊࣭ᮾி㸧㸰㸮㸯㸷ᖺ㸷݆޳㢌Ⓨ⾲‫ࠐۻ‬Luhan Zhai, Application of 7-azabicyclo[2.2.1]heptane derivatives to stabilize ȕ-strand- like extended
FRQIRUPDWLRQRIQHLJKERULQJĮ-amino acid, 27th International Society of Heterocyclic Chemistry Congress
September, 2019, Rohm Theatre Kyoto & Miyakomesse, Kyoto, Japan (Oral presentation)- 198 -



‫ࠐۻ‬Akitomo Kasahara, Conformational Analysis and cis-trans Control of Cyclized Tryptophan Tertiary
Amides 27th International Society of Heterocyclic Chemistry Congress September, 2019, Rohm Theatre Kyoto& Miyakomesse, Kyoto, Japan (Poster presentation)‫ࠐۻ‬Yuko Otani, Chain Length-dependent Acceleration of Rotation of Lactams with Nitrogen- pyramidal
Tertiary Amide, 27th International Society of Heterocyclic Chemistry Congress September, 2019, Rohm
Theatre Kyoto & Miyakomesse, Kyoto, Japan (Oral presentation)
5.ฟ∧ᐇ⦼
‫ۻ‬Conformational preference of bicyclic E-amino acid dipeptides, Yuko Otani, Seokhwi Park, Tomohiko Ohwada.
Chirality, 2020, 32, 790-807.



‫ۻ‬Exploiting a C–N bond Forming Cytochrome P450 Monooxygenase for C–S Bond Formation, Iori Morita,
Takahiro Mori, Takaaki Mitsuhashi, Shotaro Hoshino, Yoshimasa Taniguchi, Takashi Kikuchi, Kei Nagae,
Norihiro Nasu, Makoto Fujita, Tomohiko Ohwada, Ikuro Abe. Angewandte Chemie International Edition 2020,
59, 3988-3993.

‫ۻ‬Peptide-EDVHG6KRUW6LQJOHȕ-Strand Mimics without Hydrogen Bonding or Aggregation, Luhan Zhai, Yuko
Otani, Yukiko Hori, Taisuke Tomita and Tomohiko Ohwada. Chemical Communications, 2020, 56, 1573 – 1576.



‫ۻ‬2YHUDOO6KDSH&RQVWUDLQWRI$OWHUQDWLQJĮȕ-+\EULG3HSWLGHV&RQWDLQLQJ%LF\FOLFȕ-Proline, Siyuan Wang,
Yuko Otani, Luhan Zhai, Aoze Su, Masayuki Nara, Masatoshi Kawahata, Kentaro Yamaguchi, Akane Sada,
Rieko Ohki, Tomohiko Ohwada. Organic Letters, 2019, 21, 7813-7817.

‫ۻ‬8QFRYHULQJWKH1HWZRUNVRI7RSRORJLFDO1HLJKERUKRRGVLQȕ-6WUDQGDQG$P\ORLGȕ-Sheet Structures, Luhan
Zhai, Yuko Otani and Tomohiko Ohwada. Scientific Reports: 2019, 9, Article number: 10737.



Non-naturally Occurring Helical Molecules Can Interfere with p53–MDM2 and p53–MDMX Protein–Protein
Interactions, Aoze Su, Siyuan Wang, Akane Sada, Yuko Otani, Luhan Zhai, Xin Liu, Misa Sayama, Rieko Ohki,
and Tomohiko Ohwada. Chemical and Pharmaceutical Bulletin 2019, 67, 1139–1143.

- 199 -

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Rational Drug Design and Development of Novel Candidates Using theFirst-Principles Calculations
Sundaram Arulmozhiraja, Reiji Higuchi, Shogo Masuda, Kanade Shimizu, Hiroaki Tokiwa
Rikkyo University

1 Purpose of research
The main purpose of our research works is to understand the biological systems by using various computational
methods such as first-principle based quantum-mechanical (QM) fragment molecular orbital theory (FMO), molecular
dynamics (MD), and full ab initio molecular orbital calculations to work towards rational drug design and development.
For this, we have selected the following research works for this term:(a) Improving the activity of lead compound is the most important goal for any of the drug discovery program.
Typically, it has been done by changing the pharmacophores or simply varying the substituents to the lead compoundand measure its activity. However, this process involves lot of other issues – especially it is a highly time-consuming
process and involves high cost. Therefore, in order to shorten the development period and to reduce the cost, predicting
the activity of the compounds reliably through theoretical approach is required. The FMO method is a fast and accuratequantum chemical method for large molecular systems and so it is a reliable and appropriate method to achieve this goal.
It is a fragmentation approach, in which a system is subdivided into fragments. In the two-body method, FMO2,
fragments and their pairs (dimers) are calculated. The interfragment pair interaction energies (PIE) or IFIE and are used
to analyze the molecular recognition, in particular, of ligands by proteins. In the previous study, we used the FMO
method to predict activity values, but we used only hydrophobic interaction energies. This is because the electrostaticinteraction energies are overestimated due to the calculations in the vacuum, and they could not be handledappropriately. In addition, the assumption that PIEs determine the observed binding energies or activities is flawed
because PIEs do not include the destabilization polarization, desolvation, and deformation energies of fragments. Here,
we would like to account all these missed factors to deal the interfragment interactions correctly so to check whether or
not FMO calculations could predict the activity of the compounds. We also performed subsystem analysis to estimate
the binding energy, and then compared the calculated values with experimental values (IC50, KD, Ki, and ΔH). For thispurpose, we considered complexes of dipeptidyl peptidase IV (DPP-4) with its inhibitors. DPP-4 is the enzyme
responsible for the degradation of incretins such as glucagon-like peptide 1 (GLP-1) and glucose-dependent
insulinotropic polypeptide, which stimulate insulin secretion from pancreatic beta cells of the islets of Langerhans andsuppress glucagon secretion. Various DPP-4 inhibitor drugs available in the market, such as Sitagliptin, Trelagliptin,
Alogliptin, Omarigliptin, and Teneligliptin were considered for this purpose.
(b) Glycans cover the cell surface in vivo and plays a very important role in biological reactions such as cell-cellrecognition, immune responses, and tumor metastasis. The structure of glycan varies depending on the cell type and thestate in which it is synthesized and the environment in which it is present. Lectins specifically distinguish various
glycan structures. Quantitative analysis of glycan-lectin interactions can provide insight into the cell function and status.
Here we would like to use the quantum mechanical fragment molecular orbital method to study the glycan-lectin- 200 -

complexes in order to analyze the interaction between each monosaccharide constituting glycan and each amino acid in
the lectin. However, though the FMO method is well-known for the studies involving proteins and even for DNA, it has
not been utilized much for glycans. The main reason behind this might be due to its fragmentation scheme. In general,
for the FMO calculations on proteins, fragmentations are made by breaking the Cα-C bonds because peptide bonds
have considerable electron delocalization. On the other hand, in the case of glycans, it is difficult to find the regularityof the fragmentation scheme because of the complexity of the branch structure in addition to the structural flexibility.
An appropriate fragmentation scheme has not yet been established for glycans so far. So, in this topic, we would like toinvestigate and establish a general fragmentation scheme that can be used to study the glycans using FMO. In the laterpart, by using the established fragmentation scheme, we like to study a model glycan-lectin complex to verify thescheme.
(c) The other research topic we are working on is Retinoid X receptor (RXR). It is a member of nuclear receptor (NR)superfamily, which regulates various physiological metabolism, such as dietary lipid metabolism and nervous system
via forming homodimer or heterodimers with other NRs. Binding of small molecules to the ligand binding pocket of
RXR induces the conformational change of “AF-2 interface”, which plays a key role in recognizing the LXXLL motifs
located in coactivators. Although various agonists such as bexarotene targeting RXR have been developed, it has beenshown that they cause unwanted adverse effects. In continuation with our earlier work on RXR partial agonist,
CBt-PMN, which shows reduced side effects, we would like to study new possible partial/full agonists. To understandthe molecular basis behind the full/partial activity of these new compounds, computational works become essential in
addition to structural and biochemical analysis. So, we studied the newly crystallized ligand-bound hRXR complexes
using various computational methodologies.
Apart from these research topics, we are also continuing our works on anti-cancer natural products such as
termicalcicolanone. Our theoretical studies on potential reaction pathways assist organic synthetic chemists forsynthesizing these natural products.

2 Research methods, Computational methods
To establish an appropriate fragmentation scheme for glycans for the FMO calculations, we have taken 13
sialosaccharides (glycans) for the calculations. And to take the account of the flexibility of glycans and their dynamic
structural changes in actual biological medium, we performed MD simulations up to 450 ns on all the selected glycans
using the Glycam06 forcefields. One hundred structures of each glycan were extracted from the MD simulations, andFMO calculations were made on all these structures utilizing possible fragmentation schemes. By thoroughly analyzing
the FMO calculation results, we could find the most appropriate fragmentation scheme for glycans. MD simulations
were performed through normal procedures using GROMACS program and all the FMO calculations were done with
PAICS program.
For the calculations on dipeptidyl peptidase IV complexed with its inhibitor drugs, GROMACS software was used for
the MD simulations and GAMESS program was utilized for FMO calculations. The X-ray crystal structures of thecomplexes of the selected DPP-4 inhibitor drugs with DPP-4 were taken from Protein Data Bank. The interactions ofthese inhibitor drugs with DPP-4 enzyme were quantitatively obtained using the FMO approach. To describe protein
upon solvation, polarizable continuum model (PCM) was used in the FMO-PCM method. Different level of theories
and approaches were utilized in this study.

- 201 -

The crystal structures of the hRXR/agonist complexes are submitted to MD simulations up to 700 ns. FMO
calculations on these complexes were made using PAICS and GAMESS programs. Both raw crystal structures and the
MD structures were utilized for FMO calculations.
Reaction pathways involving anti-cancer natural products were studied using GAUSSIAN suite of programs atvarious levels of theories.

3 Research results
By investigating various fragmentation approaches in the present study, we established an appropriate fragmentation
scheme to handle the glycans for FMO calculations by considering 13 sialosaccharides (glycans). By utilizing thefragmentation scheme established in this study, FMO calculations were performed for the Galectin-8N-domain(-8N)/Neu5Acα2-3Galβ1-4Glc-OMe complex and

identified the amino acid residues responsible for the glycan

recognition by Galectin-8N.
In the case of DPP-4 study to check whether FMO can predict the activity of the compounds, our calculated
interaction energies and binding energies correlate well with the available experimental values (pIC50 and pKD). Our
calculations clearly indicate that FMO calculations can positively predict the activity of the DPP-4 inhibitor drugs.
These results clearly reveal that solvent effects should be considered to calculate the interfragment interaction energies.
Additionally, the study also indicates that binding energies, instead of simple interfragment interaction energies, could
be a better choice to study the activity of the compounds.
In combination with the structural (crystal) and biochemical analysis, molecular dynamics simulations were
performed to understand the structural changes of the hRXR complexed with the newly synthesized full/partial agonists.
This understanding could assist to study the activity of these compounds in detail. Quantitative binding energies wereobtained using ab initio fragment molecular orbital theory. While MD simulations clearly indicate a different
mechanism for partial and full agonist complexed-hRXR structures, the FMO results show that full agonist binds
stronger to hRXR than that by the partial agonist. These results clearly reveal that the computational analysis involving
MD simulations and FMO calculations can explain the activity of these compounds towards RXR.
Our computational reaction pathway studies greatly helped to achieve the total synthesis of anticancer natural product,a termicalcicolanone product, for the first time.

4 Talks and seminars1) S. Arulmozhiraja. “Fragment molecular orbital theory studies on protein-ligand interactions and theirapplications” presented at the 3rd International Conference on Chemical Biology and Biologics held at Dubai,
UAE on 26-27 February 2020 (Keynote Address).
2) R. Higuchi and S. Arulmozhiraja, “Can the fragment molecular orbital method predict the activity of inhibitor
drugs?”, presented at the 3rd International Conference on Chemical Biology and Biologics held at Dubai, UAE on
26-27 February 2020.
3) S. Arulmozhiraja and R. Higuchi, “Activity of dipeptidyl peptidase IV (DPP-4) inhibitors – Fragment
molecular orbital theory study”, presented at the 2020 International Symposium on Chemical Biology held at
Geneva, Switzerland on 22-24 January 2020.

- 202 -

4) D. Imai, N. Numoto, S. Arulmozhiraja, S. Masuda, H. Kakuta, H. Tokiwa, and N. Ito, “Structural analysis of
NEt-3IB/Net-4IB bound retinoid X receptor α” presented at the 16th Conference of the Asian Crystallographic
Association held at Singapore on December 17-20 2019.

5 Publications1) S. Arulmozhiraja, H. Tokiwa, and H. Shimano, “Elucidating the efficacy of clinical drugs using FMO”, In recent
advances of fragment molecular orbital method – Enhanced performance and applicability edited by Y.
Mochizuki, S. Tanaka, and K. Fukuzawa, Springer Publishers, Japan 2020 In press (Book Chapter).
2) M. Kawasaki, A. Kambe, Y. Yamamoto, S. Arulmozhiraja, S. Ito, Y. Nakagawa, H. Tokiwa, S. Nakano, and H.
Shimano, “Elucidation of molecular mechanism of a selective PPARα modulator, pemafibrate, throughcombinational approaches of X-ray crystallography, thermodynamic analysis, and first-principle calculations”,
Int. J. Mol. Sci. 21(1), 361-1-14, 2020. DOI:10.3390/ijms21010361.
3) T. Matsuzaka, M. Kuba, S. Koyasu, Y. Yamamoto, K. Motomura, S. Arulmozhiraja, H. Ohno, R. Sharma, T.
Shimura, Y. Okajima, S-I. Han, Y. Aita, Y. Mizunoe, Y. Osaki, H. Iwasaki, S. Yatoh, H. Suzuki, H. Sone, Y.
Takeuchi, N. Yahagi, T. Miyamoto, M. Sekiya, Y. Nakagawa, M. Ema, S. Takahashi, H. Tokiwa, and H. Shimano,“Hepatocyte Elovl6 fatty acid elongase 6 determines ceramide acyl-chain length and hepatic insulin sensitivity inmice”, Hepatology 71(5), 1609-1625, 2020. DOI:10.1002/hep.30953.
4) D. Imai, N. Numoto, S. Arulmozhiraja, S. Masuda, S. Nakano, H. Kakuta, H. Tokiwa, and N. Ito, “Structural
analysis and dynamics of NEt-3IB/Net-4IB bound retinoid X receptor α  5) R. Higuchi, S. Arulmozhiraja, and H. Tokiwa, “Can the fragment molecular orbital method predict the activity of
dipeptidyl peptidase IV (DPP-4) inhibitor drugs?” (To be submitted).
6) S. Masuda, S. Arulmozhiraja, and H. Tokiwa, “Interaction analysis of glycan-lectin complexes using
first-principles calculations-based fragment molecular orbital method” (To be submitted).
7) Y. Suzuki, Y. Kitahara, Y. Ejima, A. Tsunoi, S. Arulmozhiraja, K. Ozawa, T. Utsunomiya, K. Tazawa, H. Tokiwa,
K. Manabe, “Total synthesis of Termicalcicolanone B via N-heterocyclic carbene-catalysis and regioselective
Claisen cyclization” (To be submitted).

- 203 -

ບ㉳≧ែ࡜ࡑࡢ⦆࿴㐣⛬࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical studies on excited states and their relaxation processes‫⸭ۑ‬ୗ ⪽ࠊ㟢ᮌ㞞ᩥࠊஂ㈡㇂᭷ேࠊྂᶫ┤ே 㸦៞᠕኱⌮ᕤ㸧
1◊✲┠ⓗࠊෆᐜ
ᡃࠎࡣศᏊࡢບ㉳≧ែ࠿ࡽࡢᵝࠎ࡞⦆࿴㐣⛬ࢆ⌮ㄽⓗ࡟◊✲ࡋ࡚࠸ࡿࠋ᭱㏆ࡢ౛ࡣࠊග࢖࢜ࣥ໬㐣⛬ࡢ」⣲ᇶᗏ㛵ᩘ &%) ἲ࡟ࡼࡿグ㏙ࠊศᏊࡢගศゎ࡟࠾ࡅࡿᚤ⣽ᵓ㐀‽఩㛫ࡢ㠀᩿⇕㑄⛣ࠊᕼᅵ㢮ࢆྵࡴ㔠ᒓ᭷ᶵศᏊ㘒యࡢ㛤Ẇ㟁Ꮚ≧ែ࡜㟁Ꮚ≀ᛶࡢ◊✲࡞࡝࡛࠶ࡿࠋࡇࡇ࡛ࡣ &%) ἲࡢ┦ᑐㄽ⾲⌧࡬ࡢᣑᙇࠊ㓟࣭࢔ࣝࢥ࣮ࣝ࡞࡝ 52+ ศᏊࡢ 2+ ᇶఙ⦰᣺ື࡟࠾ࡅࡿ྾཰ᙉᗘࡢ⨨᥮ᇶ౫Ꮡᛶ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ*DXVVLDQࠊ*$0(66 ࡞࡝ỗ⏝ࢯࣇࢺࢆ฼⏝ࡍࡿ࡜࡜ࡶ࡟ࠊ&%) ἲࠊࢫࣆࣥ㌶㐨 &, ἲࠊ࠾ࡼࡧ㠀ㄪ࿴᣺ືࡢ⥺ᙧ࣭㠀⥺ᙧᛂ⟅⌮ㄽ࡟ࡼࡿ྾཰ᙉᗘィ⟬ἲ࡜ࣉࣟࢢ࣒ࣛࡣࠊ⊂⮬࡟㛤Ⓨ࣭సᡂࡋ࡚࠸ࡿࠋ

◊✲ᡂᯝ

3.1 」⣲ᇶᗏ㛵ᩘ &%) ἲ࡟ࡼࡿ࢘ࣛࣥࡢ . Ẇග࢖࢜ࣥ໬᩿㠃✚ࡢ⌮ㄽⓗ◊✲ࠋ 㔜ཎᏊࡢෆẆ࡛ࡣ┦ᑐㄽຠᯝࡀ㢧ⴭ࡛ࠊ≉࡟ࡑࡢ㸯㟁Ꮚ㌶㐨ࡢ኱ᡂศ࡜ᑠᡂศࡣ
␗࡞ࡿ㌶㐨ゅ㐠ື㔞࡜ࣃࣜࢸ࢕ࢆᣢࡘࡇ࡜࠿ࡽࠊࡑࡢ
ග㟁Ꮚゅᗘศᕸ࡟㢧ⴭ࡞┦ᑐㄽຠᯝࡀ⌧ࢀࡿྍ⬟ᛶࡀ࠶ࡿࠋࡉࡽ࡟ࡑࡢ࢖࢜ࣥ໬࡟ᚲせ࡞▷Ἴ㛗ࡢ㟁☢Ἴ࡜ࡢ┦஫స⏝࡟཮ᴟ㏆ఝࡣ౑࠼࡞࠸ࠋヲ⣽ࡣᚋ㏙ࡍࡿࡀ
)LJXUH ࡟♧ࡍࡼ࠺࡟ 6XMNRZVNL ࡽ࡟ࡼࡿ࢘ࣛࣥཎᏊ
ࡢ . Ẇග࢖࢜ࣥ໬ᚤศ᩿㠃✚ࡢ

1.2

5HODWLYH GıGȍ

3

1.0
0.8
0.6

0.4
0.2
0.0
0

30

60

90

120

150

180

ș GHJUHH
7KLVZRUN

3UDWW([SHULPHQWDO

1RQUHODWLYLVWLFᐃ⤖ᯝ([SHULPHQWDO >@ࡣࠊ๓᪉ᩓ஘ࡢഴྥࢆ♧ࡋࠊ㠀┦ᑐ )LJXUH  . VKHOO GLIIHUHQWLDO FURVV VHFWLRQ IRU =ㄽ 1RQUHODWLYLVWLF ࡢண ࡜ࡣ኱ࡁࡃ␗࡞ࡿࠋࡑࡇ 279 keV RQ XUDQLXP 7KH PD[LPD RI HDFK GLIIHUHQWLDO
࡛ࡇࢀࡲ࡛㠀┦ᑐㄽࡢᯟෆ࡛ᐃᘧ໬ࡋ࡚ࡁࡓ &%) ἲࢆ FURVVVHFWLRQDUHQRUPDOL]HGWRXQLW\┦ᑐㄽ໬ࡋࠊ࢘ࣛࣥཎᏊࡢ . Ẇ࠿ࡽࡢග㟁Ꮚࡢゅᗘศᕸ࡟ᛂ⏝ࡋࠊࡑࡢ᭷ຠᛶࢆㄪ࡭ࡓࠋ
ཎᏊ࣭ศᏊ࡬ࡢග↷ᑕ࡟ࡼࡗ࡚ㄏ㉳ࡉࢀࡿ  ḟᦤືἼື㛵ᩘΨ ( ) ࡣࠊ᫬㛫౫Ꮡࡢᦤືㄽ࡟ࡼࡾࠊ
( + − )Ψ ( ) =∙ Φ(1)ࡢ㠀ྠḟ᪉⛬ᘧࢆ‶ࡓࡍࠋࡇࡇ࡛Φ ࠾ࡼࡧ ࡣ᮰⦡ጞ≧ែ࡜ࡑࡢᅛ᭷࢚ࢿࣝࢠ࣮ࠊ ࡣ࣋ࢡࢺ࣏ࣝࢸࣥࢩࣕࣝࠊ ࡣධᑕගᏊ࢚ࢿࣝࢠ࣮࡛࠶ࡿࠋ ࡜ࡋ࡚'LUDFࣁ࣑ࣝࢺࢽ࢔ࣥࢆ౑࠸  ࢆ&%)ἲ>@࡛⥺ᆺ᪉⛬ᘧ࡜ࡋ࡚ࠊ
እྥἼቃ⏺᮲௳ࡢࡶ࡜࡛ゎࡁࠊΨ ( ) ࡢ⹫㒊࠿ࡽṇ๎ゎࢆᚓࡿࠋ&%)ἲ࡟ࡼࡿ࡜  ࡢゎࡣཎᏊ㡿ᇦ࡛㠀ᖖ࡟㧗⢭ᗘ࡛࠶ࡿࡀ>@ࠊ₞㏆㡿ᇦࡢ᝟ሗࡣᚓࡽࢀ࡞࠸ࠋࡑࡇ࡛㐺ᙜ࡞᥋⥆Ⅼ࡛Ψ ( ) ࡢ⹫㒊ࢆḟ5XQJH.XWWDゎ࡟᥋⥆ࡋࡓࡢࡕࠊྠḟᙧᚤศ᪉⛬ᘧࡢゎ࡜ࡋ࡚₞㏆㡿ᇦࡲ࡛ᩘ್✚ศࡋࠊ఩┦ࢩࣇࢺࢆィ⟬ࡋࡓࠋ=  ࡢỈ⣲ᵝཎᏊ 8 ࡢ . Ẇ㟁Ꮚࡀ⣧⢋࡞ࢡ࣮࣏ࣟࣥࢸࣥࢩࣕࣝࢆឤࡌࡿ࡜㏆ఝࡋࠊᇶᗏ㛵ᩘ࡜ࡋ࡚ࠊ ᘧࡢΦ ࡟ࡣ HYHQWHPSHUHG ᐇᩘ 672 ࢆࠊࡲࡓΨ ( ) ࡟ࡣ HYHQWHPSHUHG ᐇᩘ 672 ࡜」⣲ 672 ࢆ⏝࠸ࡓࠋ ࡢ࣋ࢡࢺ࣏ࣝࢸࣥࢩࣕࣝ ࡟ࡣከ㔜ᴟຠᯝࢆྲྀࡾධࢀࡿࡓࡵ㒊ศἼᒎ㛤ࢆ⾜ࡗࡓࠋ)LJXUH㸯ࡣࠊ= 279 keV࡟࠾ࡅࡿ 8 ࡢ . Ẇග࢖࢜ࣥ໬ᚤศ᩿㠃✚ࢆ♧ࡍࡀࠊᡃࠎࡢ್ 7KLV ZRUN ࡣࠊᐇ- 204 -

㦂್>@ࠊ3UDWW ࡽ࡟ࡼࡿィ⟬್>@࡜ࡼࡃ୍⮴ࡋࠊ= ࡀ኱ࡁ࠸ሙྜࠊ. Ẇ㟁Ꮚࡢ㐠ືࢆࢡ࣮࣏ࣟࣥࢸࣥࢩ࡛ࣕࣝ
⾲⌧ࡍࡿࡇ࡜ࡢጇᙜᛶࢆ♧ࡋ࡚࠸ࡿࠋᚤศ᩿㠃✚ࡢᴟ኱ࡀගࡢఏᦙ᪉ྥ࡟ࢩࣇࢺࡍࡿࡢࡣࠊ. Ẇග࢖࢜ࣥ໬
ࡢ࢚ࢿࣝࢠ࣮࡛ࠊගᏊ࠿ࡽග㟁Ꮚ࡬ࡢ㐠ື㔞⛣⾜ࡀ㢧ⴭ࡟࡞ࡿࡓࡵ࡛ࠊྂ඾ⓗ࡟ࡣ☢Ẽⓗ࡞ /RUHQW] ຊࡢᙳ㡪࡜ゎ㔘ࡍࡿࡇ࡜ࡶฟ᮶ࡿࠋࡇࡢ᣺ࡿ⯙࠸ࡣࠊ཮ᴟ㏆ఝࢆ⏝࠸ࡓ㠀┦ᑐㄽ࡛ࡣ⾲⌧࡛ࡁ࡞࠸ࠋ)LJXUH ࡟
279 keV࡟࠾ࡅࡿΨ

( )

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ࡢືᚄἼື㛵ᩘࢆ♧ࡋࡓࠋᇶᗏ㛵ᩘᒎ㛤࡟ࡼࡿIm( )=,P&%) ࡣࠊᕪศἲ࡟ࡼࡿᩘ

್ゎ ([DFW ࡜≉࡟ཎᏊ㡿ᇦ࡛⢭ᗘⰋࡃ୍⮴ࡋ࡚࠸ࡿࠋࡲࡓࠊᑠᡂศࡢ᣺ᖜࡣ኱ᡂศࡢ ⛬ᗘ࡟ࡶ࡞ࡿࠋ
D /DUJHFRPSRQHQW
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 IRUK\GURJHQOLNHDWRP =   1s / → p /  DW

5H([DFW,P([DFW= 279 keV D /DUJHDQG E 

VPDOOUDGLDOFRPSRQHQWVDUHVKRZQ ⥺ᙧᛂ⟅㛵ᩘ䜢⏝䛔䛯 52+ 㢮ศᏊ䛻䛚䛡䜛 2+ ఙ⦰᣺ື䛾⌮ㄽゎᯒ䚹ศᏊ୰ࡢ㟁Ꮚᐦᗘࡣ᰾ᗙᶆࡢኚ໬
࡟ᩄឤ࡛ࠊࡑࡢ཯ᛂᛶࡢ㆟ㄽ࡛ࡶ୰ᚰⓗ࡞ᙺ๭ࢆᯝࡓࡍࠋ52+ ศᏊࡣ⨨᥮ᇶ 5 ࡢ㐪࠸࡛཯ᛂᛶࡀ኱ࡁࡃ␗࡞
ࡿࡀࠊࡑࡢ㐪࠸ࡣ཮ᴟᏊ࣮࣓ࣔࣥࢺ㛵ᩘ㸦'0)㸧࡟㢧ⴭ࡟⌧ࢀࡿࠋᡃࠎࡣ࠸ࡃࡘ࠿ࡢ 52+ ศᏊ࡟࠾࠸࡚ࠊࡑࡢ
2+ ఙ⦰᣺ືࡢ '0) ࢆ 2+ ᇶࡢ᰾㛫㊥㞳ࡢኚ఩ ࡢከ㡯ᘧ࡜ࡋ࡚∑࡜ᒎ㛤ࡍࡿ࡜ࠊྛศᏊࡢ , ࡢ㛫࡟⥺ᆺ㛵ಀࡀ࠶ࡾࠊ ࡣศᏊࡢ㓟ᛶᗘ࡟ࠊࡲࡓ| |ࡣ㌾ࡽ࠿ࡉ࡟┦㛵ࡍࡿ࡜࠸࠺ഴྥࢆぢฟࡋ࡚࠸ࡿࠋࡑ
ࡇ࡛⥺ᙧᛂ⟅ࡢ⪃࠼᪉࡟ࡋࡓࡀ࠸ ࢆゎᯒⓗ࡟ホ౯ࡋࠊ ࡀᣢࡘ໬Ꮫⓗ࡞ᥥീࢆ᫂ࡽ࠿࡟ࡋࠊࡉࡽ࡟ ,࡜≀ᛶࡢ┦㛵ࢆ㟁Ꮚᐦᗘ࡛⌮ゎࡍࡿࡇ࡜ࢆヨࡳࡓࠋ 2+ ఙ⦰᣺ື࡟క࠺㟁Ꮚᐦᗘኚ໬ࢆホ౯ࡍࡿ㝿࡟ࠊ㟁Ꮚ㛫┦஫స⏝ࢆ௓ࡋ࡚⏕ࡌࡿ㟁Ꮚᐦᗘࡢኚ໬ࢆ 6&)ⓗ࡟⪃៖ࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡘࡲࡾ 2+ ఙ⦰᣺ື࡟ࡼࡿ㟁Ꮚᐦᗘኚ໬ࡣ( ,⌧ࡉࢀࡿࡀࠊ6&) ຠᯝ࡟ࡼࡾࠊ2 ཎᏊୖࡢᏙ❧㟁Ꮚᑐࡸ⨨᥮ᇶୖࡢ( ,⨨᥮ᇶୖ ȧ ㌶㐨ࡀ,࡟ᐤ୚ࡍࡿࠋࡲࡓࠊ∗ )ບ㉳࡛⾲∗ )ບ㉳࡬࡜㟁Ꮚᐦᗘኚ໬ࡀఏ᧛ࡋࠊ

࡟ࡘ࠸࡚ࡣ࢔ࣝࢥ࣮࣭ࣝ㓟ࢆၥࢃࡎ 2+ 㡿ᇦࡢ㟁Ꮚᐦᗘኚ໬

ࡀᨭ㓄ⓗ࡛࠶ࡿࡀࠊ

࡟㛵ࡋ࡚ࡣࠊ࢔ࣝࢥ࣮࡛ࣝࡣ 2+ 㡿ᇦࡢ᪉ࡀࠊࡲࡓ㓟࡛ࡣ⨨᥮ᇶ㡿ᇦࡢ᪉ࡀ㟁Ꮚᐦᗘኚ໬ࡢᐤ୚ࡣ኱ࡁ࠸ࠋ

ࢆỴᐃࡍࡿ㟁Ꮚᐦᗘࡢ᰾ᗙᶆ  㝵ᚤศ㔞ࢆㄪ࡭ࡓ⤖ᯝࠊ㓟࡜࢔ࣝࢥ࣮࡛ࣝࡣ 2 ཎᏊᏙ❧ᑐ㡿ᇦ࡛␗࡞ࡿᙧ≧ࢆᣢࡕࠊࡑࡢ㐪࠸ࡣ 6&) ຠᯝ࡟㉳ᅉࡋࠊ㓟࡛ࡣ 2 ཎᏊୖᏙ❧ᑐ㌶㐨ࡢ࠺ࡕࡢSȧ ㌶㐨ࡀ⨨᥮ᇶࡢ ȧ ㌶㐨࡜┦஫స⏝ࡍࡿࡇ࡜࡛㟁Ꮚᐦᗘࡢኚ໬ࡀᐜ᫆࡟࡞ࡿࡓࡵ࡜⪃ᐹࡋࡓࠋ

ཧ⪃ᩥ⊩㻌 >@=6XMNRZVNL$UN)\V  >@715HVFLJQRDQG&:0F&XUG\3K\V5HY$
 >@50DWVX]DNLDQG6<DEXVKLWD-&RPSXW&KHP  >@5+3UDWW5'/HYHH5/3H[WRQ
DQG:$URQ3K\V5HY$   㸲 Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
⸭ୗࠊ㮵ᚿᮧࠊ$3$7&&ᖺ᭶6\GQH\ ྂᶫࠊ⸭ୗࠊྠᏛ఍ ᤷԾ7DLZDQ-DSDQ:RUNVKRSRQ
7KHRUHWLFDO&KHPLVWU\ᖺ᭶,$06$FDGHPLD6LQLFD7DLSHL㸹ྂᶫࠊ⸭ୗࠊ➨ᅇศᏊ⛉Ꮫウㄽ఍ࠊᖺ᭶ࠊྡྂᒇ኱Ꮫ⸭ୗࠊ㮵ᚿᮧࠊྠᏛ఍ஂ㈡㇂ࠊ㟢ᮌࠊ⸭ୗࠊྠᏛ఍ࠋ㸳 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
7.*KRVKࠊ⸭ୗࠊ,-5&(   ྂᶫࠊ⸭ୗࠊ-3K\V%LQSUHVV 㟢ᮌࠊྂ㤋ࠊஂ㈡㇂ࠊ⸭ୗࠊᢞ✏ணᐃ すࠊ⸭ୗࠊᢞ✏ணᐃࠋ- 205 -

  
Theoretical studies on structures, reactions, and intermolecularinteractions of transition metal compoundsĤę ·ïo !(n³ »Æ jģÒę ýĥû#Ë ğdĝ±wsªêçíêĦß ¯ĥÛyêĦ
1çíäão¾çí;X[P$(1)Rh |% Ru ěĜk"0Óó-ÓóbĘöĥC=CĦ#ĉ-%ù®ĉëá¨w~§ÇÄ#ă´(2)K[N=ZF5DC Ru, Rh, Ir Ĝk#~§ÇÄ#ă´(3) ėwCBZG

2hJòÿġ"0Ë#öØ¨#ăÁ# 3 #=OE[R"çí2þ$(1)#ªÂ"0
č C=C ö#ĉ$Ģ 7IX:[¦Ā !0LH
metallacyclopropane intermediateXĜk`# C=C ö$ÊĊãµ"ĉ0 æ.1

[M]0ĉ#~§õć ð 4 ¼#Ĕëě ½î4X9Z#~§$ metallacyclopropane `ĝk2ð 5 ¼#Ĕëěoĕ4X9Z
1 #~§$}¨58Z2õà0

0 (Scheme

R2
R

R1

[M]

R2

[M]

R1

R

R1

R

R2



1)  L H X Y ? 6 S Ĝ k

[M]

R2

R

R1

[Cp*Rh{C(Ph)=C(CHMe-m)Ph}(PMe)] (1a)#á¨w$Ñ£"-Ýª×á!/25$ 1,4-Rh ĉi"-0LHX4W[ X Ĝ k [Cp*Rh{CH-2-(C(Ph)=CHPh)-4-Me}(PMe)] (2a)  50$ C=C ĉtwitterion

Scheme 1 Proposed mechanisms for C=C
bond rotation

1"÷ 1,4-Rh ĉ"-r#LHX

4W[XĜk[Cp*Rh{CH-2-(C(CHMe-m)=CHPh)}(PMe)] (2b)Ýª0(Scheme 2)[1]¾çí$LHXY?6SĜk 1a #
Ýª×#ÝªÊ#Ñ£m¨#ÜàCĩC ĉ#~§õć2ĚwãĂÔ.´."0 2äã

2

H

Rh

Rh

 £ÌĞ°ÎĥB3PW91Ħ"-/Äď¸ēwĄñĔëÙ©

2Þ

H

Rh

temp.

time

25℃

1h

0.2/1/050℃

1h

0.2/1/0.2

50℃

20h

0.1/1/2.4

50℃
1,4-Rh migration[Rh]þRh "ºuoÉQEZ>UX SDD 2Þ
Rh

e#{"¢Ğ° 6-31G(d,p)2ÞRh2arotation of
the C=C bond

50℃

Äď­ô¬v°ăÁĄñ º~§¤Å(IRC)Ąñ2 Gaussian09

50℃

[Rh]
H

1a



çí²ÎĄñ²Î

25℃
1,4-Rh migration[Rh]

1a/2a/2b

[Rh]
H
Rh


1b

2b
[Rh] = [Cp*Rh(PMe3)]

3

çíªÂ

Scheme 2  Reaction of vinyl-rhodium
complex (1a) [1]

1a #á¨w#7IX:[PYN35X2 Figure 1 "é25
# 1a . 2a &#á¨w$\ÈĠ#öTBA>@ĥ-CAMĦ"-ĐþÏ¨w7IX:[$
21.84 kcal/mol  /Ýª× 2a $~§× 1a -/, 9.88 kcal/mol \²50"0 1a 

. 2b &#á¨w$ÈĠ#bĘöĉ ħÈĠ#-CAM "-Đþ0¥ĎÈĠ$bĘöĉ#- 206 -

¸q#ÈĠ(1c 1d) ĥÏ¨w7IX:[25.63
kcal/molĦ/Ýª× 2b $~§× 1a "Ê'

8.44 kcal/mol Õtã" Ýª×#¨

Ï¨w7IX:[" _õć"!Ē $! !.C=C ĉÈĠ#`ĝkĥ1d, 1eĦ#7IX:[$11 10.61,
10.16 kcal/mol~§× 1a -/,^§õć#Č`$Õ~§

!

/~

0#

+"1a . 2b &#á¨w~§ĢÑ¿f#*Đþú.10."1a . 2b &#á¨w~§õć]#`ĝk 1d

1e #¡lÄď-% Kohn-Sham Ĉđ(Figure 2)#ăÁ.¾~§ĥLHX4W[XĜk# C=C ĉĦ$
metallacyclopropane `ĝk2õ0`ĝk 1d"é / Rh

Figure 1 Free energy profile for the isomerization from thecomplex 1a to 2b (B3PW91)

2´."

1e # HOMO 2èą0 ĆåzC #ĝ"ö¨#Ĉđ#Ýª

ā.10

±Ú 
[1] Y. Ikeda, K. Takano, M. Waragai, S. Kodama, N.
Tsuchida, K. Takano, Y. Ishii, Organometallics, 2014, 33,
2142.
Figure 2 HOMOs of the complexes 1c, 1d, and 1e4âÿø)$a Æ`Ĥę ³¾<ZMV[Bwg 2019¶ g2019 ĢÃßÍx ³¾ügð 140

g2020 ÐċĢßÍÃx ³¾ügð 140

5

6 ¹Àc

Ĩ¹cĖ
g2020Ĩ¹cĖpÖø)$a Æ, `, Ĥę, J. Comput. Chem. Jpn., 2019, 18, 162-163. DOI: 10.2477/jccj.2019-0019
 A. Suzuki, Y. Mutoh, N. Tsuchida, C-W. Fung, S. Kikkawa, I. Azumaya, S. Saito, Chem. Eur. J., 2020, 26, 3795-3802.
DOI: 10.1002/chem.201904600
 M. Kusumoto, K. Ueno-Noto, K. Takano, J. Comput. Chem., 2020, 41, 31-42.

DOI: 10.1002/jcc.26073

 T. Kuwabara, Y. Aoki, K. Sakajiri, K. Deguchi, S. Takamori, A. Hamano, K. Takano, H. Houjou, Y. Ishii,
Organometallics, 2020, 39, 711-718. doi.org/10.1021/acs.organomet.9b00856
 T. Yokaichiya, K. Takano, Bull. Chem. Soc. Jpn., «ìa
 N, Tsuchida, K. Takano, Organometallics, «ìa

- 207 -

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 ⫕࣭ఀ⸨ᗈఙ࣭ᩪ⸨೺ே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
ᖹᡂ 31࣭௧࿴ඖᖺᗘ࡟ࡣ㸪௨ୗ࡟♧ࡍ◊✲ࢆ⾜ࡗࡓࠋࣁࣟࢤࣥ⤖ྜ࡟࠾ࡅࡿ㟁Ẽᅄ㔜ᴟᏊຠᯝ࡜ศᴟຠᯝࡢᕪ㟁Ꮚᐦᗘ࡟ᇶ࡙ࡃゎᯒඹ᭷⤖ྜ࡟୚ࡿࣁࣟࢤࣥཎᏊࡣ㸪ࡑࡢ㟁Ẽ㝜ᛶᗘࡢ㧗ࡉ࡟ࡶ࠿࠿ࢃࡽࡎ㸪௚ศᏊࡢ㒊ศ㈇㟁Ⲵࢆᣢࡗࡓཎ

Ꮚ࡜ᘬຊⓗ࡟┦஫స⏝ࡍࡿࠋࡇࢀࡣ㸪ࣁࣟࢤࣥ⤖ྜ࡜࿧ࡤࢀ㸪ࣁࣟࢤࣥཎᏊࢆ᭷ࡍࡿศᏊࡀ㓝⣲ࡢ㜼ᐖ๣࡜ࡋ࡚ാࡃሙྜ࡞࡝࡟࠾࠸࡚㸪㔜せ࡞ศᏊ㛫┦஫స⏝࡜࡞ࡗ࡚࠸ࡿࠋࣁࣟࢤࣥ⤖ྜࡢ㔜せ࡞≉ᚩࡢ㸯ࡘ࡜ࡋ࡚㸪ᙉ࠸ᣦྥᛶࡀᣲࡆࡽࢀࡿࠋࡇࢀࡣ㸪s2px2py2pz 㟁Ꮚ㓄⨨ࢆ࡜ࡿࣁࣟࢤࣥཎᏊෆࡢ㟁Ꮚศᕸࡢ␗᪉ᛶ࡟⏤᮶ࡍࡿࡶࡢ࡛㸪㟁Ẽᅄ㔜ᴟᏊ࡟ࡼࡾⓗ☜࡟⾲⌧ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡋ࠿ࡋ㸪኱つᶍ⣔ࢆᑐ㇟࡜ࡋࡓ MD ィ⟬࡬ࡢ㐺⏝ࢆ⪃៖ࡍࡿ࡜㸪ࣁࣟࢤࣥཎᏊࡀ㛵ࢃࡿඹ᭷⤖ྜ㸦C–X ࡞࡝㸧ࡢᘏ㛗ୖࡢⅬ (extra point, EP) ࡟ṇ㟁Ⲵࢆ㏣ຍⓗ࡟㓄⨨ࡍࡿ᪉ἲࡀᐇ⏝ⓗ࡛࠶ࡿࠋࡑࡢ㓄⨨ἲ࡟ࡘ࠸࡚㸪ࡇࢀࡲ࡛࡟ᗄࡘ࠿ᥦ᱌ࡀ࠶ࡿࡀ [1,2]㸪⌮ㄽⓗ᰿ᣐࡀ༑ศ࡛ࡣ࡞ࡃ㸪ࡉࡽ࡞ࡿ᳨ウࡀᚲせ࡛࠶ࡿࠋࡲࡓ㸪ࣁࣟࢤࣥ⤖ྜࡢᙉᗘࡣ୍⯡ⓗ࡟ F < Cl < Br < I ࡢ㡰࡛኱ࡁࡃ࡞ࡿࡀ㸪ࣁࣟࢤࣥཎᏊࡢ㟁Ẽᅄ㔜ᴟᏊ࡜ศᴟ⋡ࡢ୧᪉ࡀࡇࡢ㡰࡛ኚ໬ࡍࡿࡓࡵ㸪ࣁࣟࢤࣥ⤖ྜᙉᗘࡢኚ໬ࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚㸪ᚑ᮶ࡢ㆟ㄽ࡟ࡣΰ஘ࡀ࠶ࡿࠋᮏ◊✲࡛ࡣ㸪㟁Ꮚᐦᗘ࡟ᇶ࡙࠸ࡓゎᯒ࡟ࡼࡾ㸪ୖグࡢⅬ࡟ࡘ࠸࡚ࡢゎỴἲࢆ᫂ࡽ࠿࡟ࡋࡓࠋ
⤖ᯝ࡜⪃ᐹ
Bromobenzene ࡜ Br– ࢖࢜ࣥࡢᕪ㟁Ꮚᐦᗘࢆᅗ㸯 (a) ࡟♧ࡍࠋBr ཎᏊ࿘㎶ࡢ✵㛫㡿ᇦ࡟࠾࠸࡚㸪ᕪ㟁Ꮚᐦᗘ㸦ࡋࡓࡀࡗ࡚ bromobenzene ࡢ㟁Ꮚᐦᗘ⮬యࡶ㸧ࡀ㍈ᑐ⛠ⓗ࡞␗᪉ᛶࢆࡶࡘࡇ࡜ࡀࢃ࠿ࡿࠋᕪ㟁Ꮚᐦᗘࡣ
C–Br ⤖ྜᘏ㛗ୖ Br ཎᏊ࠿ࡽ 0.9 Å ࡢ఩⨨࡟ᴟᑠⅬࢆࡶࡕ㸪EP ࢆࡑࡢ఩⨨࡟㓄⨨ࡍ࡭ࡁ࡛࠶ࡿࡇ࡜ࢆ♧၀ࡍࡿࠋ୍᪉㸪Br ཎᏊ࠿ࡽ 2.22 Å [1] ࡞࡝㸪ࡇࢀࡲ࡛ᥦ᱌ࡉࢀ࡚ࡁࡓ EP ࡢ఩⨨ࢆᨭᣢࡋ࡞࠸ࠋᅗ㸯 (b) ࡟♧ࡋࡓ Br ཎᏊ࡜ Br– ࢖࢜ࣥࡢᕪ㟁Ꮚᐦᗘ࡜ẚ㍑ࡍࡿ࡜㸪ࡇࡢ㍈ᑐ⛠ⓗ࡞␗᪉ᛶࡣ s2px2py2pz 㟁Ꮚ㓄⨨ࢆ࡜ࡿ Br ཎᏊ࡟ᅛ᭷ࡢࡶࡢ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡿࠋBr ཎᏊ࠿ࡽ 0.9 Å ࡢ఩⨨࡟ EP ࢆ㓄⨨ࡋ࡚ศᏊ࿘ᅖ࡟⏕ᡂࡉࢀࡿ㟼㟁࣏ࢸࣥࢩࣕࣝࡢࣇ࢕ࢸ࢕ࣥࢢࢆ⾜ࡗࡓ࡜ࡇࢁ㸪Ⰻዲ࡞⤖ᯝࡀᚓࡽࢀࡓࠋ
 C–Br ⤖ྜᘏ㛗ୖ Br ཎᏊ࠿ࡽ 3 Å ࡢ఩⨨࡟–0.1 e ࡢ㟁Ⲵࢆ㓄⨨ࡋࡓሙྜࡢ bromobenzene ࡢ㟁Ꮚᐦᗘኚ໬
ࡣ㸪ᅗ㸯࡜ࡣ␗࡞ࡾ㸪Br ཎᏊ࿘㎶ࡢ✵㛫㡿ᇦ࡟࠾࠸࡚㸪Br ཎᏊࡢ཮ᴟᏊศᴟ࡟⏤᮶ࡍࡿ࡜⪃࠼ࡽࢀࡿᙧ≧ࢆ࡜ࡿࠋࡇࢀ࡟ຍ࠼࡚㸪࣋ࣥࢮࣥ⎔ࡢศᴟࡶ⏕ࡌ࡚࠸ࡿࠋ㈇㟁Ⲵࡢゅᗘ఩⨨ࢆ㠃ෆ࣭㠃እ࡛ࢩࣇࢺࡉࡏࡓ࡜ࡇ
ࢁ㸪๓⪅ࡣࡑࢀ࡟㏣ᚑࡍࡿࡀᚋ⪅ࡣṤ࡝ኚ໬ࡏࡎ㸪ᚋ⪅ࡢ⏕ᡂ࣓࢝ࢽࢬ࣒ࡀ through-bond ࡛࠶ࡿࡇ࡜ࢆ♧၀- 208 -

(a)

(b)
-2

× 10 a0

-2

3
0
-3
-1

-1

× 2 × 10

-1

× 10 a0
4

2

2

0

0

-2
-1

-1
a0
-1

-2

× 10

-4

× 2 × 10-4-6

ᅗ㸯㸸(a) ࣈࣟࣔ࣋ࣥࢮࣥ࡜⮯໬≀࢖࢜ࣥ㸪 E s2px2py2pz 㟁Ꮚ㓄⨨࡟࠶ࡿ⮯⣲ཎᏊ࡜⮯໬≀࢖࢜ࣥ㸪ࡢ㛫࡛࡜ࡗࡓ㟁Ꮚᐦᗘᕪࡢ㸯ḟඖ࣭㸰ḟඖࣉࣟࢵࢺࠋ

ࡍࡿࠋୖグࡢ⤖ᯝࢆࡶ࡜࡟㸪ศᴟຠᯝࢆ⾲⌧ࡍࡿཎᏊࢧ࢖ࢺୖ㟁Ⲵ࣭཮ᴟᏊࢆ㓄⨨ࡋ㸪㟼㟁࣏ࢸࣥࢩࣕࣝࡢ
ࣇ࢕ࢸ࢕ࣥࢢࡢ⛬ᗘࢆゎᯒࡋࡓࠋ

[1] M. A. Ibrahim, J. Comput. Chem. 32, 2564–2574 (2011). [2] W. L. Jorgensen and P. Schyman, J. Chem. Theory
Comput. 10, 3895–3901 (2012).

3Ⓨ⾲ᐇ⦼࣭ཎⴭㄽᩥ࡯࠿㸦ᖹᡂ㸱㸯࣭௧࿴ඖᖺᗘ㸧‫ ۻ‬Hajime Torii, J. Mol. Liq. 284, 773±779 (2019).
‫ ۻ‬Hajime Torii, Phys. Chem. Chem. Phys. 21, 17118±17125 (2019).
‫ ۻ‬㫽ᒃ㸪➨ 22 ᅇ⌮ㄽ໬Ꮫウㄽ఍㸪2019 ᖺ 5 ᭶㸪ᮐᖠ㸬ఀ⸨㸪㫽ᒃ㸪➨ 22 ᅇ⌮ㄽ໬Ꮫウㄽ఍㸪2019 ᖺ 5 ᭶㸪ᮐᖠ㸬‫ ۻ‬㰻⸨㸪㫽ᒃ㸪➨ 46 ᅇ⏕యศᏊ⛉Ꮫウㄽ఍㸪2019 ᖺ 6 ᭶㸪ࡘࡃࡤ㸬‫ۻ‬Hajime Torii, 10th International Conference on Advanced Vibrational Spectroscopy (ICAVS-10), July 2019,
Auckland.
‫ۻ‬Hajime Torii, 19th International Conference on Time Resolved Vibrational Spectroscopy (TRVS 2019),
September 2019, Auckland.
ఀ⸨㸪㫽ᒃ㸪➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍㸪2019 ᖺ 9 ᭶㸪ྡྂᒇ㸬‫ ۻ‬㰻⸨㸪㫽ᒃ㸪➨ 42 ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘㸪2019 ᖺ 10 ᭶㸪௝ྎ㸬‫ ۻ‬㰻⸨㸪㫽ᒃ㸪➨ 33 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸪2019 ᖺ 12 ᭶㸪ྡྂᒇ㸬- 209 -

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ࢼࣀ࣐ࢸࣜ࢔ࣝཬࡧ⏕యศᏊࡢᶵ⬟࣭≀ᛶ࣭཯ᛂᛶ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Studies on Functions, Properties, and Reactivities ofNanomaterials and Biological Molecules‫ۑ‬୰஭ ᾈᕭࠊΎ㔝 ῟ྖࠊ஬༑ᖭ ᗣᘯࠊすᮧ ዲྐࠊᅧᮏ 㞞ᘯࠊ኱㉺ ᫀᶞࠊྜྷᕝ Ṋྖࠊᑠ㔝 ⣧୍ࠊ࿘ ᘓᩩࠊAditya Wibawa SaktiࠊToni Maierࠊᶡぢ ᮃ㒔ࠊ⸨Ἴ ⨾㉳Ⓩࠊ
ᾆ㇂ ᾈ㍤ࠊ✄᳃ ┿⏤ࠊἙᮏ ዉࠎࠊ୰ᮧ ᾏ㔛ࠊዪ㒊⏣ ຬ௓ࠊ኱㈏ ᾈ௓ࠊ㧗㔝 ⚽᫂ࠊ᪂㇂ ెஂࠊ㧗ᓥ ༓Ἴࠊ୰ᮧ ᓫ⋪ࠊ⸨௦ ኳ♸ࠊ⠛ᓮ 㧗▱㸦᪩኱ඛ㐍⌮ᕤ㸧
1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲࡛ࡣࠊࢼࣀ࣐ࢸࣜ࢔ࣝࡸ⏕యศᏊࡀ㛵ಀࡍࡿ✀ࠎࡢ⌧㇟ࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡾྲྀࡾᢅ࠸ࠊࡑࡢᶵ⬟࣭≀ᛶ࣭཯ᛂᛶࡢⓎ⌧ᶵᵓࢆ⌮ㄽⓗ࡟ゎ᫂ࡍࡿࡇ࡜ࢆ┠ᣦࡋࡓࠋࡲࡓࠊࡑࡢࡓࡵ࡟ᚲせ࡜࡞ࡿ⌮ㄽࡢ㛤Ⓨ࠾ࡼࡧࣉࣟࢢ࣒ࣛࡢᐇ⿦ࡶ⾜ࡗࡓࠋ௨ୗ࡟ࡇࡢ┠ⓗ࡟ᚑࡗ࡚⾜ࡗࡓ◊✲ࡢ࠺ࡕࠊ(1) ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ࡟ᑐࡍࡿ㔜ࡳ௜ࡁࣄࢫࢺࢢ࣒ࣛゎᯒἲࡢ㛤Ⓨࠊ(2) ໬Ꮫ⤖ྜࢆ෌⌧ྍ⬟࡞ᶵᲔᏛ⩦ᆺ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘࡢ㛤Ⓨࠊ(3)෇㗹஺ᕪᵓ㐀ࡢຠ⋡ⓗ᥈⣴ᡭἲࡢ㛤Ⓨࠊ(4) 㖄ࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺᮦᩱ࡟࠾ࡅࡿ࣏࣮ࣛࣟࣥᙧᡂ㐣⛬ࢩ࣑࣮ࣗࣞࢩࣙࣥࠊ(5) ஧ḟ㟁ụ࡟࠾ࡅࡿ Zn 㟁ᯒ࣓࢝ࢽࢬ࣒ࡢ⌮ㄽⓗゎᯒ ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ୍㐃ࡢ◊✲࡟࠶ࡓࡾࠊ㔞Ꮚ໬Ꮫィ⟬ࣃࢵࢣ࣮ࢪ GaussianࠊGAMESSࠊVASPࠊQuantum ESPRESSO ࠶ࡿ࠸ࡣ⊂⮬࡟㛤Ⓨࡋࡓࣉࣟࢢ࣒ࣛ DCDFTBMD ࠾ࡼࡧ RAQET ࢆ฼⏝ࡋ࡚ᩘ್ィ⟬ࢆ⾜ࡗࡓࠋ

3

◊✲ᡂᯝ

3-1

࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ࡟ࡼࡿ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࡢຠ⋡໬࡟ྥࡅࡓ㔜ࡳ௜ࡁࣄࢫࢺࢢ࣒ࣛゎᯒἲࡢ㛤Ⓨจ⦰┦୰࡟࠾ࡅࡿ໬Ꮫ཯ᛂ㐣⛬ࢆศᏊ࣭ཎᏊࣞ࣋
࡛ࣝゎ᫂ࡍࡿࡓࡵ࡟ࡣࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ᇶ
࡙ࡃ⮬⏤࢚ࢿࣝࢠ࣮᭤㠃㸦FES㸧ࡢᐃ㔞ⓗゎᯒࡀᚲせ࡛࠶ࡿࠋࡑࡢࡓࡵ࡟ࡣࠊ໬Ꮫ཯ᛂ㐣⛬࡟࠾ࡅࡿ㟁Ꮚ≧ែኚ໬ࢆ㐺ษ࡟グ㏙ࡍࡿ㔞Ꮚ໬Ꮫⓗᡭἲ࡜ࠊ
FES ୖ࡟࠾ࡅࡿከᩘࡢᏳᐃ࣭‽Ᏻᐃ࣭㑄⛣≧ែࢆ㧗ຠ⋡࡟᥈⣴ࡍࡿᣑᙇࢧࣥࣉࣜࣥࢢἲࡀồࡵࡽࢀࡿࠋ
ࡇࢀࡽࢆ୧❧ࡍࡿᡭἲ࡜ࡋ࡚ࠊᙜ◊✲ᐊ࡛ࡣศ๭⤫἞ᆺ㸦DC㸧ᐦᗘỗ㛵ᩘᙉ᮰⦡㸦DFTB㸧ἲ࡜࣓ࢱࢲ࢖ ࢼ ࣑ ࢡ ࢫ 㸦 MetaD 㸧 ἲ ࢆ ⤌ ࡳ ྜ ࢃ ࡏ ࡓ
DC-DFTB-MetaD ἲࢆ㛤Ⓨࡋ࡚ࡁࡓࠋᮏ◊✲࡛ࡣࠊจ⦰┦୰࡛ࡢ໬Ꮫ཯ᛂࢆᑐ㇟࡜ࡋࡓ FES ィ⟬ࡢ᭦࡞

Figure 1. Free energy surface of alanine dipeptide in theࡿ㧗ຠ⋡໬ࢆ┠ᣦࡋࠊMetaD ࡟ᑐࡍࡿ㔜ࡳ௜ࡁࣄࢫ

gas phase as a function of the main-chain dihedral anglesࢺࢢ࣒ࣛゎᯒἲ㸦WHAM㸧ࡢ㛤Ⓨࢆ⾜ࡗࡓࠋලయⓗobtained from WHAM for the forty 200-ps DFTB-MetaD
trajectories.

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࡟ࡣࠊࣂ࢖࢔ࢫ࣏ࢸࣥࢩࣕࣝୗ࡛ࡢ㔜ࡳ௜ࡁࣄࢫࢺࢢ࣒ࣛࢆ㏲ḟồࡵࡿ reweighting ἲ࡟ࡼࡾ」ᩘࡢ▷᫬㛫
MetaD ࢺࣛࢪ࢙ࢡࢺࣜ࡟࠾ࡅࡿ᭱⤊ⓗ࡞㔜ࡳ௜ࡁࣄࢫࢺࢢ࣒ࣛࢆホ౯ࡋࡓୖ࡛ࠊWHAM ࢆ⏝࠸࡚ࡑࢀࡽࡢ⤫ィᖹᆒࢆᐇ⾜ࡍࡿࡇ࡜࡟ࡼࡾ FES ࢆồࡵࡿᡭἲࢆ㛤Ⓨࡋࡓࠋࡇࢀ࡟ࡼࡾ㸪」ᩘࡢ▷᫬㛫 MetaD ࢆ୪ิ࡟ᐇ⾜ࡍࡿࡇ࡜࡟ࡼࡗ࡚ FES ࢆຠ⋡ࡼࡃ཰᮰ࡉࡏࡿࡇ࡜ࡀྍ⬟࡜࡞ࡗࡓࠋẼ┦୰ࡢ alanine dipeptide ࡢࢥࣥࣇ࢛࣓࣮
ࢩࣙࣥኚ໬ࢆᑐ㇟࡜ࡋ࡚ᮏᡭἲࡢ᳨ドࢆ⾜ࡗࡓ࡜ࡇࢁࠊࢧࣈࢼࣀ⛊࣮࢜ࢲ࣮ࡢ▷᫬㛫 DFTB-MetaD ࡢ⤫ィᖹᆒ࡟ࡼࡾ࣐࢖ࢡࣟ⛊࣮࢜ࢲ࣮ࡢ DFTB-MD ࡢ FES ࢆⰋዲ࡟෌⌧ࡋࡓ㸦Figure 1㸧ࠋᮏᡭἲࡢ㛤Ⓨ࡟ࡼࡾ㸪኱つᶍ཯ᛂ⣔࡛ࡢ㧗ຠ⋡࡞ FES ィ⟬ࢆᐇ⌧ࡍࡿࡓࡵࡢᇶ┙ᢏ⾡ࡀ☜❧ࡉࢀࡓࠋ3-2ᶵᲔᏛ⩦ࢆ⏝࠸ࡓ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘ࡟ᇶ࡙ࡃ orbital-free DFT ィ⟬࡟ࡼࡿ໬Ꮫ⤖ྜࡢ෌⌧ᐦᗘỗ㛵ᩘ⌮ㄽ㸦DFT㸧࡛ࡣࠊHohenbergKohn ᐃ⌮࡟ᇶ࡙ࡁࠊ Table 1. Equilibrium bond distances (Å).
ཎᏊ࣭ศᏊ࡟ᑐࡍࡿ㟁Ꮚࡢ࢚ࢿࣝࢠ࣮ࡀ㟁Ꮚᐦᗘࡢỗ㛵ᩘ࡜ࡋ࡚⾲⌧࡛ࡁࡿࡇ࡜ࡀಖドࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ㟁Ꮚࡢ㐠ື࢚ࢿࣝࢠ࣮ࡸ㔞Ꮚⓗ࡞஺᥮࣭┦㛵࢚ࢿࣝࢠ࣮࡟ᑐࡍࡿ
ཝᐦ࡞ỗ㛵ᩘ⾲⌧ࡣ୙࡛᫂࠶ࡿࠋࡇࢀࡲ࡛࡟ᡃࠎࡣࠊ㟁Ꮚᐦᗘࡢ᝟ሗ࠿ࡽࠊᶵᲔᏛ⩦࡟ࡼࡾ༙ᒁᡤⓗ࡞㐠ື࢚ࢿࣝࢠ
࣮ࢆᵓ⠏ࡍࡿᡭἲࢆ㛤Ⓨࡋࡓࠋᮏ◊✲࡛ࡣࠊ✀ࠎࡢศᏊ࡟
ᑐࡋ࡚࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤⥺㸦PEC㸧ィ⟬ࢆ⾜࠺ࡇ࡜࡛ࠊ໬Ꮫ⤖ྜࢆグ㏙࡛ࡁࡿ࠿ࢆ᳨ドࡋࡓࠋᮏᡭἲ࡛ࡣࠊKohnSham㸦KS-㸧DFT ィ⟬࡛ᚓࡽࢀࡿグ㏙Ꮚ࡜┠ⓗኚᩘࡢ㛫ࡢ㛵ಀࢆࠊᶵᲔᏛ⩦࡟࠾ࡅࡿᅇᖐ࡟ࡼࡾ

ศᏊ

⤖ྜᵝᘧ

ML

KS

C2H6

CC

1.55

1.56

C2H4

C C

1.34

1.33

C2H2

C{C

1.18

1.21

H2

HH

0.74

0.74

HF

HF

0.92

0.93

F2

FF

1.44

1.41

CO

C{O

1.11

1.14

N2

N{N

1.09

1.11

ᵓ⠏ࡋࡓࠋグ㏙Ꮚ࡜ࡋ࡚ࠊྛᚤᑠ✵㛫㸦ࢢࣜࢵࢻ㸧Ⅼ࡟࠾ࡅࡿ㟁ᏊᐦᗘUࠊ࠾ࡼࡧࡑࡢ 1 ḟࠊ2 ḟࠊ3 ḟ໙㓄ࢆ⏝࠸ࡓࠋࡲࡓྛࢢࣜࢵࢻⅬ࡟࠾ࡅࡿ᭱ࡶ㏆࠸ n ಶࡢཎᏊࡢ୰ᚰ࠿ࡽࡢ㊥㞳㸦|r㸫R1|ࠊ|r㸫R2|…ࠊ|r㸫Rn|㸧ࡢ㏫ᩘࡶグ㏙Ꮚ࡜ࡋ࡚ᑟධࡋࡓࠋ┠ⓗኚᩘ࡜ࡋ࡚ࠊKS 㐠ື࢚ࢿࣝࢠ࣮ᐦᗘWKS ࢆ ThomasFermivon Weizsäcker
ỗ㛵ᩘ࡛๭ࡗࡓ enhancement factor ࢆ᥇⏝ࡋࡓࠋ✀ࠎࡢศᏊࡢ PEC ࡟ᑐࡋ࡚ࠊᮏᡭἲ㸦ML㸧࡛ᵓ⠏ࡋࡓ㐠ື࢚ࢿࣝࢠ࣮ỗ㛵ᩘࡢ⢭ᗘࢆ᳨ドࡋࡓࠋ0.05 Å㛫㝸࡛␗࡞ࡿ⤖ྜ㛗ࡢศᏊࢆ KS-DFT ࡟ࡼࡾィ⟬ࡋࠊࡍ࡭࡚ࡢࢢࣜࢵࢻⅬࡢ࠺ࡕ 10%ࢆ↓సⅭ࡟ᢳฟࡋ࡚Ꮫ
⩦ࢹ࣮ࢱ࡜ࡋࡓࠋࢸࢫࢺ࡟ࡣࠊ0.01 Å 㛫㝸࡛␗࡞ࡿ⤖ྜ㛗ࡢศᏊ࡟࠾ࡅࡿࡍ࡭࡚ࡢࢹ࣮ࢱࢆ᥇⏝ࡋࡓࠋTable 1࡟ࠊᵝࠎ࡞⤖ྜᵝᘧࢆᣢࡘ 8 ศᏊ࡟ࡘ࠸࡚ࠊPEC ࡟࠾ࡅࡿ᭱ᑠ࢚ࢿࣝࢠ࣮࡜࡞ࡿ఩⨨ࢆᖹ⾮⤖ྜ㛗࡜ࡋ࡚ࡲ࡜ࡵࡓࠋࡇࡢ⤖ᯝࠊᚑ᮶ࡢỗ㛵ᩘ࡛⏝࠸ࡽࢀ࡚ࡁࡓ㟁Ꮚᐦᗘ᝟ሗ࡟ຍ࠼࡚ࠊ㧗ḟࡢ㟁Ꮚᐦᗘ໙㓄࡜㐺ษ࡞㊥㞳ࡢグ㏙Ꮚࢆᑟධࡍࡿࡇ࡜࡛ࠊKS-DFT ࡢᖹ⾮⤖ྜ㛗ࢆ෌⌧ࡍࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋᮏᡭἲ࡟ࡼࡾࠊorbital-free㸦㌶㐨㠀౫Ꮡ㸧DFT ࡟࠾ࡅࡿၥ㢟Ⅼ࡛࠶ࡿ໬Ꮫ⤖ྜࡢ෌⌧ࡢᅔ㞴ࢆゎᾘ࡛ࡁࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ3-3ᐦᗘỗ㛵ᩘᙉ᮰⦡ἲ࡟ᇶ࡙ࡃ෇㗹஺ᕪࡢᵓ㐀᭱㐺໬ィ⟬ἲࡢ㛤Ⓨ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤㠃㸦PES㸧ࡢ஺ᕪࡣࠊග≀ᛶࡸග཯ᛂ࡟࠾࠸࡚㔜せ࡞ᙺ๭ࢆᯝࡓࡍࠋࢫࣆࣥከ
㔜ᗘࡢ➼ࡋ࠸≧ែ㛫ࡢ஺ᕪࡣ෇㗹஺ᕪ࡜࿧ࡤࢀࠊ஺ᕪ㡿ᇦ࡟࠾ࡅࡿ࢚ࢿࣝࢠ࣮᭱ᑠࡢᵓ㐀ࡀ᭱ᑠ࢚ࢿࣝࢠ࣮
෇㗹஺ᕪ㸦MECI㸧࡛࠶ࡿࠋMECI ࡢᵓ㐀᭱㐺໬ィ⟬࡛ࡣࠊ෇㗹஺ᕪ㏆ഐ࡟࠾ࡅࡿ PES ࡢᙧ≧ࢆグ㏙ྍ⬟࡞㟁Ꮚ≧ែ⌮ㄽࢆ⏝࠸ࡿᚲせࡀ࠶ࡿࠋࢫࣆࣥ཯㌿ᆺ㸦SF㸧᫬㛫౫Ꮡ㸦TD㸧DFT ࡀࡼࡃ⏝࠸ࡽࢀࡿࡀࠊィ⟬ࢥࢫࢺࡢほⅬ࠿ࡽྲྀࡾᢅ࠼ࡿศᏊࢧ࢖ࢬ࡟ไ㝈ࡀ࠶ࡿࠋ- 213 - ᮏ◊✲࡛ࡣࠊSF-TDDFT ࡢ㏆ఝ⌮ㄽ࡜ࡋ࡚ SF-TDDFTBἲࢆ㛤Ⓨࡋࡓࠋᩘ᳨್ド࡟ࡼࡗ࡚ࠊࡇࡢ᪉ἲࡣ SF-TDDFT
࡜ྠᵝ࡟໬Ꮫ⤖ྜࡢ㛤⿣ࡸ H3 ศᏊࡢ෇㗹஺ᕪࢆグ㏙ྍ⬟࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡲࡓࠊ39 ✀㢮ࡢ S0/S1-MECIࢆ SF-TDDFT ࡜ SF-TDDFTB ἲ࡛ᵓ㐀᭱㐺໬ࡋᚓࡽࢀࡓ
ᵓ㐀ࢆẚ㍑ࡋࡓࠋFigure 2 ࡟୧ᡭἲ࡟ࡼࡿᵓ㐀ࢆ㔜ࡡ࡚♧ࡍࠋ㉥࡛♧ࡋ࡚࠸ࡿࡢࡀ SF-TDDFT ࡛ࡢᵓ㐀࡛࠶ࡾࠊ
SF-TDDFTB ἲ࡛ࡶྠᵝࡢᵓ㐀ࡀᚓࡽࢀࡓࠋ28 ศᏊࡢ S0ᖹ⾮ᵓ㐀࡟࠾࠸࡚ບ㉳࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓ࡜ࡇࢁࠊ

FigureSF-TDDFTB ἲࡢィ⟬᫬㛫ࡣᖹᆒ࡛ SF-TDDFT ࡢ⣙ 333

SF-TDDFT (shown in red) and SF-TDDFTB.

2.

Optimized

MECI

structuresbyศࡢ 1 ࡛࠶ࡗࡓࠋ௨ୖࡢ⤖ᯝ࠿ࡽࠊSF-TDDFTB ἲࡣ኱つᶍศᏊࡢ MECI ᵓ㐀᭱㐺໬ィ⟬࡟᭷ᮃ࡞ᡭἲ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ3-4㖄ࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺᮦᩱ࡟࠾ࡅࡿ࣏࣮ࣛࣟࣥᙧᡂ㐣⛬ࢩ࣑࣮ࣗࣞࢩࣙࣥ

㖄ࣁࣛ࢖ࢻ࣌ࣟࣈࢫ࢝࢖ࢺ㸦LHP㸧࡟ࡘ࠸࡚ࡣࠊኴ㝧㟁ụ㸦࣌ࣟࣈࢫ࢝࢖ࢺኴ㝧㟁ụ㸧࡬ࡢᛂ⏝࡟࠾࠸࡚㧗࠸ຠ⋡ࡀᚓࡽࢀࡓࡇ࡜ࢆ
ࡁࡗ࠿ࡅ࡟ࠊࡑࡢග—㟁Ꮚᮦᩱ࡜ࡋ࡚ࡢ≉ᛶࡢᇶ♏ⓗ⌮ゎ࡟ྥࡅࡓヨࡳࡀάⓎ࡟࡞ࡗ࡚࠸ࡿࠋ≉࡟ࠊLHP ࡟࠾࠸࡚ࡣ㟁Ꮚ—ṇᏍ෌⤖ྜࡀ㠀ᖖ࡟㐜࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊࡑࡢ࣓࢝ࢽࢬ࣒ゎ᫂ࡢほⅬ࠿ࡽ࣏࣮ࣛࣟࣥࡢᙧᡂ㐣⛬࡟㛵ࡋ࡚⯆࿡ࡀᣢࡓࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊLHP
࡟࠾ࡅࡿ࣏࣮ࣛࣟࣥࡣ nm ࢫࢣ࣮ࣝࡢ༙ᚄࢆᣢࡘ࡜ண᝿ࡉࢀࠊィ⟬໬Ꮫⓗ࡞ྲྀᢅࡣࢥࢫࢺ㠃࠿ࡽᐜ࡛᫆ࡣ࡞࠸ࠋᮏ◊✲࡛ࡣࠊᙜ◊✲ᐊ

Figure 3. Snapshot of spatial negative࡛㛤Ⓨࡋࡓ⥺ᙧࢫࢣ࣮ࣜࣥࢢ࡞༙⤒㦂ⓗ㔞Ꮚ໬Ꮫィ⟬ᡭἲ࡛࠶ࡿ

charge carrier distribution.

DC-DFTB ࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊ⌧ᐇⓗ࡞ィ⟬ࢥࢫࢺ࡛ LHP ࡟࠾ࡅࡿ࣏࣮ࣛࣟࣥᙧᡂ㐣⛬ࡢ㔞ᏊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋࡓࠋィ⟬࡟࠾࠸࡚ࡣ௦⾲ⓗ࡞ LHP ࡛࠶ࡿ
MAPbI3 ࢆᑐ㇟࡜ࡋࠊ3.7 nm3.7 nm5.4 nm㸦3072 ཎᏊ㸧ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢭࣝࢆ⏝࠸ࡓࠋᚓࡽࢀࡓ㈇㟁
Ⲵ࢟ࣕࣜ࢔ᐦᗘศᕸࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆ Figure 3 ࡟♧ࡍࠋFigure 3 ࡼࡾࠊ㟁Ⲵ࢟ࣕࣜ࢔ࡀ✵㛫ⓗ࡟ᒁᅾࡍࡿ
ᥥീࡀᚓࡽࢀࡓࡇ࡜ࡀࢃ࠿ࡿࠋࡉࡽ࡟ࠊ㟁Ⲵ࢟ࣕࣜ࢔ࡢᒁᅾ࡟㛵ಀࡍࡿᵓ㐀ኚᙧ࡟ࡘ࠸࡚ゎᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊ᭷ᶵศᏊ࢝ࢳ࡛࢜ࣥ࠶ࡿ MA+ࡢ㐠ື࡜ࠊ↓ᶵ㦵᱁㒊ศ㸦PbI3-㸧ࡢṍࡳࡢ୧᪉ࡀ㛵୚ࡍࡿࡇ࡜ࡀࢃ࠿ࡾࠊ
LHP ࡟࠾ࡅࡿ࣏࣮ࣛࣟࣥᙧᡂ㐣⛬ࡢヲ⣽ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ
3-5

኱つᶍ⵳㟁ࢹࣂ࢖ࢫ࡬ࡢᛂ⏝࡟ྥࡅࡓ Zn 㟁ᯒࣉࣟࢭࢫࡢ⌮ㄽⓗゎᯒ኱つᶍ⵳㟁⏝஧ḟ㟁ụ࡬ࡢ㐺⏝ࡀᮇᚅࡉࢀࡿ Zn ㈇ᴟࡣࠊ඘㟁᫬࡟⏕ࡌࡿ␗ᖖ㔠ᒓᯒฟࡢไᚚ࡟ㄢ㢟ࢆᢪ࠼࡚࠾ࡾࠊࡑࡢࡓࡵ㟁ᴟ⾲㠃ୖࡢ㔠ᒓᯒฟᙧᡂᶵᵓࡢゎ᫂ࡀ㔜せ࡜࡞ࡗ࡚࠸ࡿࠋ౛࠼ࡤࠊ㛵㐃ࡍࡿඖ⣲ࡢᛶ㉁࡟౫ᣐࡋ࡚ᯒฟᶵᵓࢆㄝ࡛᫂ࡁࢀࡤࠊ᭱㐺ῧຍ✀ࡢᑟධ࡞࡝㟁ゎᾮタィࡀྍ⬟࡜࡞ࡿࠋࡇࡢⅬ࡟ᇶ࡙ࡁᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊZn ㈇ᴟୖ␗ᖖᯒฟ⌧㇟ࡢᅉᏊ࡜࡞ࡿࣃ࣓࣮ࣛࢱ࡜ࡑࡢせᅉࢆࠊ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚᫂ࡽ
࡟ࡍࡿྲྀࡾ⤌ࡳࢆ㐍ࡵ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࡑࡢ୍⎔࡜ࡋ࡚ࠊ㟁఩ཬࡧ⁐፹ࡢ⎔ቃࢆཝᐦ࡟෌⌧ྍ⬟࡞
ESM-RISM ἲࢆ⏝࠸࡚ࠊZn 㟁ᯒ᫬ࡢᯒฟ཯ᛂཬࡧ Zn adatom ࡢ⾲㠃ᣑᩓ࡟ࡘ࠸࡚ゎᯒࢆ⾜ࡗࡓࠋ- 214 -

ࡲࡎ Zn ࡢᯒฟ཯ᛂࡢ࢚ࢿࣝࢠ࣮ࢲ࢖ࣖࢢ࣒ࣛࢆ⟬ฟࡋ࡚ࡑࡢᶵᵓࢆ
᳨ウࡍࡿ࡜ඹ࡟ࠊῧຍ✀ࡢస⏝ᶵᵓࢆ᳨ウࡋࡓࠋZn ᯒฟࡣࠊ཯ᛂ๓㥑య࡛࠶ࡿ Zn(OH)42-ࡀ㈇ᴟୖ࡛㑏ඖࡉࢀ࡚㐍⾜ࡍࡿࡀࠊ᳨ウࡢ⤖ᯝ OH✀ࡀ୍ࡘࡎࡘ⬺㞳ࡍࡿ⣲㐣⛬ࢆ⤒ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ୍᪉ Pb ῧຍ✀ࡀ⾲㠃ୖ࡟Ꮡᅾࡋࡓሙྜࠊ཯ᛂࡀ୙฼࡟࡞ࡿ࡜♧၀ࡉࢀࡓࠋヲ⣽࡞ゎᯒࡢ⤖ᯝ࠿ࡽࠊPb ࡢ᭷ࡍࡿ㌶㐨࡜ࡢ┦஫స⏝࡟ࡼࡗ࡚ྛ୰㛫యࡢ≧ែࡀ୙Ᏻᐃ໬ࡍࡿࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࠊPb ඖ⣲ࡢ㟁Ꮚ㓄⨨ࡀ㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡓࠋᐇ㦂ࣉࣟࢭࢫ࡛ࡶࠊPb ῧຍ࡟ࡼࡿ㐣㟁ᅽቑຍࡀ☜ㄆࡉ

Figure4.

The

adsorptionࢀ࡚࠾ࡾࠊᮏ᳨ウ࡟ࡼࡗ࡚ࡑࡢ୍ᅉࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

structure of Zn(OH)42- onto Zn

ḟ࡟ᯒฟ཯ᛂᚋࡢࣉࣟࢭࢫ࡛࠶ࡿ Zn adatom ࡢ⾲㠃ᣑᩓ࡟ࡘ࠸࡚ࠊࡑ
ࡢάᛶ໬㞀ቨࡢ㟁఩౫Ꮡᛶࢆ᳨ウࡋࡓࠋ⟬ฟࡉࢀࡓάᛶ໬㞀ቨࡣࡑࢀࡒࢀࠊ-0.5 V vs. Hg/HgO ࡛ࡣ+4.61 kJ/molࠊ
-1.0 V vs. Hg/HgO ࡛ࡣ+11.8 kJ/molࠊ-1.5 V vs. Hg/HgO ࡛ࡣ+18.4 kJ/mol ࡜ࠊࡑࡢ㟁఩౫Ꮡᛶࡀ♧၀ࡉࢀࡓࠋẚ㍑࡜ࡋ࡚ィ⟬ࡋࡓ Cu ୖ࡛ࡣࡇࡢࡼ࠺࡞ഴྥࡣࡳࡽࢀࡎࠊZn ≉᭷ࡢ⾲㠃ᣑᩓᣲື࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ௒ᚋ
ࡉࡽ࡟ Zn ඖ⣲ࡢᛶ㉁࡟౫ᣐࡋ࡞ࡀࡽࡇࡢᣲືࡢ࣓࢝ࢽࢬ࣒ࢆゎᯒࡍࡿ⪃࠼࡛࠶ࡿࠋᑗ᮶ⓗ࡟ࡇࢀࡽࡢ▱ぢࢆ㞟✚ࡍࡿࡇ࡜࡛ Zn ㈇ᴟࣉࣟࢭࢫࡢ⢭ᐦไᚚࡀᮇᚅ࡛ࡁࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1]

୰஭ᾈᕭ, “Theoretical Analyses of Condensed-Phase Chemical Reactions Based on Divide-and-Conquer Density-Functional
Tight-Binding Molecular Dynamics (DC-DFTB-MD) Simulations”, ➨ 35 ᅇ໬Ꮫ཯ᛂウㄽ఍, ᮾᗈᓥ, 2019 ᖺ 6 ᭶㸦ᣍᚅㅮ₇㸧[2] Hiromi Nakai, “Relativistic density functional theory with picture-change corrected electron density”, 10th congress of theInternational Society of Theoretical Chemical Physics (ISTCP-X), Tromsø, Norway, Jul 2019 (invited).
[3] J. Seino, R. Kageyama, M. Fujinami, Y. Ikabata, H. Nakai, “Orbital-free density functional theory calculation combined withsemi-local machine-learned kinetic energy density functional”, 2nd Global Forum on Advanced Materials and Technologies for
Sustainable Development (GFMAT-2), Toronto, Canada, Jul 2019 (invited).
[4] Ύ㔝῟ྖ, “࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫࢆᑟධࡋࡓᐦᗘỗ㛵ᩘ⌮ㄽࡢ㛤Ⓨ”, ➨ 29 ᅇ᱁ᏊḞ㝗ࣇ࢛࣮࣒ࣛࠕ᱁ᏊḞ㝗࡜࣐ࢸࣜ࢔ࣝࢬ࣭࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫࠖ, ㇏⏣, 2019 ᖺ 9 ᭶㸦ᣍᚅㅮ₇㸧
[5] Junichi Ono, Chika Okada, Yoshifumi Nishimura, Hiromi Nakai, “Clarification of proton transfer reactions in photoreceptive
proteins using large-scale quantum molecular dynamics simulations”, ➨ 57 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍, ᐑᓮ, 2019 ᖺ 9 ᭶㸦ᣍᚅㅮ₇㸧[6] Hiromi Nakai, “How Can Artificial Intelligence Help Quantum Chemists?”, The Ninth Conference of the Asia-Pacific
Association of Theoretical and Computational Chemists (APATCC 2019), Sydney, Australia, Oct 2019 (invited).
[7] Hiromi Nakai, “ Semi-local machine-learned kinetic energy density functional with third-order gradients of electron density”,
CECAM-Workshop "Thinking outside the box—beyond machine learning for quantum chemistry", Bremen, Germany, Oct2019 (invited).
[8] Takeshi Yoshikawa, “GPU-Accelerated Large-Scale Excited-State Simulation Based on Divide-and-Conquer Time-Dependent
Density-Functional Tight-Binding”, 8th ADAC Workshop, Tokyo, Japan, Oct 2019 (invited).
[9] Yasuhiro Ikabata, Takuro Nudejima, Junji Seino, Takeshi Yoshikawa, Hiromi Nakai, “Machine-Learned Correlation Model for
Accurate and Efficient Computation of Correlation Energy”, The 5th International Conference on Molecular Simulation(ICMS2019)”, Jeju, Korea, Nov 2019 (invited).
[10] ྜྷᕝṊྖ, “኱つᶍ㔞Ꮚ໬Ꮫィ⟬ࡢ㛤Ⓨ࡜㔞Ꮚィ⟬࡬ࡢ㐺⏝࡟ྥࡅ࡚“, 㔞Ꮚ໬Ꮫ࡜㔞Ꮚ᝟ሗ࣭㔞Ꮚ⏕࿨ࡢ᥋Ⅼ, ኱㜰,2019 ᖺ 12 ᭶㸦ᣍᚅㅮ₇㸧㸦௚ ᅜ㝿Ⓨ⾲ 21 ௳, ᅜෆⓎ⾲ 23 ௳㸧- 215 -

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] M. Fujinami, J. Seino, T. Nukazawa, S. Ishida, T. Iwamoto, H. Nakai Chem. Lett., 48, 961-964 (2019).
‫[ۻ‬2] T. Nudejima, Y. Ikabata, J. Seino, T. Yoshikawa, H. Nakai, J. Chem. Phys., 151, 024104-1-12 (2019).
[3] K. Murakami, Y. Tanaka, S. Hayashi, R. Sakai, Y. Hisai, A. Ishikawa, T. Higo, S. Ogo, J. G. Seo, H. Tsuneki, H. Nakai, Y.
Sekine, J. Chem. Phys., 151, 064708-1-8 (2019).
‫[ۻ‬4] Q. Zheng, S. Miura, S. Ko, K. Miyazaki, E. Watanabe, M. Okoshi, C.-P. Chou, Y. Nishimura, H. Nakai, T. Kamiya, T. Honda, J.
Akikusa, Y. Yamada, A. Yamada, Angew. Chem. Int. Ed., 58, 14202-14207 (2019).
‫[ۻ‬5] T. Yoshikawa, N. Komoto, Y. Nishimura, H. Nakai, J. Comput. Chem., 40, 2778-2786 (2019).
[6] T. M. Maier, Y. Ikabata, H. Nakai, J. Chem. Theory Comput., 15, 4745-4763 (2019).
‫[ۻ‬7] H. Nakai, J. Seino, K. Nakamura, J. Phys. Chem. A, 123, 7777-7784 (2019).
‫[ۻ‬8] J. Seino, R. Kageyama, M. Fujinami, Y. Ikabata, H. Nakai, Chem. Phys. Lett., 734, 136732-1-6 (2019).
[9] T. Maier, Y. Ikabata, H. Nakai, J. Chem. Phys., 151, 174114-1-9 (2019).
‫[ۻ‬10] H. Uratani, C-P. Chou, H. Nakai, Phys. Chem. Chem. Phys., 22, 97-106 (2020).
[11] K. Murakami, S. Ogo, A. Ishikawa, Y. Takeno, T. Higo, H. Tsuneki, H. Nakai, Y. Sekine, J. Chem. Phys., 152, 014707-1-7(2020).
‫[ۻ‬12] T. Yoshikawa, J. Yoshihara, H. Nakai, J. Chem. Phys., 152, 024102-1-12 (2020).
[13] K. Otake, K. Otsubo, T. Komatsu, S. Dekura, J. M. Taylor, R. Ikeda, K. Sugimoto, A. Fujiwara, Y. Nanba, T. Ishimoto, M.
Koyama, C. Chou, A. Sakti, Y. Nishimura, H. Nakai, H. Kitagawa, Nature Commun., 11, 843-1-7 (2020).
‫[ۻ‬14] N. Komoto, T. Yoshikawa, Y. Nishimura, H. Nakai, J. Chem. Theory Comput., 16, 2369-2378 (2020).
[15] R. Sakai, K. Murakami, Y. Mizutani, Y. Tanaka, S. Hayashi, A. Ishikawa, T. Higo, S. Ogo, H. Tsuneki, H. Nakai, Y. Sekine,
ACS Omega, 5, 6846-6851 (2020).
‫[ۻ‬16] A. W. Sakti, C.-P. Chou, H. Nakai, ACS Omega, 5, 6862-6871 (2020).
‫[ۻ‬17] M. Fujinami, J. Seino, H. Nakai, Bull. Chem. Soc. Jpn., 93, 685-693 (2020).
‫[ۻ‬18] M. Inamori, T. Yoshikawa, Y. Ikabata, Y. Nishimura, H. Nakai, J. Comput. Chem., 41, 1538-1548 (2020).
[19] ⸨Ἴ⨾㉳Ⓩ, Ύ㔝῟ྖ, ୰஭ᾈᕭ, ᭩⡠ 1975ࠕ࣐ࢸࣜ࢔ࣝࢬ࣭࢖ࣥࣇ࢛࣐ࢸ࢕ࢡࢫ࡟ࡼࡿᮦᩱ㛤Ⓨ࡜ά⏝㞟ࠖ,379-384 (ᢏ⾡᝟ሗ༠఍㸪2019).
[20] ୰஭ ᾈᕭ, すᮧ ዲྐ, Aditya Wibawa Sakti, Tanabat Mudchimo, ࿘ ᘓᩩ, ⾲㠃࡜┿✵, 62 (5), 486-491 (2019). (2018ᖺ᪥ᮏ⾲㠃┿✵Ꮫ఍Ꮫ⾡ㅮ₇఍≉㞟ྕ III)[21] A. Sakti, Y. Nishimura, H. Nakai, WIREs Comput. Mol. Sci., in press (2019).
[22] ኱㉺ᫀᶞ, ࿘ᘓᩩ, ୰஭ ᾈᕭ, 㟁Ẽ໬Ꮫ, in press (2019). (≉㞟:㠉᪂ⓗ஧ḟ㟁ụ࡟ྥࡅࡓ㟁ゎᾮ/㟁ゎ㉁◊✲ࡢ᭱᪂ືྥ)[23] ⸨௦ ኳభ, ኱㉺ ᫀᶞ, ୰஭ᾈᕭ, J. Comput. Chem. Jpn., in press (2019).
[24] ஬༑ᖭ ᗣᘯ, ྜྷᕝ Ṋྖ, ୰஭ ᾈᕭ, J. Comput. Chem. Jpn., in press (2019). (᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ᫓Ꮨᖺ఍⢭㑅ㄽᩥ≉㞟ྕ)[25] ୰ᮧ ᾏ㔛, Ύ㔝 ῟ྖ, ୰஭ ᾈᕭ, J. Comput. Chem. Jpn., in press (2019). (᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ᫓Ꮨᖺ఍⢭㑅ㄽᩥ≉㞟ྕ)‫[ۻ‬26] ᾆ㇂ ᾈ㍤, ࿘ ᘓᩩ, ୰஭ ᾈᕭ, J. Comput. Chem. Jpn., in press (2019). (᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ᫓Ꮨᖺ఍⢭㑅ㄽᩥ≉㞟ྕ)‫[ۻ‬27] 㧘ᓥ ༓Ἴ, ஬༑ᖭ ᗣᘯ, ᰩ⏣ ஂᶞ, 㧗㔝 ⚽᫂, ᰘ⏣ 㧗⠊, ୰஭ ᾈᕭ, J. Comput. Chem. Jpn., in press (2019). (᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ᫓Ꮨᖺ఍⢭㑅ㄽᩥ≉㞟ྕ)- 216 -

ᾮᬗศᏊࡢ⇕ఏᑟ⋡ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿண
Predicting Thermal Conductivity of Liquid Crystals using Molecular
Dynamics Simulation‫ۑ‬ᕝෆ 㐍㸪ᯘ ៞ᾈ㸪▼ᒣ ⿱㍤㸪ᷓ⬥ ᝆ㍜㸪బࠎᮌ 㑈㤿㸪ᰘ⏣ ⿱௓㸪Ἑ⏣ ᝆኴ㸪᳝㔝 Ⰻ௓㸦ᮾிᕤᴗ኱Ꮫ≀㉁⌮ᕤᏛ㝔㸧

1◊✲┠ⓗ㸪ෆᐜ
㏆ᖺࡢ㟁Ẽ࣭㟁Ꮚࢹࣂ࢖ࢫࡢ㧗㞟✚໬࡟ࡼࡿⓎ⇕ᐦᗘࡢቑ኱࡟క࠸㸪≉࡟᭷ᶵ㧗ศᏊᮦᩱࡢ㧗⇕ఏᑟ໬ࡀồࡵࡽࢀ࡚࠸ࡿ㸬ࡑࢀࡣ㸪᭷ᶵ㧗ศᏊᮦᩱࡣ㔠ᒓࡸࢭ࣑ࣛࢵࢡᮦᩱ࡟ẚ࡭࡚ຍᕤᛶ࡟ඃࢀࡿࡀ㸪⇕ఏᑟ⋡ࡀᩘ࣮࢜ࢲ࣮ࡶᑠࡉ࠸ࡓࡵ࡛࠶ࡿ[1]㸬᭷ᶵ㧗ศᏊᮦᩱࢆ㧗⇕ఏᑟ໬ࡍࡿヨࡳࡢ୍ࡘ࡜ࡋ࡚࡟ࡣᾮᬗ≉ᛶࡢᛂ⏝ࡀ࠶ࡿ㸬ࡓ࡜࠼ࡤ㸪࢚࣏࢟ࢩᶞ⬡࡟࣓ࢯࢤࣥᇶࢆᑟධࡋࡓᾮᬗᛶ࢚࣏࢟ࢩᶞ⬡ࡣ㸪ᚑ᮶ࡢ࢚࣏࢟ࢩᶞ⬡࡟ẚ࡭࡚㸪5 ಸ⛬ᗘ㧗࠸⇕ఏᑟ⋡ࢆࡶࡘࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ[2].
ࡇࡢࡼ࠺࡞ᾮᬗᛶᮦᩱࡢศᏊタィ࡟࠾࠸࡚㸪⇕ࡢ࢟ࣕࣜ࢔࡛࠶ࡿࣇ࢛ࣀࣥࡢほⅬ࠿ࡽᾮᬗ┦ࡢ⇕ఏᑟᶵᵓࢆ◊✲ࡍࡿࡇ࡜ࡣ㔜せ࡛࠶ࡿ㸬ศᏊືຊᏛἲࡣ㸪⇕ఏᑟ⋡࠾ࡼࡧࣇ࢛ࣀࣥࡢ≧ែᐦᗘ(PDoS)ࢆᚓࡿࡇ࡜ࡀ࡛
ࡁࡿ࡜࠸࠺Ⅼ࡛᭷⏝࡛࠶ࡿ㸬ࡑࡇ࡛㸪ᮏ◊✲࡛ࡣ㸪Fig. 1 ࡟♧ࡍࡼ࠺࡞ 4-n-heptyl-4̓-cyanobiphenyl (7CB) ࢆᑐ㇟࡜ࡋ࡚ศᏊືຊᏛἲࢆ⏝࠸࡚⇕ఏᑟ⋡ィ⟬ࢆ⾜ࡗࡓ㸬ࡉࡽ࡟㸪7CB ࡢࢿ࣐ࢳࢵࢡᾮᬗ┦ࡢ PDoS ࢆồࡵࡿࡇ࡜࡛㸪ࡑࡢ⇕ఏᑟᶵᵓ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲ࢆ⾜ࡗࡓ㸬Figure 1. Chemical structure of 7CB.

2◊✲᪉ἲ㸪ィ⟬᪉ἲᮏ◊✲࡛ࡣ㸪ศᏊືຊᏛィ⟬࡟ࡣ LAMMPS ࢆ㸪㔞Ꮚ໬Ꮫィ⟬࡟ࡣ Gaussian 09 ࢆ⏝࠸ࡓ㸬ศᏊຊሙࡣ㸪௨๓㸪ᡃࠎࡀࣅࣇ࢙ࢽࣝࡢ஧㠃ゅࡢෆ㒊ᅇ㌿࡟㛵ࡍࡿࣃ࣓࣮ࣛࢱ࣮ࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚㸪Lennard-Jones ┦஫స⏝࡟㛵ࡍࡿࣃ࣓࣮ࣛࢱ࣮ࢆ 7CB ࡢࢿ࣐ࢳࢵࢡᾮ
ᬗࡢᐦᗘ࡟ࡼࡗ࡚᭱㐺໬ࡋࡓຊሙ[3]ࢆ⏝࠸ࡓ㸬 ᗘࡣ
300 K㸪ศᏊᩘࡣ 1024 ࡛ィ⟬ࢆ⾜ࡗࡓ㸬⇕ఏᑟ⋡ࡣ㸪㏫㠀ᖹ⾮ศᏊືຊᏛἲ[4]࡟ࡼࡾ⟬ฟࡋࡓ㸬㏫㠀ᖹ⾮ศᏊືຊᏛἲ࡛ࡣ Figure 2 ࡟♧ࡍࡼ࠺࡞
hot region ࡢ᭱ࡶ㐜࠸ཎᏊࡢ㏿ᗘ࡜ cold region ࡢ᭱ࡶ㏿࠸ཎᏊࡢ㏿ᗘࢆ஺᥮ࡍࡿࡇ࡜࡛㸪⇕ὶ᮰࡜ᗘ໙㓄ࢆⓎ⏕ࡉࡏ㸪 Fourier ࡢἲ๎࠿ࡽ⇕ఏᑟ⋡ࢆᚓࡓ㸬
PDoS ࡣ㸪NVE ࢔ࣥࢧࣥࣈࣝୗࡢ 200 ps ࡢࢺࣛࢪ࢙

Figure 2. Schematic representation of reverse nonequilibrium molecular dynamics. The red and blue
region represent the hot region and cold region,
respectively.

- 217 -

ࢡࢺࣜ࠿ࡽ⟬ฟࡋࡓ㸬࡞࠾㸪ἼᩘȰࡢࣇ࢛ࣀࣥࡢ≧ែᐦᗘ‫ܨ‬ሺ߱ሻࡣ㸪ᘧ(1)࡟♧ࡍࡼ࠺࡟㏿ᗘࡢ⮬ᕫ┦㛵㛵ᩘ‫࢜ۃ‬ሺ‫ݐ‬ሻ ή ࢜ሺͲሻ‫࢚࣮ࣜࣇࢆۄ‬ኚ᥮ࡍࡿࡇ࡜࡟ࡼࡾồࡵࡓ[5]㸬
ஶ‫࢜ۃ‬ሺ‫ݐ‬ሻ ή ࢜ሺͲሻ‫ۄ‬ͳන ݁ ௜ఠ௧
‫ݐ‬‫ܨ‬ሺ߱ሻ ൌ‫࢜ۃ‬ሺͲሻ ή ࢜ሺͲሻ‫ۄ‬
ξʹߨ ଴

3

ሺͳሻ

◊✲ᡂᯝ
㏫㠀ᖹ⾮ศᏊືຊᏛἲ࡟ࡼࡾᚓࡽࢀࡓ 300 K ࡢࢿ࣐ࢳࢵࢡᾮᬗ┦ࡢ⇕ఏᑟ⋡ࡣ㸪㓄ྥ᪉ྥࡀ 0.273 s 0.010

W/(m K)㸪㓄ྥ࡟ᆶ┤࡞᪉ྥࡣ 0.134 s 0.002 W/(m K)࡛࠶ࡗࡓ㸬ࡇࢀࡣ㸪ᐇ㦂࡛ሗ࿌ࡉࢀ࡚࠸ࡿ㓄ྥ᪉ྥ࡟㧗࠸⇕ఏᑟ⋡ࢆࡶࡘ࡜࠸࠺␗᪉ᛶ(㓄ྥ᪉ྥ: 0.265 W/(m K) > 㓄ྥᆶ┤᪉ྥ: 0.127 W/(m K)) [6]ࢆࡼࡃ෌⌧ࡋ࡚࠸ࡿ㸬ࡉࡽ࡟㸪ࢿ࣐ࢳࢵࢡ┦࡟࠾ࡅࡿ⇕ఏᑟ⋡ࡢ␗᪉ᛶࡢ

(a)ཎᅉࢆゎ᫂ࡍࡿࡓࡵ࡟㸪PDoS ࢆィ⟬ࡋࡓ㸬ࢿ࣐ࢳࢵࢡ┦ࡢ PDoS ࡢ㓄ྥ᪉ྥᡂศ࡜㓄ྥᆶ┤ᡂศࢆ Figure

Intermolecularinteraction

Stretching vibration

Stretching vibration

Alkyl C-C Aromatic C-C Cyano C-N

Alkyl C-H

Aromatic C-H

3 ࡟♧ࡍ㸬࡞࠾㸪1000 ~ 2000 cm-1 ௜㏆ࡢࣆ࣮ࢡࡣ୺࡟
ศᏊࡢ⤖ྜఙ⦰࡟ࡼࡿࡶࡢ࡛࠶ࡾ㸪~102 cm-1 ࡢ㡿ᇦࡣ୺࡟ศᏊ㛫᣺ື࡟ࡼࡿࡶࡢ࡛࠶ࡿ㸬N ┦ࡢ㓄ྥ᪉ྥ࡛ࡣ㸪ศᏊࡢఙ⦰᣺ື㡿ᇦࡢ DoS ࡀ㓄ྥᆶ┤᪉ྥ࡟ẚ࡭࡚኱ࡁࡃ࡞ࡗ࡚࠸ࡿ㸬ࡇࢀࡣ㸪ᾮᬗ┦࡛ࡣ㸪ศᏊ㓄ྥ࡟ࡼࡾ㓄ྥ᪉ྥ࡟ἢࡗ࡚ඹ᭷⤖ྜࡀࡼࡃᥞ࠺ࡓࡵ࡛
࠶ࡿ㸬ࡇࡢࡇ࡜࠿ࡽ㸪୍᪉ྥ࡟୪ࢇࡔඹ᭷⤖ྜࡢ⤖ྜ(b)ఙ⦰࡟ࡼࡿ⇕ఏᑟࡀ㓄ྥ᪉ྥࡢ㧗⇕ఏᑟ໬࡟ᐤ୚ࡋ
࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸬୍᪉࡛㸪ศᏊ㛫ࡢ㠀⤖ྜ┦஫స⏝࡟㉳ᅉࡍࡿ~102
cm-1 ࡢ㡿ᇦ࡛ࡣ㸪㓄ྥᆶ┤᪉ྥࡢ᪉ࡀ㧗࠸≧ែᐦᗘࢆ᭷ࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸬ࡇࢀࡣ㸪㓄ྥᆶ┤᪉ྥ࡟ࡣ㸪ࣇ࢙ࢽࣝࡢࢫࢱࢵ࢟ࣥࢢࡸࢩ࢔ࣀࡢ཮ᴟᏊ-཮ᴟᏊ┦஫స⏝࡜࠸ࡗࡓᙉ࠸㠀⤖ྜ┦஫స⏝ࡀᏑᅾࡍࡿࡓࡵ
࡜ゎ㔘࡛ࡁࡿ㸬

Figure 3. (a) Phonon density of state (PDoS) for
the nematic phase of 7CB with the componentsࠕཧ⪃ᩥ⊩ࠖ

parallel to the director and perpendicular to the[1] X. Huang, P. Jiang, T. Tanaka, A IEEE Electr. Insul.
Mag., 2011, 27, 8–16.

director. The vertical bold lines denote thefrequencies of stretching vibration defined by the[2] M. Akatsuka and Y. Takezawa, J. Appl. Polym. Sci.,
2003, 89, 2464–2467.

force field. || and A represent the component of
PDoS in the directions parallel and perpendicular[3] R. Sasaki, Y. Takahashi, Y. Hayashi and S. Kawauchi,
J. Phys. Chem B, 2020, 124, 881-889.

to the director, respectively. (b) The enlarged viewof the above PDoS for the stretching vibration of[4] F. Müller-Plathe, J. Chem. Phys., 1997, 106, 6082–

the cyano group at 2087 cm-1.

6085.

- 218 -

[5] J. M. Dickey, A. Paskin, Phys. Rev., 1969, 188, 1407–1418.
[6] M. Marinelli, F. Mercuri, U. Zammit, F. Scudieri, Phys. Rev. E, 1998, 58, 5860–5866.

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬Ἑ⏣ ᝆኴ㸪ᯘ ៞ᾈ㸪㧗⏣ ༑ᚿ࿴㸪ᕝෆ 㐍, Pd ゐ፹ࢆ⏝࠸ࡓ࢔ࣜࣝ࢘ࣞࢱࣥࡢศᏊෆࣄࢻࣟ࢔࣑ࣀ໬

཯ᛂᶵᵓࡢ⌮ㄽⓗゎ㸪᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ᖺ᫓Ꮨᖺ఍㸦2019 ᖺ㸧㸬‫ۻ‬ᰘ⏣ ⿱௓㸪ᯘ ៞ᾈ㸪ᑠ➉ భ☻㸪୰ᮧ ᾈஅ㸪ᕸ᪋ ᪂୍㑻, ࢖࣑ࢲࢰ࣮ࣝㄏᑟయࢆゐ፹࡜ࡍࡿ N-࣓ࢳࣝ࢔࣑ࢻ໬཯ᛂᶵᵓࡢ⌮ㄽⓗゎ᫂㸪᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ᖺ᫓Ꮨᖺ఍㸦2019 ᖺ㸧㸬‫▼ۻ‬ᒣ ⿱㍤, ᯘ ៞ᾈ, 㧗⏣ ༑ᚿ࿴, ᕝෆ 㐍, ࢽࢺࣜࣝ࢜࢟ࢩࢻ」ᩘศᏊࡀ㛵୚ࡍࡿ࢖ࢯࢩ࢔ࢿ࣮ࢺ࡬ࡢ
␗ᛶ໬཯ᛂᶵᵓࡢ⌮ㄽⓗ◊✲, ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍㸦2019 ᖺ㸧㸬‫ۻ‬᳝㔝 Ⰻ௓㸪బࠎᮌ 㑈㤿㸪ᯘ ៞ᾈ㸪ᕝෆ 㐍㸪඲ཎᏊศᏊືຊᏛἲ࡟ࡼࡾࣇ࢓࣮ࢪ࢘࢖ࣝ ࢫࡢ⇕ఏᑟ≉ᛶホ౯㸪➨ 33 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍㸦2019 ᖺ㸧㸬‫ ۻ‬Yoshihiro Hayashi, Susumu Kawauchi, Development of a Quantum Chemical Descriptor Expressing
Aromatic/Quinoidal Character for Designing Narrow-Bandgap π-conjugated Polymers, The 16th Pacific Polymer
Conference (2019).
‫ۻ‬Ryoma Sasaki, Yoshihiro Hayashi, Susumu Kawauchi, All-atom Molecular Dynamics Study of Heat Conductive
Mechanism of Cyanobiphenyl Liquid Crystals, The 16th Pacific Polymer Conference (2019).
‫ۻ‬௚ 16 ௳㸬

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬T. Hasegawa, M. Ashizawa, S. Kawauchi, H. Masunaga, N. Ohta, H. Matsumoto, Fluorination and chlorination

effects on quinoxalineimides as an electron-deficient building block for n-channel organic semiconductors, RSC
Advances, 2019, 9, 10807-10813㸬
‫ ۻ‬S. Fukushima, M. Ashizawa, S. Kawauchi, T. Michinobu, Strain-Promoted Double Azide Addition to
Octadehydrodibenzo[12]annulene Derivatives, Helvetica Chimica Acta, 2019, 102, DOI: 10.1002/hlca.201900016.
‫ۻ‬T. Hasegawa, M. Ashizawa, Y. Hayashi, S. Kawauchi, H. Masunaga, T. Hikima, T. Manaka, H. Matsumoto, p- andn-Channel Photothermoelectric Conversion Based on Ultralong Near-Infrared Wavelengths Absorbing Polymers, ACS
Appl. Poly. Mater., 2019, 1, 542-551.
‫ۻ‬Y. Hayashi, T. Satoh, M. Miura, S. Kawauchi, Theoretical Investigation of Regioselectivity in the Rh-Catalyzed
Coupling Reaction of 3-Phenylthiophene with Styrene, Eur. J. Org. Chem., 2019, 19, 2998-3004.
‫ۻ‬K. Takamatsu, Y. Hayashi, S. Kawauchi, K. Hirano, M. Miura, Copper-Catalyzed Regioselective C–H Amination of
Phenol Derivatives with Assistance of Phenanthroline-Based Bidentate Auxiliary, ACS Catal., 2019, 9, 5336-5344.
‫ۻ‬S. Ata, Y. Hayashi, T. B. N. Thi, S. Tomonoh, S. Kawauchi, T. Yamada, K. Hata, Improving thermal durability andmechanical properties of poly(ether ether ketone) with single-walled carbon nanotubes, Polymer, 2019, 176, 60-65.
‫ۻ‬K. Takamatsu, Y. Hayashi, S. Kawauchi, K. Hirano, M. Miura, Copper-Mediated Decarboxylative C-H Arylation of
Phenol Derivatives with ortho-Nitrobenzoic Acids Using Phenanthroline-Based Bidentate Auxiliary, ChemistrySelect,
2019, 4(40), 11833-11838.
‫ۻ‬ᯘ ៞ᾈ㸪ᕝෆ 㐍, ⰾ㤶᪘࣭࢟ࣀ࢖ࢻᛶ࠾ࡼࡧࢻࢼ࣮࣭࢔ࢡࢭࣉࢱ࣮ᛶࢆ⏝࠸ࡓ⊃ࣂࣥࢻࢠࣕࢵࣉȧඹᙺ⣔㧗ศᏊணࣔࢹࣝࡢᵓ⠏, J. Comput. Chem. Jpn., 2019, 18, 224̽226.

- 219 -

‫ۻ‬బࠎᮌ 㑈㤿㸪ᯘ ៞ᾈ㸪ᕝෆ 㐍, 㠀ᖹ⾮ศᏊືຊᏛἲ࡟ࡼࡿࢩ࢔ࣀࣅࣇ࢙ࢽࣝᾮᬗࡢ⇕ఏᑟᶵᵓࡢゎ᫂,
J. Comput. Chem. Jpn., 2019, 18, 236̽238.
‫▼ۻ‬ᒣ ⿱㍤㸪ᯘ ៞ᾈ㸪㧗⏣ ༑ᚿ࿴㸪ᕝෆ 㐍, ⰾሷᇶᛶ᮲௳ୗ࡟࠾ࡅࡿࢽࢺࣜࣝ࢜࢟ࢩࢻ࠿ࡽ࢖ࢯࢩ࢔ࢿ
࣮ࢺ࡬ࡢ␗ᛶ໬཯ᛂᶵᵓࡢ⌮ㄽⓗゎ᫂, J. Comput. Chem. Jpn., 2019, 18, 230̽232.
‫ۻ‬ᰘ⏣ ⿱௓㸪ᯘ ៞ᾈ㸪ᕝෆ 㐍, ࢔ࢩࣝࣆࣜࢪࢽ࣒࢘࢝ࢳ࢜ࣥࡢᏳᐃᛶ࠾ࡼࡧ཯ᛂᛶࡢホ౯, J. Comput.
Chem. Jpn., 2019, 18, 233̽234.
‫ۻ‬Ἑ⏣ ᝆኴ㸪ᯘ ៞ᾈ㸪㧗⏣ ༑ᚿ࿴㸪ᕝෆ 㐍, Pd ゐ፹ࢆ⏝࠸ࡓ࢔ࣜࣝ࢘ࣞࢱࣥࡢศᏊෆࣄࢻࣟ࢔࣑ࣀ໬
཯ᛂᶵᵓࡢ⌮ㄽⓗゎ᫂, J. Comput. Chem. Jpn., 2019, 18, 166̽168.
‫ۻ‬Y. Hayashi, Y. Ishiyama, T. Takata, S. Kawauchi, Exploration of Unimolecular and Bimolecular Pathways for Nitrile
N-oxide Isomerization to Isocyanate through Global Reaction Route Mapping Techniques, Eur. J. Org. Chem., 2019, 39,
6646-6654.
‫ ۻ‬Y. Hayashi, S. Kawauchi, Development of a Quantum Chemical Descriptor Expressing Aromatic/Quinoidal
Character for Designing Narrow-Bandgap π-Conjugated Polymers, Polym. Chem., 2019, 10 (41), 5584-5593.
‫ۻ‬S. Ata, S. Yamane, Y. Hayashi, S. Kawauchi, Improving Thermal Durability and Mechanical Properties of Poly(ether
ether ketone) with Single-Walled Carbon Nanotubes, J. Mizukado, T. Yamada, K. Hata, Macromol. Chem. Phys., 2019,
1900235.
‫ۻ‬R. Sasaki, Y. Takahashi, Y. Hayashi, S. Kawauchi, Atomistic Mechanism of Anisotropic Heat Conduction in the
Liquid Crystal 4‑Heptyl-4’-cyanobiphenyl: All-Atom Molecular Dynamics, J. Phys. Chem. B, 2020, 124, 881-889.
‫ۻ‬S. Fuse, T. Oishi, K. Matsumura, Y. Hayashi, S. Kawauchi, H. Nakamura, The Design, Synthesis, and Evaluation of
Azo D-π-A Dyes as Photothermal Agents, Org. Biomol. Chem., 2020, 18, 93-101.
‫ۻ‬V. Deneva, N. Vassilev, S. Hristova, D. Yordanov, Y. Hayashi, S. Kawauchi, L. Antonov, Chercher de l'eau: The
Switching Mechanism of the Rotary Switch Ethyl-2-(2-(quinolin-8-yl)hydrazono)-2-(pyridin-2-yl)acetate, Comput.
Mater. Sci., 2020, 177, 109570.
‫ۻ‬Y. Nishii, M. Ikeda, Y. Hayashi, S. Kawauchi, M. Miura, Triptycenyl Sulfide: A Practical and Reactive Catalyst forElectrophilic Aromatic Halogenation using N-Halosuccinimides, J. Am. Chem. Soc., 2020, 142, 1621-1629.
‫ۻ‬G. Mihara, T. Noguchi, Y. Nishii, Y. Hayashi, S. Kawauchi, M. Miura, Rhodium-Catalyzed Annulative Coupling ofIsothiazoles with Alkynes through N-S Bond Cleavage, Org. Lett., 2020, 22, 661-665.
‫ۻ‬K. Ohtsuki, H. Walsgrove, Y. Hayashi, S. Kawauchi, B. Patrick, D. Gates, S. Ito, Diels-Alder reactions of 1phosphabutadienes: a highly selective route to P=C-substituted phosphacyclohexenes, Chem. Commun., 2020, 56, 774777.
‫ۻ‬K. Yamamoto, K. Higuchi, M. Ogawa, H. Sogawa, S. Kuwata, Y. Hayashi, S. Kawauchi, T. Takata, Macrocyclic
Metal Complexes Bearing Rigid Polyaromatic Ligands: Synthesis and Catalytic Activity, Chem. Asian J., 2020, 15, 356359.
‫ۻ‬K. Yamamoto, K. Higuchi, S. Kuwata, Y. Hayashi, S. Kawauchi, T. Takata, Open Clamshell Dinuclear Palladium(II)Complexes Possessing Out-of-Plane Anisotropy, Dalton trans., 2020, 49, 2781-2785.
‫ۻ‬Y. Otake, Y. Shibata, Y. Hayashi, S. Kawauchi, H. Nakamura, S. Fuse, N-Methylated Peptide Synthesis ThroughAcyl N-Methylimidazolium Cation Generation Accelerated by a Brønsted Acid, Angew Chem Int. Ed., 2020, DOI:
10.1002/anie.202002106- 220 -

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ゐ፹ࢆ⏝࠸ࡓ໬Ꮫ཯ᛂᶵᵓࡢ⌮ㄽⓗゎ᫂Theoretical Studies on Mechanisms of Catalytic Reactions‫ۑ‬᳃ ⪷἞ࠊᕝᓥᜤᖹࠊ୕ࢶἨᏹ᫭ࠊ㡑 㨯ࠊᓥᓮ ඃ୍ࠊ኱ୗ ᏹ⨾ࠊ㕥ᮌ ᓫࠊᗉᮧ ᗣே㸦Ⲉᇛ኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ
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ࡳࡽࢀࡿ㸦ᑐᛂࡍࡿ TD-DFTィ⟬ࡢ⤖ᯝࢆᅗ 1c ࡟♧ࡍ㸧ࡇ࡜࠿ࡽࠊ࢖ࣥࢻ࣮ࣝ⨨᥮యࡶ࣓ࢳࣝ⨨᥮య࡟࠾࠸࡚ࡶࠊș
ࢫࣆࣥ㌶㐨ࡢ HOMO ࡛ࡣࠊࢧࣞࣥ㓄఩Ꮚ඲య࡟㠀ᒁᅾ໬ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋࡇ
ࡢ㸯㟁Ꮚ㓟໬య࡟ࡘ࠸࡚ࠊ㠀ඹ᭷⤖ྜᛶ┦஫స⏝(NCI)ゎ
ᯒ࡜ QTAIM(Quantum Theoryᅗ㸯.࢖ࣥࢻ࣮ࣝ⨨᥮ Ni(II) salen 㘒యࡢ㸯㟁Ꮚ㓟໬యࡢ(a)ᴫ␎ᅗࠊ
(b)NCI ゎᯒࠊ࠾ࡼࡧ(c) TD-DFT ィ⟬࡟࠾ࡅࡿ 4859.7 cm-1 ࡟ᑐᛂࡍࡿ㑄⛣- 223 -

of Atoms in Molecules)ゎᯒࢆ⾜ࡗࡓࠋᅗ㸯࡟♧ࡍࠋ࡞࠾ࠊQTAIM ゎᯒ࡟ࡼࡗ࡚ࠊNi̽N ⤖ྜ࡟㛵ࡋ࡚ࡣࠊ❅⣲ࡢᏙ❧㟁Ꮚᑐࡀࢽࢵࢣࣝ࡜┦஫స⏝ࡍࡿ㓄఩⤖ྜ࡛࠶ࡾࠊNi̽O ⤖ྜ࡟㛵ࡋ࡚ࡣࠊࣇ࢙ࣀ࣮ࣛࢺ࢔ࢽ࢜ࣥ࡜ 2౯ࡢࢽࢵࢣࣝ࡜ࡢ┦஫స⏝࡛࠶ࡿࡇ࡜࠿ࡽ࢖࢜ࣥᛶࡢ⤖ྜ࡛࠶ࡿ࡜⌮ゎ࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
᪻⹸⑓ཎ⣒≧⳦࠿ࡽ༢㞳ࡉࢀࡓ RUELRFKURPRQH$ ࡢ㟁Ꮚ෇஧Ⰽᛶࢫ࣌ࢡࢺࣝ

᪻⹸⑓ཎ⣒≧⳦ Orbiocrella petchii ࠿ࡽ༢㞳ࡉࢀࡓ஧ḟ௦ㅰ≀࡛࠶ࡿ orbiochromone A㸦ᅗ㸰㸧ࡢ㟁Ꮚ෇஧Ⰽᛶ(ECD)ࢫ࣌ࢡࢺࣝ࡜ࠊTD-DFT ィ⟬(B3LYP-D3BJ/6-311+G(d,p))ࡢ⤖ᯝ࡜ẚ㍑ࡋ࡚ࠊࡑࡢ⤯ᑐ❧య㓄⨨ࢆỴࡵࡿࡇ࡜ࡀ࡛ࡁࡓ㸦ᅗ㸰㸧ࠋ┦ᑐ❧య㓄⨨࡟ࡘ࠸࡚ࡣ NMR ࢫ࣌ࢡࢺࣝゎᯒ࡛ỴࡵࡓࠋECD ࢫ࣌ࢡࢺࣝࡢ TDDFT ィ⟬࡟ࡘ࠸࡚ࡣࠊMerck Molecular Force Field (MMFF)࡛㓄ᗙゎᯒࢆ⾜࠸ࠊ㸷ࡘࡢ᭱Ᏻᐃ㓄ᗙࢆࠊィ⟬ࣞ࣋ࣝࡢ㧗࠸ B3LYP-D3BJ(SMD)/6-311+G(d,p)//B3LYP-D3BJ(SMD)/6-31G(d) ࡛ࡉࡽ࡟ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋồࡵࡓ ECD ࢫ࣌ࢡࢺࣝࡣ Boltzmann ศᕸ࡟ᇶ࡙ࡁຍ㔜ᖹᆒࢆྲྀࡗࡓࠋࡇࡢ◊✲ࡣࢱ࢖࣭BIOTEC ࡢఀᆏ㞞ᙪ༤ኈ࡜ࡢඹྠ◊✲࡛࠶ࡿࠋࡉࡽ࡟ࡇࡢㄽᩥࡣࠊTetrahedron ㄅࡢ⾲⣬࡟᥇⏝ࡉࢀࡓࠋᅗ㸰 (+)-orbiochromone A ࡢ⌮ㄽ ECD ࢫ࣌ࢡࢺࣝ㸦㟷㸧࡜ᐇ㦂 ECD ࢫ࣌ࢡࢺࣝ㸦㯮㸧ࣂࢼࢪ࣒࢘1ࢧࣜࢳࣜࢹࣥᆺ㓄఩Ꮚ༠ዌゐ፹࡟ࡼࡿ࢜ࣞࣇ࢕ࣥࡢ 㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ

໬཯ᛂ⤒㊰᥈⣴᭷ᶵࣇࢵ⣲໬ྜ≀ࡣࠊᵝࠎ࡞ศ㔝࡛฼⏝ࡉࢀ࡚࠾ࡾࠊ≉࡟ࠊ་⸆ศ㔝࡟࠾࠸࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋCF3 ᇶࢆᑟධࡍࡿ࡜ࠊᙉ࠸㟁Ꮚ྾ᘬᛶࠊ㓟໬ⓗ௦ㅰ࡟ᑐࡍࡿᏳᐃᛶࡢྥୖ(ᙉ࠸ C-F ⤖ྜ)ࠊ⬡⁐ᛶࡢྥୖ࡞࡝ࡢᶵ⬟ࢆ᭷ᶵ໬ྜ≀࡟୚࠼ࡿࡇ࡜ࡀ࡛ࡁࡿࠋᮏᖺᗘࠊtert-ࣟ࢖ࢩࣥ࠿ࡽㄏᑟࡉࢀࡓ୕ᗙ Schiff ሷᇶ㓄఩Ꮚ㸦N-ࢧࣜࢳࣜࢹ
ࣥᆺ㓄఩Ꮚ㸧ࢆྵࡴ࢜࢟ࢯࣂࢼࢪ࣒࢘ゐ፹࡜ Togni ヨ⸆ࡢ⤌ࡳྜࢃࡏ࡟ࡼࡿࠊ࢜ࣞࣇ࢕ࣥ࡬ࡢ㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬཯ᛂࡀ᳨ウࡉࢀࡓࠋ(ୗᘧ)- 224 -

ࡇࡢ࢜ࣞࣇ࢕ࣥࡢ 1,2-㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳ ࣝ໬ ࡢ ཯ᛂ ᶵ ᵓ ࢆᅗ 㸱 ࡟ ♧ࡍࠋᇶ㉁࡛࠶ࡿ࢜ࣞࣇ࢕ࣥ࡟ᑐࡋࠊTogni
ヨ⸆࠿ࡽᨺฟࡉࢀࡓ CF3 ࣛࢪ࢝ࣝࡀ௜
ຍࡍࡿ㸦A㸧ࠋࡑࡢᚋࠊO2 ࡜࢜࢟ࢯࣂࢼ
ࢪ࣒࢘㸦Ⅳ㸧㓄఩Ꮚ࡟ A ࡀ௜ຍࡋࠊ୰
㛫య B ࢆᙧᡂࡋࡓࡢࡕࠊ1,3-Ỉ⣲㌿఩ࠊࡲࡓࡣࠊ1,4-Ỉ⣲㌿఩ࡀ㉳ࡇࡿ࡜ண᝿ࡉ
ࢀ࡚࠸ࡓࠋ཯ᛂࡢ㏵୰ࠊࣅࣛࢪ࢝ࣝ୰㛫య D ࢆ⤒⏤ࡍࡿ࠿୙࡛᫂࠶ࡗࡓࠋࡑࡇ
࡛ᡃࠎࡣࠊDFT ィ⟬࡟ࡼࡿ཯ᛂᶵᵓ᥈⣴ ࢆ ࠾ ࡇ ࡞ ࡗ ࡓ ࠋ DFT ィ ⟬ ࡣ ࠊ
UBP86+D3BJ(SMD)/def2-TZVPP/W06//
UBP86+D3BJ(SMD)/def2-SVP/W06 ࣞ࣋E࡛ࣝ⾜ࡗࡓ(⁐፹: ࢔ࢭࢺࣥ)ࠋ
ࡑࡢ⤖ᯝࠊ
1,3-Ỉ⣲㌿఩࡛ࡣ࡞ࡃࠊࣂࢼࢪ࣒࢘ࡢ࢔
ࣆ࢝ࣝ఩࡟⤖ྜࡋࡓ࢜࢟ࢯ㓟⣲ࡀࠊᇶᅗ㸱. ࢜ࣞࣇ࢕ࣥࡢ 1,2-㓟໬ⓗࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ໬཯ᛂᶵᵓ㉁ࡢỈ⣲ཎᏊࢆᘬࡁᢤࡃ༠ዌⓗ࡞ 1,5Ỉ⣲㌿఩࡛཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓ(ᅗ㸲)ࠋࡇࡢ⤒㊰࡛ࡣࠊࣅࣛࢪ࢝ࣝ୰㛫యࢆ⤒⏤ࡍࡿࡇ࡜࡞ࡃ཯
ᛂࡀ㐍⾜ࡍࡿࠋ

ᅗ㸲㸬༠ዌⓗ 1,5-Ỉ⣲㌿⛣ࡢ TSࠊཬࡧࡑࡢ๓ᚋࡢ୰㛫యࡢᵓ㐀ࠋཎᏊ㛫㊥㞳ࡢ༢఩ࡣ Åࠋᅗ㸲࡟♧ࡋ࡚࠸ࡿࢫࣆ୍ࣥ㔜㡯≧ែࡢ㑄⛣≧ែ(TSB’-E+pro)࡟࠾࠸࡚ࠊࣅࣛࢪ
࢝ࣝᛶࡣ☜ㄆࡉࢀ࡞࠿ࡗࡓࠋỈ⣲㌿⛣ࡢ㑄⛣≧ែࡀ୕㔜㡯࡛ࡣࠊ୍㔜㡯࡟ẚ
࡭࡚ 97.4 kJ/mol Gibbs ࢚ࢿࣝࢠ࣮ⓗ࡟㧗࠿ࡗࡓࠋࡲࡓ࢜࢟ࢯ㓟⣲௨እࡢࠊࣂ
ࢼࢪ࣒࢘࡟⤖ྜࡋ࡚࠸ࡿ N-ࢧࣜࢳࣜࢹࣥᆺ㓄఩Ꮚୖࡢ㓟⣲ཎᏊࡀࠊᇶ㉁ࡢ
Ỉ⣲ࢆᘬࡁᢤࡃ 1,5-Ỉ⣲㌿⛣ࡢ㑄⛣≧ែ᥈⣴ࡶྠᵝ࡟᳨ウࡋࡓࠋ⤖ᯝࡢ୍㒊ࢆᅗ㸳࡟♧ࡍࠋTSB’-E+pro ࡢ᪉ࡀ TSB’-II ࡼࡾࡶࠊ12.4 kJ/mol Gibbs ࢚ࢿࣝࢠ࣮
ⓗ࡟Ᏻᐃ࡛࠶ࡗࡓࠋࡲࡓࠊ2 ࡘࡢ⤒㊰࡟࠾ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮ࡢᕪࢆẚ㍑- 225 -ᅗ㸳  TSB-IIࡋࡓ࡜ࡇࢁࠊTSB’-E+pro ࢆ㎺ࡿ⤒㊰ࡢ᪉ࡀ 57.4 kJ/mol Ᏻᐃ࡛࠶ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ⇕ຊᏛⓗ࠿ࡘ㏿ᗘㄽⓗ࡟ࠊ࢜࢟ࢯ㓟⣲ࡀỈ⣲ࢆᘬࡁᢤࡃ⤒㊰㸦ᅗ㸲㸧࡛ࣂࢼࢪ࣒࢘ゐ፹ࡢ཯ᛂࡀ㐍⾜ࡍࡿ࡜♧၀ࡉࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
մ1. Seiji Mori, “Bridges between Experiment and Theory on Catalytic functions”, 23rd International Annual

Symposium on Computational Science and Engineering (ANSCSE23), June 27-29 2019, Chiang Mai, Thailand (invitedlecture)մ2. Seiji Mori, “Mechanistic Insights into Metal-Catalyzed Highly Selective Homogeneous Organic Transformation
Reactions”, The 10th International Conference of the Asian Consortium on Computational Materials Science (ACCMS10), July 22-26, 2019, Hong Kong (invited lecture)մ3. Seiji Mori, “Bridges between experiment and theory on catalytic functions”, 31st IUPAP Conference on
Computational Physics (CCP2019), July 28-August 1, 2019, Hong Kong (invited lecture)մ4. Seiji Mori, “Computational Insights into Structures and Reactions of Homogeneous and Enzymatic Catalysts”,
The Organic & Biomolecular Chemistry conference co-organised by The Royal Australian Chemical Institute (RACI),Royal Melbourne Institute of Technology (RMIT) and the National Organic Symposium Trust (NOST), 6-8 November
2019, Melbourne, Australia (invited lecture)մ5. ᕝᓥ ᜤᖹ, ➲㔝 ⿱௓, ᑠᬽ ┤㈗, ➟⏿ Ὧᕼ, ᒾῲ ዲ἞, ᳃ ⪷἞, DFT Investigations of
Oxidative Kinetic Resolution of Racemic Secondary Alcohols Using Chiral Ligand-Hybridized Nitroxyl Radical/Copper
Cooperative Catalysisࠊ㘒య໬Ꮫ఍➨㸴㸷ᅇウㄽ఍ࠊྡྂᒇࠊ2019 ᖺ㸷᭶ 21 ᪥̿23 ᪥
մ6. ୕ࢶἨᏹ᫭ࠊ᳃ ⪷἞ࠊ3Ș-ࢪࣄࢻࣟ࢟ࢩࢫࢸࣟ࢖ࢻࢹࣄࢻࣟࢤࢼ࣮ࢮ-5Ș-ࢪࣄࢻࣟࢸࢫࢺࢫࢸࣟࣥ
」ྜయᵓ㐀࡟㛵ࡍࡿศᏊືຊᏛⓗ◊✲ࠊ᪥ᮏ໬Ꮫ఍ ➨ 100 ᫓Ꮨᖺ఍, 2020 ᖺ 3 ᭶ 22-25 ᪥ࠊ㔝⏣5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬1. Oshita, H.; Suzuki, T.; Kawashima, K.; Abe, H.; Tani, F.; Mori, S.; Yajima, T.; Shimazaki, Y. Chem. Eur. J. 2019, 25,7649-7658.
‫ۻ‬2.

Oshita, H.; Suzuki, T.; Kawashima, K.; Abe, H.; Tani, F.; Mori, S.; Yajima, T.; Shimazaki, Y. Dalton Trans., 2019,48, 12060-12069.
‫ۻ‬3.

᳃ ⪷἞ࠊᕝᓥᜤᖹࠊࣇࣟࣥࢸ࢕࢔ࠊ2020, 2, ༳ๅ୰‫ ۻ‬4. Isaka, M.; Palasarn, S.; Choowong, W.; Kawashima, K.; Mori, S. Mongkolsamrit, S.; Thanakitpipattana, D.
Tetrahedron, 2019, 75, 130646.
‫ۻ‬5. Chen, C.-T.; Chen, Y.-P.; Tsai, B.-Y.; Liao, Y.-Y.; Su, Y.-C.; Chen, T.-C.; Lu, C.-H.; Fujii, R.; Kawashima, K.; Mori,
S. ACS Catalysis, 2020, 10, 3676-3683.

- 226 -

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ከඖ⣲ࢡࣛࢫࢱ࣮ࡢ㉥እゎ㞳ศගࡢࡓࡵࡢ㉥እࢫ࣌ࢡࢺࣝࡢண
Prediction of infrared spectra of multi-element clusters
for infrared photodissociation spectroscopy‫ۑ‬ᕤ⸨ ⪽ࠊᒣཱྀ 㞞ே㸦ᮾி኱㝔⥲ྜᩥ໬㸧
1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲࡛ࡣࠊ㔞Ꮚ໬Ꮫィ⟬࡜㉥እゎ㞳ศගἲࢆే⏝ࡋ࡚ࠊྛ✀㔠ᒓࢡࣛࢫࢱ࣮(Mnn+, CaMnn+ Ptn+࡞࡝)࡟㓟⣲ࡸỈศᏊࡀ྾╔ࡋࡓࢡࣛࢫࢱ࣮ࡢᵓ㐀ࢆỴᐃࡋࡓࠋࡇࢀ࡟ᇶ࡙ࡁࢡࣛࢫࢱ࣮ࡢ཯ᛂᛶ࡞࡝ࢆ㆟ㄽࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian09 ࢆ౑⏝ࡋ࡚㔠ᒓࢡࣛࢫࢱ࣮࡟ O, H2O ࡞࡝ࡀ྾╔ࡋࡓࢡࣛࢫࢱ࣮ࡢᵓ㐀᭱㐺໬ࢆ࠾ࡇ࡞࠸ࠊᚓࡽ

ࢀࡓᏳᐃᵓ㐀࡟ᑐࡋ࡚᣺ືᩘィ⟬ࢆ࠾ࡇ࡞ࡗ࡚ࢫ࣌ࢡࢺࣝࣃࢱ࣮ࣥࢆసᡂࡋࡓࠋィ⟬᪉ἲࡣࠊB3LYP ࢆ୺࡟౑⏝ࡋࠊᇶᗏ㛵ᩘࡣ㑄⛣㔠ᒓཎᏊ࡟ࡣ୺࡟ SDD ࢆࠊࡑࢀ௨እࡢཎᏊ࡟ࡣ୺࡟ 6-311+G(d)ࡸ aug-cc-pVDZ ࢆ⏝࠸ࡓࠋ㉥እゎ㞳ศග࠿ࡽᚓࡽࢀࡓᐇ

3ࡢࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡍࡿࡇ࡜࡛ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࢆỴᐃࡋࡓࠋ◊✲ᡂᯝ㉥እࢫ࣌ࢡࢺࣝ࡜ࣃࢱ࣮ࣥࡢẚ㍑࡟ࡼࡾ Pt3(H2O)m+ (m=1Ѹ4)ࢡࣛࢫࢱ࣮࡛ࡣỈศᏊࡣศᏊࡢࡲࡲ྾╔ࡋ࡚࠸ࡿࡇ࡜࡞࡝ࡀࢃ࠿ࡗࡓ㸦ヲ⣽ࡣฟ∧ᐇ⦼[1]ࢆཧ↷ࠊࡲࡓࠊࡑࡢ࡯࠿ࡢᡂᯝ࡟ࡘ࠸࡚ࡣୗグᐇ⦼ࢆཧ↷㸧
ࠋ

4

Ⓨ⾲ᐇ⦼
[1] ‫ۻ‬㜿㒊㸪ᕤ⸨㸪ᐑᓥ㸪┿⯪㸪ࠕ㉥እゎ㞳ศග࡟ࡼࡿẼ┦ⓑ㔠ࢡࣛࢫࢱ࣮ୖࡢỈࡢ྾╔ᵓ㐀ࡢゎ᫂ࠖ㸪➨

13 ᅇศᏊ⛉Ꮫウㄽ఍
[2] ‫ۻ‬ᕤ⸨㸪㜿㒊㸪Zhang㸪┿⯪㸪ࠕ㉥እゎ㞳ศග࡟ࡼࡿ࢝ࣝࢩ࣒࣮࣐࢘ࣥ࢞ࣥ」ྜ㓟໬≀ࢡࣛࢫࢱ࣮ୖࡢ
Ỉࡢ྾╔ᵓ㐀ࡢゎ᫂ࠖ㸪➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍
[3] ‫ۻ‬Liu, Zhang, Miyajima, Kudoh, Mafune, "Oxidation states of Cu atoms adsorbed on Al oxide clusters
investigated by thermal desorption spectrometry", ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍
[4] ‫ۻ‬㜿㒊㸪ᕤ⸨㸪ᙇ㸪ᒣཱྀ㸪ᐑᓥ㸪┿⯪㸪ࠕ㉥እゎ㞳ศග࡟ࡼࡿ࣐ࣥ࢞ࣥ㓟໬≀ࢡࣛࢫࢱ࣮ୖࡢỈࡢ྾╔ᵓ㐀ࡢゎ᫂ࠖ㸪᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍[5] ‫ۻ‬ᕤ⸨㸪/LX㸪=KDQJ㸪┿⯪㸪ࠕẼ┦᪼⬺㞳ᐇ㦂࡜ ')7 ィ⟬࡟ࡼࡿ㖡ཎᏊ࠿ࡽ࢔࣑ࣝࢽ࣒࢘㓟໬≀ࢡࣛࢫࢱ࣮࡬ࡢ㟁Ⲵ⛣ືࡢゎ᫂ࠖ㸪᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍5ฟ∧ᐇ⦼[1] ‫ۻ‬Mafuné, Abe, Kudoh, "Adsorption Forms of Water Molecules on Gas-Phase Platinum Clusters Pt3+ Studied byVibrational Photodissociation Spectroscopy", Z. Phys. Chem., 233(6), 881-894 (2019).
[2] ‫ۻ‬Wang, Miyajima, Kudoh, Mafuné, "Effect of atomicity on the oxidation of cationic copper clusters studied
using thermal desorption spectrometry", Phys. Chem. Chem. Phys., 21(41), 23129-23135 (2019).
[3] ‫ۻ‬Mafuné, Zhang, Liu, Wang, Kudoh, "Electron Donation from Cu Atoms to Al Oxide Clusters upon Mixing
Revealed by Thermal Desorption Spectrometry", J. Phys. Chem. C, 124(1), 659-667 (2020)- 228 -

㔜ཎᏊࢆྵࡴ໬ྜ≀ࡢᇶᗏ࣭ບ㉳㟁Ꮚ≧ែ࡜ศᏊ≀ᛶ࡟㛵ࡍࡿ㔞Ꮚ໬Ꮫィ⟬
Quantum-Chemical Calculation for Ground and Excited Electronic
States and Molecular Properties of Molecules Containing Heavy
Elements‫ۑ‬Ἴ⏣㞞ᙪࠊ୰㇂┤㍤ࠊ㜿㒊✨㔛ࠊ௒ᮧ✨ࠊከ⏣ ᐓࠊ∵ᑿ஧㑻ࠊ◁㈡ᙬගࠊⳢ㔝⩧ᖹࠊYi Junࠊᐑᮏ ඃᘺࠊSalmahaminatiࠊMa Zhifengࠊబ⸨ ᭷ử␃ࠊⳢ἟ 㯞Ⳁዉࠊᶫᮏ ᣅ☻ࠊྜྷ⏣ ⋹ࠊ㐨᫂ Ṋಙ㸦㤳㒔኱Ꮫᮾி㸧1◊✲┠ⓗࠊෆᐜ

┦ᑐㄽࢆ⪃៖ࡋࡓ㟁Ꮚ≧ែࡢ㧗⢭ᗘ࣭኱つᶍィ⟬ࣉࣟࢢ࣒ࣛࡢ㛤Ⓨཬࡧࠊࡑࢀࡽ࡟㛵㐃ࡍࡿୗ㏙ࡢ◊✲ࢸ࣮࣐ࢆ㐍ࡵࡓࠋ 㕲 ࢜ ࢟ ࢯ ࣏ ࣝ ࣇ ࢕ ࣜ ࣥ ࡟ ࡼ ࡿ ࢜ ࣞ ࣇ ࢕ ࣥ ࡢ ࢚ ࣏ ࢟ ࢩ ໬ ཯ ᛂ ࡢ ゎ ᯒ
2. ప ẘ ᛶ ࣭ ప ౯ ᱁ ඖ ⣲ ࠿ ࡽ ᙧ ᡂ ࡉ ࢀ ࡿ 500 ࡢ ᪂ つ ࣌ ࣟ ࣈ ࢫ ࢝ ࢖ ࢺ ᆺ Ỉ ศ ゎ ග ゐ ፹ ᮦ ᩱ ࡢ 㟁 Ꮚ≧ែィ⟬
3. ศᏊࢹࣂ࢖ࢫ࡟⏝࠸ࡿ π 㟁Ꮚ⣔ఏᑟᛶศᏊ࡟᪊ࡅࡿ㟁Ꮚ┦㛵ຠᯝࡢ᳨ウ࡜ࠊᖹᆒሙ㏆ఝ(mean field theory)࡟ᇶ࡙ࡃᚑ᮶ࡢࢼࣀࢫࢣ࣮ࣝ㟁Ꮚ㍺㏦⌮ㄽࣔࢹࣝࡢ㐺⏝㝈⏺࡟ࡘ࠸࡚ࡢ⌮ㄽⓗ◊✲4.

2 ᡂศ┦ᑐㄽἲࢆ⏝࠸ࡓ࢘ࣛࣥ㘒యࡢྠ఩యศูィ⟬ࠋ

5 ᭷ ᶵ 㔠 ᒓ ࢆ ྵ ࡴ Ⰽ ⣲ ቑ ឤ ග ゐ ፹ ࡢ ⌮ ㄽ ィ ⟬6㸬ࣟࢪ࣒࢘㘒య࠾ࡼࡧ࢖ࣜࢪ࣒࢘㘒యゐ፹࡟ࡼࡿ࢚ࢼ࣑ࣥྜᡂ཯ᛂࡢゐ፹ᶵᵓࡢゎ᫂࡜ࠊ㓄఩Ꮚ࡟ࡼࡿ཯ᛂ
ไᚚᅉᏊࡢ≉ᐃ࠾ࡼࡧィ⟬࡟ࡼࡿண7㸬㑄⛣㔠ᒓ㘒య࠾ࡼࡧ㑄⛣㔠ᒓࢡࣛࢫࢱ࣮ࡢ K, L ➃ X ⥺྾཰ࢫ࣌ࢡࢺࣝ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲8㸬➨୍ཎ⌮ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿᫍ㛫ị⾲㠃࡟࠾ࡅࡿ໬Ꮫ㐍໬ࡢ⌮ㄽⓗ◊✲9. ⮬↛ᦤື㌶㐨ࢆ⏝࠸ࡓ⾲㠃ቑᙉ࣐ࣛࣥᩓ஘㸦SERS㸧࡟㛵ࡍࡿゎᯒ
10. 7Be ཎᏊ᰾ࡢ㟁Ꮚᤕ⋓ቯኚࢆ᪩ࡵࡿ໬ྜ≀ࡢ᥈ᰝ

2 ◊✲᪉ἲࠊィ⟬᪉ἲ
ࢸ࣮࣐ 1 ࡟ࡘ࠸࡚ࡣ HONDO ࢆ࣮࣋ࢫ࡟ᨵⰋࡋࡓᮏ◊✲ᐊࡢࣉࣟࢢ࣒ࣛࢆ⏝࠸ࠊ
ࢸ࣮࣐ 2 ࡟ࡘ࠸࡚ࡣ VASP࡜ᮏ◊✲ᐊࡢᶵᲔᏛ⩦ࣉࣟࢢ࣒ࣛࢆࠊࢸ࣮࣐ 4 ࡛ࡣ DIRAC16 ࡟ࡼࡿ┦ᑐㄽィ⟬ࠊࢸ࣮࣐ 9 ࡛ࡣ NWChemࠊࡑࡢ௚ࡢࢸ࣮࣐࡟ࡘ࠸࡚ࡣ Gaussian09, Gaussian16 ࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

ୖグ◊✲࡟ᑐࡋࠊ୺࡟ 2019 ᖺᗘ࡟◊✲㐍ᤖࡀ࠶ࡗࡓࢸ࣮࣐ 8, 9,10 ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ

ࢸ࣮࣐ 8 ࡛ࡣࠊᫍ㛫ሻ⾲㠃࡟࠾ࡅࡿศᏊࡢ཯ᛂᛶ⬺㞳࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࠊ➨୍ཎ⌮ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ
⏝࠸࡚⌮ㄽⓗ࡞᳨ドࢆ⾜ࡗࡓࠋᫍ㛫✵㛫࡛ほࡉࢀࡿᵝࠎ࡞ศᏊࡣࠊᫍ㛫ሻ࡜࿧ࡤࢀࡿ࢔ࣔࣝࣇ࢓ࢫị࡛そࢃࢀࡓ㖔≀ࡢᚤ⢏Ꮚୖ࡛⏕ᡂࡉࢀࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࡀࠊᴟప

- 229 -

ࡢᫍ㛫✵㛫࡟࠾࠸࡚ࡣᫍ㛫ሻ⾲㠃࡟྾╔ࡋࡓศᏊࡀẼ┦୰࡬ᨺฟࡉࢀࡿࡇ࡜ࡣ࡞ࡃࠊẼ┦୰࡟ࢃࡎ࠿࡞ࡀࡽᏑᅾࡍࡿศᏊࡢ㉳※ࡣศ࠿ࡗ࡚࠸࡞࠸ࠋࡇ
ࢀࢆㄝ᫂ࡍࡿ௬ㄝ࡜ࡋ࡚ࠊศᏊࡀ⏕ᡂࡍࡿ㝿࡟ᨺฟࡉࢀࡿ཯ᛂ⇕ࢆ฼⏝ࡋ࡚ศᏊࡀ⬺㞳ࡍࡿ࡜࠸࠺཯ᛂᛶ⬺㞳࣓࢝ࢽࢬ࣒ࡀᥦၐࡉࢀࡓࠋ໭኱࣭Ώ㒊ࡽࡢࢢ࣮ࣝࣉ࡛ࡣࠊH2S ศᏊࢆ౑ࡗࡓࣛࢪ࢝ࣝⓗ H ஺᥮཯ᛂࢆ฼⏝ࡋ࡚ࠊᴟపୗ࡟࠾ࡅࡿ཯ᛂᛶ⬺㞳࣓࢝ࢽࢬ࣒ࢆᨭᣢࡍࡿᐇ㦂⤖ᯝࢆሗ࿌ࡋ࡚࠸ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊDFTἲ㸦ȦB97XD ỗ㛵ᩘ㸧࡟ᇶ࡙ࡃ➨୍ཎ⌮ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸࡚ࠊH2S ศᏊࡢ཯ᛂᛶ⬺㞳࣓࢝ࢽࢬ࣒࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣࠊH2O࣭20 ศᏊ࠿ࡽ࡞ࡿ࢔ࣔࣝࣇ࢓ࢫịࡢࣔࢹࣝࢡࣛࢫࢱ࣮࡟྾╔ࡉࡏࡓ HSࣛࢪ࢝ࣝ࡟ H ࣛࢪ࢝ࣝࢆึ㏿ᗘ 500K ࡛⾪✺ࡉࡏࠊࡑࡢᚋࡢ཯ᛂࢲ࢖ࢼ࣑ࢡࢫࢆ㏣㊧ࡋࡓࠋỈࢡࣛࢫࢱ࣮ࡢ
ᵓ㐀࡜ HS ࣛࢪ࢝ࣝࡢึᮇ఩⨨ࢆኚ࠼ࡓ 160 ᮏࡢࢺࣛࢪ࢙ࢡࢺࣜࢆィ⟬ࡋࠊ6 ᮏࡢࢺࣛࢪ࢙ࢡࢺࣜ࡟࠾࠸࡚
H2S ศᏊࡀ཯ᛂ⇕ࢆ౑ࡗ࡚⬺㞳ࡍࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊH2S ศᏊࡢ⬺㞳ࡀ㉳ࡁࡓࢺࣛࢪ࢙ࢡ
ࢺ࡛ࣜࡣࠊỈࢡࣛࢫࢱ࣮࡬ࡢ཯ᛂ⇕ࡢ⦆࿴ࡀ㏿ࡸ࠿࡟㐍⾜ࡋ࡚࠾ࡾ㸦ᅗ 1㸧ࠊࡇࢀ࡟ࡼࡗ࡚⏕ࡌࡿ H2S ศᏊ࡜㞄᥋ࡍࡿ H2O ศᏊ࡜ࡢỈ⣲⤖ྜࢆ௓ࡋࡓ࢚ࢿࣝࢠ࣮ࡢᤵཷ࡟ࡼࡗ࡚⬺㞳᪉ྥ࡬ࡢ㐠ືࡀㄏ㉳ࡉࢀ࡚࠸ࡿࡇ࡜
ࡀ♧၀ࡉࢀࡿ⤖ᯝ࡜࡞ࡗࡓࠋ

ᅗ 1 ࢔ࣔࣝࣇ࢓ࢫịࡢࢡࣛࢫࢱ࣮ࣔࢹࣝ㸦ᕥ㸧࡜ࠊ཯ᛂᚋࡢỈࢡࣛࢫࢱ࣮ࡢ

ᗘኚ໬

ࢸ࣮࣐ 9 ࡛ࡣ⾲㠃ቑᙉ࣐ࣛࣥᩓ஘㸦SERS㸧ࡢỗ㛵ᩘ౫Ꮡᛶࢆ⮬↛ᦤື㌶㐨࡟ࡼࡗ࡚ゎᯒࡋࡓࠋ㔠ᒓࢼࣀ⢏Ꮚ࡟྾╔ࡋࡓศᏊࡢ࣐ࣛࣥᩓ஘ᙉᗘࡀⴭࡋࡃቑᙉࡉࢀࡿ⌧㇟ࢆ SERS ࡜࿧ࡪࠋቑᙉᶵᵓࡢ୰࡛ࡶࠊ㟁Ꮚ≧ែࡢኚ໬࡟⏤᮶ࡍࡿ໬Ꮫⓗቑᙉຠᯝࡣ㔠ᒓࡢ⾲㠃ᵓ㐀ࡸศᏊࡢ㓄ྥ࡟౫Ꮡࡋࠊ≉ᐃࡢ≧ἣୗ࡛኱ࡁ࡞ቑᙉࢆ♧ࡍࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᐦᗘỗ㛵ᩘ⌮ㄽ㸦DFT㸧࡟ࡼࡗ࡚ィ⟬ࡉࢀࡓ Ag20–pyrazine–Ag20 ࡢ໬Ꮫⓗቑᙉຠᯝࡣ
105–106 Å4/amu ࡜㠀ᖖ࡟኱ࡁ࡞್ࢆ♧ࡍࡀࠊࡇࡢ⤖ᯝࡣ⏝࠸ࡿỗ㛵ᩘ࡟ⴭࡋࡃ౫Ꮡࡍࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋ
ᮏ◊✲࡛ࡣࠊࣔࢹࣝ⣔࡛࠶ࡿ Ag2–pyrazine–Ag2 ࢆ⏝࠸࡚ࠊࡑࡢỗ㛵ᩘ౫Ꮡᛶࢆ⮬↛ᦤື㌶㐨࡟ࡼࡗ࡚ゎᯒࡋ
ࡓࠋCoupled Cluster Single Double㸦CCSD㸧ἲ࡛ᚓࡽࢀࡓ⤖ᯝࢆཧ↷࡜ࡋ࡚ࠊ୍⯡໬໙㓄㏆ఝ࡛ࡣ࣐ࣛࣥᩓ஘
ᙉᗘࢆⴭࡋࡃ㐣኱ホ౯ࡍࡿࡢ࡟ᑐࡋࠊ㛗㊥㞳⿵ṇࢆຍ࠼ࡓࣁ࢖ࣈࣜࢵࢻỗ㛵ᩘࡣẚ㍑ⓗⰋ࠸୍⮴ࢆ♧ࡋࡓࠋ࣐ࣛࣥᩓ஘ᙉᗘࢆศᏊ㌶㐨ࡢᐤ୚࡟ศゎࡍࡿ࡜ࠊ༨᭷㌶㐨࡜௬᝿㌶㐨࡜ࡢ࢝ࢵࣉࣜࣥࢢ࡟ࡼࡗ࡚グ㏙ࡉࢀࠊ᭱኱࡛༨᭷㌶㐨ࡢᩘ௬᝿㌶㐨ࡢᩘࡢ㡯ࡀᏑᅾࡍࡿࠋṇ‽㌶㐨ࢆ⏝࠸ࡓሙྜ࡛ࡣࠊ㠀ᖖ࡟」㞧࡞ഴྥࢆ♧ࡋࠊ」ᩘࡢ㌶㐨ࡀᐤ୚ࢆᣢࡘࡓࡵ୺せ࡞㡯ࢆุู࡛ࡁ࡞࠸㸦ᅗ 2 ᕥ㸧ࠋ୍᪉࡛ࠊ⮬↛ᦤື㌶㐨ࢆ⏝࠸ࡿࡇ࡜࡛ࠊࡑ
ࡢ㡯ࡢᩘࢆ༨᭷㌶㐨ࡢᩘࡲ࡛ῶᑡࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋ᭱⤊ⓗ࡟ࠊAg2–pyrazine–Ag2 ࡢ࣐ࣛࣥᩓ஘ᙉᗘ࡟ࡣ 4
ࡘࡢ㌶㐨ᑐ㸦1ı–1ı*, 2ı–2ı*, 1ʌ–1ʌ*, 2ʌ–2ʌ*㸧ࡢࡳࡀᐤ୚ࢆᣢࡘࡇ࡜ࡀศ࠿ࡗࡓ㸦ᅗ 2 ྑ㸧ࠋ୰࡛ࡶࠊṇ࿡ࡢỗ㛵ᩘ౫Ꮡᛶࡣ 1ʌ–1ʌ*㌶㐨ᑐ࡟⏤᮶ࡋࠊゎᯒࡢ⤖ᯝࠊࡑࡢཎᅉࡣศᏊ᣺ື࡟ᑐࡍࡿ㌶㐨࢚ࢿࣝࢠ࣮ᕪࡢኚ໬
ࡀṇ☜࡟グ㏙࡛ࡁ࡞࠸ࡇ࡜࡟⏤᮶ࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

- 230 -

ᅗ 2. Ag2–pyrazine–Ag2 ࡢ࣐ࣛࣥᩓ஘ᙉᗘࡢศゎ㸸ṇ‽㌶㐨㸦ᕥ㸧࡜⮬↛ᦤື㌶㐨㸦ྑ㸧ࢸ࣮࣐ 10 ࡛ࡣࠊ᰾ୖࡢ㟁Ꮚᐦᗘ ρ(0)ࡀቑຍࡍࡿ Be ໬ྜ≀ࡢ᥈ᰝࢆࠊ➨୍ཎ⌮ィ⟬ࢆ⏝࠸࡚⾜ࡗࡓࠋ㟁Ꮚᤕ⋓ቯኚ࡛ࡣࠊཎᏊ᰾࡟㌶㐨ࡢ㟁Ꮚࢆྲྀࡾ㎸ࢇ࡛㝧Ꮚࡀ୰ᛶᏊ࡟࡞ࡾࠊࢽ࣮ࣗࢺࣜࣀࢆᨺฟࡍࡿࠋࡇࡢቯኚ
࡛ࡣࠊρ(0)࡜༙ῶᮇ T1/2 ࡀ཯ẚ౛㛵ಀ࡟࠶ࡾࠊࡇࢀࢆ฼⏝ࡋ࡚ ρ(0)ࢆቑຍࡉࡏࠊ༙ῶᮇ T1/2 ࢆ▷ࡃࡍࡿ◊✲ࡀ࡞ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ᭱ࡶ༙ῶᮇ T1/2 ࢆ▷ࡃࡉࡏࡓ C60 ෆໟࣇ࣮ࣛࣞࣥࡢඛ⾜◊✲࡛ࡶࠊ7Be ࡢ༙ῶᮇ T1/2
ࡣ 1.5%⛬ᗘῶᑡࡋࡓࡔࡅ࡛࠶ࡗࡓࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊBe ࡢ᰾ୖࡢ㟁Ꮚᐦᗘ ρ(0)ቑຍࡢ࣓࢝ࢽࢬ࣒ࢆ⌮ㄽⓗ࡟ゎ᫂ࡋࠊρ(0)ࢆ๻ⓗ࡟ቑຍࡉࡏࡿ໬ྜ≀ࢆ➨୍ཎ⌮ィ⟬࠿ࡽ᥈⣴ࡋࡓࠋึࡵ࡟ࠊ࠸ࡃࡘ࠿ࡢ Be ໬ྜ≀ࡢ ρ(0)ࡢቑῶ࡟ࡘ࠸࡚ゎᯒࡋࡓࠋ୍⯡ⓗ࡞໬Ꮫ⤖ྜ࡛ࡣࠊBe ࡢእẆ 2s 㟁Ꮚࡣ௚ࡢཎᏊഃ࡟⛣ືࡋ࡚ࡋࡲ࠸ࠊρ(0)ࡣ
ῶᑡࡋ࡚ࡋࡲ࠺ࠋࡋࡓࡀࡗ࡚ࠊρ(0)ࢆቑຍࡉࡏࡿࡓࡵ࡟ࡣࠊ௚ࡢཎᏊ࡟㟁Ꮚࢆᐤ୚ࡋ࡞࠸≉Ṧ࡞໬ྜ⤖ྜࢆᙧᡂࡍࡿᚲせࡀ࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋḟ࡟ࠊඛ⾜◊✲࡛⏝࠸ࡽࢀࡓࣇ࣮ࣛࣞࣥ࡟╔┠ࡋࠊᵝࠎ࡞ࢧ࢖ࢬࡢ Be ෆໟࣇ࣮ࣛࣞࣥࡢ ρ(0)ࡢഴྥ࡟ࡘ࠸࡚ゎᯒࡋࡓࠋC50 ࣇ࣮ࣛࣞࣥࡣࠊඛ⾜◊✲ࡀ࠶ࡿ C60 ࣇ࣮ࣛࣞࣥࡼࡾࡶ኱ࡁ࡞ ρ(0)ࢆ♧ࡋࡓࠋࡋ࠿ࡋࠊࣇ࣮ࣛࣞࣥࡢⅣ⣲ࡀ Be ࡟㏆᥋ࡋࡍࡂࡿ࡜ࠊBe ࡢ㟁ᏊࡀⅣ⣲ഃ࡟ὶࢀ࡚ࡋࡲ࠺ࡇ
࡜ࡀศ࠿ࡾࠊC50 ࡜ C48 ࣇ࣮ࣛࣞࣥࡢ㛫࡛ࠊ㟁Ꮚὶධࡢ⮫⏺ⅬࡀᏑᅾࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋC50 ࣇ࣮ࣛࣞࣥ⮬యࡣྜᡂሗ࿌౛ࡀ࡞࠸ࡀࠊሷ⣲ࡀ㓄఩ࡋࡓ C50Cl10 ࣇ࣮ࣛࣞࣥ࡟ࡘ࠸࡚ሗ࿌౛ࡀ࠶ࡾࠊࡇࡢሙྜ࡛ࡶ Be ෆໟ C50
ࣇ࣮ࣛࣞࣥ࡜ྠ➼ࡢ ρ(0)ࡀᚓࡽࢀࡓࠋࡋࡓࡀࡗ࡚ Be ෆໟ C50Cl10 ࣇ࣮ࣛࣞࣥࡣෆໟࣇ࣮ࣛࣞࣥ⣔ิ࡛ࡣࠊ᭱
ࡶቯኚ㏿ᗘࢆ㏿ࡵࡿྜᡂྍ⬟࡞⣔࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

ᅗ 3 Be ෆໟᕼ࢞ࢫ⤖ᬗ ᕥ㸧࡜᰾ୖࡢ㟁Ꮚᐦᗘ ρ(0) ྑ- 231 -

᭱ᚋ࡟ Be ࢆෆໟࡋࡓᕼ࢞ࢫ⤖ᬗ㸦ᅗ 3㸧࡟ࡘ࠸࡚ࠊ᱁Ꮚᐃᩘ࡟ࡼࡗ࡚ ρ(0)ࡀ࡝ࡢࡼ࠺࡞ഴྥࢆ♧ࡍ࠿ゎᯒࡋࡓࠋᕼ࢞ࢫࢆ⏝࠸ࡿ⌮⏤ࡣࠊ໬Ꮫ⤖ྜ࡟ࡼࡾࠊBe ࡢ㟁Ꮚࡀᕼ࢞ࢫഃ࡟ὶධࡋ࡟ࡃ࠸࡜⪃࠼ࡓ࠿ࡽ࡛࠶ࡿࠋ
ࡑࡢ⤖ᯝࠊ㧗ᅽୗࢆ௬ᐃࡋࡓᑠࡉ࡞᱁Ꮚᐃᩘࢆᣢࡘ⤖ᬗෆ㒊࡟࠾࠸࡚ࡣࠊBe ࢆෆໟࡋࡓᕼ࢞ࢫ⤖ᬗࡢ ρ(0)ࡀ
᭱኱࡛⣙ 10%ቑຍࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡣࠊ༙ῶᮇ࡟᥮⟬ࡍࡿ࡜⣙ 10%ῶᑡ࡟࡞ࡾࠊ๻ⓗ࡟༙ῶᮇࢆ᪩
ࡵࡿ໬ྜ≀⣔࡛࠶ࡿ࡜ゝ࠼ࡿࠋ

4Ⓨ⾲ᐇ⦼ᐑᮏඃᘺ et al., ➨ 22 ᅇ⌮ㄽ໬Ꮫウㄽ఍ࠊ2019 ᖺ 5 ᭶ 27-29 ᪥ࠊ໭ᾏ㐨኱Ꮫ Ꮫ⾡஺ὶ఍㤋; ᐑᮏඃᘺ etal., ᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ᖺ᫓Ꮨᖺ఍ࠊ2019 ᖺ 6 ᭶ 6-7 ᪥ࠊᮾிᕤᴗ኱Ꮫ ኱ᒸᒣ࢟ࣕࣥࣃࢫ; 㜿㒊✨㔛 et al., 㔞Ꮚ໬Ꮫ᥈⣴◊✲ᡤࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ 2019ࠖ2019 ᖺ 9 ᭶
16 ᪥ࠊྡྂᒇ኱Ꮫᮾᒣ࢟ࣕࣥࣃࢫ㔝౫グᛕᏛ⾡஺ὶ㤋; ྜྷ⏣⋹ et al., Ⳣ἟㯞Ⳁዉ et al., 㐨᫂Ṋಙ et al., ෠ᒣᑦ኱ et al., ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ྡྂᒇ 2019ࠊ2019 ᖺ 9 ᭶ 17 ᪥-20 ᪥ࠊྡྂᒇ኱Ꮫᮾᒣ࢟ࣕࣥࣃࢫ; బ⸨᭷ử␃ et al., ᪥ᮏᆅ⌫໬Ꮫ఍➨ 66 ᅇᖺ఍ࠊ2019 ᖺ 9 ᭶ 17 ᪥-19 ᪥ࠊᮾி኱Ꮫᮏ㒓࢟ࣕࣥࣃࢫ; Ⳣ㔝⩧ᖹ
et al. ➨ 80 ᅇᛂ⏝≀⌮Ꮫ఍⛅ᏘᏛ⾡ㅮ₇఍ࠊ2019 ᖺ 9 ᭶ 18 ᪥-21 ᪥ࠊ໭ᾏ㐨኱Ꮫᮐᖠ࢟ࣕࣥࣃࢫ; Naoki
Nakatani et al. 㘒య໬Ꮫ఍➨ 69 ᅇウㄽ఍ࠊ2019 ᖺ 9 ᭶ 21 ᪥-23 ᪥ࠊྡྂᒇ኱Ꮫᮾᒣ࢟ࣕࣥࣃࢫ; బ⸨᭷ử␃
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5

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⏕య㉸ศᏊࡢ❧యᵓ㐀ኚ໬࡜ᶵ⬟Conformational change of biological supramolecules andits relation to functions‫ۑ‬໭ᑿ ᙲᮁࠊ➉ᮧ ࿴ᾈࠊTRAN Phuoc Duyࠊ⏿ ᏹ᫂ࠊ㮚⩚ ೺୍㑻ࠊ
SOBEH Mohamed Marzouk, ᐑ⃝ ెᕼࠊᮌෆ 㱟அ௓㸦ᮾᕤ኱⏕࿨⌮ᕤ㸧

1◊✲┠ⓗ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࠸ࡿࠋ31 ᖺᗘࡣୗグࡢ 3 ࡘࡢࢸ࣮࣐ࢆ୰ᚰ࡟ィ⟬ࢆ⾜ࡗࡓࠋ1 ࡘ┠ࡢㄢ㢟࡛࠶ࡿࠕCheY-FliM 」ྜయ࡟ཬࡰࡍᅽຊຠᯝࡢゎᯒࠖࡢᑐ㇟࡛࠶ࡿ CheY-FliM 」ྜయࡣࠊࣂࢡ
ࢸࣜ࢔ࡢ㉮໬ᛶࢩࢢࢼࣝ⺮ⓑ㉁ CheY ࡜࡭ࢇẟ࣮ࣔࢱ࣮⺮ⓑ㉁ FliM ࡢ」ྜయ࡛࠶ࡿࠋᡃࠎࡣࠊ㧗ᅽຊࡀ࡭ࢇ
ẟ࣮ࣔࢱ࣮ࡢᅇ㌿᪉ྥษ᭰࡟ᙳ㡪ࡍࡿ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࠊ≉࡟ CheY ࡜ FliM ࡢ┦஫స⏝࡟ὀ┠ࡋ࡚ゎᯒࢆ㐍ࡵ࡚ࡁࡓࠋ≉࡟ࠊᡃࠎࡢࢢ࣮ࣝࣉ࡛㛤Ⓨࡋࡓ୪ิ࢝ࢫࢣ࣮ࢻ㑅ᢥศᏊືຊᏛἲ㸦Parallel Cascade Selection
Molecular Dynamics; PaCS-MD㸧㸦J. Chem. Phys., 2013㸧࠾ࡼࡧ࣐ࣝࢥࣇ≧ែࣔࢹࣝ㸦Markov State Model; MSM㸧࡜⤌ࡳྜࢃࡏࡓ PaCS-MD/MSM ἲࢆ⏝࠸࡚ࠊ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࡢᅽຊ౫Ꮡᛶ➼ࢆ᳨ウࡋࡓࠋ
2 ࡘ┠ࡢㄢ㢟࡛࠶ࡿࠕPaCS-MD/MSM ࢆ⏝࠸ࡓ⺮ⓑ㉁」ྜయࡢ㏿ᗘᐃᩘホ౯࡛ࠖࡣࠊୖ㏙ࡋࡓ PaCS-MD/MSMࢆ⏝࠸࡚ࠊ㧗࠸㑅ᢥᛶࡸపẘᛶࢆ᭷ࡍࡿࡇ࡜࠿ࡽ๰⸆࡟࠾ࡅࡿ㨩ຊⓗ࡞ᶆⓗ࡛࠶ࡿ⺮ⓑ㉁」ྜయࡢ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮࠾ࡼࡧゎ㞳㏿ᗘᐃᩘࡢホ౯ࢆ⾜ࡗࡓࠋ⺮ⓑ㉁」ྜయ࡟࠾ࡅࡿ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࡸ⤖ྜࡢᣢ⥆᫬㛫࡛࠶ࡿ⁫␃᫬㛫ࡢホ౯ࡣࠊ」ྜయࡢ┦஫స⏝ࢆṇ☜࡟⌮ゎࡍࡿୖ࡛㔜せ࡜࡞ࡿࠋ⁫␃᫬㛫ࡣࠊゎ㞳㏿ᗘᐃᩘࢆ௓ࡋ࡚᥎ᐃࡍࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࡀࠊࡑࡢィ⟬࡟ࡣࠊ⤖ྜ/ゎ㞳࡟࠾ࡅࡿ඲࡚ࡢ㑄⛣⾜ิࢆᵓ⠏ࡍࡿᚲせࡀ⏕ࡌ⭾኱࡞ィ⟬ࣜࢯ࣮ࢫࡀᚲせ࡜࡞ࡿࠋᚑࡗ࡚ࠊຠ⋡ࡼࡃ⺮ⓑ㉁」ྜయࡢ⤖ྜぶ࿴ᛶ࠾ࡼࡧ⁫␃᫬㛫ࢆィ⟬ࡍࡿࡇ࡜ࡣᣮᡓⓗ࡞ㄢ㢟࡜࠸࠼ࡿࠋ⺮ⓑ㉁/⺮ⓑ㉁」ྜయࡢ୍౛࡜ࡋ࡚ࠊBarnase-Barstar 」ྜయࢆᑐ㇟࡜ࡍࡿࠋBarnase ⺮ⓑ㉁ࡣࣂࢡࢸࣜ࢔ࡢࣜ࣎᰾㓟ศゎ㓝⣲࡛࠶ࡾࠊࡑࢀ༢య࡛Ⓨ⌧ࡉࢀࡿ࡜⣽⬊Ṛࢆᘬࡁ㉳ࡇࡍࡀࠊ
Barstar ⺮ⓑ㉁ࡢᏑᅾୗ࡛ࡣ Barnase-Barstar 」ྜయࢆᙧᡂࡋࠊࡑࡢάᛶࡀ㜼ᐖࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋᮏ
ㄢ㢟࡛ࡣ PaCS-MD/MSM ィ⟬ࢆ Barnase-Barstar 」ྜయ࡟㐺⏝ࡋࠊࡑࡢ⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮࠾ࡼࡧ⁫␃᫬㛫ࡢホ౯ࢆ⾜ࡗ࡚࠸ࡿࠋ
3 ࡘ┠ࡢㄢ㢟࡛࠶ࡿࠕ㧗⃰ᗘ᮲௳ࢆ฼⏝ࡋࡓ⺮ⓑ㉁」ྜయࡢ⤖ྜࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࠖࡣࠊ㧗⃰ᗘ࡛」ྜ
యᵓᡂせ⣲㸦⺮ⓑ㉁ࠊ࣌ࣉࢳࢻࠊࣜ࢞ࣥࢻ㸧ࢆ㓄⨨ࡍࡿࡇ࡜࡟ࡼࡾ⮬Ⓨⓗ࡞」ྜయᙧᡂࢆಁ㐍ࡋࡓ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࠋ⺮ⓑ㉁」ྜయᵓ㐀ணࡢศ㔝࡟࠾࠸࡚ࠊ⁐፹ࡸ⺮ⓑ㉁ࡢᰂ㌾ᛶࡢṇ☜࡞ྲྀࡾᢅ࠸ࡸ⤒㦂ⓗ࡞ホ౯㛵ᩘࡢ⢭ᗘࡀࡋࡤࡋࡤၥ㢟࡜࡞ࡿࠋMD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡣࠊࡑࢀࡽࡢⅬ࡟࠾࠸࡚᭷ຠ࡛࠶ࡿ࡜
⪃࠼ࠊᡃࠎࡣࣜ࢞ࣥࢻࢆ㧗⃰ᗘ࡛⺮ⓑ㉁࿘㎶࡟㓄⨨ࡍࡿࡇ࡜࡟ࡼࡾ⮬Ⓨⓗ࡞⤖ྜࢆಁ㐍ࡋࠊ」ྜయᵓ㐀ࢆᚓࡿᡭἲ࡛࠶ࡿ㧗⃰ᗘࣜ࢞ࣥࢻ⤖ྜἲ㸦Concentrated Ligand Docking; ColDock㸧ࢆ㛤Ⓨࡋࡓ㸦JPCB 2018㸧ࠋColDockἲࢆ⏝࠸ࡓ⺮ⓑ㉁̿࣌ࣉࢳࢻ」ྜయࠊ⺮ⓑ㉁̿⺮ⓑ㉁」ྜయࡢゎᯒࢆ㐍ࡵ࡚࠸ࡿࠋ
ᮏᖺᗘࡣࠊ኱ࡁ࡞ᡂᯝࡀᚓࡽࢀࡓࠕPaCS-MD/MSM ࢆ⏝࠸ࡓ⺮ⓑ㉁」ྜయࡢ㏿ᗘᐃᩘホ౯ࠖ࡟㛵ࡍࡿ⤖ᯝࢆ୰ᚰ࡟ሗ࿌ࡍࡿࠋ

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2◊✲᪉ἲࠊィ⟬᪉ἲ
᭱ึ࡟ PaCS-MD ࢆ⏝࠸࡚ࠊBarnase-Barstar 」ྜయࡢゎ㞳ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ㸦ᅗ 1㸧ࠋPaCS-MD 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」ྜయ
ࡢ⤖ྜ࣭ゎ㞳ࢆຠ⋡ⓗ࡟ࢧࣥࣉࣜࣥࢢ࡛ࡁࡿࠋࢧ࢖ࢡࣝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ᫬㛫ࢆ 100 ps ࡜ࡋ࡚ࠊ100 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 3 nm ࡟࡞ࡿࡲ࡛⧞ࡾ㏉ࡋࡓࠋMD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡣ GROMACS 5.1.2
ࢆ⏝࠸ࠊຊሙࡣ AMBER ff14SBࠊỈࣔࢹࣝࡣ SPC/Eb ࣔࢹࣝࢆ౑⏝ࡋࡓࠋḟ࡟ PaCS-MD ࡟ࡼࡗ࡚ᚓࡽࢀࡓゎ㞳㐣⛬ࡢࢺࣛࢪ࢙ࢡࢺࣜࢆ࣐ࣝࢥࣇ≧ែࣔࢹࣝ㸦MSM㸧࡟ࡼࡾゎᯒࡋࡓࠋ⤖ྜ࣭ゎ㞳≧ែ㛫ࡢᖹᆒຊ࣏ࢸࣥࢩࣕࣝࡢᕪ࡟ࠊᶆ‽≧ែ࡜ࡢ⃰ᗘᕪ࡟㛵ࡍࡿ⿵ṇࢆຍ࠼ࠊᶆ‽⤖ྜ࢚ࢿࣝࢠ࣮ࢆồࡵࡓࠋ⏺㠃㊥㞳࡟ࡘ࠸࡚ࡢ MSM ࡟ࡣ MSM Builder ࢆ౑⏝ࡋࡓࠋᅗ 1 PaCS-MD ࢆ⏝࠸ࡓ Barnase-Barstar 」ྜయࡢゎ㞳౛

3◊✲ᡂᯝ
PaCS-MD ࢆ⏝࠸࡚ Barnase-Barstar 」ྜయࡢゎ㞳ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆィ 25 ᅇᐇ⾜ࡋࡓࠋࡑࢀࡒࢀࡢヨ⾜࡟࠾࠸࡚ࠊ⏺㠃ṧᇶࡢ᭱ᑠཎᏊ㛫㊥㞳ࡀ 3 nm ࡟࡞ࡿࡲ࡛ィ⟬ࡋ࡚࠸ࡿࡓࡵࠊᅗ 2 ࡟♧ࡋࡓࡼ࠺࡟ゎ㞳࡟ᚲせ࡞ࢧ࢖ࢡࣝᩘࡣヨ⾜ࡈ࡜࡟␗࡞ࡗ࡚࠾ࡾࠊ44㹼76 ࢧ࢖ࢡ࡛ࣝ࠶ࡿࠋ25 ᅇࡢヨ⾜࡛᭱኱࡛ࡶ 76 ࢧ࢖ࢡࣝࠊࡍ࡞
ࢃࡕ 760 ns㸦100 ps100 ୪ิ76 ࢧ࢖ࢡࣝ㸧࡛ゎ㞳ࡢほྜయࡢຠ⋡ⓗ࡞ゎ㞳ほ࡟ᡂຌࡋ࡚࠾ࡾࠊPaCS-MD ࡣ⺮ⓑ㉁̿⺮ⓑ㉁」࡟᭷ຠ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡿࠋ⯆࿡῝࠸ࡇ࡜࡟ࠊ25 ヨ⾜ࡢゎ㞳㐣⛬㸦ࣃࢫ࢙࢘࢖㸧ࢆゎᯒࡍࡿ࡜ᅗ 3㸦Barstar ⏺㠃ṧᇶ㔜ᚰࡢ㌶㊧㸧࡟♧ࡋࡓࡼ࠺࡟኱ࡁࡃ஧ࡘ࡟ศ㢮࡛ࡁࠊ࡝ࡕࡽࡢࣃࢫ࢙࢘࢖

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࡟࡞ࡿ࠿ࢆỴᐃ࡙ࡅࡿせᅉ࡟࢔ࣝࢠࢽࣥ㸦ARG59㸧ࡀ኱ࡁࡃᐤ୚ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࢀࡣ Barstar⏺㠃࡟࢔ࢫࣃࣛࢠࣥ㓟㸦ASP35㸧ࡸࢢࣝࢱ࣑ࣥ㓟㸦GLU76㸧ࡢ㈇㟁Ⲵࢆࡶࡘ࢔࣑ࣀ㓟ࡀᏑᅾࡍࡿࡇ࡜࡟ࡼࡿ
㟼㟁┦஫స⏝࡟ࡼࡿࡶࡢ࡛࠶ࡿࠋ

ᅗ 2. PaCS-MD ࡢྛࢧ࢖ࢡࣝ࡟࠾ࡅࡿ⏺㠃㊥㞳ᅗ 3ゎ㞳㐣⛬࡟࠾ࡅࡿ Barstar ࡢ⏺㠃ṧᇶ㔜ᚰࡢ㌶㊧ࡑࢀࡒࢀࡢヨ⾜ࡼࡾᚓࡽࢀࡓᖹᆒຊ࣏ࢸࣥࢩࣕࣝࢆᅗ 4 ࡟♧ࡋࡓࠋᶆ‽≧ែ࡜ࡢ⃰ᗘᕪ࡟㛵ࡍࡿ⿵ṇࢆຍ࠼ࡓᚋࡢᶆ‽⤖ྜ࢚ࢿࣝࢠ࣮ࡣࠊ඲ 25 ヨ⾜ࢆ⏝࠸ࡓሙྜࡣ-18.5 ± 0.8 kcal/molࠊᅗ୰㟷⥺࠾ࡼࡧ㉥⥺࡛♧ࡋࡓ
Major ࣃࢫ࢙࢘࢖࡜ Minor ࣃࢫ࢙࢘࢖ࡢࡳࢆ⏝࠸ࡓሙྜࡣࡑࢀࡒࢀࠊ-17.7 ± 0.8 kcal/molࠊ-24.3 ± 2.0 kcal/mol࡛࠶ࡗࡓࠋሗ࿌ࡉࢀ࡚࠸ࡿᐇ㦂್ࡣ-16.8 kcal/mol ࡛࠶ࡾࠊMajor ࣃࢫ࢙࢘࢖ࢆ⏝࠸ࡓሙྜ࡟ᐇ㦂್࡟㏆࠸್ࡀᚓࡽࢀࡓࠋMinor ࣃࢫ࢙࢘࢖࡟㛵ࡋ࡚ࡣ 3 ヨ⾜ࡢࡳ࡜⤫ィ㔞ࡀᑡ࡞ࡃࠊࡲࡓ࡝ࡕࡽࡢࣃࢫ࢙࢘࢖ࢆྲྀࡿ࠿
࡟㛵ࡋ࡚ࡣ PaCS-MD ࡟⏝࠸ࡿᵓ㐀㑅ᢥࡢᣦᶆ㸦ᮏሗ࿌࡛ࡣ⏺㠃㊥㞳㸧࡟౫Ꮡࡍࡿྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋୖ㏙
ࡋࡓ࢔ࣝࢠࢽࣥṧᇶࡢᙺ๭ࢆྵࡵࠊ௒ᚋࡼࡾヲ⣽࡞ゎᯒࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ
௨ୖࡢࡼ࠺࡟ࠊPaCS-MD ࡣ⺮ⓑ㉁̿⺮ⓑ㉁」ྜయࡢゎ㞳㐣⛬ࢆຠ⋡ࡼࡃゎᯒࡍࡿୖ࡛㠀ᖖ࡟᭷ຠ࡞᪉ἲ࡛
࠶ࡾࠊMSM ࢆ⏝࠸ࡿࡇ࡜࡛ṇ☜࡞⤖ྜ⮬⏤࢚ࢿࣝࢠ࣮ࢆホ౯ࡍࡿࡇ࡜࡟ࡶᡂຌࡋ࡚࠸ࡿࠋ௒ᚋࡣ㏿ᗘᐃᩘ➼ࡢホ౯ࢆ㐍ࡵࡿ࡜క࡟ࠊୖ㏙ࡋࡓᵓ㐀㑅ᢥ᫬ࡢᣦᶆࡢ᳨ウ࡞࡝᭦࡞ࡿᡭἲࡢᨵၿࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ

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Interface distance (nm)
ᅗ 4 ྛヨ⾜ࡼࡾᚓࡽࢀࡓᖹᆒຊ࣏ࢸࣥࢩࣕࣝࡢ⏺㠃㊥㞳౫Ꮡ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃx(‫ )ۻ‬D.P. Tran and A Kitao, Kinetic selection and relaxation of the Intrinsically Disordered Region of a Protein
upon Binding. J. Chem. Theory Comput., 16, 2835 (2020).

x(‫ )ۻ‬H. Hata, Y. Nishihara, M. Nishiyama, Y. Sowa, I. Kawagishi, A. Kitao, A. High pressure inhibits signaling
protein binding to the flagellar motor and bacterial chemotaxis through enhanced hydration. Sci. Rep., 10, 2351
(2020).

x(‫ )ۻ‬H. Hata, M. Nishiyama, A. Kitao, A. Molecular dynamics simulation of proteins under high pressure:
Structure, function and thermodynamics. Biochim. Biophys. Acta,1864, 7 (2020).

x(‫ )ۻ‬K. Terayama, A. Shinobu, K. Tsuda, K. Takemura, and A. Kitao, evERdock BAI: Machine-learning-guided
selection of protein-protein complex structure. J. Chem. Phys, 151, 215104 (2019).

x(‫ )ۻ‬Y. Yokochi et. al. Impact of key residues within chloroplast thioredoxin-f on recognition for reduction andoxidation of target proteins. J. Biol. Chem., 294, 17437 (2019).

x(‫ )ۻ‬K. Hanawa-Suetsugu et. al., Phagocytosis is mediated by two-dimensional assemblies of the F-BAR protein
GAS7. Nat. Commun., 10, 4763 (2019).

x

Y. Joti and A. Kitao, Cancellation between auto-and mutual correlation contributions of protein/water dynamics interahertz time-domain spectra. Biophys. Physicobiol., 16, 240 (2019).

x

K. Shin, D.P. Tran, K. Takemura, A. Kitao, K. Terayama, and K. Tsuda, Enhancing Biomolecular Sampling withReinforcement Learning: A Tree Search Molecular Dynamics Simulation Method. ACS Omega, 4, 13853 (2019).

x(‫ )ۻ‬K. Takemura and A. Kitao, More efficient screening of protein-protein complex model structures for reducing
the number of candidates. Biophys. Physicobiol., 16, 295 (2019).

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➨୍ཎ⌮ィ⟬ᡭἲ࡟ࡶ࡜࡙ࡃࢼࣀᵓ㐀࠾ࡼࡧཎᏊᒙ≀㉁ࡢᙧᡂ࡜
ᶵ⬟࡟㛵ࡍࡿ◊✲)LUVWSULQFLSOHVVWXG\IRUIRUPDWLRQDQGQRYHOIXQFWLRQVRIQDQRVWUXFWXUHVDQGOD\HUHGVWUXFWXUHV‫⛅ۑ‬ᒣ ஽ࠊ┦ྍᣅᕭࠊ℩⏣㞝ᇶࠊ㛗㇂ᕝ⿱ஓࠊ⡿ᮏ࿴ᘯࠊΎỈ⣖ᚿࠊỌ஭຾ஓ㸦୕㔜኱㝔ᕤ㸧   ◊✲┠ⓗࠊෆᐜᮏ◊✲ࣉࣟࢪ࢙ࢡࢺ࡛ࡣࠊࢼࣀ㛵㐃≀㉁࡟ὀ┠ࡋ࡚ᐦᗘỗᩘ⌮ㄽ࡟ᇶ࡙ࡃ඲࢚ࢿࣝࢠ࣮㟁Ꮚ≧ែィ⟬࡟ࡼࡾᵓ㐀Ᏻᐃᛶ࠾ࡼࡧ㟁Ꮚ≧ែࢆゎ᫂ࡋࠊࢼࣀᵓ㐀ᙧᡂᶵᵓࡢゎ᫂࠾ࡼࡧ᪂つ≀ᛶ᥈⣴ࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ ᖺᗘࡣࠊ❅໬≀༙ᑟయ *D1 ࠾ࡼࡧ $O1 ࡟࠾ࡅࡿ࢚ࣆࢱ࢟ࢩ࢚ࣕࣝࣆࢱ࢟ࢩࣕࣝᡂ㛗᫬ࡢẼ┦࠿ࡽࡢཎᏊ࠾ࡼࡧศᏊࡢ⾲㠃࡬ࡢ྾╔࠾ࡼࡧ⬺㞳㐣⛬ࠊࡇࢀࡽཎᏊ࠾ࡼࡧศᏊࡢ⾲㠃࡛ࡢ ࣐࢖ࢢ࣮ࣞࢩࣙࣥ➼ࡢ ᣲືࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊཎᏊᒙ≀㉁ࡢᵓ㐀࡜㟁Ꮚ≧ែ࡟㛵ࡍࡿ◊✲࡜ࡋ࡚ࠊࡇࢀࡲ࡛࡟ᑐ㇟࡜ࡋ࡚
ࡁࡓ ,9 ᪘⣔࡟࠾ࡅࡿ ࢢࣛࣇ࢓࢖ࢺ≧ ཎᏊᒙ≀㉁ࡢᙧᡂྍ⬟ᛶ࡟ຍ࠼࡚ࠊ໬ྜ༙ᑟయ࡟࠾ࡅࡿཎᏊᒙ≀㉁ࡢ
ᙧᡂྍ⬟ᛶࡢ᳨ウࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊ༙ᑟయࢼࣀᵓ㐀ᙧᡂ࡟㛵ࡍࡿ◊✲࡜ࡋ࡚ ,Q$V*D$V ⣔㔞Ꮚࢻࢵࢺᙧᡂ
࠾ࡼࡧ 6L& ⷧ⭷ࡢ㓟໬㐣⛬࡟㛵ࡍࡿ᳨ウࡶ⾜ࡗࡓࠋ ◊✲᪉ἲ࠾ࡼࡧィ⟬᪉ἲィ⟬ࡣࠊᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃ඲࢚ࢿࣝࢠ࣮㟁Ꮚ≧ែィ⟬࡟ࡼࡗ࡚ᐇ⾜ࡋࡓࠋཎᏊ᰾࡜ෆẆ㟁Ꮚࡣᨃ࣏ࢸࣥࢩࣕࣝࢆ⏝࠸࡚ᶍࡋࠊ౯㟁Ꮚࡢ┦஫స⏝࡟ᑐࡋ࡚ࡣ୍⯡໬໙㓄㏆ఝ **$3%( ࠶ࡿ࠸ࡣࣁ࢖ࣈࣜࢵࢻ
ᐦᗘỗ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⟬ࡣࠊሯ⏣ᤩᩍᤵ ᮾ໭኱Ꮫ ࠾ࡼࡧᒣෆ῟෸ᩍᤵ ៞ᛂ኱Ꮫ ࡽࢆ୰ᚰ࡜ࡍࡿ࣓ࣥࣂ࣮࡛సᡂࡉࢀࡓ 7RN\RAb-initio3URJUDP3DFNDJH 7$33 ࡟ࠊᮏィ⟬⏝࡟ᨵⰋࢆ᪋ࡋࡓࣉࣟࢢ
࣒ࣛ࡟ࡼࡗ࡚ᐇ⾜ࡋࡓࠋࡲࡓ➨୍ཎ⌮ィ⟬ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪ࡜ࡋ࡚ 4XDQWXP (VSUHVVR ࢆ㐺ᐅ฼⏝ࡋࡓࠋࡇࢀࡽࡢ㟁Ꮚ≧ែィ⟬࡟ຍ࠼ࠊ)/$3: ἲ࡟ࡼࡿ඲㟁Ꮚィ⟬ࠊ⤒㦂ⓗཎᏊ㛫࣏ࢸࣥࢩࣕࣝࢆ⏝࠸ࡓࣔࣥࢸ࢝ࣝ
ࣟィ⟬࠾ࡼࡧศᏊືຊᏛィ⟬ࡶᐇ⾜ࡋࡓࠋ ◊✲ᡂᯝ
 ࢼࣀᵓ㐀࢚ࣆࢱ࢟ࢩࣕࣝ⤖ᬗᡂ㛗᫬ࡢ⣲㐣⛬࡟㛵ࡍࡿ◊✲ࢼࣀᮦᩱᙧᡂ࡟㛵ࡍࡿ◊✲࡜ࡋ࡚ࠊ*D1 ࠾ࡼࡧ $O1 ➼ࡢ❅໬≀༙ᑟయࡢ⤖ᬗᡂ㛗ᶵᵓࢆゎ᫂ࡍࡿࡓࡵ࡟࢚
ࣆࢱ࢟ࢩࣕࣝᡂ㛗᫬ࡢẼ┦࠿ࡽࡢཎᏊ࠾ࡼࡧศᏊࡢ⾲㠃࡬ࡢ྾╔࠾ࡼࡧ⬺㞳㐣⛬ࠊࡉࡽ࡟ࡇࢀࡽཎᏊ࠾ࡼࡧ
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ኚ໬ࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋࡲࡓࠊࡇࢀࡽࢫࢸࢵࣉࡢᙳ㡪࡟ࡼࡾᡂ㛗ᵝᘧࡶ኱ࡁࡃኚ໬ࡍࡿࡇ࡜ࢆぢฟࡋࠊࡇࢀࡽࡢィ⟬⤖ᯝࡣᐇ㦂⤖ᯝ࡜ࡶࢥࣥࢩࢫࢸࣥࢺ࡛࠶ࡿࡇ࡜ࡶ᳨ドࡋࡓࠋࡉࡽ࡟ ,Q$V*D$V ⣔㔞Ꮚࢻࢵࢺᙧᡂ
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࡟࠾ࡅࡿཎᏊᒙ≀㉁ࡢᙧᡂྍ⬟ᛶ࡟㛵ࡍࡿ᳨ウࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣࠊ ✀㢮ࡢ ,9,9 ᪘ 6L& ࠊ,,,9 ᪘໬ྜ≀ $O3$O$V$O6E*D3*D$V*D6E,Q3,Q$V,Q6E ࠾ࡼࡧ ,,9, ᪘໬ྜ≀ =Q6=Q6H=Q7H&G6&G6H&G7H ࡟
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ࢡࣛࢫࢱ࣮࢖࢜ࣥࡢᗄఱᵓ㐀ࠊ཯ᛂᛶ࠾ࡼࡧ⾪✺᩿㠃✚ࡢィ⟬Calculations of geometrical structures, reactivities and collision crosssections of cluster ions‫ۑ‬኱ୗ ៞ḟ㑻ࠊᓊᮏ ┤ᶞࠊ୰㔝 ඖၿࠊỌ⏣ ฼᫂ࠊࣛࢸ࢕ࣇ ࢔ࣈࢻࢗࣝࠊ୰ᓥ ♸ྖࠊఀ⸨ ᝆྣࠊ⏣஭୰ ๰ኴࠊᇼ⏣ ຊࠊᐑ㷂 ⯗ࠊ㛛ཱྀ ┿அࠊ⸽ ᬸࠊ᭹㒊 ᆂ࿃㸦ᮾ໭኱㝔⌮㸧1◊✲┠ⓗࠊෆᐜ
ᩘಶ࠿ࡽᩘⓒಶ⛬ᗘࡢཎᏊ࣭ศᏊࡀ㞟ྜࡋࡓࢡࣛࢫࢱ࣮࢖࡛࢜ࣥࡣࠊᅛయ⤖ᬗ≧ែࡢᛶ㉁ࡀᾘኻࡍࡿ࡜࡜

ࡶ࡟ண᝿ࢆ㉸࠼ࡓ≀ᛶࡸᵓ㐀ࡀฟ⌧ࡋࠊࡑࢀࡽࡀᵓᡂཎᏊᩘ㸦ࢧ࢖ࢬ㸧࡟ᑐࡋ࡚ᩄឤ࡟ኚ໬ࡍࡿࠋࡉࡽ࡟ࢧ
࢖ࢬࡀྠࡌࢡࣛࢫࢱ࣮࢖࢜ࣥ࡟ࡣࠊ」ᩘࡢᵓ㐀␗ᛶయࡀྵࡲࢀ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿࠋᮏ◊✲࡛ࡣࠊ㉁㔞ศᯒ࡜࢖࢜ࣥ⛣ືᗘศᯒࢆ⤌ࡳྜࢃࡏࡓ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒࢆ⏝࠸࡚ࠊࢡࣛࢫࢱ࣮࢖࢜ࣥࡢࢧ࢖ࢬ࡜␗ᛶయࡢ
୧᪉ࢆ㑅ูࡋࠊྛ␗ᛶయࡢᵓ㐀≉ᐃࡸ཯ᛂᛶࡢほࢆ⾜࠺ࠋྛ␗ᛶయࡢᗄఱᵓ㐀࡜㟁Ꮚᵓ㐀ࠊ཯ᛂᛶࢆ᫂ࡽ

࠿࡟ࡍࡿࡇ࡜ࡀᮏ◊✲ࡢ┠ⓗ࡛࠶ࡿࠋ2◊✲᪉ἲࠊィ⟬᪉ἲᐦᗘỗ㛵ᩘἲ㸦DFT㸧ࢆ⏝࠸ࡓᵓ㐀᭱㐺໬ィ⟬࡟ࡼࡾ㔠ᒓ㓟໬≀ࢡࣛࢫࢱ࣮࢖࢜ࣥࡢᏳᐃᵓ㐀ࢆồࡵࠊࡑࡢᵓ㐀ࢆࡶࡘ࢖࢜ࣥ࡜࣒࣊ࣜ࢘࡜ࡢ⾪✺᩿㠃✚ࢆィ⟬ࡋࠊᐇࡢ⾪✺᩿㠃✚࡜ẚ㍑ࡋࡓࠋᵓ㐀᭱㐺໬ィ⟬࡟ࡣ Gaussian 09 ࠶ࡿ࠸ࡣ Gaussian 16 ࢆ⏝࠸ࡓࠋ⾪✺᩿㠃✚ࡢィ⟬࡟ࡣ Jarrold ࡽࡀ㛤Ⓨࡋࡓ MOBCAL ࣉࣟࢢ࣒ࣛࡢࢺࣛࢪ࢙ࢡࢺࣜἲࠊࡲࡓࡣᢞᙳ㏆ఝἲࢆ᥇⏝ࡋࡓࠋ

3 ◊✲ᡂᯝ
㓟໬࢖ࢵࢺ࣒ࣜ࢘ࡣࢭ࣑ࣛࢵࢡᮦᩱ࡞࡝࡜
ࡋ࡚฼⏝ࡉࢀࡿࠋ࢖ࢵࢺ࣒ࣜ࢘㓟໬≀ࢡࣛࢫ
ࢱ࣮ࡣ㉁㔞ศᯒࡸ DFT ィ⟬࡟ࡼࡗ࡚◊✲ࡉࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣ࢖࢜ࣥ⛣ືᗘ㉁㔞ศᯒἲ࡟ࡼࡾ YnOm+ (n = 1–11)ࡢ⾪✺᩿㠃✚ࢆᐃࡋࠊ㔞Ꮚ໬Ꮫィ⟬࡛ᚓࡽࢀࡓᏳᐃᵓ㐀࡟ᑐࡋ࡚⟬ฟࡋࡓ⾪✺᩿㠃✚ࡢ⌮ㄽ್࡜ࡢẚ㍑࡟ࡼࡾࠊࢡࣛࢫࢱ࣮ࡢᵓ㐀ࢆᖐᒓࡋࡓࠋYnOm+ࡢᏳᐃ⤌ᡂࡣ Y ཎᏊᩘ(n)ࡀഅᩘࡢ࡜ࡁ(Y2O3)x+ (n = 2x)ࠊወᩘࡢ࡜ࡁ YO(Y2O3)x+ (n = 2x+1)࡛࠶ࡗࡓࠋ࠸
ࡎࢀࡢࢡࣛࢫࢱ࣮ࡶ 3 ḟඖᆺࡢ❧యᵓ㐀࡟ᖐᒓࡉࢀࡓ(ᅗ 1)ࠋ≉࡟ᅗ 1 ࡟♧ࡍࡼ࠺࡟ࠊn ≥ 6࡛ࡣࢧ࢖ࢬࡢቑຍ࡟కࡗ࡚ඵ㠃యᆺ Y6O8 ࣘ)LJ$UULYDOWLPHGLVWULEXWLRQVDQGDVVLJQHGVWUXFWXUHVRI
<n2m n ± ࢽࢵࢺࢆᇶ࡟ࡋ࡚ᡂ㛗ࡍࡿᵓ㐀ࡀ♧၀ࡉࢀࡓࠋࡇࢀࡣ௨๓ࡢ⌮ㄽィ⟬ࡢሗ࿌ 1)࡜ࡶᑐᛂࡋ࡚࠸ࡿࠋ
1) A. B. Rahane et al., J. Phys. Chem. A 2013, 117, 5542.

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‫ۻ‬୰ᓥ♸ྖ, ዟὠ㈼୍, ఀ⸨ᝆྣ, ୰㔝ඖၿ, ኱ୗ៞ḟ㑻, ⨾㰺ὠᩥ඾ࠊ➨ 8 ᅇ࢖࢜ࣥ⛣ືᗘ◊✲఍‫ۻ‬ᐑ㷂⯗, 㛗㇂ᕝⓡᖹ, ⏣஭୰๰ኴ, ▮㒊ㅬኴ, ኱ୗ៞ḟ㑻, ⨾㰺ὠᩥ඾ࠊ➨ 8 ᅇ࢖࢜ࣥ⛣ືᗘ◊✲఍‫ۻ‬Ọ⏣฼᫂ࠊ➨ 8 ᅇ࢖࢜ࣥ⛣ືᗘ◊✲఍㸦ᣍᚅㅮ₇㸧‫ۻ‬୰ᓥ♸ྖ, ዟὠ㈼୍, ఀ⸨ᝆྣ, ୰㔝ඖၿ, ኱ୗ៞ḟ㑻, ⨾㰺ὠᩥ඾ࠊ➨ 67 ᅇ㉁㔞ศᯒ⥲ྜウㄽ఍‫ۻ‬ᐑ㷂⯗, ⏣஭୰๰ኴ, ኱ୗ៞ḟ㑻, ⨾㰺ὠᩥ඾ࠊ➨ 67 ᅇ㉁㔞ศᯒ⥲ྜウㄽ఍‫ۻ‬ఀ⸨ᝆྣ㸪୰ᓥ♸ྖ㸪ዟὠ㈼୍㸪୰㔝ඖၿ㸪኱ୗ៞ḟ㑻㸪⨾㰺ὠᩥ඾ࠊ➨ 35 ᅇ໬Ꮫ཯ᛂウㄽ఍‫ۻ‬୰㔝ඖၿ㸪▼ᮧඃ኱㸪ᇼ⏣ຊ㸪⺬ཱྀ኱᥹㸪Ọ⏣฼᫂㸪⨾㰺ὠᩥ඾ࠊ➨ 35 ᅇ໬Ꮫ཯ᛂウㄽ఍‫ۻ‬㛛ཱྀ┿அ㸪ఀ⸨ுభ㸪ᒣᮏᏹ᫭㸪ᡞྡṇⱥ㸪ሯᮏᜨ୕㸪኱ୗ៞ḟ㑻㸪⨾㰺ὠᩥ඾ࠊ➨ 76 ᅇ⸨ཎࢭ࣑ࢼ࣮
‫ۻ‬Ọ⏣฼᫂ࠊ➨ 76 ᅇ⸨ཎࢭ࣑ࢼ࣮
‫⨾ۻ‬㰺ὠᩥ඾ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍㸦ᣍᚅㅮ₇㸧‫ۻ‬ᐑ㷂⯗㸪⏣஭୰๰ኴ㸪኱ୗ៞ḟ㑻㸪⨾㰺ὠᩥ඾ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍‫ۻ‬୰ᓥ♸ྖ㸪ఀ⸨ᝆྣ㸪ዟὠ㈼୍㸪୰㔝ඖၿ㸪⨾㰺ὠᩥ඾ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍‫ۻ‬ᇼ⏣ຊ㸪Ọ⏣฼᫂㸪୰㔝ඖၿ㸪⨾㰺ὠᩥ඾ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍‫ۻ‬M. A. Latif㸪T. Nagata㸪M. Nakano㸪F. Misaizuࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍‫ۻ‬Ọ⏣฼᫂㸪୰㔝ඖၿ㸪⨾㰺ὠᩥ඾ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍‫ۻ‬ᑠ‖⍞ኸ㸪ఀ⸨ᝆྣ㸪୰ᓥ♸ྖ㸪ዟὠ㈼୍㸪୰㔝ඖၿ㸪⨾㰺ὠᩥ඾ࠊᖹᡂ 31 ᖺᗘ໬Ꮫ⣔Ꮫ༠఍ᮾ໭኱఍
‫➎୕ۻ‬ὒኴᮁ㸪୰㔝ඖၿ㸪⨾㰺ὠᩥ඾ࠊᖹᡂ 31 ᖺᗘ໬Ꮫ⣔Ꮫ༠఍ᮾ໭኱఍
‫ۻ‬బ⸨Ⰻு㸪⏣஭୰๰ኴ㸪ᐑᓮ⯗㸪኱ୗ៞ḟ㑻㸪⨾㰺ὠᩥ඾ࠊᖹᡂ 31 ᖺᗘ໬Ꮫ⣔Ꮫ༠఍ᮾ໭኱఍
‫ۻ‬ᑠ‖⍞ኸ㸪ఀ⸨ᝆྣ㸪୰ᓥ♸ྖ㸪୰㔝ඖၿ㸪Evan J. Bieske㸪⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍‫ۻ‬ఀ⸨ுభ㸦௚ 7 ྡ㸧ࠊ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍‫ۻ‬ᇼ⏣ຊ㸪Ọ⏣฼᫂㸪୰㔝ඖၿ㸪኱ୗ៞ḟ㑻㸪⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍‫ۻ‬Ọ⏣฼᫂㸪୰㔝ඖၿ㸪⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍‫➎୕ۻ‬ὒኴᮁ㸪ᇼ⏣ຊ㸪Ọ⏣฼᫂㸪୰㔝ඖၿ㸪⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍‫⏣ۻ‬஭୰๰ኴ㸪Ặᖹᬛ❶㸪ᮧᯇᝅ㸪஭ཱྀెဢ㸪኱ୗ៞ḟ㑻㸪⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍‫ۻ‬ᐑ㷂⯗㸪᭹㒊ᆂ࿃㸪኱ୗ៞ḟ㑻㸪⨾㰺ὠᩥ඾ࠊ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍5 ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬R. Tomihara, K. Koyasu, T. Nagata, J. W. J. Wu, M. Nakano, K. Ohshimo, F. Misaizu, T. Tsukuda, J. Phys. Chem.
C, 123, 15301 (2019).
‫ۻ‬Y. Nakashima, M. Nakano, K. Okutsu, Y. Ito, F. Misaizu, J. Phys.: Conf. Ser. accepted.
‫ۻ‬F. Misaizu, M. A. Latif, J. W. J. Wu, R. Moriyama, M. Nakano, K. Koyasu, K. Ohshimo, AIP Conf. Proc., 2186,
030017 (2019).
‫ۻ‬T. Nagata, J. W. J. Wu, M. Nakano, K. Ohshimo, F. Misaizu, J. Phys. Chem. C, 123, 16641 (2019).
‫ۻ‬M. A. Latif, J. W. J. Wu, T. Nagata, M. Nakano, K. Ohshimo, F. Misaizu, J. Phys. Chem. C, 123, 17580 (2019).
‫ۻ‬Y. Ito, Y. Nakashima, K. Okutsu, M. Nakano, K. Ohshimo, F. Misaizu, Chem. Phys. Lett., 739, 137022 (2020).
‫ۻ‬M. Nakano, D. Hebiguchi, S. Azuma, R. Moriyama, K. Ohshimo, F. Misaizu, J. Phys. Chem. A, 124, 101 (2020).
‫ۻ‬K. Ohshimo, S. Miyazaki, K. Hattori, F. Misaizu, Phys. Chem. Chem. Phys., 22, 8164 (2020).

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ࢱࣥࣃࢡ㉁ࡢᵓ㐀࡜ᶵ⬟Ⓨ⌧ࡢ㛵㐃ᛶ
Relation between functional expression and structure in protein‫ࢺ࢜ࣝࢗࢺࣥࣜۑ‬ṇ⨾ࠊᑠᒣ࡞ࡘࡳ(ி㒔ᗓ❧኱Ꮫ኱Ꮫ㝔⏕࿨⎔ቃ⛉Ꮫ◊✲⛉)1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ㄢ㢟࡛ࡣࢱࣥࣃࢡ㉁ࡢᵓ㐀ኚ໬ࠊከ㔞య໬ࡸ⾲㠃ಟ㣭࡟ࡼࡿᶵ⬟ࡢኚ໬࡟ࡘ࠸࡚ศᏊ࡛ࣞ࣋ࣝ᫂ࡽ

࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚௨ୗࡢࢸ࣮࣐࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ
1-1. CD44 ࡬ࡢࣄ࢔ࣝࣟࣥ㓟⤖ྜ࡜ᵓ㐀ᖹ⾮ᦂࡽࡂ࡟㛵ࡍࡿ◊✲
CD44 ࡣ⣽⬊᥋╔ࡸ⣽⬊㐟㉮࡟㛵୚ࡍࡿࢱࣥࣃࢡ㉁࡛ࣄ࢔ࣝࣟࣥ㓟 (HA)࡜⾑ὶୗ୍࡛㐣ⓗ࡞᥋╔࡜⬺╔
ࢆ⧞ࡾ㏉ࡍࡇ࡜࡛⣽⬊ࡢ࣮ࣟࣜࣥࢢࢆᢸ࠺ࠋCD44 ࣄ࢔ࣝࣟࣥ㓟⤖ྜࢻ࣓࢖ࣥ㸦HABD㸧ࡣᐃᖖ≧ែ࡛ࡣ Cᮎ➃ࡀ୍ᐃࡢᵓ㐀ࢆࡶࡘ Ordered (O) ᵓ㐀࡛ࠊ⾑ὶ࡞࡝ࡢᦤື࡟ࡼࡗ࡚ C ᮎ➃ࡢ୍㒊㸦disorder 㡿ᇦ㸧ࡀ࡯࡝
ࡅࡓ Partially Disordered (PD) ᵓ㐀࡟㑄⛣ࡍࡿᶵᵓࡀᐇ㦂⤖ᯝ࠿ࡽᥦ᱌ࡉࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣ disorder 㡿ᇦࡢᵓ㐀ኚ໬࡟ࡼࡿ࢔ࣟࢫࢸࣜࢵࢡ࡞ HA ⤖ྜぶ࿴ᛶࡢኚ໬࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵࡓࠋ
1-2. CAP ࡬ࡢ cAMP ⤖ྜࢲ࢖ࢼ࣑ࢡࢫ࠾ࡼࡧ࢔ࣟࢫࢸࣜࢵࢡᵓ㐀ኚ໬኱⭠⳦࡞࡝ࡢ⣽⳦࡟Ꮡᅾࡍࡿ CAP(Catabolite Activator Protein)ࡣ㑇ఏᏊ㌿෗ㄪ⠇ᅉᏊ࡜ࡋ࡚ാ࠸࡚࠸ࡿࠋ
CAP ࡣ࣍ࣔ஧㔞య࡛ྛࢧࣈࣘࢽࢵࢺࡣ cAMP ⤖ྜࢧ࢖ࢺ࡛࠶ࡿ cAMP Binding Domain (CBD)࡜ DNA ⤖ྜࢧ࢖ࢺ࡛࠶ࡿ DNA Binding Domain (DBD)࠿ࡽᵓᡂࡉࢀࡿࠋcAMP ࡢ CBD ࡬ࡢ⤖ྜ࡟ࡼࡗ࡚ DBD 㡿ᇦࡀᵓ㐀ኚ໬ࡋ࡚άᛶ≧ែ࡟࡞ࡿᶵᵓࡀᥦ᱌ࡉࢀ࡚࠸ࡿࠋ㸰㔞య໬࡟ࡼࡿ༢㔞యࢧࣈࣘࢽࢵࢺࡢᵓ㐀ኚ໬ࡀ DBD ࡢࣇࣞ࢟ࢩࣅࣜࢸ࢕࣮࡟୚࠼ࡿᙳ㡪ࠊDBD ࡢࢲ࢖ࢼ࣑ࢡࢫࡢヲ⣽࡟㛵ࡋ࡚◊✲ࢆ㐍ࡵࡓࠋ
1-3. Cu,Zn-SOD ࡟࠾ࡅࡿᵓ㐀࡜ᶵ⬟ࡢ㛵㐃ᛶ㸱✀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 SOD1 ࡟࠾ࡅࡿ༢㔞య໬ࠊ⏺㠃࡟࠾ࡅࡿⅬኚ␗ࡸ Zn Ḟᦆ࡟ࡼࡿᵓ㐀ኚ໬࡜㓝⣲άᛶ࡟୚࠼ࡿᙳ㡪࡟ࡘ࠸࡚◊✲ࢆ㐍ࡵࡓࠋ
1-4. kallikrein ࣇ࢓࣑࣮ࣜࡢ⢾ಟ㣭࡜ᶵ⬟ࡢ㛵㐃ᛶࢱࣥࣃࢡ㉁ศゎ㓝⣲ KLK ࣇ࢓࣑࣮ࣜ࡟ᒓࡋ࡚࠸ࡿࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ࡛࠶ࡿࢽ࣮ࣗࣟࣉࢩࣥࡣࠊ኱⬻㎶⦕⣔࡛Ⓨ⌧ࡉࢀࠊࡇࡢࢱࣥࣃࢡ㉁ࡢᶵ⬟㞀ᐖࡣ⢭⚄⑌ᝈࡢཎᅉ࡜࡞ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࢽ
࣮ࣗࣟࣉࢩࣥࡢศᏊㄆ㆑ᶵᵓࡢヲ⣽ࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋ」ྜయ⤖ᬗᵓ㐀ࢆึᮇᵓ㐀࡜ࡋ࡚ࠊ㸴✀ࡢ࣌ࣉࢳࢻࢆ⏝࠸ࡓ」ྜయࢆసᡂࡋ KLK8 ࡢศᏊㄆ㆑ᶵᵓࡢヲ⣽ࠊάᛶ㒊఩࿘㎶ࡢ࣮ࣝࣉࡢᙺ๭ࠊ⢾ಟ㣭ࢧ࢖ࢺࢆྵ᭷ࡍࡿ Loop D ࡟╔┠ࡋ࡚◊✲ࢆ㐍ࡵࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲMD ィ⟬࡟ࡣ Gromacs2018 ࢆ⏝࠸ࠊQM ィ⟬࡟ࡣ Gaussian16 ࢆ⏝࠸ࡓࠋSOD1 ࡟ᑐࡋ࡚ࡣ MD ィ⟬ࢆ⏝࠸࡚඲యᵓ㐀࡟ᑐࡍࡿ⪃ᐹࢆ⾜࠸ࠊࡉࡽ࡟㔠ᒓࢆྵࡴάᛶ㒊఩࠾ࡼࡧࡑࡢ࿘㎶ࡢᵓ㐀ࢆษࡾฟࡋࡓ QM/MMࣔࢹࣝࢆ⏝࠸άᛶ㒊఩࿘㎶ࡢᒁᡤⓗ࡞ᵓ㐀ࡸ㟁Ꮚ≧ែኚ໬࡟ࡘ࠸࡚ㄪ࡭ࡓࠋ

3

◊✲ᡂᯝ

3-1. CD44 ࡬ࡢࣄ࢔ࣝࣟࣥ㓟⤖ྜ࡜ᵓ㐀ᖹ⾮ᦂࡽࡂ࡟㛵ࡍࡿ◊✲- 243 -

ィ⟬⤖ᯝࡼࡾᐃᖖ≧ែ࡛ࡣ O ᵓ㐀ࡀࡼࡾᏳᐃ࡛࠶ࡿࡀࠊHA ⤖ྜ࡟ࡼࡗ࡚ PD ᵓ㐀࡬ࡢ㑄⛣ࡀᐜ᫆࡟㉳ࡇࡿࡇ࡜ࡀศ࠿ࡗࡓࠋHA ⤖ྜ≧ែࡢ O ࠿ࡽ PD ᵓ㐀࡬ࡢ㑄⛣ࡀ㉳ࡇࡿ࡜ࡉࡽ࡟Ᏻᐃ࡞ HA ⤖ྜᵓ㐀࡬࡜ኚ໬ࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓࠊdisorder 㡿ᇦ࡟࠾ࡅࡿኚ␗ࡀ HA ⤖ྜ⁁ࡢయ✚࡟ᙳ㡪ࢆཬࡰࡋࠊࡑࡢ⤖ᯝ HA ぶ
࿴ᛶࡀኚ໬ࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

3-2. CAP ࡬ࡢ cAMP ⤖ྜࢲ࢖ࢼ࣑ࢡࢫ࠾ࡼࡧ࢔ࣟࢫࢸࣜࢵࢡᵓ㐀ኚ໬
CAP ༢㔞య࡛ࡣ CBD ࡜ DBD ࡢ⏺㠃ࡀࠕ㛢ࡌࡓࠖ≧ែ࡟࡞ࡿࡇ࡜࡟ࡼࡗ࡚Ᏻᐃ໬ࡋࠊ㸰㔞య໬࡟ࡼࡗ࡚
CBD ࡜ DBD ࡣࠕ㛤࠸ࡓ≧ែࠖ࡜࡞ࡾࠊDBD ࡢࣇࣞ࢟ࢩࣅࣜࢸ࢕࣮ࡀቑຍࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋcAMP ⤖ྜ࡟ࡼࡿ DBD 㡿ᇦࡢ࢔ࣟࢫࢸࣜࢵࢡᵓ㐀ኚ໬࡜࠸࠺ᚑ᮶ࡢᶵᵓ࡛ࡣ࡞ࡃࠊࢱࣥࣃࢡ㉁ࡢ 2 㔞య໬ࡸ cAMP ⤖ྜ࡟ࡼࡿ DBD ࡢࣇࣞ࢟ࢩࣅࣜࢸ࢕࣮ኚ໬ࡀ CAP ࡢᶵ⬟࡟㔜せ࡛࠶ࡿ࡜௬ᐃࡋ࡚◊✲ࢆࡉࡽ࡟㐍ࡵ࡚࠸ࡿࠋ

3-3. Cu,Zn-SOD ࡟࠾ࡅࡿᵓ㐀࡜ᶵ⬟ࡢ㛵㐃ᛶ
SOD㸯ࡣ࣍ࣔ㸰㔞య࡛࠶ࡿࡀࠊ༢㔞య໬࡟ࡼࡗ࡚㸰㔞య⏺㠃࡜ࡣ㐲㝸ࡢ཯ᛂάᛶ㒊఩ࡢᵓ㐀ኚ໬ࢆㄏᘬ
ࡍࡿࠋࡲࡓࠊfALS ࡬ࡢ㛵㐃ᛶࡀሗ࿌ࡉࢀ࡚࠸ࡿⅬኚ␗యࡢ࠺ࡕ㸰㔞య⏺㠃࡟ኚ␗ࡀᏑᅾࡍࡿ㸲✀ࡢኚ␗య࡛
༢㔞య໬ࡸ཯ᛂάᛶ㒊఩࡟ᵓ㐀ኚ໬ࡀぢࡽࢀࡓࠋ୍᪉ࠊZn Ḟᦆࡣ SOD1 ඲యࠊCu ࿘㎶ࡢᒁᡤⓗ࡞ᵓ㐀࡟ኚ໬ࢆ୚࠼࡞࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ2 㔞య⏺㠃ኚ␗యࡸ Zn Ḟᦆ≧ែ࡟࠾ࡅࡿ Cu 㑏ඖ≧ែ࡛ࡣ Cu ࡢỈ࿴⎔ቃ࡟ኚ໬ࡀぢࡽࢀࡓࡇ࡜࠿ࡽࠊ㓝⣲άᛶ࡟ᑐࡍࡿᙳ㡪࡟ࡘ࠸࡚ᘬࡁ⥆ࡁ◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ

3-4. kallikrein ࣇ࢓࣑࣮ࣜࡢ⢾ಟ㣭࡜ᶵ⬟ࡢ㛵㐃ᛶࢭࣜࣥࣉࣟࢸ࢔࣮ࢮ࡛ࡣᇶ㉁ࡢษ᩿㒊఩ࡢ๓᪉࡟࠶ࡿ࢔࣑ࣀ㓟ṧᇶࡢ㔜せᛶ࡟ࡘ࠸࡚㆟ㄽࡉࢀࡿࡇ࡜ࡀ
ከ࠸ࡀࠊ௒ᅇࡢ◊✲࡟ࡼࡗ࡚ᇶ㉁࣌ࣉࢳࢻࡢษ᩿㒊఩ࡢᚋ᪉࡟࠶ࡿ࢔࣑ࣀ㓟ṧᇶࡀ⤖ྜᏳᐃ໬࡟ᙳ㡪ࢆ୚࠼ࡿࡇ࡜ࠊゐ፹୕ṧᇶࡢ┦ᑐⓗ࡞఩⨨㛵ಀ࡟ᙳ㡪ࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡲࡓࠊLoop D ࡢ⢾໬࡟ࡼࡗ࡚࣌ࣉ
ࢳࢻ⤖ྜ⁁ࡢయ✚ኚ໬ࢆࡶࡓࡽࡍࡇ࡜ࡶ᫂ࡽ࠿࡟ࡋ࡚࠸ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬㖡㸪ள㖄ྵ᭷ SOD ࡢ 2 㔞య⏺㠃࡟࠾ࡅࡿⅬኚ␗࡟ࡼࡿάᛶ࡜ᵓ㐀ኚ໬ࠊ ࣜࣥࢺࢗࣝ࢜ࢺ㸪ᑠᒣ㸪ࣜࣥࢺࢗࣝ࢜ࢺ (2019: ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ ྡྂᒇ)‫ۻ‬Investigation on role of zinc atom and electrostatic loop by comparing human SOD1 with Zndeficient SOD ᑠᒣࠊࣜࣥࢺࢗࣝ࢜ࢺࠊࣜࣥࢺࢗࣝ࢜ࢺ(2019: ➨ 57 ᅇ⏕≀≀⌮Ꮫ఍ ᐑᓮ)‫ۻ‬Allosteric regulation of hyaluronan binding on CD44 by point mutation‫ࠊࢺ࢜ࣝࢗࢺࣥࣜۻ‬ᇼᒸࠊ㜿㒊ࠊᮏ㒓ࠊࣜࣥࢺࢗࣝ࢜ࢺ(2019: ➨ 57 ᅇ⏕≀≀⌮Ꮫ఍ ᐑᓮ)‫ۻ‬N ⤖ྜᆺ⢾㙐ಟ㣭࡟ࡼࡿࢽ࣮ࣗࣟࣉࢩࣥࡢ⤖ྜ㒊఩ࡢᵓ㐀ኚ໬ ࣜࣥࢺࢗࣝ࢜ࢺࠊࣜࣥࢺࢗࣝ࢜ࢺ(2019:᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ⛅Ꮨᖺ఍ ᗈᓥ)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬Molecular dynamics study into allosteric regulation by conformational change in hyaluronan binding on CD44, M.
Lintuluoto*,1, Y. Horioka1,et al ᢞ✏‽ഛ୰‫ۻ‬Insight into allosteric conformational change induced by point mutation at dimer interface of SOD1
through molecular dynamics study, M. Lintuluoto, N. Koyama and J. Lintuluoto, ᢞ✏‽ഛ୰

- 244 -

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0@6/(9('$*/0+(0:/0@(4( :<)40;;,+ B#/,94(3 463,*<3(9 46;065 *(5 (4730-@ 05;,9463,*<3(9 05;,9(*;065:C ' $*/0+(  &(;(5(), # 20;( 

0:/0@(4( :<)40;;,+ B%,9;0*(33@ 5;,.9(;,+ ,:0.5 6- "7/,90*(3 0*9696)6; <5*;065(30A,+ >0;/ 9.(50* (.5,;67/6;650* 08<0+9@:;(3C # 20;(  0@6/(9( " (2(.(40 # '(4(A(20 ! 0104( # (9<;( ' $*/0+(  0:/0@(4( ;6 ),
:<)40;;,+- 246 -

ศᏊᛶᑟ㟁࣭☢ᛶᮦᩱ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical study on molecular conducting and magnetic materials‫ۑ‬୰㔝 ⩏᫂ࠊ⚟ᓥ ኴ㝧ࠊ▼ᕝ Ꮫ㸦ி㒔኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉໬Ꮫᑓᨷࠊி㒔኱Ꮫ⎔ቃᏳ඲ಖ೺ᶵᵓ㸧1◊✲┠ⓗࠊෆᐜ
࣋ࣥࢰࢳ࢚ࣀ࣋ࣥࢰࢳ࢜ࣇ࢙ࣥ㸦BTBT㸧ࡣࠊ㧗᫆ືᗘࡢ FET ᮦᩱࡸࠊ㧗ฟຊᅉᏊࢆ♧ࡍ᭷ᶵ⇕㟁ᮦᩱ࡜ࡋ࡚ࡢᛂ⏝◊✲ࡶᒎ㛤ࡉࢀ࡚࠸ࡿ᭷ᮃ
࡞ᶵ⬟ᛶ㦵᱁࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ⮯⣲࣭ࣚ࢘⣲ཎᏊࢆᑟධࡋࡓ X2BTBT (XBTBT: X = H
Br2BTBT: X = Br
I2BTBT: X = I= Br, I)ࢆᨵⰋࡋࡓᡭἲ࡛ྜᡂࡋࠊ༢⤖ᬗ X ⥺ᵓ㐀ゎᯒࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ୧⪅ࡣ஫࠸࡟ྠᙧ࡛࠶ࡾࠊʌ ࢫࢱࢵࢡᆺࡢศᏊ㓄ิࢆ࡜ࡗ࡚࠸ࡓࠋศᏊ㛗㍈᪉ྥ࡟ࡣࠊࣁࣟࢤࣥཎᏊୖࡢṇ㟁Ⲵ࡜㈇㟁Ⲵࡢ㡿ᇦࡢ㛫࡟ศᏊ㛫▷㊥㞳᥋ゐࡀᏑᅾࡋࠊࣁࣟࢤࣥ⤖ྜࢆ௓ࡋࡓࢪࢢࢨࢢ㙐㸦ᅗ 1㸧ࡀᙧᡂࡉࢀ࡚࠸
ࡓࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ㞄᥋ศᏊ㛫࡟࠾ࡅࡿ HOMO 㛫ࡢ㔜࡞ࡾ✚ศࠊ࠾ࡼࡧࠊศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࡢゎᯒࢆ⾜ࡗࡓࠋ2

ᅗ 1. I2BTBT ࡟࠾ࡅࡿࣁࣟࢤࣥ⤖ྜ

◊✲᪉ἲࠊィ⟬᪉ἲ㞄᥋ศᏊ㛫࡟࠾ࡅࡿ HOMO 㛫ࡢ㔜࡞ࡾ✚ศࡣࠊᣑᙇࣄࣗࢵࢣࣝἲ࡟ࡼ

ࡾồࡵࡓࠋศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࡣࠊGaussian 09 ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࠊ

t

s d
t

d

s

ᇶᗏ㛵ᩘ࡜ࡋ࡚ࠊ⮯⣲࡜ࣚ࢘⣲࡟ࡣ Aug-cc-pVTZ-PPࠊࡑࡢ௚ࡢඖ⣲࡟ࡣ
spAug-cc-pVTZ ࢆ⤌ࡳྜࢃࡏࠊMP2ࠊM06-2XࠊCAM-B3LYP-D3(BJ)ἲ࡟ࡼ
ࡾồࡵࡓࠋᇶᗏ㛵ᩘ㔜࡞ࡾㄗᕪࡣࠊCounterpoise ἲ࡟ࡼࡾ⿵ṇࡋࡓࠋ

3

ᅗ 2. I2BTBT ࡢศᏊ㓄ิ࡜㔜࡞ࡾ✚ศ㻔300 K㻕: s = 6.6, t =0.4, d = 0.0 㻔×10−3㻕◊✲ᡂᯝ㞄᥋ศᏊ㛫࡟࠾ࡅࡿ HOMO 㛫ࡢ㔜࡞ࡾ✚ศࡣࠊ✚ᒙ᪉ྥ࡟ᙉࡃ 1 ḟඖⓗ࡛࠶ࡾ㸦ᅗ 2㸧ࠊ࣮࣊ࣜࣥ࣎ࣥᆺ
ࡢศᏊ㓄ิ࡛࠶ࡿ↓⨨᥮ BTBT ࡀ 2 ḟඖⓗ࡛࠶ࡿࡇ࡜࡜኱ࡁࡃ␗࡞ࡗ࡚࠸ࡓࠋ୍᪉ࠊMP2ࠊM06-2Xࠊ
CAM-B3LYP-D3(BJ)ἲ࡟ࡼࡾồࡵࡓศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࡶࠊィ⟬ᡭἲ࡟ࡼࡽࡎ 1 ḟඖⓗ࡛࠶ࡗࡓࠋ౛
࠼ࡤ MP2 ἲ࡛ồࡵࡓศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࡣࠊI2BTBT ࡟ࡘ࠸࡚ࠊs íࠊt íࠊd íNFDOmolí࡛ࠊࣁࣟࢤࣥ⤖ྜ࡟㛵ࡍࡿศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࡣࠊíNFDOPROíࠊBr2BTBT ࡟ࡘ࠸࡚ࠊs íࠊtíࠊd íNFDOPROí ࡛ࠊࣁࣟࢤࣥ⤖ྜ࡟㛵ࡍࡿศᏊ㛫┦஫స⏝࢚ࢿࣝࢠ࣮ࡣࠊíNFDOPROí ࡛࠶ࡗ
ࡓࠋI2BTBT ࡜ Br2BTBT ࡢ ʌʌ ┦஫స⏝ࡣྠ⛬ᗘ࡛࠶ࡿࡀࠊࣁࣟࢤࣥ⤖ྜࡣ Br2BTBT ࡢ᪉ࡀᑠࡉࡃ࡞ࡗ࡚࠾
ࡾࠊ୍⯡ⓗ࡞ࣁࣟࢤࣥ⤖ྜࡢᙉࡉࡢഴྥ㸦Br < I㸧ࢆ཯ᫎࡋ࡚࠸ࡿࠋࣁࣟࢤࣥ໬ BTBT ࡛ࡣࠊศᴟࡋࡸࡍ࠸ࣁ
ࣟࢤࣥཎᏊࡢᑟධ࡟ࡼࡗ࡚ࠊศᩓຊ࡟ࡼࡿᏳᐃ໬ࡢᐤ୚ࡀ኱ࡁ࡞ ʌʌ ┦஫స⏝ࡀ CH/ʌ ┦஫స⏝ࡼࡾࡶඃໃ࡟
࡞ࡾࠊʌ ࢫࢱࢵࢡᆺࡢศᏊ㓄ิࢆ࡜ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ㟁ゎ⤖ᬗᡂ㛗ἲ࡟ࡼࡾ㝧ࣛࢪ࢝ࣝሷ(I2BTBT)PF6
ࢆస〇ࡋࠊX ⥺ᵓ㐀ゎᯒࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊI2BTBT ศᏊࡢࣚ࢘⣲ཎᏊ࡜ PF6 ࡢࣇࢵ⣲ཎᏊ࡜ࡢ㛫࡟ࣁࣟࢤࣥ⤖ྜࡀᏑᅾࡋࠊI2BTBT ศᏊࡣศᏊ㛗㍈᪉ྥ࡟ศᏊࡢ༙ศࡔࡅࢫࣜࢵࣉࡋࡓ ʌ ࢫࢱࢵࢡᆺ✚ᒙᵓ㐀ࢆ࡜ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋI2BTBT࡟࠾࠸࡚ࡶࠊʌʌ ┦஫స⏝ࡀඃໃ࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠾ࡾࠊ௒ᚋࠊ௚ࡢ⣔࡟

- 247 -

ࡘ࠸࡚ࡶศᏊ㛫┦஫స⏝ࡢゎᯒࢆ⾜࠺ணᐃ࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

[1] ࠐ⏣୰㸪ᐑ⏣㸪⚟ᮏ㸪୰㔝㸪▮ᣢ㸪⭜ཎ㸪ᜠ⏣㸪➨ 31 ᅇ㓄఩໬ྜ≀ࡢග໬Ꮫウㄽ఍㸪P-4‫[ۻ‬2] ࠐ⚟ᓥ㸪୰㔝㸪▼ᕝ㸪▮ᣢ㸪➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ 2019 ྡྂᒇ㸪1P041‫[ۻ‬3] ࠐ୰㔝㸪ᮧୖ㸪⚟ᓥ㸪▼ᕝ㸪▮ᣢ㸪➨ 18 ᅇி㒔኱Ꮫ≀ᛶ⛉Ꮫࢭࣥࢱ࣮ㅮ₇఍࣭◊✲஺ὶ఍㸪P31[4] ࠐ▼ᕝ㸪୰㔝㸪኱ሯ㸪▮ᣢ㸪➨ 18 ᅇி㒔኱Ꮫ≀ᛶ⛉Ꮫࢭࣥࢱ࣮ㅮ₇఍࣭◊✲஺ὶ఍㸪P32‫[ۻ‬5] ࠐ⚟ᓥ㸪୰㔝㸪▼ᕝ㸪▮ᣢ㸪➨ 18 ᅇி㒔኱Ꮫ≀ᛶ⛉Ꮫࢭࣥࢱ࣮ㅮ₇఍࣭◊✲஺ὶ఍㸪P33‫[ۻ‬6] ࠐᒸᮏ㸪ᶫᮏ㸪୰㔝㸪▼ᕝ㸪▮ᣢ㸪➨ 18 ᅇி㒔኱Ꮫ≀ᛶ⛉Ꮫࢭࣥࢱ࣮ㅮ₇఍࣭◊✲஺ὶ఍㸪P34‫[ۻ‬7] ࠐ⚟Ọ㸪㧘ᶫ㸪▼⏣㸪ᑠ㔝⏣㸪୰㔝㸪▼ᕝ㸪▮ᣢ㸪➨ 18 ᅇி㒔኱Ꮫ≀ᛶ⛉Ꮫࢭࣥࢱ࣮ㅮ₇఍࣭◊✲஺ὶ఍㸪P35‫[ۻ‬8] ࠐᑠᕝ㸪ΎỈ㸪▼⏣㸪୰㔝㸪▼ᕝ㸪▮ᣢ㸪➨ 18 ᅇி㒔኱Ꮫ≀ᛶ⛉Ꮫࢭࣥࢱ࣮ㅮ₇఍࣭◊✲஺ὶ఍㸪P36

5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

[1] H. Yoshino, A. Hasegawa, N. Kuroda, M. Ishikawa, R. Tanaka, M. Kozaki, Y. Nakano, A. Otsuka, H. Yamochi, J.
Phys. Soc. Jpn., 88(10), 104708/1-7 (2019)- 248 -

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8DmM)Œé'ńŔć8Ɓ*573Ʈ£'ć¨iuX;ą!cPs]uG(ƢÂ8%9# 8ƧêHarmonic dUsKjoLennard-Jones(LJ)dUsKjo;Ŏ

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#cPs]uG;ţºĵď573ºĵďǇÈ$ŸĘ$*Ŋ9' ŭƽŔ(áÅ©ć¨iuXÕÅV[@ (õ:''%Ė6('ŊÚ)Ŵ%)Ýù* /(Ė6('#/DmM*^mLnU?(Ķû©AZoFu)ĺíÕû)(5 #¨Ŕûơ'&Î©8%- 249 -

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iVo°,^mLnU?(ÕÕÅ8%

$Pk < 0.01 ;áÅ©iuX%ÙŽ8%áÅ©iuX)ć¨ňýÜí^mLnU?(56 g(ω)ω4 (õ %;ƌ
3.2 ǋÔDmM)ć¨ňýÜí ĝŞŬ$*ǋÔƹƺ; L %#L = 3, 50 (! #DmMňý(8ć¨ňýÜíƑģ;' 
V[@ŋƞ%)ıƥ;' )ŸĥǋÔû)DmMňý$ć¨ňýÜí g(ω)/ω2 )ºĵďÕû
6V[@ŋƞ573Ʈ£']uG!/7cPs]uG069/)cPs]uGV[@pao(57MIuo$8%Ė6%' 6(V[@pao)ƋŶ$ðûď(!

#)Ƒģ6ūðûď(ı.#¢ēðûďƯ(ß8)*¢ēðûď$Vo$

2cPs]uG;čƲ

%;ƌ)%*cPs]uG%eGq'ðû(ŗƾ%;ţ#7 LJ DmMŴ%)Ÿĥ%śŘ'

%

4

8%

8ūðûďt¢ē

8

!/7ĝŞŬ)Ÿĥ*ę3­ŵ'DmMi

8 LJ DmMŴ$þ7Ů!ŋƞǋÔDmMŴ$3þ7Ů!%%;ţ¾83)$8

œƉÚŻ/*Ù Ðƻ žÑ, ĲƵ ƄÒ, Ʒ Ƹ,ĢĤ ë, “DmMòþĸ)ć¨ňý%)^mLnU?Õû”,ĕĝņŋ×ů 75 ÁêİÐ, 2020 ê 3 Ě
 Ʒ Ƹ, Ĳŏ Æ, ŝ ƂĮ, ĢĤ ë, “Ô¨¥×KfkpuKls*ķ¥×;&/$ƕƨ$8)ǐ:ķ¥×«ó)ÔƞŔ'ċ”, ©×è×ů 85 Áê, 2020 ê 3 Ě- 250 - Ĩ § , äæ Æv, Ĩ đ, Ʒ Ƹ,ĢĤ ë, “Ɗǃ'ÔŴ)ƀŐAZoFu;Ň÷"8²ùîĭ)ĉŷǏJfTQu%ęàĊÙĴ)Ɔ¶”, ů 33 ÁÔKfkpuKlsƔƞ, 2019 ê 12 Ě ±ƴ Ŗ, ĲƵ ƄÒ, Ĩ ǌ, Ʒ Ƹ, ĢĤ ë, “ǋÔDmM)cPs]uGǏŲƎ©Ô¨¥×KfkpuKls(58ƢļƑĖ”, ů 33 ÁÔKfkpuKlsƔƞ, 2019 ê 12 Ě ƅƦ Ōš, Ʒ Ƹ, ĢĤ ë, “Ĳ{( #Ïď)ÔƾyïƢ98ĲŶŸ¶şē)ƗĀĴ”, ů 33 ÁÔKfkpuKlsƔƞ, 2019 ê 12 Ě Ðƻ žÑ, ĲƵ ƄÒ, Ʒ Ƹ,ĢĤ ë, “DmMòþĸ)ć¨ňýÜí%)^mLnU?Õû”, ů 33 ÁÔKfkpuKlsƔƞ, 2019 ê 12 Ě Ʒ Ƹ, “R@YfGM;ư(ƕƨ8ƀŐAZoFu%²ùîĭ)ĉŷ, ů 9 ÁO^WeQuŞŬ
, 2019 ê 11 ĚăôƟĿ Ðƻ žÑ, ĲƵ ƄÒ, Ʒ Ƹ, ĢĤ ë, “DmMòþĸ)ć¨ňýÜí%^mLnU?Õû,
ů 9 ÁO^WeQuŞŬ, 2019 ê 11 Ě Ĩ § , äæ Æv, Ĩ đ, Ʒ Ƹ,ĢĤ ë, “Ĳ{$)@BsƑǄ)R@YfGM;Ň÷"8²ùîĭ)ĉŷǏJfTQu%ęàĊÙĴ)Ɔ¶”, ů 9 ÁO^WeQuŞŬ, 2019 ê 11 Ě ƅƦ Ōš, Ʒ Ƹ, ĢĤ ë, “ĲŶŸ¶ZTWruG(É"IuLtLjs`iVo)Ƽœ%)Ʈ®Ĳ(8ĄĎR@YfGM-)ùŎ”, ů 9 ÁO^WeQuŞŬ, 2019 ê 11 Ě ±ƴ Ŗ, ĲƵ ƄÒ, Ĩ ǌ, Ʒ Ƹ, ĢĤ ë, “ǋÔDmM(8cPs]uG(ŀ<ėƭûǏV[@ŋƞ%ðû¥×(É"ć¨ňýÜí)MIunsH”, ů 9 ÁO^WeQuŞŬ, 2019ê 11 Ě
 Kang Kim, “Bridging the gap between molecular dynamics and hydrodynamics in nanoscale Brownian
motions”, 5th International Conference on Molecular Simulation, 2019 ê 11 ĚăôƟĿ Naoya Tomoshige, Hideyuki Mizuno, Kang Kim, and Nobuyuki Matubayasi, “Boson peak, elasticity, and glasstransition temperature in polymer glasses: Effects of rigidity of chain bendings”, 5th International Conference
on Molecular Simulation, 2019 ê 11 Ě
 Takuma Kikutsuji, Kang Kim, and Nobuyuki Matubayasi, “Diffusion dynamics of supercooled water modeledwith the cage-jump motion and hydrogen-bond rearrangement”, 5th International Conference on Molecular
Simulation, 2019 ê 11 Ě Yusuke. Mori, Kei-ichi. Okazaki, Toshifumi Mori, Kang Kim, and Nobuyuki Matubayasi, “Exploring reaction
coordinates for alanine dipeptide isomerization: Committor and likelihood maximization”, 5th International
Conference on Molecular Simulation, 2019 ê 11 Ě ±ƴ Ŗ, ĲƵ ƄÒ, Ʒ Ƹ,ĢĤ ë, “ŲƎ©Ô¨¥×KfkpuKls;Ŏ

ǋÔDmM)ć¨ňýÜíƑģ”, ů 68 ÁǋÔƔƞ, 2019 ê 9 Ě
 Ĩ § , äæ Æv, Ĩ đ, Ʒ Ƹ,ĢĤ ë, “Lb`SX)Œû©;Ň÷"8²ùîĭǏJf

TQu%ęàĊÙĴ(58Ƒĳ”, ů 13 ÁÔť×Ɣƞ, 2019 ê 9 Ě
 ƅƦ Ōš, Ʒ Ƹ, ĢĤ ë, “Ĳ{( #Ïď)ÔƾyïƢ98ĲŶŸ¶şē)ƗĀĴ”, ů 13 ÁÔť×Ɣƞ, 2019 ê 9 Ě
 Ĩ §, äæ Æv, Ĩ đ, Ʒ Ƹ,ĢĤ ë, “ľÓ{)@BsƑǄ;Ň÷"8²ùîĭ)ĉ

ŷ”, ĕĝņŋ× 2019 êŤÖÐ, 2019 ê 9 Ě Ðƻ žÑ, ĲƵ ƄÒ, Ʒ Ƹ, ĢĤ ë, “KnCDmM)iVoÕû)Ô¨¥×Ƒģ”, ĕĝņ- 251 -

ŋ× 2019 êŤÖÐ, 2019 ê 9 Ě
 Ʒ Ƹ, Ĳŏ Æ, ŝ ƂĮ, ĢĤ ë, “Jq@XĎŴ(8Ô¨¥×6ķ¥×-)įĹǏľÓ¼ƀŐAZoFu%qsHQ@gUuo”, ĕĝņŋ× 2019 êŤÖÐ, 2019 ê 9 Ě
 Kang Kim, “Cage-jump model connecting hydrogen-bond rearrangements and molecular diffusion insupercooled water”, International school: “Water and water systems’’ 2nd Course: “Polymers and Soft
Materials: Glasses, Gels and Networks’’, 2019 ê 7 Ě ăôƟĿ Takuma Kikutsuji, Kang Kim, and Nobuyuki Matubayasi, “Diffusion dynamics of supercooled water modeledwith the cage-jump motion and hydrogen-bond rearrangement”, Roma Tre Congress on Water under Extreme
Conditions, 2019 ê 6 Ě
 Kang Kim and Takeshi Kawasaki, “Classification of mobile- and immobile-molecule timescales for the
Stokes–Einstein and Stokes–Einstein–Debye relations in supercooled water”, Roma Tre Congress on Water
under Extreme Conditions, 2019 ê 6 ĚĢĤ ë, “Ô¨¥×KfkpuKls(58KnCDmM)ć¨ Ðƻ žÑ, ĲƵ ƄÒ, Ʒ Ƹ,ňýÜíƑģ”, ů 22 Áŋƞ©×Ɣƞ, 2019 ê 5 Ě
 Ĩ § , äæ Æv, Ʒ Ƹ,ĢĤ ë, “Lb`SX)Œû©Ʈũ;ƕƨ8²ùîĭ)ĉŷǏJf

TQu%ęàĊÙĴ)Ɔ¶”, ů 22 Áŋƞ©×Ɣƞ, 2019 ê 5 Ě5ŅÚŻ/*Ù Yusuke Mori, Kei-ichi Okazaki, Toshifumi Mori, Kang Kim, and Nobuyuki Matubayasi, “Learning reaction
coordinates via cross-entropy minimization: Application to alanine dipeptide”, arXiv:2003.13186 (2020).
 Naoya Tomoshige, Hideyuki Mizuno, Tatsuya Mori, Kang Kim, and Nobuyuki Matubayasi, “Boson peak,elasticity, and glass transition temperature in polymer glasses: Effects of the rigidity of chain bending”,
Scientific Reports 9, 19514 (2019).
 Takuma Kikutsuji, Kang Kim, and Nobuyuki Matubayasi, “Consistency of geometrical definitions of hydrogenbonds based on the two-dimensional potential of mean force with respect to the time correlation in liquid waterover a wide range of temperatures”, Journal of Molecular Liquids 294, 111603 (2019).
 Takeshi Kawasaki and Kang Kim, “Spurious violation of the Stokes–Eeinstein–Debye relation in supercooled
water”, Scientific Reports 9, 8118 (2019).
 Takuma Kikutsuji, Kang Kim, and Nobuyuki Matubayasi, “Diffusion dynamics of supercooled water modeledwith the cage-jump motion and hydrogen-bond rearrangement”, Journal of Chemical Physics 150, 204502(2019).
 Keisuke Mizuta, Yoshiki Ishii, Kang Kim, and Nobuyuki Matubayasi, “Bridging the gap between molecular
dynamics and hydrodynamics in nanoscale Brownian motions”, Soft Matter 15, 4380-4390 (2019).

- 252 -

᭷ᶵศᏊࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿศᏊ㛫┦஫స⏝ࡢᙺ๭
Role of intermolecular interaction in chemical reactions of organic
molecules‫ۑ‬ᒣᓮ ⚈ᖹࠊఀ⸨ ᖾᫍ㸦ᘯ๓኱㝔⌮ᕤ㸧

1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ㄢ㢟ࡢ┠ⓗࡣࠊ᭷ᶵศᏊࡢከ㔞య࡟࠾ࡅࡿග໬Ꮫ཯ᛂࡢᶵᵓࢆศᏊ࡛ࣞ࣋ࣝ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡛࠶

ࡿࠋ≉࡟ࠊ༢㔞య࡜ࡢ཯ᛂᶵᵓࡢ㐪࠸ࢆ᳨ウࡍࡿࡇ࡜࡟ࡼࡾࠊศᏊ㛫┦஫స⏝ࡀ໬Ꮫ཯ᛂ࡟ᑐࡋ࡚ᯝࡓࡍᙺ
๭ࡢゎ᫂ࢆ┠ᣦࡍࠋࡇࡢ┠ⓗࡢࡓࡵࠊ⸛Ⰽࢆ࿊ࡍࡿⰍ⣲࢖ࣥࢹ࢕ࢦࠊ୪ࡧ࡟ࡑࡢ␗ᛶయ࡛࠶ࡿ࢚ࣆࣥࢻࣜࢪ࢜ࣥ࠾ࡼࡧ࢖ࣥࢹ
࢕ࣝࣅࣥ࡟࠾ࡅࡿ≉ᚩⓗ࡞⺯ග≉ᛶࡢ㉳※ࢆゎ᫂ࡍࡿࡓࡵࡢ⌮ㄽⓗ◊✲ࢆ㐙⾜ࡋࡓࠋࡲࡎࠊ࠸ࡎࢀࡢศᏊࡶྍど㡿ᇦࡢගࢆ྾཰ࡍࡿࡀࠊ࢚ࣆࣥࢻࣜࢪ࢜ࣥࡢࡳࡀᙉ࠸⺯ගࢆ♧ࡋ[1]ࠊ࢖ࣥࢹ࢕ࢦ࡜࢖ࣥࢹ࢕ࣝࣅࣥࡢ⺯ගࡣ㠀ᖖ࡟ᙅ࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࡢ㐪࠸ࡀ⏕ࡌࡿཎᅉࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊ୕✀㢮ࡢศᏊࡢ࠸ࡎࢀ࡟
࠾࠸࡚ࡶ㉳ࡇࡾ࠺ࡿග໬Ꮫ㐣⛬ࡢ୍ࡘ࡛࠶ࡿບ㉳≧ែศᏊෆࣉࣟࢺࣥ⛣ື཯ᛂ࡟ࡘ࠸࡚ࠊࡑࡢ࣏ࢸࣥࢩࣕࣝ
࢚ࢿࣝࢠ࣮᭤⥺ࢆィ⟬ࡍࡿ࡜࡜ࡶ࡟ࠊࣉࣟࢺࣥ⛣ືᚋࡢศᏊᵓ㐀࡟࠾ࡅࡿ෇㗹஺ᕪࡢ᥈⣴ࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊ
ᅛయ≧ែࡢ࢚ࣆࣥࢻࣜࢪ࡛࢜ࣥࡣࠊ⁐ᾮ୰࡟ẚ࡭࡚㠀ᖖ࡟Ἴ㛗ࡢ㛗࠸⺯ගࡀほࡉࢀࡿ[1]ࠋࡑࡇ࡛ࠊ࢚ࣆࣥ

ࢻࣜࢪ࢜ࣥ࡜࢖ࣥࢹ࢕ࢦࡑࢀࡒࢀࡢỈ⣲⤖ྜ஧㔞య࡟ࡘ࠸࡚ບ㉳≧ែศᏊ㛫ࣉࣟࢺࣥ⛣ື཯ᛂࡢ࣏ࢸࣥࢩࣕ
࢚ࣝࢿࣝࢠ࣮ィ⟬ࢆ⾜࠸ࠊศᏊ㛫Ỉ⣲⤖ྜࡢᙧᡂࡀ⺯ගἼ㛗࡟ཬࡰࡍᙳ㡪ࢆ᳨ウࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ࢖ࣥࢹ࢕ࢦ࣭࢚ࣆࣥࢻࣜࢪ࣭࢜ࣥ࢖ࣥࢹ࢕ࣝࣅࣥࡢ༢㔞య࡟࠾ࡅࡿศᏊෆࣉࣟࢺࣥ⛣ື཯ᛂࠊ୪ࡧ࡟࢖ࣥ

ࢹ࢕ࢦ࡜࢚ࣆࣥࢻࣜࢪ࢜ࣥࡢỈ⣲⤖ྜ஧㔞య࡟࠾ࡅࡿศᏊ㛫ࣉࣟࢺࣥ⛣ື཯ᛂࡢࡑࢀࡒࢀ࡟ࡘ࠸࡚ࠊTDDFTἲ㸦CAM-B3LYP ỗ㛵ᩘ㸧ࢆ⏝࠸ࡓບ㉳≧ែࡢᵓ㐀᭱㐺໬࡟ࡼࡾ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤⥺ࢆィ⟬ࡋࡓࠋࡉࡽ࡟ࠊ༢㔞య࡟ࡘ࠸࡚ࡣࠊᚓࡽࢀࡓ᭱㐺໬ᵓ㐀࡟࠾ࡅࡿ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮ࢆ MS-CASPT2 ἲ࡛෌ィ
⟬ࡋࠊTDDFT ἲ࡟ࡼࡿィ⟬⤖ᯝࡢጇᙜᛶࢆ☜ㄆࡋࡓࠋࡲࡓࠊ༢㔞య࡟ࡘ࠸࡚ࡣࠊ≧ែᖹᆒ CASSCF ἲࢆ⏝࠸ࡓ෇㗹஺ᕪࡢ᥈⣴ࡶᐇ⾜ࡋࡓࠋCASSCF ἲ࠾ࡼࡧ MS-CASPT2 ἲࡢ active ✵㛫ࡣ (2,2) ࡘࡲࡾ 2 㟁Ꮚ 2 ㌶㐨࡜ࡋࡓࠋ௨ୖࡢィ⟬࡟࠾࠸࡚ࠊᇶᗏ㛵ᩘ࡟ࡣ Sapporo-DZP-2012 ࢆ᥇⏝ࡋࡓࠋࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪ࡜ࡋ࡚ࠊTDDFT ἲ࡟ࡣ GAMESSࠊCASSCF ἲ࠾ࡼࡧ MS-CASPT2 ἲ࡟ࡣ Molpro ࢆ౑⏝ࡋࡓࠋ3◊✲ᡂᯝ༢㔞య࡟ࡘ࠸࡚ࠊ࢖ࣥࢹ࢕ࢦศᏊࡣ஧࠿ᡤࡢศᏊෆỈ⣲⤖ྜࢆᣢࡘࡀࠊࡇࡢ࠺ࡕ୍࠿ᡤࡢࡳ࡟࠾࠸࡚ບ㉳≧ែࣉࣟࢺࣥ⛣ືࡀ⏕ࡌࡿ཯ᛂ⤒㊰ࡀぢฟࡉࢀࡓࠋ࢚ࣆࣥࢻࣜࢪ࢜ࣥ࡜࢖ࣥࢹ࢕ࣝࣅ࡛ࣥࡶྠᵝ࡟ࠊບ㉳≧ែ࡟࠾ࡅࡿ༢ࣉࣟࢺࣥ⛣ືࡢ཯ᛂ⤒㊰ࡀᚓࡽࢀࡓࠋᅗ 1 ࡟ࠊࡑࢀࡒࢀࡢศᏊ࡟ࡘ࠸࡚ MS-CASPT2 ἲ࡛ィ⟬ࡋࡓศᏊෆࣉࣟࢺࣥ⛣ື཯ᛂࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤⥺ࢆ♧ࡍࠋS1 ≧ែ࡟ࡘ࠸࡚ࠊ࢚ࣆࣥࢻࣜࢪ࢜ࣥࡣ
0.36 eV ࡢ཯ᛂ㞀ቨࢆ♧ࡍࡢ࡟ᑐࡋࠊ࢖ࣥࢹ࢕ࢦ࡜࢖ࣥࢹ࢕ࣝࣅ࡛ࣥࡣ㞀ቨࡀ 0.1 eV ᮍ‶࡜࡞ࡗࡓࠋࡲࡓࠊ඲
࡚ࡢศᏊ࡟࠾࠸࡚ࠊࣉࣟࢺࣥ⛣ືᚋࡢ෇㗹஺ᕪᵓ㐀ࡀぢࡘ࠿ࡗࡓࠋ෇㗹஺ᕪࡢ࢚ࢿࣝࢠ࣮ࢆẚ㍑ࡍࡿ࡜ࠊࡸ
ࡣࡾ࢚ࣆࣥࢻࣜࢪ࢜ࣥ࡟࠾࠸࡚௚ࡢ஧ࡘࡼࡾࡶ㧗ࡃ࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ௨ୖࡢ⤖ᯝࡣࠊศᏊෆࣉࣟࢺࣥ⛣- 253 -

ᅗ 1. MS-CASPT2(2,2)/Sapporo-DZP-2012 ࡛ࣞ࣋ࣝィ⟬ࡋࡓࠊບ㉳≧ែศᏊෆࣉࣟࢺࣥ⛣ື཯ᛂࡢ࣏ࢸࣥ
ࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤⥺㸸(a) ࢖ࣥࢹ࢕ࢦࠊ(b) ࢚ࣆࣥࢻࣜࢪ࢜ࣥࠊ(c) ࢖ࣥࢹ࢕ࣝࣅࣥ

ື཯ᛂࠊ࠾ࡼࡧࡑࡢᚋࡢ↓㍽ᑕኻάࡢ࠸ࡎࢀ࡟ࡘ࠸࡚ࡶ࢚ࣆࣥࢻࣜࢪ࡛࢜ࣥ᭱ࡶ㉳ࡇࡾ࡟ࡃ࠸ࡇ࡜ࢆ♧၀ࡋ࡚࠾ࡾࠊ࢚ࣆࣥࢻࣜࢪ࢜ࣥࡢࡳ࡛ᙉ࠸⺯ගࡀほࡉࢀࡿ࡜࠸࠺ᐇ㦂⤖ᯝࢆㄝ࡛᫂ࡁࡿࡶࡢ࡟࡞ࡗ࡚࠸ࡿࠋ

୍᪉ࠊ஧㔞య࡟ࡘ࠸࡚ࡣࠊ࢖ࣥࢹ࢕ࢦ࣭࢚ࣆࣥࢻࣜࢪ࢜ࣥࡢࡑࢀࡒࢀ࡟࠾࠸࡚ࠊᒁᡤບ㉳≧ែ࡟࠾ࡅࡿ஧
㔜ࣉࣟࢺࣥ⛣ື࠾ࡼࡧ㟁Ⲵ⛣ື≧ែ࡟࠾ࡅࡿ༢ࣉࣟࢺࣥ⛣ືࡢ஧㏻ࡾࡢ཯ᛂ⤒㊰ࡀᚓࡽࢀࡓࠋࡇࡢ࠺ࡕ࢚ࣆ
ࣥࢻࣜࢪ࢜ࣥ࡟࠾ࡅࡿ஧㔜ࣉࣟࢺࣥ⛣ື࡟ࡘ࠸࡚ࠊ⛣ືᚋࡢᵓ㐀࡟࠾ࡅࡿⓎග࢚ࢿࣝࢠ࣮ࡀࠊᐇ㦂࡛ほࡉࢀࡿ㛗Ἴ㛗⺯ගࡢἼ㛗࡜ࡼ࠸୍⮴ࢆ♧ࡍࡇ࡜ࡀศ࠿ࡗࡓࠋࡋ࠿ࡋࠊࣉࣟࢺࣥ⛣ືࡢ཯ᛂ㞀ቨࡣ 1 eV ࢆ㉸࠼ࡿ㧗࠸್ࢆ♧ࡋ࡚࠸ࡿࡓࡵࠊࡇࡢ཯ᛂࡀ㛗Ἴ㛗⺯ගࡢཎᅉ࡛࠶ࡿ࡜ࡣ᩿ᐃ࡛ࡁ࡞࠸ࠋࡇࡢⅬ࡟ࡘ࠸࡚ࡣࠊ௒ᚋ
ࡢ◊✲࡟࠾࠸࡚ࠊ࿘㎶ศᏊ࡜ࡢ┦஫స⏝ࢆ⪃៖ࡋࡓィ⟬ࢆ⾜࠺➼ࡢࡉࡽ࡞ࡿ᳨ウࡀᚲせ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

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(1) A. D. Sonawane, A. Shimozuma, T. Udagawa, M. Ninomiya, M. Koketsu, Org. Biomol. Chem., in press. (2) A.
Kawafuchi, S. Kutsumizu, Y. Kawase, I. Tokiwa, T. Udagawa, Y. Miwa, Phys. Chem. Chem. Phys., 22, 10132-10141(2020). (3) Y. Ishida, H. Funahashi, M. Tachikawa, T. Udagawa, Chem. Lett., in press. (4) R. A. Iwaki, T. Udagawa,Chem. Phys. Lett., 745, 137271 (2020). (5) Y. Miwa, J. Kurachi, Y. Sugino, T. Udagawa, S. Kutsumizu, Soft Matter,
16, 3384-3394 (2020). (6) M. Baba, A. Kanaoka, A. Nishiyama, M. Misono, T. Ishimoto, T. Udagawa, Chin. J. Chem.
Phys., 33, 8-12 (2020). (7) N. Suematsu, M. Ninomiya, H. Sugiyama, T. Udagawa, K. Tanaka, M. Koketsu, Bioorg.
Med. Chem. Lett., 29, 2243-2247 (2019). (8) T. Matsuyama, K. Nakata, H. Hagiwara, T. Udagawa, Crystals, 9, 276(2019). (9) J. Fujimoto, S. Hayashi, H. Kainuma, K. Manseki, T. Udagawa, H. Miyaji, Chem. Asian J., 14, 2567-2572(2019). (10) N. Komura, K. Kato, T. Udagawa, S. Asano, H. Tanaka, A. Imamura, H. Ishida, M. Kiso, H. Ando,
Science, 364, 677-180 (2019). (11) Y. Miwa, K. Taira, J. Kurachi, T. Udagawa, S. Kutsumizu, Nat. Commun., 10,1828 (2019).

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ᩘಶ࠿ࡽᩘⓒಶࡢ㔠ᒓཎᏊ࡛ᵓᡂࡉࢀࡿ㔠ᒓࢡࣛࢫࢱ࣮ࡣ㸪ࣂࣝࢡࡢ㔠ᒓࡸࢼࣀ⢏Ꮚ࡟ࡣぢࡽࢀ࡞࠸, ≉␗ⓗ࡞ᵓ㐀ࡸ㞳ᩓⓗ࡞㟁Ꮚᵓ㐀ࢆࡶࡘࠋ㓄఩Ꮚಖㆤ㔠ᒓࢡࣛࢫࢱ࣮ࡣࡑࡢ౯㟁Ꮚࡀ㉸ཎᏊ㌶㐨 1S, 1P, …࡟཰
ᐜࡉࢀࡿࡇ࡜࠿ࡽ㸪໬Ꮫಟ㣭ࡉࢀࡓ㉸ཎᏊ࡜ࡳ࡞ࡍࡇ࡜ࡀ࡛ࡁࡿࠋᡃࠎࡣ㸪6 㟁Ꮚ⣔㉸ཎᏊ[PtAu24(SC2H4Ph)18]0(PtAu240)࡜ 1 ➼㔞ࡢ NaBH4 ࡜ࡢ཯ᛂ࡟ࡼࡾ, 㛤Ẇ 7 㟁Ꮚ⣔㉸ཎᏊ[PtAu24(SC2H4Ph)18]– (PtAu24–)ࡀ㑅ᢥⓗ࡟ᚓࡽࢀࡿࡇ࡜ࢆ, ༢⤖ᬗ X ⥺⤖ᬗᵓ㐀ゎᯒ 㸦SCXRD㸧, 1H ᰾☢Ẽඹ㬆㸦NMR㸧ศග, ࠾ࡼࡧ㟁Ꮚࢫࣆࣥඹ㬆ศග㸦ESR㸧࡟ࡼࡿホ౯࠿ࡽ᫂ࡽ࠿࡟ࡋࡓࠋู㏵༢㞳ࡋࡓ 2 㟁Ꮚ㑏ඖయ[PtAu24(SC2H4Ph)18]2– (PtAu242–)࡜ PtAu240
࡜ࡢ཯ᛂ࡟ࡼࡗ࡚ PtAu24–ࡀ⏕ᡂࡋࡓࡇ࡜࠿ࡽ㸪᭷ᶵ㓄఩Ꮚᒙ࡛ಖㆤࡉࢀࡓ㉸ཎᏊ㛫࡟࠾࠸࡚⮬Ⓨⓗ࡞㟁Ꮚ⛣ື࡟ࡼࡿ㟁Ⲵࡢᆒ୍໬ࡀ㉳ࡇࡿࡇ࡜ࢆぢฟࡋࡓࠋᮏ◊✲࡛ࡣ㸪ᐦᗘỗ㛵ᩘ㸦DFT㸧ィ⟬࡟ࡼࡾ, ୖグࡢ㟁Ⲵᆒ୍໬཯ᛂࡢ཯ᛂ⇕ࢆồࡵ࡚㸪཯ᛂࡀ⮬Ⓨⓗ࡟㐍⾜ࡍࡿࡇ࡜ࢆㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 09 ࣃࢵࢣ࣮ࢪࢆ⏝࠸㸪B3LYP/lanl2dz ࠾ࡼࡧ 6-31G(d)࡛ࣞ࣋ࣝ[PtAu24(SMe)18]n (n = 0, –1, –2)ࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋࡲࡓ㸪Turbomole 7.2.1 ࢆ⏝࠸㸪[PtAu24(SMe)18ÂPtAu24(SMe)18]2–ࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝ
SCXRD, 1H NMR, ESR ࡢ⤖ᯝ࠿ࡽ㸪PtAu240 ࡜ 1 ᙜ㔞ࡢ NaBH4 ࡢ཯ᛂ࡛ᚓࡽࢀࡓ⏕ᡂ≀ࡣ㛤Ẇ 7 㟁Ꮚ⣔㉸

ཎᏊ PtAu24–࡛࠶ࡾ, ࡑࡢ⏕ᡂᶵᵓࡣ NaBH4 ࡟ࡼࡾ 2 㟁Ꮚ㑏ඖࡉࢀࡓ PtAu242– ࡜⣔୰࡟ṧᏑࡍࡿᮍ㑏ඖ≧ែࡢ PtAu240 ࡜ࡢ㛫ࡢ⮬Ⓨⓗ㟁Ꮚ⛣ື཯ᛂ࡛࠶ࡿࡇ࡜ࢆぢฟࡋࡓࠋࡑࡇ࡛, ࡇࡢ㟁Ꮚ⛣ື཯ᛂࡢ཯ᛂ⇕ࢆ㸪㓄఩Ꮚࢆ⡆␎໬ࡋࡓࣔࢹࣝᵓ㐀[PtAu24(SMe)18]n (n = 0, –1, –2)ࢆ⏝࠸, [PtAu24(SMe)18]–ࡢ᩿⇕㟁Ꮚぶ࿴ຊ㸦AEA㸧࠿ࡽ[PtAu24(SMe)18]0 ࡢ AEA ࢆᕪࡋᘬࡃࡇ࡜࡛⌮ㄽⓗ࡟ぢ✚ࡶࡗࡓࠋࡑࡢ⤖ᯝ, ୖグ཯ᛂࡣⓎ⇕཯ᛂ࡛࠶ࡿࡇ࡜
ࡀศ࠿ࡗࡓࠋ

4Ⓨ⾲࣭ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫ۻ‬R. Tomihara, K. Koyasu, T. Nagata, J. W. J. Wu, M. Nakao, K. Ohshimo. F. Misaizu, T. Tsukuda, J. Phys. Chem.
C 2019, 123, 15301–15306.
[2] ‫ۻ‬M. Suyama, S. Takano, T. Nakamura, and T. Tsukuda, J. Am. Chem. Soc. 2019, 141, 14048–14051.
[3] ‫ ۻ‬K. Koyasu et al. “Size evolutions of specific structures of metal clusters generated in the gas phase”,
Symposium on Size Selected Clusters 2020, Davos, Switzerland, 2020 March, Oral, Hot Topic.
[4] ‫ۻ‬Megumi Suyama et al. “Stoichiometric Formation of Open-Shell [PtAu24(SR)18]– via Spontaneous Intercluster Electron Transfer”, 10th ISCAN, Richmond, US, 2019 November. Oral. Hot Topic.
㸦௚ ཱྀ㢌 4 ௳㸪࣏ࢫࢱ࣮ 1 ௳㸧

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790" <୧ぶ፹ᛶศᏊ㞟ྜయ࠿ࡽ࡞ࡿ኱つᶍ୙ᆒ୍⣔୰ࡢ≀㉁㍺㏦ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢᵓ⠏Construction of mass transfer simulation in large heterogeneous
systems consisting of amphiphilic molecular aggregates‫ྜྷۑ‬஭ ⠊⾜㸦ྡྂᒇ኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ⁐㉁ศᏊࡀ⬡㉁⭷ࡸ࣑ࢭࣝ࡟⤖ྜࡍࡿ㐣⛬ࡣࠊ≀㉁ࡢศ㞳ᢳฟࡸ≀㉁㍺㏦࡟฼⏝ࡉࢀࠊ⸆ᏛࡸᕤᏛࡢᵝࠎ࡞ศ㔝࡛ᗈࡃ฼⏝ࡉࢀ࡚࠸ࡿࠋࡇࢀࡲ࡛ࠊ࣑ࢭࣝࡢྍ⁐໬࡟ࡘ࠸࡚ᡃࠎࡣศᏊືຊᏛ㸦MD㸧ィ⟬࡟ࡼࡿ⮬⏤࢚ࢿࣝࢠ࣮ゎᯒࢆ⏝࠸࡚ࠊ࣑ࢭࣝ࡬ࡢⅣ໬Ỉ⣲ࠊ࢔ࣝࢥ࣮ࣝࠊ࢔࣑ࣥ㢮ࡢྍ⁐໬࡟࠾ࡅࡿ⤖ྜ㒊఩ࡸᙉᗘ࡟
ࡘ࠸࡚ࡢ▱ぢࢆᚓ࡚ࡁࡓࠋࡲࡓࠊ⬡㉁࣋ࢩࢡࣝ࡬ࡢࢱࣥࣃࢡ㉁ࠊᢠࡀࢇ๣ࠊ⎔ቃ࣍ࣝࣔࣥࡢ⤖ྜ࡟ࡘ࠸࡚ࠊ
ࣃࣝࢫ☢ሙ໙㓄 NMR ࢆ⏝࠸ࡓ◊✲ࢆ⾜࠸ࠊ⤖ྜ㔞ࢆồࡵࡿ࡜࡜ࡶ࡟ࠊ⤖ྜゎ㞳ࡢ㏿ᗘㄽࢆᒎ㛤ࡋ࡚ࡁࡓࠋ
ࡇ࠺࠸ࡗࡓ◊✲࡛ࡣࠊ୍⯡࡟⭷ࡸ࣑ࢭࣝࡣప⃰ᗘ࡛࠶ࡾࠊࡑࢀࡽࡀከᩘᏑᅾࡍࡿࡇ࡜࡟ࡼࡿᣑᩓ࡬ࡢᙳ㡪ࡣ↓どࡉࢀ࡚ࡁࡓࠋ୍᪉ࠊࢻࣛࢵࢢࢹࣜࣂ࣮ࣜࢩࢫࢸ࣒ࢆࡣࡌࡵ࡜ࡍࡿ⏕యෆศᏊ㍺㏦ࡣࠊ⬡㉁ࡸࡓࢇࡥࡃ㉁࠿ࡽ࡞ࡿศᏊ㞟ྜయࡀከᩘඹᏑࡍࡿ」ྜࢥࣟ࢖ࢻศᩓ⣔࡟࠾࠸࡚⏕ࡌ࡚࠸ࡿࠋศᏊ㞟ྜయࡀከᩘ࠶ࡿ⎔ቃ࡛⁐㉁ศᏊࡣࡑࢀࡽ࡟⤖ྜゎ㞳ࡋࡘࡘࠊศ㓄ࡋࠊᗈᇦ࡟ᣑᩓࡋ࡚࠸ࡃࠋࡋ࠿ࡋ࡞ࡀࡽࠊ⭷ࡸ࣑ࢭࣝ࠿ࡽ࡞ࡿ」ྜࢥࣟ࢖ࢻศᩓ⣔ࡢศᏊ㍺㏦࡟࠾࠸࡚ࠊከయ࡟ࡼࡿᙳ㡪ࢆ⪃៖ࡋࡓ◊✲౛ࡣⓙ↓࡛࠶ࡾࠊࡑࡢࡼ࠺࡞⣔ࡢ≀⌮໬Ꮫⓗ᳨ウࡣ࡞ࡉࢀ࡚࠸࡞࠿ࡗࡓࠋᮏ◊✲࡛ࡣࠊࡲࡎࢩࣥࣉࣝ࡞ࣔࢹࣝ⣔࡜ࡋ࡚ࠊ⬡㉁࣋ࢩࢡࣝ࡜⸆≀ࡢඹᏑࡍࡿ⣔࡟࠾ࡅࡿ⸆≀ࡢ㍺㏦ࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚᫂ࡽ࠿࡟ࡍࡿࠋ࡞࠾ࠊࡇࡇ࡛ࡣ⌫≧࣋ࢩࢡࣝࡀ༢ศᩓ
ࡋ࡚࠸ࡿࡶࡢ࡜ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ࣋ࢩࢡࣝ࡜⸆≀ࡀඹᏑࡍࡿỈ⁐ᾮ⣔ࡢࣔࢹࣝ໬ࢆ௨ୗࡢࡼ࠺࡟⾜ࡗࡓࠋࡲࡎࠊ࣋ࢩࢡࣝࢆ⌫ࠊ⸆≀ࢆ㉁Ⅼ࡜ࡍࡿࠋ࣋ࢩࢡࣝ࠾ࡼࡧ⸆≀ࡣࠊࡑࢀࡒࢀࡢᣑᩓಀᩘ࡟ᚑࡗ࡚ࣛࣥࢲ࣒࢛࣮࢘ࢡࡍࡿࡶࡢ࡜ࡍࡿࠋ୍᪉ࠊ⸆
≀ࡢ࣋ࢩࢡࣝ࡬ࡢ⤖ྜゎ㞳ࡣࠊ㏿ᗘᐃᩘ࡟ᚑࡗ࡚⏕ࡌࡿࠋࡇࢀࡽࡢᣑᩓಀᩘࠊ⤖ྜゎ㞳ࡢ㏿ᗘᐃᩘࡣࠊNMRᐃ࡟ࡼࡗ࡚࠶ࡽ࠿ࡌࡵホ౯ࡋࡓࡶࡢࢆ⏝࠸ࡓࡀࠊMD ィ⟬࡟ᇶ࡙࠸࡚ࡶホ౯ྍ⬟࡛࠶ࡿࠋḟ࡟ࠊᣑᩓࡋࡘࡘ⤖ྜゎ㞳ࢆ⧞ࡾ㏉ࡍ࣋ࢩࢡࣝ࡜⸆≀ࡢ㐠ືࢆ෌⌧ࡍࡿࡓࡵ࡟ࠊᣑᩓಀᩘ࠾ࡼࡧ㏿ᗘᐃᩘࢆ⏝࠸࡚ࠊ௨ୗࡢࡼ࠺࡞࢔ࣝࢦࣜࢬ࣒ࡢ Monte Carlo㸦MC㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ᪂ࡓ࡟ᵓ⠏ࡋࡓࠋࡲࡎࠊ㸦㸯㸧࣋ࢩࢡࣝࠊ⸆≀ࡀᣑᩓಀᩘࢆ෌⌧ࡍࡿࡼ࠺࡟஘ᩘ࡟ࡼࡗ࡚ኚ఩ࡉࡏࡿࠋኚ఩ࡋࡓ⸆≀ࡀ࣋ࢩࢡࣝࡢእ㸦ෆ㸧㒊࠿ࡽෆ㸦እ㸧㒊࡬࡜ኚ఩ࡋࡓሙྜࠊ2 ẁ㝵ࡢ࣓ࢺ࣏ࣟࣜࢫุᐃ࡟ࡼࡗ࡚ኚ఩ࡢྍྰࢆุᐃࡍ
ࡿࠋ㸦㸰㸧ࡲࡎ⤖ྜゎ㞳㏿ᗘᐃᩘ kFBࠊkBF ࢆ⏝࠸࡚㑄⛣☜⋡ࢆホ౯ࡋࠊ୍⯡໬࣓ࢺ࣏ࣟࣜࢫἲࢆ⏝࠸࡚ኚ఩ࡢ
ヨ⾜ࢆ᥇ᢥࡍࡿ࠿ྰ࠿ࢆỴᐃࡍࡿࠋ㸦㸱㸧㸦㸰㸧࡛ࡣ⤖ྜゎ㞳ࡢẚࢆไᚚ࡛ࡁࡿࡀᐇ㏿ᗘࡣไᚚ࡛ࡁ࡞࠸ࠋࡑ
ࡇ࡛㸦㸰㸧࡛࢔ࢡࢭࣉࢺࡉࢀࡓ⸆≀࡟ࡘ࠸࡚ࠊ㏱㐣㏿ᗘࢆไᚚࡍࡿࡓࡵ࡟ 2 ẁ┠ࡢ࣓ࢺ࣏ࣟࣜࢫุᐃࢆࡉࡽ࡟⾜࠺ࠋ㸦㸰㸧࡜㸦㸱㸧ࡢ࠸ࡎࢀࡶ࢔ࢡࢭࣉࢺࡢ⸆≀ࡢࡳኚ఩ࢆチྍࡍࡿࠋ- 263 -

ࡇࢀࡽ㸦㸯㸧࠿ࡽ㸦㸱㸧ࡢࢫࢸࢵࣉࢆ⧞ࡾ㏉ࡋ࡚࣋ࢩࢡࣝ࡜⸆≀ࢆኚ఩ࡉࡏࡿࡇ࡜࡟ࡼࡾࠊᗈᇦࡢᣑᩓᣲືࢆ
ࢩ࣑࣮ࣗࣞࢺࡍࡿࠋ

3◊✲ᡂᯝ࣋ࢩࢡࣝ࡟⸆≀ࡀከᩘ⤖ྜࡋࡓึᮇ≧ែ࠿ࡽゎ㞳ࡀ㐍ࡴヨ⾜ⓗ࡞㠀ᖹ⾮㐣⛬࡟ࡘ࠸࡚ࠊୖグ࡛♧ࡋࡓ࢔ࣝࢦࣜ
ࢬ࣒࡟ࡼࡿ MC ィ⟬ࢆ⾜ࡗࡓ⤖ᯝࡢࢫࢼࢵࣉࢩࣙࢵࢺࢆ
ᅗ 1 ࡟♧ࡍࠋゎ㞳ࡀ㐍ࡳࡘࡘࠊ࣋ࢩࢡࣝෆࡢ⸆≀ࡀῶᑡࡋ࡚࠸ࡃᵝᏊࡀぢ࡚ྲྀࢀࡿࠋࡉࡽ࡟ࠊ࣋ࢩࢡࣝ࡜⸆≀࡜ࡢ⤖ྜゎ㞳ࡀᖹ⾮≧ែ࡟࠶ࡿ⣔࡟ࡘ࠸࡚ࠊᚓࡽࢀࡓ⸆≀ࡢᣑᩓࡍࡿࢺࣛࢪ࢙ࢡࢺࣜࢆ⏝࠸࡚ࠊࣃࣝࢫ☢ሙ໙㓄
NMRᐃࡢࢩࢢࢼࣝῶ⾶ࢆィ⟬ࡍࡿࡇ࡜ࡶྍ⬟࡛࠶ࡿࠋࡇࡢࡼ࠺࡞ MC ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜ᐇ

࡜ࡢẚ㍑࡟ࡼࡗ

࡚ࠊ࣋ࢩࢡࣝࡢࡼ࠺࡞ศᏊ㞟ྜయࡀΰ㞧ࡍࡿ」㞧࡞⣔࡟

ᅗ 1㸬MC ィ⟬ࡼࡾᚓࡽࢀࡓ⸆≀ࡀᣑᩓࡋࡘࡘ࣋
ࢩࢡࣝ࡟⤖ྜゎ㞳ࢆ⧞ࡾ㏉ࡍᵝᏊࡢࢫࢼࢵࣉࢩ
ࣙࢵࢺ㸬࣋ࢩࢡࣝࢆ༙㏱᫂ࡢ⌫ࠊึᮇ≧ែ࡛࣋ࢩࢡࣝෆࡢ⸆≀ࢆ㉥ࠊ࣋ࢩࢡࣝእࡢ⸆≀ࢆ㟷࡛ࡑࢀࡒࢀ♧ࡍ㸬⸆≀ࡣᐇ㝿ࡼࡾ኱ࡁࡃ⾲♧ࡋ࡚࠶ࡿ㸬࠾ࡅࡿᐇ㦂⤖ᯝࡢゎᯒ࡟⏝࠸ࡿࡇ࡜ࡀ࡛ࡁࡿ࡜ᮇᚅࡉࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬ᾆ㔝 ㄹࠊ⸨ᮏ࿴ኈࠊᏳ⸨჆೔ࠊྜྷ஭⠊⾜ࠊ⠛⏣ ΅ࠊᒸᓮ 㐍ࠊ➨ 22 ᅇ⌮ㄽ໬Ꮫウㄽ఍.
‫ྜྷۻ‬஭⠊⾜ࠊᏳ⸨჆೔ࠊᆏୗ㐩ဢࠊᒸᓮ 㐍ࠊ➨ 22 ᅇ⌮ㄽ໬Ꮫウㄽ఍.
‫ۻ‬ᾆ㔝 ㄹࠊ⸨ᮏ࿴ኈࠊᏳ⸨჆೔ࠊྜྷ஭⠊⾜ࠊ⠛⏣ ΅ࠊᒸᓮ 㐍ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍.
‫ྜྷۻ‬஭⠊⾜ࠊᏳ⸨჆೔ࠊᆏୗ㐩ဢࠊᒸᓮ 㐍ࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍.
‫ ۻ‬R. Urano, K. Fujimoto, Y. Andoh, N. Yoshii, W. Shinoda, S. Okazakiࠊ➨ 57 ᅇ᪥ᮏ⏕≀≀⌮Ꮫ఍ᖺ఍.
‫ྜྷۻ‬஭⠊⾜㸪ᒸᓮ 㐍ࠊ➨ 42 ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘.
‫ྜྷۻ‬஭⠊⾜ࠊ➨ 42 ᅇ⁐ᾮ໬Ꮫࢩ࣏ࣥࢪ࣒࢘.
‫ ۻ‬N. Yoshii, Y. Andoh, S. OkazakiࠊThe 5th International Conference on Molecular Simulation.
‫ۻ‬ᾆ㔝 ㄹࠊ⸨ᮏ࿴ኈࠊᏳ⸨჆೔ࠊྜྷ஭⠊⾜ࠊ⠛⏣ ΅ࠊᒸᓮ 㐍ࠊ➨ 33 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ ۻ‬K. Takeda, K. Fujimoto, N. Yoshii, S. Okazaki, Molecular dynamics study of solubilization of cyclohexane,

benzene, and phenol into mixed micelles composed of sodium dodecyl sulfate and octaethylene glycol monododecyl
ether, Journal of Computational Chemistry 40, 2722-2729 (2019).
‫ ۻ‬N. Yoshii, Y. Andoh, S Okazaki*, Fast multipole method for three dimensional systems with periodic boundary
condition in two directions, Journal of Computational Chemistry 41, 940-948 (2020).
‫ ۻ‬Y. Andoh, N. Yoshii, S Okazaki, Extension of the fast multipole method for the rectangular cells with ananisotropic partition tree structure, Journal of Computational Chemistry, in press.
ྜྷ஭⠊⾜, 㧗㏿ከ㔜ᴟᒎ㛤ἲ, ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥᏛ఍ㄅࠕ࢔ࣥࢧࣥࣈࣝࠖ21(4), (2019).
ྜྷ஭⠊⾜, ⌫㠃ୖࡢ⁐ᾮ໬Ꮫ࣑̿ࢭࣝࠊ࣋ࢩࢡࣝࡢ⾲㠃ᵓ㐀ࠊࢲ࢖ࢼ࣑ࢡࢫ, ⁐ᾮ໬Ꮫ◊✲఍ࢽ࣮ࣗࢫ 72(2019).

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䜰䝹䝁䞊䝹༢ศᏊ⭷㻛Ỉ⏺㠃䛷䛾ᵓ㐀䛸᣺ື䝇䝨䜽䝖䝹䛾㻌ศᏊືຊᏛ䝅䝭䝳䝺䞊䝅䝵䞁◊✲㻌 㻙᰾䛾㔞Ꮚຠᯝ䛻㛵䛩䜛▱ぢ㻙㻌
0ROHFXODU'\QDPLFV6WXG\RI6WUXFWXUHDQG9LEUDWLRQDO6SHFWUDDW$OFRKROPRQROD\HU:DWHU,QWHUIDFH(IIHFWRI1XFOHDU4XDQWXP(IIHFW‫▼ۑ‬ᒣ 㐩ஓ,  ໭୰ ୍ஓ㸦ᐩᒣ኱Ꮫ⌮ᕤᏛ◊✲㒊㸧
1◊✲┠ⓗࠊෆᐜ Ỉ⾲㠃ࡣ㸪≀⌮Ꮫ㸪໬Ꮫ㸪⏕≀Ꮫ࡟࠾ࡅࡿᵝࠎ࡞ㅖ⌧㇟ࡢ୰࡛㔜せ࡞ᙺ๭ࢆᢸࡗ࡚࠸ࡿࠋ⌧ᅾ㸪ศᏊࣞ࣋ࣝࡢឤᗘ࡛⏺㠃ࡢศᏊᵓ㐀ࢆࣉ࣮ࣟࣈࡍࡿᐇ㦂ᡭἲ࡜ࡋ࡚࿴࿘ἼⓎ⏕(Sum Frequency Generation, SFG)ศගἲ
ࡀᗈࡃ⏝࠸ࡽࢀࡿࡼ࠺࡟࡞ࡗࡓࠋ㉥እග㸪ྍどගࢆ⏺㠃㡿ᇦ࡟↷ᑕࡍࡿ࡜㸪㠀⥺ᙧศᴟຠᯝ࡟ࡼࡾ㸪ᑐ⛠ᛶࡀ◚ࢀࡓ⏺㠃㡿ᇦ࠿ࡽࡢࡳ㸪ࡑࢀࡽ㸰ࡘࡢගࡢ࿴ࡢ࿘Ἴᩘࢆࡶࡘග(࿴࿘Ἴග)ࡀⓎ⏕ࡍࡿࠋSFGศගἲ࡛ࡣ㸪SFGගࡢ㟁ሙ(⏺㠃ࡢ஧ḟឤཷ⋡ ( ) ࡟ẚ౛)ࡀほࡉࢀࡿࡀ㸪ධᑕ㉥እගࢆศᏊ᣺ື㡿ᇦ࡛ᤲᘬࡍࢀࡤ㸪

SFGศගἲࡣ⏺㠃ᩄឤ࡞᣺ືศගἲ࡜ࡋ࡚฼⏝࡛ࡁࡿࠋ᭱㏆࡛ࡣ㸪఩┦ࡀ᪤▱ࡢཧ↷ග࡜࿴࿘Ἴගࢆᖸ΅ࡉࡏࡿࡇ࡜࡟ࡼࡾ㸪SFG⹫㒊ࢫ࣌ࢡࢺࣝ(Im[ ( ) ]ࢫ࣌ࢡࢺࣝ)ࡀᚓࡽࢀ㸪ࡑࡢࢫ࣌ࢡࢺࣝࡢ➢ྕ࠿ࡽ⏺㠃࡛ࡢศᏊࡢ㓄ྥᵓ㐀ࡀ㆟ㄽࡉࢀ࡚࠸ࡿࠋ௒ᅇ㸪ᡃࠎࡣỈ⾲㠃ࡢ࢔ࣝࢥ࣮ࣝ༢ศᏊ⭷࡟㛵ࡍࡿ◊✲ࢆ⾜࠺࡟࠶ࡓࡾ㸪ࡑࡢᇶ♏࡜࡞ࡿ✵Ẽ/Ỉ⏺㠃࡛ࡢIm[ ( ) ]ࢫ࣌ࢡࢺࣝ࡟㛵ࡍࡿ◊✲ࡢᚲせࡀ⏕ࡌࡓࡓࡵ㸪௒ᅇࡣࡑࡢ◊✲ᡂᯝ࡟ࡘ࠸࡚ሗ࿌ࡉࡏ࡚㡬ࡃࠋ  ᅗ㸯࡟♧ࡍࢫ࣌ࢡࢺࣝࡣ㸪Tianࡽࡢᐇ㦂࡟ࡼࡗ࡚㏆ᖺሗ࿌ࡉࢀࡓ✵Ẽ/Ỉ(H2O㸪࠶ࡿ࠸ࡣD2O)⏺㠃࡟࠾ࡅࡿIm[ ( ) ]ࢫ࣌ࢡࢺࣝࢆ⾲ࡋ࡚࠸ࡿࠋࡣࡌࡵ࡟㸪OHఙ⦰᣺ື㡿ᇦ(3000cm-1㹼4000cm-1)࡟ὀ┠ࡍࡿ࡜㸪⣙
3700 cm-1࡟ṇࡢࣂࣥࢻ㸪3200cm-1㹼3600cm-1࡟㈇ࡢࣂࣥࢻࡀぢࡽࢀࡿࠋIm[ ( ) ]ࢫ࣌ࢡࢺࣝࡀṇ➢ྕࢆࡶࡘࡇ
࡜ࡣ㸪ࣉࣟࢺࣥࡀ✵Ẽഃࢆྥ࠸ࡓOHࡀᏑᅾࡍࡿࡇ࡜ࢆ⾲ࡋ࡚࠾ࡾ㸪⣙3700cm-1ࡢṇࣂࣥࢻࡣỈ⾲㠃࡛Ỉ⣲⤖ྜࡋ࡚࠸࡞࠸Free OHࡀ✵Ẽഃࢆྥ࠸࡚࠸
ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ୍᪉㸪3200cm-1㹼
3600cm-1ࡢ㈇ࡢࣂࣥࢻࡣ㸪Ỉ⣲⤖ྜࡋࡓ
Bond OHࡀỈഃࢆྥ࠸࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋODఙ⦰᣺ື㡿ᇦ(2000cm-1㹼3000cm1)ࡶྠᵝ࡞ᵓ㐀ࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿ

ࡀ㸪OH᣺ື㡿ᇦ࡜ẚ࡭࡚OD᣺ື㡿ᇦ࡟࠾࠸࡚Ỉ⣲⤖ྜࣂࣥࢻࡢపἼᩘഃ࡟ᙅ࠸ṇࣂࣥࢻࡀ⌧ࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿ[1]ࠋࡇࡢỈࡢIm[ ( ) ]ࢫ࣌ࢡࢺࣝ࡟పἼᩘࡢṇࣂࣥࢻࡀᏑᅾࡍࡿ࠿࡝࠺࠿࡜࠸࠺㆟ㄽࡣ㸪㏆ᖺᐇ㦂㛫࡛኱ኚ㆟ㄽ࡟࡞ࡗ࡚࠸ࡿࡀ㸪௒ᅇࡢTianᅗ  Ỉ⾲㠃ࡢ Im[ ( ) ]ࢫ࣌ࢡࢺࣝࡢᐇ㦂⤖ᯝ>@ࡽࡢᐇ㦂࡟ࡼࡾ㸪పἼᩘࣂࣥࢻ࡟ྠ఩యຠ
ᯝࡀ࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋᮏ◊✲࡛ࡣ㸪ࡇࡢOH᣺ື࡜OD᣺ືࡢࢫ࣌ࢡࢺࣝᛂ⟅ࡢ㐪࠸ࡣ᰾ࡢ㔞Ꮚᛶ࡟㉳ᅉࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࡓࡵ㸪ࡑࡢຠᯝࢆᢅ࠺஦ࡀྍ⬟࡞⤒㊰✚ศࢭࣥࢺࣟ࢖ࢻศᏊືຊᏛࢩ࣑࣮ࣗࣞ

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ࢩࣙࣥࢆ⏝࠸࡚Im[ ( ) ]ࢫ࣌ࢡࢺࣝࢆィ⟬ࡋ㸪ࡑࡢⓎ⏕࣓࢝ࢽࢬ࣒ࢆ㆟ㄽࡋࡓ[2]ࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ⤒㊰✚ศࢭࣥࢺࣟ࢖ࢻศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡣ PIMD ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࢆ⏝࠸ࡓ[3]ࠋ3 ḟඖ࿘ᮇቃ⏺᮲௳ࡢࡶ࡜ 128 ಶࡢ HOD ỈศᏊࢆ××

= 15.0 Å × 15.0 Å × 100.0 Åࡢ┤᪉యࢭࣝ࡟ࢫࣛࣈ≧࡟㓄⨨ࡉࡏࡓࠋຊሙ࡜ࡋ࡚㸪Ỉࡢ᣺ືࢫ࣌ࢡࢺࣝࡀ෌⌧ࡉࢀࡿࡼ࠺ศᏊෆ࣏ࢸࣥࢩࣕࣝࢆಟṇࡋࡓ q-SPC/Fw
ࣔࢹࣝ[4]ࢆ⏝࠸ࡓࠋࣅ࣮ࢬᩘࢆ 24 ࡜ࡋ㸪ᗘࢆ 300K ࡜ࡋࡓࠋ240ps ࡢ⤒㊰✚ศศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙ

ࣥ࡟ࡼࡿᖹ⾮໬ࢆ 32 ᮏࡢ⊂❧࡞ trajectory ࡟ᑐࡋ࡚⾜࠸㸪ࡑࡢᚋ 120ps ࡢࢭࣥࢺࣟ࢖ࢻศᏊືຊᏛࢩ࣑ࣗࣞ
࣮ࢩࣙࣥ(㔞Ꮚ MD)࡟ࡼࡾ⤫ィᖹᆒࢆ࡜ࡗࡓࠋẚ㍑ࡢࡓࡵྠᵝࡢィ⟬ࢆྂ඾ MD(ࣅ࣮ࢬᩘࡀ 1)࡟ᑐࡋ࡚⾜ࡗࡓࠋIm[ ( ) ]ࢫ࣌ࢡࢺࣝィ⟬࡟ࡣ㸪ᡃࠎࡀ㛤Ⓨࡋ࡚ࡁࡓ Charge Response Kernel ࣔࢹࣝ࡟ᇶ࡙ࡃศᴟ⋡࡜཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ᫬㛫┦㛵㛵ᩘἲ[5,6]ࢆ⏝࠸ࡓࠋ

3◊✲ᡂᯝ
ᅗ 2 ࡟㸪௒ᅇࡢྂ඾ MD ࡜㔞Ꮚ MD ࡛ᚓࡽࢀࡓỈࡢᩘᐦᗘศᕸ(ᅗ 2(a))࡜ᩘᐦᗘ㓄ྥศᕸ(ᅗ 2(b))ࢆ㸪⏺

㠃ᆶ┤᪉ྥࡢᗙᶆ z ࡢ㛵ᩘ࡜ࡋ࡚♧ࡍࠋᅗ
2(a)࡟♧ࡉࢀࡿྂ඾ MD ࡜㔞Ꮚ MD ࡟ࡼࡿᩘᐦᗘࡣ୧⪅࡜ࡶྠᵝࡢ⤖ᯝࢆ୚࠼ࡿࡇ࡜ࡀ
ࢃ࠿ࡿࠋḟ࡟㸪ᅗ 2(b)ࡢᩘᐦᗘ㓄ྥศᕸ࡟ὀ┠ࡍࡿ࡜㸪ྂ඾ MD㸪㔞Ꮚ MD ࡜ࡶ࡟㸪4Å ≲≲ 8Åࡢ㡿ᇦ࡛㈇ࡢ್ࢆ㸪8Å ≲ ࡢ㡿ᇦ࡛ṇࡢ್ࢆ࡜ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ๓⪅ࡣ㸪Ỉഃ࡟ྥ࠸ࡓ Bond OH(OD)㸪ᚋ⪅ࡣ✵Ẽഃ࡟ྥ࠸ࡓ
Free OH(OD)ᵓ㐀࡟⏤᮶ࡋ࡚࠸ࡿࠋྂ඾ MDィ⟬࡛ࡣ OH ࡜ OD ศᕸࡢᕪࡣ࡯࡜ࢇ࡝࡞࠸
ࡀ㸪㔞Ꮚ MD ࡢ⤖ᯝ࡟ࡣ H ࡜ D ࡢ᰾ࡢ㔞Ꮚᛶࡢ㐪࠸ࡀ⾲ࢀ࡚࠸ࡿࠋOH ࡼࡾࡶ OD ࡢ᪉ࡀᙉ࠸Ỉ⣲⤖ྜࢆᙧᡂࡍࡿࡢ࡛㸪4Å ≲≲8Åࡢ㡿ᇦ࡛ OD ࡢศᕸࡢ᪉ࡀࡼࡾ኱ࡁ࠸㈇ࡢ➢ྕࢆ♧ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ
ᅗ 3 ྑ࡟㸪௒ᅇィ⟬ࡋࡓ HOD ⾲㠃࡟࠾ࡅࡿィ⟬ࡉࢀࡓ Im[ ( ) ]ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋࣉࣟࢺࣥࢆ㔜Ỉ⣲໬ࡋࡓ 2200cm-1 㹼3000cm-1 ࡢ
OD ᣺ື㡿ᇦࡢࣂࣥࢻ࡟ὀ┠ࡍࡿ࡜㸪OH ᣺ືࣂࣥࢻ࡜ྠᵝ࡟㸪㧗Ἴᩘഃ࡟ṇࡢ Free OHࣂࣥࢻ㸪పἼᩘഃ࡟㈇ࡢ Bond OH ࣂࣥࢻࡀᅗ  D ⏺㠃ᆶ┤᪉ྥ㹸࡟ᑐࡍࡿᩘᐦᗘ ࡢศᕸࠋ㯮⥺ࡣྂ඾ 0'㸪⥳⥺ࡣ㔞Ꮚ 0' ࡢィ⟬⤖ᯝࠋ E Ỉࡢ〈cos 〉ศᕸࠋ

- 266 -

ぢࡽࢀࡿࠋOD ᣺ື㡿ᇦ࡟ࡣ㸪ࡉࡽ࡟పἼᩘഃ࡟ṇࣂࣥࢻࡀ⌧ࢀࡿࡇ࡜ࡀࢃ࠿
ࡿࠋࡇࡢṇࣂࣥࢻࡣ OH ᣺ື㡿ᇦ࡟ࡣ࡯࡜ࢇ࡝ぢࡽࢀ࡞࠸ࡇ࡜ࡶࢃ࠿ࡿࠋࡇࢀࡣ㸪ඛ࡟♧ࡋࡓ Tian ࡽࡢᐇ㦂ࡢほ࡜୍⮴ࡋ࡚࠸ࡿࠋ㟁Ꮚ≧ែࡣ OH ࡶ OD ࡶྠࡌࡣࡎ࡛࠶ࡾ㸪㐪࠸ࡣ H ࡜ D ࡢ
᰾ࡢ㉁㔞࡛࠶ࡿࠋ௒ᅇ㸪ࡇࡢᅗ  Ỉ⾲㠃ࡢ 6)* ⹫㒊ࢫ࣌ࢡࢺࣝࡢ⤒㊰✚ศࢭࣥࢺࣟ࢖ࢻศᏊືຊᏛィ⟬⤖ᯝ ྑ ࡜㸪ࡑࡢศᏊᥥീ ᕥ 㔞Ꮚᛶࡢ㐪࠸ࡀ㸪ィ⟬࡟ࡼࡾపἼᩘࡢṇࣂࣥࢻࡢᏑᅾ࡜ࡋ࡚☜ㄆࡉࢀࡓࠋ
࡛ࡣ㸪࡝ࡢࡼ࠺࡞࣓࢝ࢽࢬ࣒࡛ OD ᣺ືࡢࡳప
Ἴᩘࡢṇࣂࣥࢻࡀ⏕ࡌࡿࡢࡔࢁ࠺࠿ࠋࡇࡇ࡛ࡣゎᯒࡢヲ⣽ࡣ๭ឡࡍࡿࡀ㸪ලయⓗ࡞ศᏊᥥീ࡜
ࡋ࡚㸪ᅗ 3 ᕥ࡟♧ࡍࡼ࠺࡞ᵓ㐀ࡀ᫂ࡽ࠿࡟࡞ࡗ
ࡓࠋỈ⾲㠃࡟ࡣ⏺㠃ᖹ⾜᪉ྥ࡟ᙉࡃỈ⣲⤖ྜࡍࡿ dimer complex ࡀẚ㍑ⓗከࡃᏑᅾࡍࡿࡇ࡜ࡀ
ࢃ࠿ࡗ࡚࠾ࡾ㸪ᅗ 3 ᕥᅗࡢྑഃ࡟ᏑᅾࡍࡿỈศᏊࡢ㟁Ꮚ≧ែࡀ㸪ࡑࡢᕥഃࡢỈศᏊࡢ᣺ື࡟ࡼ
ࡾṇࣂࣥࢻࢆ⏕ᡂࡍࡿࡇ࡜ࡀ㐣ཤࡢᡃࠎࡢ◊✲࠿ࡽ᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿ[5,6]ࠋࡇࡢ㸰ࡘࡢỈศᏊࢆỈ⣲⤖ྜࡉࡏ࡚࠸ࡿࢻࢼ࣮OH(OD)࡟㛵ࡋ࡚㸪H ࡀỈ⣲⤖ྜࡋ࡚࠸ࡿሙྜ࡜ẚ࡭࡚㸪DࡀỈ⣲⤖ྜࡋ࡚࠸ࡿ᪉ࡀ㸰ࡘࡢỈศᏊࡢ OOᅗ ᗘ . ᐇ⥺ ࡜ . ◚⥺ ࡛ィ⟬ࡉࢀࡓྂ඾ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿ Im[ ( ) ]ࢫ࣌ࢡࢺࣝ

㛫㊥㞳ࡀᑠࡉࡃ࡞ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡣ㸪H ࡢ㔞Ꮚຠᯝ࡛Ỉ⣲⤖ྜࡀⱝᖸᙅࡃ࡞ࡿࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀ㸪H ࡜ D ࡢ㔞Ꮚᛶࡢ㐪࠸ࡀ OO 㛫㊥㞳ࡢ㐪࠸ࢆ⏕ࡌࡉࡏࡿ࡜ゝ࠼ࡿࠋࡲࡓ㸪ඛࡢ Im[ ( ) ]ࢫ࣌ࢡࢺࣝࡢṇࡢపἼᩘࣂࣥࢻࡣ㸪OO ㊥㞳ࡀᑠࡉ࠸᪉ࡀ㢧ⴭ࡟⏕ࡌࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿ[5,6]ࠋࡇࢀࡽࡢࡇ࡜࠿ࡽ㸪H ࡜ D ࡢ㔞Ꮚᛶࡢ㐪࠸ࡀ㸪Im[ ( ) ]ࢫ࣌ࢡࢺࣝࡢṇࡢపἼᩘࣂࣥࢻࡢ⏕ᡂࡢ㐪࠸ࢆ⏕ࡌࡉࡏࡿཎᅉ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ[2]ࠋ
᭱ᚋ࡟㸪ྂ඾ MD ࡛ィ⟬ࡋࡓ Im[ ( ) ]ࢫ࣌ࢡࢺࣝ࡜㸪ࡑࢀࡢ
300K ࡟࠾ࡅࡿྂ඾ MD ࡟ࡼࡿ Im[( )ᗘ౫Ꮡᛶࢆ㆟ㄽࡍࡿࠋᅗ 4 ࡢᐇ⥺ࡣ㸪ᗘ]ࢫ࣌ࢡࢺࣝࡢィ⟬⤖ᯝࢆ⾲ࡋ࡚࠸ࡿࠋOD ᣺ື࡜ྠᵝ࡟㸪OH ࡢపἼᩘഃ࡟ࡣṇࣂࣥࢻࡢ≉ᚩࡀぢࡽࢀ࡚࠸ࡿࠋࡇࢀࡣ㸪ᅗ 3 ࡢ OD ᣺ື㡿ᇦࡢ⤖ᯝ࡜ྠᵝࡢഴྥ࡛࠶ࡾ㸪ྂ඾⢏Ꮚ࡟㏆࡙ࡃ࡟ࡘࢀ㸪పἼᩘࣂࣥࢻࡀ⌧ࢀࡿ࡜࠸࠺ゎ㔘࡟୍⮴ࡍࡿࡇ࡜ࡀࢃ࠿ࡿࠋḟ࡟㸪 ᗘࢆ 330K ࡟ࡋࡓሙྜ
ࡢࢫ࣌ࢡࢺࣝࡢ⤖ᯝࢆᅗ 4 ࡢ◚⥺࡟♧ࡍࠋࡇࢀࡣ㸪ᗘୖ᪼࡟క࠸㸪పἼᩘࣂࣥࢻࡢ≉ᚩࡀኻࢃࢀࡿࡇ࡜ࡀࢃ࠿ࡿࠋ

ᗘୖ᪼࡜࡜ࡶ࡟ OO 㛫㊥㞳ࡀ኱ࡁࡃ࡞ࡿࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ௨ୖࡢ◊✲࠿ࡽ㸪పἼᩘࣂࣥ

ࢻࡣ㸪᰾ࡢ㔞Ꮚᛶ㸪ࡑࡋ࡚⣔ࡢᗘ࡟ᩄឤ࡛࠶ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡾ㸪ᡃࠎࡀᥦၐࡋ࡚ࡁࡓỈ⣲⤖ྜ complex࡟㉳ᅉࡍࡿ࡜࠸࠺ศᏊᥥീ[5,6]࡟▩┪ࡋ࡞࠸ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

- 267 -

>ཧ⪃ᩥ⊩@
[1] X. Xu and Y. Shen and C. Tian, J. Chem. Phys. 150 (2019) 144701
[2] T. Ishiyama and A. Morita, J. Phys. Chem. Lett. 10 (2019) 5070
[3] M. Shiga, PIMD, version 2.2; http://ccse.jaea.go.jp/ja/download/pimd/index.en.html.
[4] F. Paesani, W. Zhang, D. Case, T. Cheatham, and G. Voth, J. Chem. Phys. 125 (2006) 184507[5] T. Ishiyama and A. Morita, J. Chem. Phys. 131 (2009) 244714[6] T. Ishiyama and A. Morita, Ann. Rev. Phys. Chem. 68 (2017) 1

4Ⓨ⾲ࠊฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬T. Sugimoto, Y. Otsuki, T. Ishiyama, A. Morita, K. Watanabe, and Y. Matsumoto, Topologically Disordered
Mesophase at Topmost Surface of Crystalline Ice between 120 and 200 K, Physical Review B (Rapid
Communication), Vol.99, p.121402(R) (2019).
‫ۻ‬K. Isoda, T. Ishiyama, Y. Mutoh, and D. Matsukuma, Stimuli-Responsive Room Temperature N-Heteroacene
Liquid: In situ Observation of Self-Assembling Process and Its Multiple Properties, ACS Applied Materials &Interfaces, Vol.11, (2019), pp.12053-12062.
‫ۻ‬T. Ishiyama and A. Morita, Nuclear Quantum Effect on the χ(2) Band Shape of Vibrational Sum Frequency
Generation Spectra of Normal and Deuterated Water Surfaces, The Journal of Physical Chemistry Letters, Vol.10,(2019), pp.5070-5075.
‫ۻ‬ᮡᮏᩄᶞ㸪▼ᒣ㐩ஓ㸪"࿴࿘ἼⓎ⏕᣺ືศගィ࡜ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽࡳࡿị⾲㠃ࡢศᏊᵓ㐀"ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥᏛ఍࢔ࣥࢧࣥࣈࣝ, Vol.21, No.3, pp.177-184, (2019).
୍⯡ㅮ₇㸸ᅜ㝿఍㆟ 1 ௳ࠊศᏊ⛉Ꮫウㄽ఍ 2 ௳ࠊศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍ 2 ௳ࠊᣍᚅㅮ₇ 1 ௳ࠊࡑࡢ௚ࢭ࣑ࢼ࣮➼ 2 ௳- 268 -

᭷ᶵග㉳㟁ຊࢹࣂ࢖ࢫࡢ㟁Ⲵᵓ㐀ゎᯒ࡜ᶵ⬟᥈⣴ࢆ┠ᣦࡋࡓ⌮ㄽ◊✲
Theoretical Studies of Structure Analysis in Organics Photovoltaic
Deviceżᮧᒸ ᱻࠊኴ⏣ ᕼ㸦᪥ᮏዪᏊ኱Ꮫ ⌮Ꮫ㒊㸧

1◊✲┠ⓗࠊෆᐜʌ ඹᙺ໬ྜ≀ࡣࠊʌ 㟁Ꮚ࡟⏤᮶ࡋࡓග྾཰ࡸⓎග≉ᛶࢆ♧ࡋࠊศᏊ㛫┦஫స⏝࡜࢟ࣕࣜ࢔Ⓨ⏕ࢆไᚚࡍࡿࡇ

࡜࡛㟁Ẽࢆὶࡍࡇ࡜ࡀྍ⬟࡛࠶ࡿࡇ࡜࠿ࡽࠊ࢚ࣞࢡࢺࣟࢽࢡࢫࡢศ㔝࡛ά⏝ࡉࢀ࡚࠸ࡿࠋ୰࡛ࡶࠊⰾ㤶⎔ ʌඹᙺ㧗ศᏊࡣࠊᑟ㟁ᛶࡸⓎගᛶ࡞࡝ࡢ㟁Ẽⓗ࣭ගᏛⓗ࡟≉᭷ࡢᛶ㉁ࢆ♧ࡍࡓࡵࠊ᭷ᶵ⣔ኴ㝧㟁ụ࡞࡝᭷ᶵ༙
ᑟయ㉳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
ᮏ◊✲࡛ࡣࠊ௨ୗ 2 Ⅼ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ
(1)ʌ ඹᙺ໬ྜ≀࡜ࡋ࡚▱ࡽࢀ࡚࠸ࡿ᭷ᶵ≀㉁㸦ࣂࢵ࣮࢟࣎࢘ࣝศᏊ㸧࡟࠾ࡅࡿᵓ㐀ࡢ᥈⣴࡜㟁Ꮚ≧ែࠊග྾཰ࡸⓎග≉ᛶཬࡧගບ㉳࡟క࠺ᵓ㐀ኚ໬ࡢỴᐃࠊศᏊ㛫┦஫స⏝࡜㟁Ⲵ⛣ືࡢ࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚⌮ㄽⓗ࡟ゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡍࡿࠋ(2)㠀ࣇ࣮ࣛࣞࣥศᏊࢆ࢔ࢡࢭࣉࢱ࣮࡜ࡋࡓ࣏࣐࣮ࣜ/㠀ࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụ㸦௨ୗࠊ㠀ࣇ࣮ࣛࣞࣥᆺ㸧ࡢసᡂ࡟ᡂຌࡋࠊ࣏࣐࣮ࣜ/ࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụ㸦௨ୗࠊࣇ࣮ࣛࣞࣥᆺ㸧ࡼࡾࡶ㧗࠸ග㟁ኚ᥮ຠ⋡(PCE)ࢆ♧ࡍࡇ࡜ࡀሗ࿌ࡉࢀࡓࠋࡲࡓࢻࢼ࣮࣏࣐࣮ࣜࡢࣇࢵ⣲໬࡟ࡼࡾࠊ㟁Ⲵ㑄⛣ࡢಁ㐍ࠊHOMO࣭
LUMO ࢚ࢿࣝࢠ࣮‽఩ࡢࢩࣇࢺ࡞࡝࣏࣐࣮ࣜࡢศᴟᛶࡀ㧗ࡵࡽࢀࠊ࣏࣐࣮ࣜ/ࣇ࣮ࣛࣞࣥᆺࡣࠊࣇࢵ⣲໬࡟ࡼࡾ PCE ࡀྥୖࡍࡿࡇ࡜ࡀሗ࿌ࡉࢀࡓࠋࡉࡽ࡟ࠊ㠀ࣇ࣮ࣛࣞࣥᆺ࢔ࢡࢭࣉࢱ࣮࡟ᑐࡋ࡚ࡶࣇࢵ⣲໬ࡀᡂຌࡋࠊ
ࣇࢵ⣲໬ࡉࢀ࡚࠸࡞࠸㠀ࣇ࣮ࣛࣞࣥᆺࡼࡾ㧗࠸ PCE(Ү 15.6%)ࢆ♧ࡍࡇ࡜ࡀሗ࿌ࡉࢀࡓࠋᮏ◊✲࡛ࡣࠊ㟁Ꮚᵓ㐀࡜྾཰ࢫ࣌ࢡࢺࣝࠊHOMO-LUMO ࢠࣕࢵࣉࠊ㟁Ⲵ⛣ື㊥㞳ࡢほⅬ࠿ࡽࠊ㠀ࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụ࡟࠾ࡅࡿࣇࢵ⣲໬ࡢᙳ㡪࡟ࡘ࠸࡚ᐦᗘỗ㛵ᩘἲ(DFT)ࢆ⏝࠸࡚⌮ㄽⓗ࡟⪃ᐹࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ(1) ʌ ඹᙺ໬ྜ≀࡛㏆ᖺὀ┠ࡉࢀ࡚࠸ࡿࣂࢵ࣮࢟࣎࢘ࣝศᏊ࡜ C60 ࡢ」ྜయศᏊࡢศᏊ㛫┦஫స⏝ࢆ⪃࠼ࡿࠋࣂࢵ࣮࢟࣎࢘ࣝศᏊࡣࠊ2 ࡘࡢࢥࣛࢾࣞࣥ㒊ศࡀ࠾ࢃࢇᆺ࡟‴᭤ࡋࠊศᏊࡢ୰ኸ㒊ࢆ୰ᚰᢡࢀ᭤ࡀࡗ࡚
࠸ࡿᵓ㐀ࢆᣢࡘࠊʌ ඹᙺⅣ⣲໬ྜ≀࡛࠶ࡿࠋᮏᖺᗘࡣࠊࢥࣛࢾࣞࣥᆺࠊ
ཬࡧࢫ࣐ࢿࣥᆺ㸦ᅗ 1㸧ࣂࢵ࣮࢟࣎࢘ࣝศᏊ࡜ C60 ࡢศᏊ࡟ࡼࡿ」ྜయ
ᅗ 1. ࢫ࣐ࢿࣥᆺ Buckycatcher- 269 -

ࡢศᏊᵓ㐀ࢆỴᐃࡍࡿࠋḟ࡟ගບ㉳࡟క࠺ᵓ㐀ኚ໬ࢆỴᐃࡍࡿࡓࡵࠊGaussian 16 ࢆ⏝࠸࡚ TD-DFT ࢆ⾜࠸ࠊ྾཰ࢫ࣌ࢡࢺࣝゎᯒࡋࠊ㟁Ꮚ㓄⨨࡟╔┠ࡋ」ྜయࡢศᏊ㛫ࡢ㟁Ⲵ⛣ືࡢ࣓࢝ࢽࢬ࣒ࢆ⪃ᐹࡍࡿࠋィ⟬ࣞ࣋ࣝࡣඹ࡟ ȦB97XD/6-31G(d)࡛࠶ࡿࠋ

(2) ᭷ᶵග㉳㟁ຊ࡟ࡼࡿࢹࣂ࢖ࢫ࡟࠾࠸࡚ࠊࢻࢼ࣮࡜࢔ࢡࢭࣉࢱ࣮
ᒙࡢ⏺㠃࡛⏕ᡂࡍࡿ㟁Ⲵ࢟ࣕࣜ࢔㟁Ꮚ࡜࣮࣍ࣝࡣບ㉳Ꮚࢆᙧᡂࡍࡿࠋ
ຠ⋡ⓗ࡞㟁ὶ⏕ᡂࢆᚲせ࡜ࡍࡿኴ㝧㟁ụ࡟ࡣࠊࡇࡢບ㉳Ꮚࡢศゎ࡜⮬⏤㟁Ꮚ࢟ࣕࣜ࢔ࡣᚲせࡔࠋGaussian 16 ࢆ⏝࠸࡚ ab initio ィ⟬ࢆ⾜ࡗࡓࠋࢻࢼ࣮ศᏊ(D)࡟࣏࣐࣮ࣜPBDB-Tࠊ࢔ࢡࢭࣉࢱ࣮ศᏊ(A)࡟ȧඹᙺᑠศᏊ ITIC㸦ᅗ 2㸧ࢆࣔࢹࣝ⣔࡜ࡋࡓ PBDB-T/ITIC 」ྜయ㸦D/A㸧࡟ᑐࡋᅗ 2 ࢔ࢡࢭࣉࢱ࣮ศᏊ ITIC

࡚ࠊᇶᗏ≧ែࡢ࢚ࢿࣝࢠ࣮ィ⟬࡜ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋࡲࡓࠊD ࡜ Aඹ࡟ࣇࢵ⣲໬ࡋࡓ PBDB-T-SF/IT-4F 」ྜయ(FD/FA)࡟ᑐࡋ࡚ࠊ᫬㛫౫Ꮡᆺ DFT ࢆ⏝࠸࡚ບ㉳≧ែィ⟬ࢆ⾜ࡗࡓࠋィ⟬ࣞ࣋ࣝࡣඹ࡟ ȦB97XD/6-31G(d)࡛࠶ࡿࠋ

3◊✲ᡂᯝ
3.1 ࢥࣛࣥࢾࣞࣥᆺࠊࢫ࣐ࢿࣥᆺ Buckycatcher ศᏊ/C60 」ྜయࡢ㟁Ꮚ≧ែࢫ࣐ࢿࣥᆺ Buckycatcher ࡟ࡘ࠸࡚ᵓ㐀᭱㐺໬࡜᣺ືᩘィ⟬ࢆ⾜ࡗࡓ⤖ᯝࠊࢥࣛࣥࢾࣞࣥᆺ Buckycatcher ࡜ྠᵝ࡟ࠊࢫ࣐ࢿࣥ㒊ศࡀ࠾ࢃࢇᆺ࡟‴᭤ࡋ㗑ᙧࢆᣢࡘࠋࡇࢀࡣࠊࢫ࣐ࢿࣥศᏊࡢ ʌ 㟁Ꮚࡀྥࡁྜ࠺ࡇ࡜࡛Ᏻ
ᐃᛶࢆ㧗ࡵ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋࢫ࣐ࢿࣥᆺ Buckycatcher ࡟ C60
ࢆໟ᥋ࡉࡏࡓ」ྜయࡣ§aQP ࡢ྾཰ᖏࢆᣢࡘࠋ᭱ࡶᙉ࠸྾཰ࣆ࣮
ࢡ࡟╔┠ࡍࡿ࡜ࠊἼ㛗 QP ࡛୺せ࡞᣺ື㑄⛣ࡣ Buckycatcher ศᏊ࠿ࡽ C60 ࡬㟁Ⲵ⛣ືᆺ㑄⛣ࡋ࡚࠸ࡿᵝᏊࡀศ࠿ࡗࡓࠋCorannulene ᆺ BC
」ྜయࡢᏳᐃ໬࡜ഴྥࡣྠࡌࡔࡀࠊ
㌶㐨ࡸ㟁Ꮚᐦᗘ࠿ࡽ SXPDQHQH ᆺ BC
」ྜయ࡛ࡣࠊග↷ᑕ࡟ࡼࡾ㟁Ⲵ⛣ືᆺ㑄⛣ࡀࠊࡼࡾ㢧ⴭ࡟࡞ࡿࡇ࡜ࡀ᫂
ࡽ࠿࡟࡞ࡗࡓࠋ

3.2 PTB7/ITIC 㠀ࣇ࣮ࣛࣞࣥᆺ᭷ᶵⷧ⭷ኴ㝧㟁ụ࡟࠾ࡅࡿ㟁Ⲵ⛣ື࣓࢝ࢽࢬ࣒
㠀ࣇ࣮ࣛࣞࣥᆺ࢔ࢡࢭࣉࢱ࣮ศᏊ ITIC ࡢ྾཰ࢫ࣌ࢡࢺࣝࡣࣇ࣮ࣛࣞ
ࣥᆺ࡜ẚ࡭࡚ࠊ㛗Ἴ㛗㡿ᇦ࡟྾཰ᖏࢆᣢࡕࠊᗈᖏᇦ࡟྾཰ࢆᗈࡆࡿࡇ࡜

ᅗ 3 」ྜయࡢ྾཰ࢫ࣌ࢡࢺࣝ

ࡀ࡛ࡁࡿࠋD/A 」ྜయࠊFD/FA 」ྜయඹ࡟ࠊITIC ࡢ୺㙐࡟ᑐࡋ࡚ PBDB-Tࡢࢪࢳ࢜ࣇ࢙ࣥ㒊ศࡀ face-on ᵓ㐀࡛Ᏻᐃ໬ࢆ♧ࡋࡓࠋ
ᅗ 3 ࡣ D/AࠊFD/FA」ྜయࡢ྾཰ࢫ࣌ࢡࢺ࡛ࣝ࠶ࡿࠋD/A ࡜ FD/FA ࢆẚ㍑ࡍࡿ࡜㸦ᅗ 3 (a)(b)㸧
ࠊҮ400- QP ࡛ࠊFD/FA ࡢ᣺ືᏊᙉᗘࡀᙉࡃ࡞ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ
௨ୖࡼࡾࠊศᏊࡢࣇࢵ⣲໬ࡣྍどග㡿ᇦࡢ྾཰㔞ࡢቑຍ࡟ᐤ୚ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋPBDB-TࠊITIC ཬࡧࡇࢀࡽࡢࣇࢵ⣲໬ศᏊࡢ HOMO࣭LUMO
࢚ࢿࣝࢠ࣮࡟╔┠ࡍࡿ㸦ᅗ 4㸧
ࠋDࠊA ࢆࣇࢵ⣲໬ࡍࡿࡇ࡜࡛ HOMO࣭- 270 -

ᅗ 4HOMO/LUMO ࢚ࢿࣝࢠ࣮LUMO ࡀୗࡀࡿࡓࡵࠊFD/FA ࡛ࡣࠊD/A ࡜ẚ࡭ VOC ࡣ኱ࡁࡃ࡞ࡾࠊǻ+202࣭ǻ/802 ࡀ኱ࡁࡃ࡞ࡿࡇ࡜ࡀ
ࢃ࠿ࡗࡓࠋ௨ୖࡼࡾࠊศᏊࡢࣇࢵ⣲໬࡟ࡼࡗ࡚ࠊ㛤ᨺ㟁ᅽ VOC ࢆపୗࡉࡏࡿࡇ࡜࡞ࡃࠊග྾཰㔞ቑຍ࡟ࡼࡾ
▷⤡㟁ὶᐦᗘ JSC ࡀྥୖࡋࡓࡇ࡜࡛ PCE ࡣྥୖࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
մ12KWD$0XUDRND.<DPDVKLWD$360DUFK0HHWLQJ2020㸪Denver㸪2020 ᖺ 3 ᭶ մS. ,NH\DPD12KWD

. <DPDVKLWD $. Muraoka㸪$36 0DUFK 0HHWLQJ 㸪Denver㸪2020 ᖺ 3 ᭶  մS. ,NH\DPD $ 0XUDRND
Ewha-JWU-2FKDQRPL]X-RLQW6\PSRVLXP㸪Tokyo㸪2019 ᖺ 12 ᭶  մA. Muraoka㸪WK,QWHUQDWLRQDOZRUNVKRSRQTXDQWXPV\VWHPVLQFKHPLVWU\SK\VLFVDQGELRORJ\ TVFS 㸪Odessa㸪2019 ᖺ 8 ᭶  մኴ⏣ᕼ㸪ᒣୗ᫭୍㸪ᮧᒸᱻ㸪᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ⛅Ꮨᖺ఍㸪ᗈᓥ㸪2019 ᖺ 10 ᭶  մụᒣࡍࡳࢀ㸪ᮧᒸᱻ㸪ᒣୗ᫭୍㸪᪥ᮏࢥࣥࣆ࣮ࣗࢱ໬Ꮫ఍ 2019 ⛅Ꮨᖺ఍㸪ᗈᓥ㸪2019 ᖺ 10 ᭶մኴ⏣ᕼ㸪ᮧᒸᱻ㸪ᒣୗ᫭୍㸪➨ 9 ᅇ CSJ ໬Ꮫࣇ࢙ࢫࢱ 2019㸪⯪ᇼ㸪2019 ᖺ 10 ᭶ մኴ⏣ᕼ㸪ᮧᒸᱻ㸪ᒣୗ᫭୍ ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ 2019 ྡྂᒇ㸪ྡྂᒇ㸪2019 ᖺ 9 ᭶  մᮧᒸᱻ㸪ᯘ⨾ᬕ㸪㔠ᮡ⨾ຍᏊ ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ 2019 ྡྂᒇ㸪ྡྂᒇ㸪2019ᖺ 9 ᭶ 5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
մA. Muraoka, M. Ha\DVKL ³(OHFWURQLF 6WUXFWXUH RI 6XPDQHQH-W\SH %XFN\FDWFKHU E\ ')7 &DOFXODWLRQV´ Chem.

Phys. Lett., Chem. Phys. Lett., 748, 137393-1-137393-5 (2020)մ6 .DMLNDZD $ 0XUDRND ³7KHRUHWLFDO 6WXG\ RI WKH )H EWU  1&6  6SLQ-&URVVRYHU &RPSOH[ ZLWK5HSDUDPHWHUL]HG'HQVLW\)XQFWLRQDOV´ Chem. Phys. Lett., 738, 136867-1-136867-5 (2020)
մ, 0DVXPRWR 1 :DVKLGD 6 ,QRPDWD $ 0XUDRND . <DPDVKLWD, “Laser-induced fluorescence of the CHFCHOUDGLFDODQGUHDFWLRQRI2+UDGLFDOVZLWKKDORJHQDWHGHWK\OHQHV´J. Chem. Phys., 150, 174302-1-174302-8 (2019),- 271 -



Theoretical Studies on Vibronic Couplings
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jz#Ã"(¶+ïz´#Ïå"át+.) "gëã$ï¾Zc·}(VCC).®+k+ qÒ+CNPPE #>2ITMAP$ C iÃ.Ïå+FRS@10âè$Yjz"-*ðvm#Î¤VCD 'Yjz"ðvmVCD

Yjz"ðvm+#ÇíÅj"(),+ VCC $Ujz), VCC #Ë 1/2 e!!-hî"(jz+ïz´$Ïå°¬W¨ägëã4Ã.4O9IT.

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ºÙ~Ð&$X}[1] a× ¸ ½§”sñbÃ6N;=TA " +l»Ã”¡m|_É 100 {_(2020)
10¢\[2] ^y ÄÕLori Gonnet¸ ½§a× Michel Baron” :F3CPFPHSIQ2JB#L5
D8J5Po"5+Èbê#á¯” ¡m|_É 100 {_(2020)¢\i²~Ð&$X}

[1] N. Haruta et al., J. Phys. Chem. C, 123, 21581 (2019).
[2] W. Ota et al., J. Mater. Chem. C, DOI: 10.1039/c9tc07067b, in press.

- 272 -

᭷ᶵศᏊ⤯⦕⭷୰ࡢ㔠ᒓཎᏊࢡࣛࢫࢱ࣮ࡢືⓗᣲືࡢ◊✲First-principles study on dynamics of metal-atom clusters
in organic molecular insulating films‫ۑ‬୰ᒣ㝯ྐ㸪Ώ㑓㥴ử㸪ⓑ▼ᝆே㸪㉿⚈໏㸪➓ᕝᣅஓ㸪᳜⏣ኟⴥ㸪ึ㮵⣧ዉ㸦༓ⴥ኱Ꮫ㸧

1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࡢ┠ⓗࡣࠊ➨୍ཎ⌮ィ⟬ࢆ⏝࠸࡚ࠊ᭷ᶵศᏊ⤯⦕య⭷୰࡟㔠ᒓཎᏊࢡࣛࢫࢱ࣮ࡀᙧᡂࡉࢀ࡚࠸ࡃ㐣⛬࡜ࠊᏳᐃ࡞ࢡࣛࢫࢱ࣮ࡢᙧែࡸࡑࡢ≉ᛶࢆゎ᫂ࡍࡿࡇ࡜࡛࠶ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛ࡣᐦᗘỗ㛵ᩘ⌮ㄽ࡟ᇶ࡙ࡃ➨୍ཎ⌮㟁Ꮚ≧ែィ⟬ࢆ⏝࠸ࠊ᭷ᶵ⤯⦕⭷㸦࢔ࣝ࢝ࣥࢳ࣮࢜ࣝ⣔㙐≧ศᏊᅛయ SAM㸧୰࡛㔠ᒓཎᏊ(Au, Al)ࡢࢡࣛࢫࢱ࣮ࡀᡂ㛗ࡍࡿ㐣⛬ࡸᏳᐃ࡞ᙧែࢆᣑᩓ᩿⇕࣏ࢸࣥࢩࣕࣝ࡜
⮬⏤࢚ࢿࣝࢠ࣮ࡢほⅬ࠿ࡽㄪ࡭ࠊࡑࡢ㟁Ẽఏᑟࡸᖏ㟁≉ᛶࢆ᳨ウࡋࡓࠋᩘ್ィ⟬࡟ࡣࠊ⮬๓࡛㛤Ⓨࡋ࡚࠸ࡿ
xTAPP (Tokyo Ab-initio Program Package)ࠊ࠾ࡼࡧỗ⏝ࡢ VASP,

3

Siesta code ࢆ⏝࠸ࡓࠋ◊✲ᡂᯝ
ᅗ 1 ᕥࡣ㟁ᴟ࠿ࡽ౵ධࡋࡓ Au ཎᏊࡀ
SAM ୰࡟ᙧᡂࡋࡓࢡࣛࢫࢱ࣮࡛࠶ࡿࠋࢡࣛ
ࢫࢱ࣮ࡣࠊ㔠ᒓ㛫⤖ྜࡀᘬຊ࡜࡞ࡗ࡚⮬Ⓨⓗ࡟ᙧᡂࡉࢀࠊ࿘㎶ศᏊ࡟ᩚྜࡋࡓ㸰ཎᏊᖜࡢࢺࣛࢫᵓ㐀ࢆᣢࡕࠊࣃ࢖࢚ࣝࢫ㌿⛣ࡣ㉳ࡇࡽ࡞࠸ࠋࡇࡢ Au ࣡࢖ࣖࡣࠊࣇ࢙࣑ࣝ
࢚ࢿࣝࢠ࣮ࢆᶓษࡿࣂࣥࢻ㸦ᅗ 1 ୰ࡢ㟷୸)

ᅗ 1. SAM ୰ࡢ Au ࢡࣛࢫࢱ࣮ࡢᵓ㐀ࠊ㟁Ꮚ≧ែࠊఏᑟ⋡ࠋࢆ཯ᫎࡋ࡚ࠊᅗ 1 ྑࡢࡼ࠺࡟ 2e2/h ࡟㔞Ꮚ໬ࡉࢀࡓఏᑟ⋡ࢆ♧ࡍࠋAl ࡶྠᵝࡢ⤖ᯝ࡛࠶ࡿࠋࡇࢀࡽ⤖ᯝ࠿ࡽ᭷ᶵ⤯⦕⭷୰ࡢ㔠ᒓࢡࣛࢫࢱ࣮ࡣ⌮᝿ⓗ࡞㸯ḟඖ㓄⥺࡜࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬S. Watanabe, T. Nakayama, “Generation of one-dimensional metal-atom nano-rods in insulating SAM films:
first-principles study”, Int. Conf. Solid State Devices and Materials (SSDM 2019), Nagoya Japan, Sept.2-5 2019.
‫ۻ‬Ώ㑔㥴ử,୰ᒣ㝯ྐ, “࣌ࣥࢱࢭࣥ⭷୰ࡢᵓ㐀Ḟ㝗ࡢ㟁Ꮚ≧ែ࡜୙⣧≀ࡢྲྀ㎸ࡳ≉ᛶ:➨୍ཎ⌮ィ⟬࡟ࡼࡿ
᳨ウ”,➨ 67 ᅇᛂ⏝≀⌮Ꮫ఍᫓ᏘᏛ⾡ㅮ₇఍,ୖᬛ኱Ꮫ,2020 ᖺ 3 ᭶ࠊཬࡧ” ᭷ᶵ SAM ⭷୰࡟࠾ࡅࡿ㔠ᒓᰕࡢᙧᡂ࡜ఏᑟ≉ᛶ”, ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣡ࢡࢩࣙࢵࣉ 2019, ⮬↛⛉Ꮫ◊✲ᶵᵓᒸᓮ, 2019 ᖺ 12 ᭶.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬S. Watanabe, T. Nakayama, “Generation of one-dimensional metal-atom nano-rods in insulating SAM films:
first-principles study”, 㸦Jpn. J. Appl. Phys.࡟ᢞ✏ணᐃ㸧

- 273 -

ᕼⷧ⁐ᾮ୰ࡢ⌫≧࠾ࡼࡧᲬ≧ศᏊࡢᅇ㌿ᣑᩓಀᩘ࡜
6WRNH(LQVWHLQ'HE\H ࡢ㛵ಀࡢศᏊㄽⓗ⾲ᘧࡢ☜❧
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1◊✲┠ⓗࠊෆᐜᗘ T ࡢ⁐፹୰࡟࠶ࡿ༙ᚄ RS ࡢ Brownian ⢏Ꮚࡢ⮬ᕫᣑᩓಀᩘ Di ࡜⁐፹ࡢ⢓ᛶ⋡ Ksv ࡜ࡢ㛫࡟ࡣࠊ

Stokes-Einstein㸦SE㸧ࡢ㛵ಀk BT
nS RS K sv

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ࡣ stick ቃ⏺᮲௳࡟ࡑࢀࡒࢀᑐᛂࡍࡿࠋࡇࡢ⾲ᘧࡣ⁐፹ࢆ㐃⥆యࣔࢹ࡛ࣝ⾲ࡍ Stokes ࡢᘧ࡟ᇶ࡙࠸࡚࠾ࡾࠊศ
Ꮚࢫࢣ࣮࡛ࣝࡢ㐺⏝ᛶ࡟ࡣ㆟ㄽࡢవᆅࡀ࠶ࡗࡓࠋࡑࡇ࡛ᡃࠎࡣࠊศᏊືຊᏛ㸦MD㸧ἲ࡟ࡼࡗ࡚༢⣧ᾮయΰྜ⣔ࡢ㍺㏦ಀᩘࡢ⇕ຊᏛኚᩘ౫Ꮡᛶࢆホ౯ࡋࡓ⤖ᯝ࠿ࡽࠊศᏊㄽ࡟ᇶ࡙ࡃ SE ᘧ

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ࢆᑟ࠸ࡓ[5-5]ࠋࡇࡇ࡛ࠊN/V ࡣᩘᐦᗘࠊVi, mi, Hi ࡣ⁐㉁⢏Ꮚ i ࡢ┤ᚄࠊ㉁㔞ࠊ┦஫స⏝࢚ࢿࣝࢠ࣮ࠊVA, mA, HAࡣ⁐፹࡛ࡢࡑࢀࡽࡢᖹᆒ್ࢆࡑࢀࡒࢀ⾲ࡍࠋࡍ࡞ࢃࡕ(2)ᘧࡣࠊศᏊࢫࢣ࣮ࣝࡢ SE ࡢ㛵ಀࡀࠊᩘᐦᗘ࡟ຍ࠼
࡚ࠊ⁐㉁㸫⁐፹㛫ࡢࢧ࢖ࢬẚࠊ┦஫స⏝࢚ࢿࣝࢠ࣮ẚࠊ࠾ࡼࡧ㉁㔞ẚ࡟ᑐࡍࡿ౫Ꮡᛶࢆࡶࡘࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋࡉࡽ࡟ࠊ༢⣧ᾮయ୰ࡢࣇ࣮ࣛࣞࣥࢼࣀ⢏Ꮚࡢᕼⷧ⁐ᾮ࡟ࡘ࠸࡚ MD ィ⟬ࢆ⾜ࡗࡓ⤖ᯝࠊ㉁㔞ẚ౫Ꮡᛶࡣ⁐㉁ศᏊࡢ㉁㔞ࡀ⁐፹ศᏊࡼࡾࡶ኱ࡁࡃ࡞ࡿ࡟ࡘࢀ࡚ᾘኻࡍࡿࡇ࡜ࠊࡲࡓ┦஫స⏝࢚ࢿࣝࢠ࣮ẚ౫Ꮡᛶࡣ࢜
ࣜࢪࢼࣝࡢ SE ᘧ࡟࠾ࡅࡿቃ⏺᮲௳࡟┦ᙜࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ[5-5]ࠋ
㻝㻜

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DrKsv/kBT [1029 rad2 m-3 ]

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Dr[1012rad2 s-1]

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: O2

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㻤

N2
Cl2

㻞

O2

㻝

㻜

㻝㻜

m0 (N/V)0K7/3H -1/2(kBT)1 I -1/2(l/V)-2 [1012 s-1]

F2

㻜

㻞

㻠

㻢

㻤


㻝㻜

m (N/V) I K H (l/V [10 m ]ᅗ 1. ஧ཎᏊศᏊࡢ⣧ᾮయࡢᅇ㌿ᣑᩓಀᩘ      ᅗ 2. ஧ཎᏊศᏊࡢ⣧ᾮయࡢ SED ᘧ
1/2- 274 -

2/3 -1/2 1/3

0

29

-3

୍᪉ࠊศᏊࡢᅇ㌿㐠ືࡣࠊ୪㐍ࡸ᣺ື㐠ື࡜ඹ࡟ࠊ≀㉁ࡢືⓗᛶ㉁ࢆグ㏙ࡍࡿ୺せ࡞㐠ື࣮ࣔࢻࡢ୍ࡘ࡛
࠶ࡿࠋᾮయࡢὶືᛶࡣ୪㐍㐠ື࡟౫Ꮡࡋ࡚࠸ࡿࡀࠊ୪㐍ᣑᩓ࡜ᅇ㌿ᣑᩓࡢ㛫࡟ࡣᙉ࠸┦㛵㛵ಀ㸦⤖ྜ㸧ࡀ⌮ㄽⓗ࡟♧ࡉࢀࠊ㏆ᖺࡑࡢ㛵ಀࡢ◚ࢀࡀືⓗ୙ᆒ୍ᛶࡢุ᩿ᇶ‽࡜ࡋ࡚㔜せどࡉࢀ࡚࠸ࡿࠋ࡜ࡇࢁࡀࠊࡇࡢࡼ
࠺࡞୪㐍࡜ᅇ㌿ᣑᩓࡢ⤖ྜ࠾ࡼࡧࡑࡢ◚ࢀࢆ୍⯡ⓗ࠿ࡘᐃ㔞ⓗ࡟ㄽࡌࡿୖ࡛ࠊᅇ㌿ᣑᩓ࡟㛵ࡍࡿᇶ┙ⓗ᝟ሗ㸦ᐇ㦂್ࡸ⌮ㄽⓗぢ✚ࡾ㸧ࡣ୪㐍ᣑᩓ࡜ẚ㍑ࡋ࡚ⴭࡋࡃஈࡋ࠸ࠋࡇࢀࡣࠊᅇ㌿㐠ືࡀ≀ᛶ࡟ཬࡰࡍᙳ㡪ࡢ⠊ᅖࡶࡉࡿࡇ࡜࡞ࡀࡽࠊᐇ㦂ᡭẁ࡜ࡑࡢ㐺⏝ᑐ㇟ࡀ࡜ࡶ࡟㝈ᐃⓗ࡛࠶ࡿࡇ࡜ࡀ୺࡞ཎᅉ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ
ࡇࡢ≧ἣࢆඞ᭹ࡋࠊ୧⪅ࡢ㛵ಀࢆ୍⯡ⓗ࠿ࡘᐃ㔞ⓗ࡟ㄽࡌ࡚ṇ☜࡞⤖ㄽ࡟฿㐩ࡍࡿ᭱▷ࡢ᪉ἲࡣࠊᅇ㌿ᣑᩓ࡟㛵ࡍࡿἲ๎ᛶࢆᐃᘧ໬ࡍࡿࡇ࡜࡛࠶ࡿࠋ
ᮏ◊✲ࡢ┠ⓗࡣࠊᡃࠎࡀࡇࢀࡲ࡛☜❧ࡋࡓᡭἲ࡟ᇶ࡙࠸࡚ࠊ⌫≧࠾ࡼࡧ㠀⌫≧㸦ᮏㄢ㢟࡛ࡣᴃ෇ᙧ࡜Წ≧࡟㝈ᐃ㸧ࡢࣇ࣮ࣛࣞࣥศᏊࡢᕼⷧ⁐ᾮ୰࡛ࡢᅇ㌿ᣑᩓಀᩘࢆᐃᘧ໬ࡋࠊStokes-Einstein-Debye㸦SED)ࡢ㛵ಀࡢ
ᚤどⓗ⾲ᘧࢆồࡵࡿࡇ࡜࡛࠶ࡿࠋᮏᡭἲࡣࠊᚑ᮶ࡢᅇ㌿ᣑᩓ࡟㛵ࡍࡿ◊✲᪉ἲ࡜ࡣ୍⥺ࢆ⏬ࡋ࡚࠸ࡿࠋࡍ࡞
ࢃࡕࠊᚑ᮶ࡢ◊✲࡛ࡣ⊂❧࡟ホ౯࡛ࡁ࡞࠿ࡗࡓࠊศᏊࡢᙧ≧ࠊ័ᛶ࣮࣓ࣔࣥࢺࠊ࠾ࡼࡧ඘ሸ⋡ࡢຠᯝ࡟ࡘ࠸
࡚ࠊಶู࡟᫂☜࡟ࡍࡿࠋ౛࠼ࡤࠊ័ᛶ࣮࣓ࣔࣥࢺ࡜඘ሸ⋡ࢆ୍ᐃ࡟ಖᣢࡋࡓࡲࡲᙧ≧ࢆኚ໬ࡉࡏࡿࡇ࡜࡟ࡼ
ࡗ࡚ᙧ≧ࡢࡳࡢ౫Ꮡᛶࢆࠊࡲࡓ㏫࡟ᙧ≧࡜඘ሸ⋡ࢆಖᣢࡋࡓࡲࡲ័ᛶ࣮࣓ࣔࣥࢺࢆኚ໬ࡉࡏࡿࡇ࡜࡟ࡼࡗ࡚
័ᛶ࣮࣓ࣔࣥࢺࡢࡳࡢ౫Ꮡᛶࢆ᫂ࡽ࠿࡟ࡍࡿࠋᮏㄢ㢟࡟ඛ❧ࡗ࡚ࠊ୍㐃ࡢ஧ཎᏊศᏊࡢ⣧ᾮయ࡟ᮏᡭἲࢆ㐺⏝ࡋࠊᅇ㌿ᣑᩓಀᩘ࡜ SED ᘧࢆᐃᘧ໬ࡋࡓ⤖ᯝࢆᅗ㸯࡜㸰࡟♧ࡍࠋࡍ࡞ࢃࡕࠊ࢜ࣜࢪࢼࣝࡢ SED ᘧࡀ

Dr

k BT

(3)

n ' SRs K sv
3࡛⾲ࡉࢀࡿࡢ࡟ᑐࡋ࡚ࠊᮏᡭἲ࡛ồࡵࡓ஧ཎᏊศᏊࡢ⣧ᾮయ࡟ᑐࡍࡿ SED ᘧࡣࠊ

DrK sv§N·
v m1 2 I 1 2 ¨ ¸
k BT
©V ¹

2/3

§l ·
K ¨ ¸
©V ¹
13

2

   

(4)࡛⾲ࡉࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡇ࡛ࠊDr ࡣᅇ㌿ᣑᩓಀᩘࠊI ࡣ័ᛶ࣮࣓ࣔࣥࢺࠊKࡣ඘ሸ⋡ࠊl ࡣ⤖ྜ㊥㞳࡛࠶ࡿࠋΰྜ⣔࡛ࡣࠊ(2)ᘧ࡜ྠᵝࠊ⁐㉁࡜⁐፹ࡢ␗㉁ᛶࢆ⾲ࡍࠊࢧ࢖ࢬẚࠊ㉁㔞ẚࠊ┦஫స⏝࢚ࢿࣝࢠ࣮ẚ࡟ࡀ᪂ࡓ࡟ᑟධࡉࢀࡿࠋᮏㄢ㢟࡛ࡣࠊࢧ࢖ࢬẚ࡜┦஫స⏝࢚ࢿࣝࢠ࣮ẚ࡟ࡘ࠸࡚ㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛ࡣࠊ࢔ࣝࢦࣥᾮయࢆ⁐፹࡜ࡋࠊ✀ࠎࡢࣇ࣮ࣛࣞࣥศᏊࢆ⁐㉁࡜ࡋ࡚⁐Ꮡࡉࡏࡓᕼⷧ⣔ࡢ MD ィ⟬ࢆ Gromacs 4.5.5 ࠾ࡼࡧ 5.4.1 ࢆ⏝࠸࡚ᐇ⾜ࡋࡓࠋศᏊ㛫┦஫స⏝࡟ࡣ Lennard-Jones㸦LJ㸧ᆺ࣏ࢸࣥࢩࣕࣝࢆ
᥇⏝ࡋࡓࠋ⣔ࡢᗘ࡜ᐦᗘࡣᾮయ࢔ࣝࢦࣥࡢẼᾮᖹ⾮⥺ୖࡢᐇ㦂್࡜ࡋࡓࠋᑐ㇟࡜ࡋࡓࣇ࣮ࣛࣞࣥศᏊࡢᙧ

≧ࢆᅗ 3 ࡟♧ࡍࠋC60 ࠿ࡽ C150 ࡲ࡛ࠊ▷㍈᪉ྥࡢ᩿㠃ࢆ෇ᙧࡢࡲࡲࠊ࠿ࡘࡑࡢ┤ᚄࢆಖᣢࡋࠊ㛗㍈᪉ྥࡢࡳࢆ
Წ≧࡟ఙ㛗ࡉࡏࡓࠋᅗ 4 ࡟♧ࡍࡼ࠺࡟ࠊศᏊࡢᙧ≧ࢆ⾲ࡍኚᩘ࡜ࡋ࡚ࠊ஧ཎᏊศᏊ࡛⏝࠸ࡽࢀࡿ elongation l/ıࡢ௦ࢃࡾ࡟ a/b ࢆ⏝࠸ࡓࠋࡇࢀࡣࠊelongation ࢆ⏝࠸ࡿ࡜ࠊ⌫≧ࣇ࣮ࣛࣞࣥࡢሙྜ࡟ l = 0 ࡜࡞ࡗ࡚Ⓨᩓࡀ⏕ࡌࡿࡓࡵ࡛࠶ࡿࠋ୧⪅࡟ࡣ a/b = 1+ l/ı ࡢ㛵ಀࡀ࠶ࡿࠋࡲࡓࠊ⁐㉁࡜⁐፹ࡢࢧ࢖ࢬẚࡸ┦஫స⏝࢚ࢿࣝࢠ࣮ẚ࡞࡝ࡢ⇕ຊᏛኚᩘ౫Ꮡᛶࢆㄪ࡭ࡿ࡟࠶ࡓࡗ࡚ࠊC90 ࡟┦ᙜࡍࡿࢧ࢖ࢬ࡜ᙧ≧ࢆ᭷ࡍࡿ௬᝿ⓗ࡞஧ཎᏊศᏊ X2 ࢆ
LJ ࣏ࢸࣥࢩࣕࣝ࡟ࡼࡗ࡚ࣔࢹࣝ໬ࡋࠊ஧ཎᏊศᏊྠᵝ࡟ィ⟬ࡋࡓࠋ⣔ࡢ⤌ᡂࡣࠊ⁐㉁࡛࠶ࡿࣇ࣮ࣛࣞࣥ࠶ࡿ
࠸ࡣ௬᝿ศᏊᩘࡀ 8 ಶࠊ࢔ࣝࢦࣥཎᏊᩘࡀ 160,000 ಶ࡜ࡋࡓࠋࣇ࣮ࣛࣞࣥศᏊࡢ⤖ྜ㊥㞳ࡣ඲࡚ LINCS ἲࢆ⏝࠸࡚ᣊ᮰ࡋࡓࠋ᫬㛫้ࡳࡣ 2.0 fs ࡜ࡋࠊNVE ᮲௳ୗ࡛ MD ィ⟬ࢆᐇ⾜ࡋࡓࠋࣇ࣮ࣛࣞࣥศᏊࡢ⮬ᕫᣑᩓಀ- 275 -

ᩘ Di ࡣ Einstein ࡢබᘧࢆ⏝࠸࡚ホ౯ࡋࠊ⁐፹㸦ᾮయ࢔ࣝࢦࣥ㸧ࡢ⢓ᛶ⋡࡟ࡣࠊ㐣ᖺᗘࡢ◊✲ㄢ㢟࡛ࡢィ⟬⤖ᯝࢆ⏝࠸ࡓࠋ

ᅗ 3. ᮏ◊✲࡟࠾ࡅࡿྛ✀ࣇ࣮ࣛࣞࣥศᏊࡢᙧ≧      ᅗ 4. ࣇ࣮ࣛࣞࣥศᏊࡢᙧ≧ࢆ⾲ࡍኚᩘ 3ᕥୖ࠿ࡽ㡰࡟ࠊC60, C70, C90, C110, C150◊✲ᡂᯝ(4)ᘧࢆ࣮࣋ࢫ࡟ࠊ௬᝿ⓗ஧ཎᏊศᏊ X2 ࡟ᑐࡋ࡚ᮏ◊✲࡛ㄪ࡭ࡓᅇ㌿ᣑᩓಀᩘࡢࢧ࢖ࢬẚ࡜┦஫స⏝࢚ࢿࣝࢠ࣮ẚ࡞࡝ࡢྛኚᩘ౫Ꮡᛶࢆ㏣ຍ⤫ྜࡍࡿ࡜ࠊࣇ࣮ࣛࣞࣥศᏊࡢᕼⷧ⁐ᾮ࡟ᑐࡍࡿᚤどⓗ SED ᘧࡣࠊ

DrK sv§N·
v m1 2 I 1 2 ¨ ¸
k BT
©V ¹

2/3

§a·
K ¨ ¸
©b¹

7

13

§ Vi ·
¨¨
¸¸
©VA ¹

3

§ Hi ·
¨¨ ¸¸
©HA ¹

0.6

§ mi ·¨¨¸¸© mA ¹x(5)ࡢࡼ࠺࡟⾲ࡉࢀࡿࠋᮏ◊✲ㄢ㢟࡟࠾࠸࡚ࡣ㉁㔞ẚ౫Ꮡᛶࡣᮍᐃ࡛࠶ࡿࡓࡵࠊࡇࡢ㡯ࡢḟᩘࢆ x ࡜ࡋࡓࠋࡇࡇ
࡛ࠊ(4)ᘧ࡟࠾ࡅࡿ elongation ౫Ꮡᛶ (l/ı)-2 ࢆୖ㏙ࡢ a/b ࡛㏆ఝⓗ࡟⾲ࡍ࡜-7 ஌࡜࡞ࡿࡓࡵࠊ(5)ᘧ࡛ࡣ(a/b)-7࡛⨨ࡁ᥮࠼ࡽࢀ࡚࠸ࡿࠋࡍ࡞ࢃࡕࠊ(4)ᘧ࡟ẚ࡭࡚ࢧ࢖ࢬẚࡢ-3 ஌࠾ࡼࡧ┦஫స⏝࢚ࢿࣝࢠ࣮ẚࡢ-0.6 ஌ࡢ౫
Ꮡᛶࡀ㏣ຍࡉࢀ࡚࠸ࡿࠋ࡞࠾ࠊ㉁㔞ẚ౫Ꮡᛶࡣ୙᫂ࡢࡓࡵ⌧᫬Ⅼ࡛ࡣ x = 0 ࡜ࡋ࡚࠸ࡿࠋྛ✀ࣇ࣮ࣛࣞࣥศᏊ
ࡢᕼⷧ⁐ᾮ୰࡛ࡢィ⟬⤖ᯝࢆᅗ 5 ࡟♧ࡍࠋ஧ཎᏊศᏊࡣ୍ࡘࡢ㍈ࡢᅇ㌿㐠ືࡢࡳࢆ⪃៖ࡋࡓࡀࠊࣇ࣮ࣛࣞࣥ
ศᏊ࡛ࡣ㛗㍈࡜▷㍈ࡢᅇ㌿㐠ືࢆ⪃៖ࡍࡿᚲせࡀ࠶ࡿࠋᅗ୰ࡢ long ࡜ short ࡣࡑࢀࡒࢀ㛗㍈࡜▷㍈ࡢᅇ㌿ᣑᩓಀᩘ࡟ᑐᛂࡋ࡚࠸ࡿࠋᅗ 5 ࠿ࡽࢃ࠿ࡿ
㻤ࡼ࠺࡟ࠊࣇ࣮ࣛࣞࣥศᏊࡢᅇ㌿ᣑᩓಀᩘ

㻌: C60ࡇ࡜ࡀ࡛ࡁ࡚࠸ࡿࡶࡢࡢࠊ⥺ᙧ࡛ࡣ࡞࠸
ࡓࡵࠊࡲࡔࡑࡢ⾲ᘧࡣ୙᏶඲࡛࠶ࡿ࡜ゝ࠼ࡿࠋ࡞࠾ࠊᅗ 5 ୰ࡢᐇ⥺ࡣࠊ஧ཎᏊศ
Ꮚࡢ⣧ᾮయࡢ⤖ᯝ࡟᭱㐺໬ࡋࡓ┤⥺ࢆ⾲ࡋ࡚࠸ࡿࠋ⣧ᾮయ࡛ࡣࠊ⁐㉁࡜⁐፹ࡢ␗㉁ᛶࢆ⾲ࡍ㡯ࡀࠊࡍ࡭࡚ 1 ࡜࡞ࡗ࡚ᾘኻ
ࡍࡿࡶࡢࡢࠊࡑࡢ࡜ࡁ(5)ᘧࡣ(4)ᘧ࡟ྜ⮴ࡍࡿࡓࡵࠊࡶࡋ⣧ᾮయ࡜ྠࡌᣲືࢆྲྀࡿ
࡞ࡽࡇࡢ⥺ୖ࡟஌ࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋ
㏫࡟ゝ࠼ࡤࠊࡇࡢ┤⥺࠿ࡽࡢ㞳⬺ࡣࠊࡲ

DrKsv/kBT [1026 rad2 m-3 ]ࡢᣲືࡣࠊ(5)ᘧ࡟ࡼࡗ࡚ࠊ⣔⤫ⓗ࡟⾲ࡍ㻌: C70 (long)㻢㻌: C70 (short)
㻌: C90 (long)
㻌: C90 (short)㻠㻌: C110 (long)
㻌: C110 (short)
㻌: C150 (long)㻞㻜㻌: C150 (short)

㻜

m

㻝
1/2

(N/V) IK

2/3 -1/2 1/3㻞-7 (b/a)㻟-0.6

(HL㻛H㻭)-3(VL㻛V㻭) [10 m-3]25

ᅗ 1. ᾮయ࢔ࣝࢦࣥ୰ࡢࣇ࣮ࣛࣞࣥศᏊ࡟ᑐࡍࡿ
Stokes-Einstein-Debye ࡢ㛵ಀ- 276 -

ࡔ⪃៖࡛ࡁ࡚࠸࡞࠸㉁㔞ẚࡢᐤ୚࡜ࠊ⁐㉁࡜⁐፹ࡢ␗㉁ᛶ࡜ࡋ࡚ᙧ≧ࡢ㐪࠸ࡢᐤ୚ࡀ⪃࠼ࡽࢀࡿࠋᮏ◊✲࡛ࡣࠊ⏝࠸ࡓィ⟬ࢥ࣮ࢻ࡛ᢅ࠼ࡿศᏊෆࡢ㉁㔞ศᕸࡢၥ㢟ࡢࡓࡵࠊṇ☜࡞㉁㔞ẚ౫Ꮡᛶࡢホ౯ࡀ࡛ࡁ࡚࠸࡞࠸ࠋ
ࡇࡢࡓࡵࠊ௒ᚋࡣࡇࡢ㡯ࡢ౫ᏑᛶࡢỴᐃ࡜ࡑࡢᐤ୚ࡢ⪃ᐹࡀㄢ㢟࡛࠶ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] N. Ohtori, Y. Hattori, Y. Ishii, M. Salanne, P. A. Madden, and I. Okada, Revisiting the Chemla effect after 60
years from the discovery (oral), MS11, Orleans (France), May 19-23 2019.
‫[ۻ‬2]

ᚺ୫݊ଣ ಼ࢃٍ ੶Ҭྒྷध ୉௙൥࿪ գྮ‫٭‬য়ସͶ͕͜Ζୱ९ӹର͹༎ૻ‫਼ܐ‬ͶଲͤΖӀྙͳੳྙ͹ްՎ ϛηνʖ  ୊ 33 յ෾ࢢεϝϣϪʖεϥϱ౾࿨ճ Ѭஎ 2019 ೧ 12 ݆ 9-11 ೖ.

‫[ۻ‬3]

᭹㒊⏤ె㸪▼஭Ⰻᶞ㸪ᒸ⏣໏㸪኱㫽⠊࿴㸪ศᏊືຊᏛἲ࡟ࡼࡿ⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀ࡢෆ㒊⛣ືᗘࡢホ౯㸦ཱྀ㢌㸧ɾۜ଒ָճ๼཰৶ӿࢩ෨ʀర߱‫ڢ‬ճ๼཰৶ӿࢩ෨ྫ࿪‫ݫ‬೧ౕ࿊߻ߪԍճɾ৿‫׃‬ɾ2019೧ 11 ݆ 30 ೖ.

‫[ۻ‬4]

ᚺ୫݊ଣ ‫ٸ‬ຌষฑ ੶Ҭྒྷध ୉௙൥࿪ KA ϠυϩΝ༽͏ͪգྮ‫྘٭‬ҮͶ͕͜Ζ Stokes-Einstein ͹‫ܐؖ‬㸦ཱྀ㢌㸧㸪㔠ᒓᏛ఍໭㝣ಙ㉺ᨭ㒊࣭㕲㗰༠఍໭㝣ಙ㉺ᨭ㒊௧࿴ඖᖺᗘ㐃ྜㅮ₇఍㸪᪂₲㸪2019 ᖺ
11 ᭶ 30 ᪥.

‫[ۻ‬5]㏆⸨ඃከ ୉௙൥࿪ ੶Ҭྒྷध 0' ‫ࢋܯ‬ͶΓΖ௜ત‫ܗ‬෾ࢢͶଲͤΖ Stokes-Einstein-Debye ͹‫ܐؖ‬͹ఈࣞԿ ϛηνʖ  ୊ 42 յ༻ӹԿָεϱϛζΤϞ ‫ٸ‬৕ 2019 ೧ 10 ݆ 30-11 ݆ 1 ೖ.

‫[ۻ‬6]

ᚺ୫݊ଣ ಼ࢃٍ ੶Ҭྒྷध ୉௙൥࿪ գྮ‫ ٭‬LJ ӹର͹༎ૻ‫਼ܐ‬ͶଲͤΖӀྙͳੳྙ͹ްՎ ϛηνʖ  ୊ 42 յ༻ӹԿָεϱϛζΤϞ ‫ٸ‬৕ 2019 ೧ 10 ݆ 30-11 ݆ 1 ೖ.

‫[ۻ‬7]

ᮧୖᬛኸ㸪▼஭Ⰻᶞ㸪኱㫽⠊࿴ ࠱য়෾ࢢ͹‫ي‬Ϊη༻ӹͶ͕͜ΖηφʖέηʀΠ΢ϱεϣν΢ϱ͹‫ؖ‬‫ ܐ‬ϛηνʖ  ୊ 42 յ༻ӹԿָεϱϛζΤϞ ‫ٸ‬৕ 2019 ೧ 10 ݆ 30-11 ݆ 1 ೖ.

‫[ۻ‬8]ಙ⏣Ẹ⏕㸪▼஭Ⰻᶞ㸪኱㫽⠊࿴MD ‫ࢋܯ‬ͶΓΖӹରϗϱκϱ͹༎ૻద੓࣯ͳ Stokes-Einstein ͹‫ ܐؖ‬ϛηνʖ  ୊ 42 յ༻ӹԿָεϱϛζΤϞ ‫ٸ‬৕ 2019 ೧ 10 ݆ 30-11 ݆ 1 ೖ.

‫[ۻ‬9]

᭹㒊⏤ె㸪▼஭Ⰻᶞ㸪ᒸ⏣໏㸪኱㫽⠊࿴㸪ศᏊືຊᏛἲ࡟ࡼࡿ⁐⼥࢔ࣝ࢝ࣜࣁࣟࢤࣥ໬≀ࡢෆ㒊⛣ືᗘࡢホ౯㸦ཱྀ㢌㸧㸪➨ 51 ᅇ⁐⼥ሷ໬Ꮫウㄽ఍㸪໭ᾏ㐨㸪2019 ᖺ 10 ᭶ 24-25 ᪥.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] Y. Ishii, T. Murakami, and N. Ohtori, ࠕMolecular heterogeneity between solute and solvent: Effect on thetranslational diffusion and the Stokes-Einstein relationࠖ, in preparation.
‫[ ۻ‬2] N. Ohtori, Y. Kondo, and Y. Ishii, ࠕ Molecular size and shape effects: Rotational diffusion and the
Stokes-Einstein-Debye relationࠖ, under review.
‫[ۻ‬3] N. Ohtori, Y. Kondo, K. Shintani, T. Murakami, T. Nobuta, and Y. Ishii, ࠕThe Stokes-Einstein relation for
non-spherical molecular liquidsࠖ, Chem. Letters, 49, 379(2020).
‫[ۻ‬4] N. Ohtori, H. Uchiyama, and Y. Ishii, ࠕThe Stokes-Einstein relation for simple fluids: From hard-sphere to
Lennard-Jones via WCA potentialsࠖ, J. Chem. Phys. 149, 214501 (2018).
‫[ۻ‬5] Y. Ishii and N. Ohtori, ࠕMolecular insights into the boundary conditions in the Stokes-Einstein relationࠖ, Phys.
Rev. E 93, 050104 (2016).

- 277 -APEX  APEX 


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




Elucidation of reaction mechanisms of APEX reaction and polymerization,
structural and photophysical properties of nanocarbons moleculesoĞĝiĀĽġÙ®Ù¯tvŐ­¢¢Ńõ¢ĂĊąő1ĂĊýû{§

ı±öĜŌÏì ãďŐPAHőLOBZR;_BZR;_LO[W_(GNR)-TI^öĜŌÏñ N-PAH #"ĕö² z·°ŉ5,ĕöz· ñĘØÌ ¢-ÝĵÕß ¢%}Ľ ŏ çý5Ň+ 1Ò$2/ ñĘ%ôû#¾æ%Łú-ăûñ¼%ĥÐĂĊü6$ğ42 12) $¿&ĕöz· ñĘ5¤Ě 2 #xÀ§Ñ#ĜŌÏ 
ñ5, aâń ¾1Í ¾ÀæĕöÃµŐAnnulative π-Extension: APEXő»%Łú
5ğ#APEX »&¶´û$ĜŌö%hmb%dè¼#ìď-ãďē5þÆÈamb%Í ĕöĜŌö5ÝČ1»
12) QZC:YĦ$.1 % APEX »5Łú
%ď»1ĜŌö C–H ē%þÆ7[`\ %ßÝ5ľ¢ħċ5ø Ð/$
j¿&¦Ŏ ¢!ľ¢ħċ5ÿĢû$ø Í# APEX »%Łú5ýÄ»è¼Ĉ-»ßÝ%Ç¥è¼ ņ%ħċ#"5ğ# #/¦Ņ$¦Ŏ$R8`KPHA1!$.
¦øû#ÍĤ APEX »5ôû$Łú 1!Ö¸21)Łú % APEX » º/
2LOBZR;_N-PAHőGNR #"%ň ñ¼#"5ľ
¢ħċ ģĉ,2ĂĊÎæħċÎæ
×ĂĊ%ÔĹ&y%ħċ5 Gaussian 16 S^BZY5ø!Åħċ$&¨³åłÊæ(DFT)$ M06-2X/-6-31+G(d)łÊ5ø

&.0č³%ŏ

M06-2X/6-311++G(d,p)łÊ5ø)¾Ĉ

3ğ»ßÝĥÐĂĊ$ñ%ÝĵÔĹ

Truhlar /%ëĬĢá5ø

}

Ýĵ

<N\@`aíħċ$ěù<N\@`5ħċ

-wñ¼ħċ$& B3LYP/6-31+G(d)Ď- 6/311+G(d,p)Ď,ø



ĂĊ¾Ú

)TI^ 5Õ1TI^LOBZR;_- N-PAC %ôû#¾æ%Łú5ýÄ2)%¿% APEX »%āģ5÷¤Ě 2 # öĜŌÏì ãďŐPAHő/TI^ĜŌö 15Ì$aâń N-PAC ŋ¾ # ĈÜĨ%ēÚ7XK/§Ñ$ĬËº/21C7[`\9XK9\A^[K 2 5»!V_FR\=^[_ļĿ5CA^^<F_e80 °C
ïÉÂ1! Í$?O[_öÃµl2 N-PACŐ4ő5º1!$¾ŐTable 1őu 'R;L_J]_Ő1aőCR;M\>\WCXK9\A^[KŐ2aő5»1!CU_ER;
LC_ī¬sº/2Ő4aaők$,Þ# PAH9XK9\A^[K5ø 1! aĶ% N-PAH
5ôû$¾1!Ě!#0ó ĳ0Í aza-APEX »5Łú1!$¾[1])
¾aĶ%ÍĤLOBZR;_[2]- N-PAH[1]GNR[3]$ ×û#ň ñ¼wñ¼DVAJ\%gêħċ#",ğ ñõÕß ¢û#Í āģ5ģ|!$,¾×Ó &f$ÍĤ aza-APEX »%Łú!%ßÝĥÐĂĊ$ 1
à$Ô,×û#į 1a, 2a 5ø  aza-APEX »$ DFT ħċ$.1»ßÝ%ęª5ğ)×»$>G=_¼%Ŀ!9XK9\A^[K 2a »1!$.0äň ¼$©
*è¼#MJ[[:Y 5 ÷1% &# !n¥ŐFigure 1aőĈħċ-«î¦Ŏ$.1Üĩ5ğēÚ5 9XK9\A^[K 2a -9XK9\R\=[K 5′#".0£¥$¡ 1!Ą
2Ĕ R;L_J]_!%»5ÜĨ!3Figure 1b $Ą»ĸć5ĒÔđû$÷¾ñ

- 278 -

4aa (!È21!4#45 ! 1a %>G=_-π ŀs Int1 %÷¾ĜŌÏäň l%ìďìďē¶¾$.1ls Int2 %÷¾} {ĜŌÏäň ėÈ%ĕö»$.1 Int3 -ōs
3aa %÷¾5Ē1!4Ĳeģ|2ĺĆò½ TS1, TS2, TS3 & 2, 24–27 kcal/mol ć³%
è¼ ņ5, 0»ķğ1!!,$#úï5p !,4/$R;L_J]_% K ŊŐC9-C10 qő %ĻÁû#»İ1õù$ ĬÛŐFigure 1cőK Ŋm %»&R;L_J]_%ĜŌÏ£¥ %³ rc¹Ĵâń!#1~Ö%l»%è¼ ņ#1!4mb.0MJ[[:Y5Ãµ!ø Í APEX »Ď%ĪĐ
$ Įĭ5é+1!$¾
Ar′

+

N

Cl
Ar

PAHs/heteroarenes
1(0.40 mmol)
1a: phenanthrene

N
H
Ar

Ar

aza-APEX

diarylcarbimidoyl
chlorides
2 (2.0 equiv.)
2a: Ar = Ar′ = Ph

Ar′

via

N

ClCH2CH2Cl
80 °C, 17 hthen p-chlorail

H

H

Ar′

AgPF6
(2.0 equiv)

H

3

N-PACs 4
yield: up to 80%
25 examples

tBu

R

R

N

N

N

N

N

X

N

X = O,S

R

tBu

4aa

R
R = Me, tBu, OMe, CO2Me, F, Cl, Br, Bpin

Table 1. Aza-APEX reaction of unfunctionalized aromatics with diarylimidoyl chlorides.
(b) ΔG / kcal·mol–1(a)with Truhlar quasi harmonic correction

27.8

30.0
AgPF6
N+
–AgCl

PF6–

0.0

5′

ΔG = 20.9 lca/mol

C3

C1 TS1C2N+

N+ PF –

24.7

PF6– H

TS3

19.0

C

Int3

0.0

N

+

H

H

6.2
Int1

3aa·HPF6

PF6–

+

-10.0

TS1C2
C2

PF6–

+

N

N C

‡

C

N

C

H

-20.0

PF6–

+

H

–21.9

PF6–
H+
N

6

TS1C3

C9
TS1C9

-30.0

Int1

-40.0

transition state

ΔG‡

TS1C1
TS1C2
TS1C3
TS1C9

30.3 kcal/mol
32.0 kcal/mol
29.7 kcal/mol
27.8 kcal/mol

H

N

-60.0
-70.0

Int2

N

N

‡
C

C

-50.0

TS1C9
‡

+

H

H

PF6–

H

Int3

TS2

H

H

+

PF6–

N

10.0
5
0.0 kcal/mol

(c)

F5P F

1a + 5+ p-chloranil

25.7
TS2

20.0
Int2

+

2a

20.0

TS1C9

4aa·HPF6+ tetrachlorohydroquinone

C
PF6–

H

HH
PF6–

–56.2

TS3

M06-2X/6-311++G(d,p)//M06-2X/6-31+G(d) at 353.15 K in ClCH2CH2Cl (IEF-PCM)
with Truhlar quiasi-harmonic correction; scalling factor = 0.967

Figure 1. Suggested reaction mechanism of aza-APEX reaction computed by DFT calculation.

4

úĠ|ð¦Ė)&g¥(1) K. P. Kawahara, W. Matsuoka, H. Ito,* K. Itami,* Angew. Chem. Int. Ed. 2020, 59, 6383–6388. (2) Chaolumen,

H. Ito,* K. Itami,* Chem. Commun. 2019, 55, 9606–9609. (3) (a) Y. Yano, N. Mitoma, K. Matsushima, F. Wang, A.
Takakura, K. Matsui, Y. Miyauchi, H. Ito,* K. Itami,* Nature 2019, 571, 387–392. (b)Y. Yano, F. Wang, N. Mitoma, Y.
Miyauchi, H. Ito,* K. Itami,* J. Am. Chem. Soc. 2020, 142, 1686–1691. (c) N. Mitoma, Y. Yano, H. Ito,* Y.
Miyauchi,* K. Itami,* ACS Appl. Nano Mater. 2019, 28, 4825–4831.

- 279 -

Accurate estimation of electrode potential on TiO2 type cathodes
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l0Ü¡ßān Ø]ÕôÛ ÔÍ0Úó xìĈ®&.ßā9TGU0nt-1H NMR(CD3CN)
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4HR9TWRIGRÔîæċªõÆgÛĆ17 ppm 9TGUÑµ* ÊÓÛÎ0´-EHßā0¹ä©r'Č(1) EH¹ûVÉ¦čEH»èV¥Ïþf{|;UL<4Mċv^°ăëČ2020  2 ³ 2-3 ¯Ð[ï_ Organometallic Molecular Wires For Single-Molecule Devices(2) 3rd International Caparica Christmas Conference on Translational Chemistry 2019ċCaparica, PortugalČ2019 
12 ³ 2-5 ¯Y. TanakaCharge Transport Through Single-Molecule Junctions of Organometallic Polyyne Wires(3) 7th Asian Conference on Coordination ChemistryċKuala Lumpur, MalaysiaČ 2019  10 ³ 15-18 ¯
37 Y. Tanaka Single-Molecule Conductance Study of Metal Acetylide Molecular Wires(4) á 8  uJTUB21ÙÞf ċA3POUD´ĉÃ¿?:5B2Č 2019  8 ³ 24-25 ¯Ð[ï_ p5S6CTF6=0«}´»ÿĀhu

5còã»uÙÞ>U@W0qÏ©· ÔîċXêyćÔî 10 eL=@WÔî 4 eČoÈæ(1)M. Yamashina, Y. Tanaka, R. Lavendomme, T. K. Ronson, M. Pittelkow, J. R. Nitschke“An antiaromatic-walled nanospace”
Nature, 2019, 574, 511-515.
(2) M. Osawa, H. Yamayoshi, M. Hoshino, Y. Tanaka, M. Akita“Luminescence color alteration induced by trapped solvent molecules in crystals of tetrahedral gold(I) complexes:
near-unity luminescence mixed with thermally activated delayed fluorescence and phosphorescence”
Dalton Trans., 2019, 48, 9094-9013.
(3)Y. Oyama, R. Kawano, Y. Tanaka, M. Akita“Dinuclear Ruthenium Acetylide Complexes with Diethynylated Anthrahydroquinone and Anthraquinone
Frameworks: A Multi-Stimuli-Responsive Organometallic Switch”
Dalton Trans., 2019, 48, 7432-7441. (New Talent: Asia Pacific themed issue)(4)K. Matsumoto, S. Kusaba, Y. Tanaka, Y. Sei, M. Akita, K. Aritani, M. Haga, M. Yoshizawa
A Peanut-Shaped Polyaromatic Capsule: Solvent-Dependent Transformation and Electronic Properties of a NonContacted Fullerene Dimer
Angew. Chem. Int. Ed., 2019, 58, 8463-8467.
(5) Y. Tanaka, M. Akita
Organometallic Radicals of Iron and Ruthenium: Similarities and Dissimilarities of Radical Reactivity and Charge
Delocalization
Coord. Chem. Rev., 2019, 388, 334-342. (a special issue dedicated to Prof. Pombeiro)- 283 - 

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ÚøğxÐï)%h[1] S. Asako, S. Ishihara, H. Keiya, K. Takai, J. Am. Chem. Soc. 2019, 141, 9832.
[2]T. Doba, T. Matsubara, L. Ilies, R. Shang, E. Nakamura, Nat. Catal. 2019, 2, 400.
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Chemistry (ISOM XXIII), 2019 July, Barcelona.
[7] Ë, ¶¾mæ 100 ¹m, æ 34 õdl$ÒząÍm, 2020  3 ¼ĝöĞĠ[8] Ilies, Nanyang Research Conference on Synthetic Chemistry and Catalysis, 2020  1 ¼ĝA`;Ub]Ğ

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Computational Molecular Spectroscopy: Computational Chemistryon the Structure and Reaction of Molecules‫ۑ‬ᖹ㔝ᜏኵ㸦࠾Ⲕ኱⌮㸧ࠊ㛗ᔱ㞼ර㸦ィ⟬⛉Ꮫ᣺⯆㈈ᅋ㸧ࠊ௒ᇛ ᑦᚿ㸦᪥ᮏዪᏊ኱⌮㸧 ◊✲┠ⓗࠊෆᐜ๓ᖺᗘࡢㄢ㢟࡟ᘬࡁ⥆ࡁࠊࠕィ⟬ศᏊศගᏛࠖࡢどⅬ࡟❧ࡗ࡚ࠊḟࡢⅬ࡟㛵ࡍࡿ◊✲ࢆ⾜ࡗࡓࠋ ኱᣺
ᖜኚゅ᣺ືࢆࡍࡿศᏊ࡟㛵ࡋ࡚ࠊࠕศගᏛ⢭ᗘࡢab initioศᏊ㌶㐨ἲィ⟬࡟ࡼࡾ㉸㧗⢭ᗘࡢ࣏ࢸࣥࢩ࢚ࣕࣝࢿ
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ᖹ㔝ࢢ࣮ࣝࣉ࡟ࡼࡿab initioィ⟬࡛ࠊศගᏛ⢭ᗘ㸦cm-1 ࣞ࣋ࣝ㸧ࡢPESࡀồࡲࡿࡼ࠺࡟࡞ࡿ࡜ࠊ70ᖺ௨ୖࡢ
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HCN࡟㛵ࡍࡿ1௳ࡢࡳ㸦Carter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㸧ࠖࡢᴫᛕࢆࠊศගᏛ⪅ࡣ⌮ゎࡋ࡚࠸࡞࠸ࠊ࡞࡝࡞࡝࡛࠶ࡿࠋ
ィ⟬ศᏊศගᏛ࡛ࡣࠊึࡵ࠿ࡽPESࡀศ࠿ࡗ࡚࠸ࡿࡢ࡛ࠊᚑ᮶ࡢศගᏛ࡛ࡢࡇࢀࡽࡢḞ㝗ࢆ᫝ṇࡍࡿࡇ࡜ࡀฟ᮶ࡿࠋศᏊศගᏛࡢ෌ᵓ⠏࡛࠶ࡿࠋᖹ㔝ࠊ㛗ᔱࠊ㤿ሙࢢ࣮ࣝࣉࡢᡭ࡟వࡿၥ㢟࡛ࡣ࠶ࡿࡀࠊࢳࣕࣞࣥࢪ
࡟್ࡍࡿ㔜せㄢ㢟࡛࠶ࡿ࡜ᛮࡗ࡚ࡸࡗ࡚࠸ࡿࠋ
ᡃࠎࡣࠊ2008 ᖺ࡟┤⥺ศᏊNiCN ࡢ᣺ືᅇ㌿ᖹᆒࡢ⤖ྜゅࡢᮇᚅ್ࡀ171°࡛࠶ࡿࡇ࡜ࢆぢ࠸ࡔࡋ࡚௨᮶ࠊ
┤⥺ศᏊࡢ᣺ືᅇ㌿ᖹᆒᵓ㐀ࡣࠕ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿࠖࢆ୺ᙇࡋ࡚ࡁࡓࠋᴟࡃ᭱㏆࡟⮳ࡿࡲ࡛ࠊᅄ㠃ᴆḷ࡛࠶ࡗࡓࡀࠊศᏊ◊ࡢィ⟬⛉Ꮫࢭࣥࢱ࣮࡛ィ⟬ࡋࡓ㉸㧗⢭ᗘ࡞PES࡟ᇶ࡙ࡃ㆟ㄽࢆᒎ㛤ࡋ࡚࠸ࡿ࠺ࡕ࡟ࠊᡃࠎ
ࡢ୺ᙇ࡟㈶ྠࡍࡿศගᏛ⪅ࡀ⌧ࢀ࡚ࡁࡓࠋE pur si muove࡛࠶ࡿࠋ ◊✲ᡂᯝ- 286 -

ィ⟬ศᏊศගᏛ䛛䜙䛾䜰䝥䝻䞊䝏䛸㻌 䛭䛾ᡂᯝ㻌㻟㻚㻝㻌 ᪂䝟䝷䝎䜲䝮䠗㻌 ┤⥺ศᏊ䛾᣺ືᅇ㌿ᖹᆒᵓ㐀䛿䛂᭤䛜䛳䛶ぢ䛘䛶䛔䜛䛃㻌 㻙㻙㻙㻌 䛭䛾䠍䠖㻌 ⌮ㄽィ⟬㻌ᖹ㔝ࡽࡣ2004 ᖺ࡟ጞࡵࡓ FeNC, CoCN, NiCN ࡟࠾ࡅࡿࠕC-N

⾲1┤⥺ 3 ཎᏊศᏊ䛾 ‫ߩۃ‬ҧ ‫ۄ‬0

⤖ྜ㊥㞳ࡢ▷ࡍࡂࡿᐇ㦂್ࠖ࡟㛵ࡍࡿ◊✲௨᮶ࠊ┤⥺ᆺ 3 ཎᏊศᏊࡢ᣺ືᅇ㌿ᖹᆒᵓ㐀ࢆ⪃࠼࡚ࡁࡓࠋ
┤⥺ᆺ 3 ཎᏊศᏊࡢ PES ࡣ┤⥺ᵓ㐀࡛ᴟᑠ್ࢆ࡜ࡿࡢ࡛ࠊ☜⋡ᐦᗘ㸦Ἴື㛵ᩘࡢ᣺ᖜࡢ 2 ஌㸧ࡣࠊ┤⥺ᵓ㐀࡛ᴟ኱࡟࡞ࡿࠋ
ࡘࡲࡾࠊ⮬↛⏺㸦Schrödinger ᪉⛬ᘧ࡛グ㏙ࡉࢀࡿୡ⏺㸧࡛ࡣࠊ
ኚゅ᣺ືࡣ┤⥺ᵓ㐀ࢆ୰ᚰ࡟ࡋ࡚㉳ࡗ࡚࠾ࡾࠊᚑࡗ࡚┤⥺ศᏊࡢ᣺ື࣭ᅇ㌿ᖹᆒᵓ㐀ࡣ┤⥺ᆺ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚ࡁࡓ㸦ᪧࣃࣛࢲ࢖࣒㸧ࠋࡇࡇࡲ࡛ࡣࠊṇࡋ࠸ࠋࡋ࠿ࡋࠊࡑࢀࢆࠕほࡍࡿࠖ࡜࡝࠺ぢ࠼ࡿ࠿ࢆ▱ࡿࡓࡵ࡟ࠊࡑࡢἼື㛵ᩘࡢᮇᚅ್ࢆィ⟬ࡋ࡚ࡳࡼ࠺ࠋ3 ཎᏊศᏊ A-B-C ࡟࠾࠸࡚ࠊࡑࡢ┤⥺ᵓ㐀࠿ࡽࡢࢬ
ࣞࡢゅᗘࢆߩҧ㸦⤖ྜゅ(A-B-C)ࡢ⿵ゅ㸧ࠊศᏊ㍈ࡢ࿘ࡾࡢᅇ㌿ࢆF࡛⾲ࡍ࡜ࠊኚゅ᣺ືࡢἼື㛵ᩘ߮௩,௟ (ߩҧ , ߯)࠿ࡽࡢᮇᚅ್‫ߩۃ‬ҧ ‫ࠊࡣ ۄ‬గ‫ߩۃ‬ҧ ‫ = ۄ‬ൻ߮௩,௟ (ߩҧ , ߯)หߩҧ ห߮௩,௟ (ߩҧ , ߯)ൿ = 2ߨ ܰ ଶ ‫׬‬଴ ߶௩,௟ (ߩҧ )ଶ ߩҧ ଶ ݀ߩҧ>0‫ߩۃ‬ҧ ‫ۄ‬0 / degreesศᏊ6CO2
3 
6 FeCO
23 NCS
23 BrCN+
3) CoCN2 +6 MgNC
2' NiCN
6' FeCN
1 +6 HCO+
1 +6 DCO+
1 +
6 HCN
1 +
6 DCN
6
' FeNC
1
6 CsOH1 +6 C3
1ᮇᚅ್㻌 B0 䛾෌ゎ㔘
6.7°
8.8°
7.4°
9.5°
7.8°
7.8°
8°
8°
9.1°
9°
11°
11.0°
12.5°
9.8°
9.8°
12.0°
14.3°
10.7°
11.6°
13°
17°
19.7°
22.5°

࡟࡞ࡿ 1,2)ࠋࡘࡲࡾࠊ┤⥺ศᏊࡢኚゅ᣺ືࡣศᏊ㍈ࡢᘔࡾ࡟ 2 㔜
⦰㏥ࡋ࡚࠸ࡿࡢ࡛ࠊ᣺ື࣭ᅇ㌿ᖹᆒᵓ㐀ࢆࠕほ ࠖࡍࡿ࡜ࠊᇶᗏ≧ែࢆྵࡵ࡚࡝ࡢ᣺ື࣭ᅇ㌿≧ែ࡛ࡶࠕ᭤ࡀࡗ࡚ࠖぢ࠼ࡿ ‫ߩۃ‬ҧ ‫ >ۄ‬0 ࠋࡇࢀࡀࠊᖹ㔝ࡽࡢ୺ᙇ࡛࠶ࡿࠋ ࢮࣟⅬ᣺ື≧ែ࡟㛵ࡋ࡚ࠊᖹ㔝ࡽࡣࠊ‫ߩۃ‬ҧ ‫ۄ‬0㸻 0 ࡜ࡍࡿศගᏛࡢᖖ㆑㸦ࣃࣛࢲ࢖࣒㸧ࢆそࡍ࡭ࡃࠊἼື㛵ᩘࡢᮇᚅ್࡜ࡋ࡚ࠊ15 ✀㢮ࡢ┤⥺ 3ཎᏊศᏊࡢ‫ߩۃ‬ҧ ‫ۄ‬0 ࢆィ⟬ࡋ࡚ࡳࡓࠋ⾲  ࡟♧ࡍᵝ࡟ࠊ☜࠿࡟ᮇᚅ್‫ߩۃ‬ҧ ‫ۄ‬0> 0 ࡜࡞ࡗ࡚ࠊほ ࡍࢀࡤࠕ᭤ࡀࡗ࡚ぢ࠼ࡿࠖࡇ࡜ࡀぢ஦࡟❧ドࡉࢀࡓࠋ㻟㻚㻞㻌 ┤⥺ศᏊ䛾᣺ືᖹᆒᵓ㐀䛿䛂᭤䛜䛳䛶ぢ䛘䛶䛔䜛䛃㻌 㻙㻙㻙㻌 䛭䛾 㻞䠖㻌 ᐇ㦂䛷ᚓ䜙䜜䜛ᅇ㌿ᐃᩘ B0 䛾ゎ㔘ᐇ㦂ࡶ⮬↛ࡢࠕほ ࡛ࠖ࠶ࡿࠋࡑ࠺࡛࠶ࢀࡤࠊ
ࠕ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿࠖ≧ែ࡟ᑐᛂࡋࡓᅇ㌿ᐃᩘࡀồࡲࡗ࡚࠸ࡿࡣࡎ࡛࠶ࡿࠋࡇࢀࢆ᳨ドࡍࡿ࡟ࡣࠊ┤⥺ᆺ 3 ཎᏊศᏊࡢ 3 ಶࡢᵓ㐀ࣃ࣓࣮ࣛࢱ࣮ࡢ࠺ࡕࠊᚑ
᮶ a priori ࡟ 0 ᗘ࡜ࡋ࡚ᅛᐃࡋ࡚࠸ࡓ┤⥺࠿ࡽࡢࢬࣞࡢゅᗘ ߩҧ ࢆࠕኚᩘࠖ࡜ࡋ࡚ᢅ࠸ࠊ3 ಶ௨ୖࡢྠ఩
య␗ᛶయࡢᅇ㌿ᐃᩘ B0 ࡢᐇ㦂್ࢆṇ☜࡟෌⌧ࡍࡿ᣺ືᅇ㌿ᖹᆒᵓ㐀ࢆồࡵ࡚ࡳࢀࡤⰋ࠸ࠋ ⤖ᯝࡣ⾲ 1
䛾䛂B0 ࡢ෌ゎ㔘ࠖḍ࡟♧ࡋ࡚࠶ࡿࡀࠊ᣺ືᅇ㌿ࡢᖹᆒ್ ߩҧ଴ ࡣ ߩҧ଴ > 0 ࡛࠶ࡾࠊࡋ࠿ࡶᮇᚅ್࡜ࡼࡃ୍⮴ࡋࡓ⤖ᯝࡀᚓࡽࢀ࡚࠸ࡿࠋᚑࡗ࡚ࠊᐇ㦂ⓗ࡟ࡶࠊ⌮ㄽⓗ࡟ࡶࠊߩҧ଴ > 0 ࡣṇࡋ࠸ࡢ࡛࠶ࡿࠋ

㻟㻚㻟㻌 ┤⥺ศᏊ䛾᣺ືᖹᆒᵓ㐀䛿䛂᭤䛜䛳䛶ぢ䛘䛶䛔䜛䛃㻌 㻙㻙㻙㻌 䛭䛾 㻟䠖㻌 㟁Ꮚ⥺ᅇᢡ䛛䜙䛾᳨ド㻌 ᖺ௦ࠊ᳃㔝࣭ᮙὠ࡟ࡼࡗ࡚ Shrinkage㻌 effect ࡀᥦ᱌ࡉࢀࡓࠋᮎ➃㛫ࡢཎᏊ㛫㊥㞳ࡣࠊᵓᡂࡍࡿ⤖ྜ㛗ࡢ࿴ࡼࡾᚲࡎ
▷ࡃ࡞ࡿ⌧㇟࡛ࠊᙼࡽࡣࡑࡢཎᅉࢆṇࡋࡃ⌮ゎࡋ࡚࠸ࡓࡀࠊ
ᪧࣃࣛࢲ࢖࣒ࡢୗ࡛ࡣࠊᐇࡣ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿࡢ࡟ࠊࡇࢀ
ࢆ┤⥺ᙧࡔ࡜ࡋ࡚⌮ゎࡋࡼ࠺࡜ࡋࡓࡢ࡛࠶ࡿࠋᖹ㔝ࡽࡣࠊィ⟬ศᏊศගᏛ࠿ࡽࡢ r0 ᵓ㐀࡜ẚ㍑ࡋ࡚ࠊshrinkage ࡛ࡣ࡞ࡃ࡚ࠊ
ᐇ㝿࡟᭤ࡀࡗ࡚ほ ࡉࢀ࡚࠸ࡿࡇ࡜ࢆ♧ࡋࡓ 3)ࠋHCN ࡢሙྜࢆྑᅗ࡟♧ࡍࠋ㟁Ꮚ⥺ᅇᢡࡣ ; ⥺ᅇᢡ࡜ྠࡌཎ⌮࡞ࡢ࡛ࠊࠕᢠᘚ୙⬟࡛࠶ࡾࠊᩍ⛉᭩ࢆ᭩ࡁ᥮࠼ࡿ࡭ࡁㄽᩥ࡛࠶ࡿࠖ࡜ࠊࣞ
ࣇ࢙࣮ࣜ࠿ࡽ⃭㈶ࢆཷࡅࡓࠋ

- 287 -

㻟㻚㻠㻌 ▷䛩䛞䜛 㻯㻙㻺 ⤖ྜ㊥㞳䠄ᐇ㦂್䠅㻦㻌 ┤⥺ศᏊ FeNC, CoCN, NiCN
ᅇ㌿ᐃᩘࡢᐇ㦂್࡟཯ᫎࡉࢀࡿࡢࡣࠊ᣺ືᅇ㌿ᖹ⾲ 2㻌 CN ⤖ྜ㊥㞳䛾ᐇ㦂್䛸⌮ㄽ್䛾ẚ㍑
ᆒࡢ⤖ྜ㛗 r0 ࡛ࡣ࡞ࡃ࡚ࠊࡑࡢ୺㍈࡬ࡢࠕᢞᙳ㛗ࠖ
FeNC
CoCN
NiCN
࡛࠶ࡿࠋ᣺ືᖹᆒᵓ㐀ࡀࠕ᭤ࡀࡗ࡚ぢ࠼ࡿࠖࡢ࡛࠶
1.03(8)1.1313(10) 1.1591(29)Obs. (r0 / Å)ࢀࡤࠊ୺㍈࡬ࡢᢞᙳ㛗ࡣ᣺ືᅇ㌿ᖹᆒࡢ⤖ྜ㛗 r0 ࡼࡾ▷ࡃ࡞ࡿࠋᐇ㦂࡛ሗ࿌ࡉࢀ࡚࠸ࡿ FeNC, CoCN,
Calc. (re / Å)
1.1823 1.1677
1.1665
NiCN ࡢ▷ࡍࡂࡿ CN ⤖ྜ㛗ࡣࠊᐇࡣࠕ᭤ࡀࡗ࡚ぢ࠼
1.17181.1705(r0 / Å) 1.1866
࡚࠸ࡿࠖᖹᆒ⤖ྜ㛗ࡢ a ୺㍈࡬ࡢᢞᙳ㛗࡛࠶ࡿ࡜ࡍ
(¢ߩҧ ²0 /deg.) 1389ࡿ࡜ࠊࡍ࡭࡚ࡢᐇ㦂್ࡀ⌮ゎ࡛ࡁࡿࠋᐇ㝿࡟ᮏᖺᗘࡢ෌ィ⟬࡛ࠊNiCN࡟ᑐࡍࡿᐇ㦂್ 1.1591(29) Åࡣࠊᐇࡣr0࡛ࡣ࡞ࡃ࡚ࠊr0 = 1.1705 Åࡢa୺㍈࡬ࡢᢞᙳ㛗r0,proj(C-N)࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ

㻟㻚㻡㻌 ᐇ㦂䛷ⰾ㤶⎔䛻䛴䛔䛯㻌㻯㻙㻴㻌⤖ྜ㛗䛸㻌㻯㻙㻰㻌⤖ྜ㛗䛜ྠ䛨㛗䛥䛻䛺䜛⌮⏤㻌୍⯡࡟ࠊ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮㛵ᩘࡢ㠀ㄪ࿴ᛶࡢࡓࡵ࡟ࠊC-H ⤖ྜࡣC-D ⤖ࡼࡾ㛗ࡃ࡞ࡿࡀࠊⰾ㤶⎔࡟ࡘ࠸ࡓC-H䠄D䠅ࡢ⤖ྜ㛗ࡣࠊ࡯ࡰྠࡌ࡟࡞ࡿࡇ࡜ࡀ㤿ሙṇ᫛ࡽ࡟ࡼࡗ࡚ሗ࿌ࡉࢀ࡚࠸ࡿࠋ࣋ࣥࢮࣥࢆ
(C5H5)CDHDࡢ3ཎᏊศᏊ࡜ぢ❧࡚ࡿࡇ࡜࡟ࡼࡗ࡚ࠊ㠃እ᣺ື࡟࠾ࡅࡿC-H(D)⤖ྜࡢ୺㍈࡬ࡢᢞᙳ㛗ࢆ⪃࠼ࡿ࡜㸦ࡘࡲࡾࠊ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿ࡜ࡍࡿ࡜㸧ࠊ㠃እ᣺ື࡟࠾ࡅࡿኚゅࡢゅᗘࡢ኱ࡁ࠸C-H⤖ྜࡢ᪉ࡀ▷ࡃ࡞ࡿࡓࡵࠊ㠀ㄪ࿴ᛶ࡟ᇶ࡙ࡃఙࡧ࡜࢟ࣕࣥࢭࣝࡋ࡚ࠊศගᐇ㦂࡛ࡢ effective࡞ᅇ㌿ᐃᩘ࠿ࡽồࡲࡿ effective࡞⤖ྜ㛗㸦a୺㍈࡬ࡢᢞᙳ㛗࡛࠶ࡿ㸧࡛ࡣࠊr0,eff(C-H) §r0,eff(C-D)࡜࡞ࡿࡇ࡜ࢆ♧ࡋࡓࠋ㻟㻚㻢 ኱᣺ᖜኚゅ᣺ືࢆ⾜࠺┤⥺ศᏊ࡟࠾ࡅࡿ␗ᖖ㸽࡞㛵ಀ㸸 r0 < re୍⯡࡟ࠊC-HࡸO-H⤖ྜࡢ⤖ྜ㊥㞳ࡣࠊ᣺ື࣏ࢸࣥࢩࣕࣝࡢ㠀ㄪ࿴ᛶࡢࡓࡵ࡟ࠊᑐᛂࡍࡿ㸦C-D㸧ࡸO-D⤖ྜ㛗ࡼࡾ㛗ࡃ࡞ࡿࠋࡇࡢᖖ㆑࡟཯ࡋ࡚ࠊ኱᣺ᖜኚゅ᣺ືࢆ⾜࠺┤⥺ศᏊ࡛ࡣࠊᐇ㦂࡛ᚓࡽࢀࡿeffective ࡞ᅇ㌿ᐃᩘ࠿ࡽᑟ࠿ࢀࡿࢮࣟⅬ᣺ື≧ែ࡛ࡢᖹᆒ⤖ྜ㛗r0,effࡣࠊࡑࢀࡒࢀࡢᖹ⾮⤖ྜ㛗reࡼࡾ▷ࡃ࡞ࡿࡇ࡜ࡀ࠶
ࡿࠋࡇࡢ୍ぢࠊወጁ࡞ᖖ㆑࡟཯ࡍࡿ⌧㇟ࡣࠊᐇࡣࠊᅇ㌿ᐃᩘࡢᐇ㦂್࠿ࡽᚓࡽࢀࡿ⤖ྜ㛗ࡣࠊa ୺㍈࡬ࡢᢞᙳ㛗r0,proj࡞ࡢ࡛ࠊᢞᙳゅࡀ኱ࡁࡃ࡞ࡿ࡜ࡑࡢᢞᙳ㛗ࡣ▷ࡃ࡞ࡗ࡚r0,proj < re࡜࡞ࡿࡇ࡜ࡀ࠶ࡿᚓࡿࡇ࡜ࠊ࠾
ࡼࡧࠊࡑࡢሙྜ࡛ࡶࠊᩥᏐ㏻ࡾࡢࢮࣟⅬ᣺ື⤖ྜ㛗r0࡟㛵ࡋ࡚ࡣࠊᚑ᮶ࡢᖖ㆑㏻ࡾr0 > reࡀᡂࡾ❧ࡘࡇ࡜ࢆ♧ࡍࡇ࡜ࡀฟ᮶ࡓࠋ

㻟㻚㻣㻌 ኱᣺ᖜኚゅ᣺ື䛾ィ⟬ศᏊศගᏛ㻌ᡃࠎࡣࠊab initioศᏊ㌶㐨ἲ࡟ᕤኵࢆจࡽࡋ࡚ Bauschlicher᫬௦䛻㍑䜉䛶㻌1䡚2᱆䜒ィ⟬⢭ᗘ䜢ୖ䛢䚸⢭⦓䛺ᐇ㦂ศගᏛ䛻䜒ຎ䜙䛼༑ศ䛺⢭ᗘ䠄ศගᏛ⢭ᗘ䠖ㄗᕪ cm-1䝺䝧䝹䠅䜢㄂䜛㻌ab initioศᏊ㌶㐨ィ⟬䜢⾜䛖䛣䛸䜢ྍ⬟䛻䛧䛯䚹䛣䛖䛧䛶ồ䜑䛯㻌PES䛻ᇶ䛵䛔䛶䚸᣺ືᅇ㌿䛾㻌Schrödinger᪉⛬ᘧ䜢ゎ䛝䚸䛭䛾Ἴື㛵ᩘ䛾ᮇᚅ್䛸䛧䛶㻌r0ᵓ㐀䠄᣺ືᅇ㌿䜢ྵ䜣䛰ᖹᆒ⤖ྜ㛗䜔⤖ྜゅ䠅䜢⟬ฟ䛩䜛䛣䛸䛻ᡂຌ䛧ࠊᐇ㦂ศᏊศගᏛ࡛ࡣᚓࡽ
ࢀ࡞࠸ᵝࠎ࡞▱ぢࢆᥦ౪ࡋ࡚ࡁࡓࠋᪧࣃࣛࢲ࢖࣒ࢆそࡋ࡚ࠊ┤⥺ศᏊࡢ᣺ືᅇ㌿ᖹᆒᵓ㐀ࡣࠕ᭤ࡀࡗ࡚
ぢ࠼࡚࠸ࡿࠖ࡜࠸࠺᪂ࡋ࠸ࣃࣛࢲ࢖࣒ࢆᡴࡕ❧࡚ࡿ࡭ࡃᣮᡓࡣ⥆࠸࡚࠸ࡿࠋ

㻟㻚㻤㻌 ཯ᛂ䛻䛚䛡䜛ືⓗ㐣⛬䛾ゎᯒ㻦㻌 㻌 㻟㻌㔜㡯㓟⣲䛻䜘䜛㓟໬཯ᛂ㻌㻌✵Ẽ୰ࡢ㓟⣲ศᏊࡣࠊ
3㔜㡯 O2 ࡛࠶ࡿࡀࠊ
࢔ࢫࢥࣝࣅࣥ㓟࢔ࢽ࢜ࣥ ࣅࢱ࣑ࣥ & ࡢ࢔ࢽ࢜ࣥ ࡜ࡢ཯ᛂ࡛ࡣࠊ
3㔜㡯O2࡛ࡶࠊ1㔜㡯O2࡛ࡶྠࡌ⏕ᡂ≀ࡀᚓࡽࢀࡿࡇ࡜ࡀศ࠿ࡗ࡚࠸ࡿࠋࡲࡓࠊSc + O2 ࡢ཯ᛂࡢゎᯒ࠿ࡽࠊ
3㔜㡯O2 ࡜ࡢ཯ᛂ࡛ࡶࠊ཯ᛂࡢ㏵୰࡛Sc࠿ࡽO2࡬ࡢ1㟁Ꮚ⛣⾜ࡀ㉳ࡁࡿࡓࡵࠊ⤖ᯝ࡜ࡋ࡚ࠊ2㔜㡯O2࡜ࡢ཯ᛂ࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗ࡚ࡁࡓࠋ୍⯡໬ࡍࢀࡤࠊ㟁Ꮚ౪୚ᛶࡢ㧗࠸ศᏊ࡜O2࡜ࡢ཯ᛂ࡛ࡣࠊ཯ᛂࡢ㏵୰࡛㟁Ⲵ⛣ືࡀ㉳ࡇࡿࡓࡵ࡟ࠊ3㔜㡯O2࡛ࡶࠊ1㔜㡯O2࡛ࡶO2㒊ศࡢ୙ᑐࢫࣆࣥࡀ1ಶᾘ࠼࡚2㔜㡯O2࡜

- 288 -

ࡋ࡚཯ᛂࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗ࡚ࡁࡓࠋከ㓄⨨ࡢ MCSCF ィ⟬࡞ࡢ࡛཰᮰ࡋ࡟ࡃ࠸ࡀࠊ࡯ࡰ 80%ࡢィ⟬ࢆ⤊࠼ࡿࡇ࡜ࡀ࡛ࡁࡓࠋィ⟬ࡣḟᖺᗘ࡟ᘬࡁ⥆࠸࡚⾜࠺ࠋ Ⓨ⾲ᐇ⦼ㄽᩥ࠾ࡼࡧᏛ఍Ⓨ⾲>ㄽᩥ@1) ‫ ۻ‬Ro-vibrationally averaged dipole moments of linear triatomic molecules, Tsuneo Hirano, Umpei
Nagashima, Per Jensen, Hui Li, J. Mol. Spectrosc., 362, 29-36. (2019)2) ‫ ۻ‬More evidence for bent ro-vibrationally averaged structures of linear triatomic molecules: The non-zer b axis
component of the dipole moment and the rg structure in electron diffraction, Tsuneo Hirano, Umpei Nagashima,
Masaaki Baba, J. Mol. Spectrosc., 369, 111252 (2020).
3) ‫ ۻ‬The well-established relation r0 > re holds always?, Tsuneo Hirano, Umpei Nagashima, Masaaki Baba, J. Mol.
Struct., in press (2020).
4) ‫ ۻ‬Almost the same C-H(D) bond lengths found in each H and D isotopologues for benzene,
naphthalene, and anthracene: Why? , Tsuneo Hirano, Umpei Nagashima, Masaaki Baba, J. Chem. Phys.,submitted.
[Ꮫ఍Ⓨ⾲]‫ۻ‬┤⥺ศᏊࡣ᭤ࡀࡗ࡚࠸ࡿ࠿?! ࣁ࢖ࠊ᭤ࡀࡗ࡚ࠕぢ࠼ࡲࡍࠖ!!
ᖹ㔝ᜏኵࠊ㛗ᔱ㞼රࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇ‫ⰾ ۻ‬㤶᪘Ⅳ໬Ỉ⣲䛾 C-H 䛸 C-D 䛾⤖ྜ㛗䛿䜋䜌➼䛧䛔䚹䛺䛬䛰䜝䛖䛛䠛㤿ሙṇ᫛䚸㛗ᔱ㞼රࠊᖹ㔝ᜏኵࠊ ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇ‫ ۻ‬Ẽ┦࡟࠾ࡅࡿ ScO ࣛࢪ࢝ࣝ࡜㓟⣲࡜ࡢ཯ᛂ㏿ᗘᐃ௒ᇛᑦᚿ, ᒣ໭ዉ⨾, ᖹ㔝ᜏኵࠊ➨ 13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇ
‫⥺┤ ۻ‬ศᏊࡢ᣺ືᖹᆒᵓ㐀ࡣࠊ᭤ࡀࡗ࡚ぢ࠼࡚࠸ࡿ㸟ᖹ㔝ᜏኵࠊ㛗ᔱ㞼ර 㤿ሙṇ᫛,㻌 SCCJ ⛅Ꮨᖺ఍䚸㻌 ᗈᓥ‫ ۻ‬ィ⟬ศᏊศගᏛ㸸ࣃࣛࢲ࢖࣒ࢩࣇࢺ࡬ࡢᣮᡓ
ᖹ㔝ᜏኵࠊ㧗ศゎ⬟ศᏊศගࢩ࣏ࣥࢪ࣒࢘ࠊி㒔‫ ۻ‬ィ⟬ศᏊศගᏛ࠿ࡽࡢᥦゝ㸸 ᐇ㦂ศᏊศගᏛࡢ෌ᵓ⠏㸽ᖹ㔝ᜏኵࠊ㛗ᔱ㞼ර 㤿ሙṇ᫛䚸ᶓ὾ᕷ❧኱Ꮫࢩ࣏ࣥࢪ࣒࢘ࠊᶓ὾
‫ࣥࢮࣥ࣋ ۻ‬ศᏊࡢᅇ㌿ᐃᩘ࡜ᖹᆒ⤖ྜ㛗࡟㛵ࡍࡿ ab initio ⌮ㄽィ⟬㤿ሙṇ᫛䚸㛗ᔱ㞼රࠊᖹ㔝ᜏኵࠊ➨  ᅇศᏊศග◊✲఍B໭㔛኱Ꮫ 㸦ࢥࣟࢼ࢘࢖ࣝࢫ࡛୰Ṇ㸧‫ ۻ‬Ab initio calculations on rotational constant and averaged C-H(D) bond lengths of benzene,
Tsuneo Hirano, Umpei Nagashima, International Symposium on Molecular Spectroscopy 2020, Illinois,
USA (ࢥࣟࢼ࢘࢖ࣝࢫ࡛୰Ṇ㸧㸬ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋཧ⪃ᩥ⊩1) T. Hirano and U. Nagashima, J. Mol. Spectrosc., 314, 35-47 (2015).
2) Tsuneo Hirano, Umpei Nagashima, and Per Jensen, J. Mol. Spectrosc., 343, 54-61 (2018).
3) Tsuneo Hirano, Umpei Nagashima, Masaaki Baba, J. of Molecular Spectrosc., 369, 111252 (2020).

- 289 -

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/2o¾ûGYC:RAJ * Cs BUJV9@8Y
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Fig 1  Cs1 FA12 MA3 Pb16 I40 Br8!ªës²è

- 290 -

FA3 MA1 Pb4 I12 ¯¥2s ! valence band maximum (VBM)  , #conduction band minimum (CBM)2JXAB*!2 Fig 2 ÉûMAPbI3 " tetragonal ²èú
FAPbI3 " cubic ²è Ä/2ÙúFA3 MA1 Pb4 I12  tetragonal Ä,#
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V:[ _s/ûCBM " Pb(6p)!òÕu
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AJ"º/ úÄæÌ (/GYC:R
AJ" útetragonal ²è/o#GYC:RAJ º/ 1 û Fig. 3 " cubic ²èú`î²èútetragonal ²è
! !S6Ô{.!Þθ(Pb-I-Pb)2JXAB
*!/ûßÏ FA3 MA1 Pb4 I12 " 12i!θ(Pb-I-Pb) .ú#1~#8 (" equatorial eú#9~#12 (" apical e!S6Ô2y3ÕuÞ/ûCubic ²è"!wË -¨- , %! Pb-I-Pb &'Ã×/û( tetragonal ²è" equatorial e!θ(Pb-I-Pb)" 165 & û-!Ä*¯;5>!s dθ(Pb-I-Pb)s/" û\§`î²è " cubic²è ç a=6.33 C - >1><-3:9-7 ²è ç-  CéÖÂ θ(Pb-I-Pb) s.ú0 d VBM !j cubic  tetragonal! !j!n¢ / 1 ûFig 2  FA3 MA1 Pb4 I12 ! tetragonal ,# cubic ²è
! VBM/CBM

Fig 3 cubic ²èú`î²èútetragonal ²è!
S6Ô{.!Þθ(Pb-I-Pb)

4 )' Ryota JONO, Hiroshi SEGAWA: “Structure-Bandgap Relation on the Lead Halides based
Perovskite Materials” Asia-Pacific International Conference on Perovskite, Organic Photovoltaics
and Optoelectronics (IPEROP20) Poster099 Tsukuba, Japan, 2020 January5 '+ ,*(-931>-7 “!:0?7->5:9=:2@-<5:?=-76-7581>-7/->5:9=:9:<3-9:81>-74-7501;1<:@=65>1=-90>415<5927?19/1:9
;4:>:@:7>-5/;1<2:<8-9/1D        + , & :9: -90  '13-A- (41:<1>5/-7 '>?0B :2 >41 -90-; 5221<19/1= -8:93 1-0 (<55:0501 $1<:@=65>1
!->1<5-7==$.!$.-90$.    - 291 -

࣯ྖ෾ੵ๑ͶΓΖਫ਼ର෾ࢢ͹ϧζΩϩ෾մգఖͶ‫ͤؖ‬Ζ‫ڂݜ‬
Analysis of Radical Dissociation Process of Biomolecules by
Mass Spectrometryὸᕝ ኱ᶞ㸦⏘ᴗᢏ⾡⥲ྜ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
୍⯡ⓗ࡟ࠊࢱࣥࣃࢡ㉁ࡢྠᐃࡣ㓝⣲ᾘ໬࡟ࡼࡾ⏕ᡂࡋࡓᾘ໬࣌ࣉࢳࢻࢆ࣐ࢺࣜࢵࢡࢫᨭ᥼࣮ࣞࢨ࣮⬺㞳࢖࢜ࣥ໬㉁㔞ศᯒ㸦MALDI-MS㸧࡞࡝࡛ศᯒࡋࠊᚓࡽࢀࡓ࣐ࢫࢫ࣌ࢡࢺࣝࢆ MASCOT ࡞࡝ࡢࢹ࣮ࢱ࣮࣋ࢫ࡜↷ྜࡍࡿ࡜࠸࠺ࣉࣟࢭࢫ࡛⾜ࢃࢀࡿࠋ୍᪉࡛ࠊᮍ▱ࡢ⩻ヂᚋಟ㣭ࢆྵࡴࢱࣥࣃࢡ㉁ࡸࠊࢹ࣮ࢱ࣮࣋ࢫࡀ༑ศ࡟
ᩚഛࡉࢀ࡚࠸࡞࠸⏕≀⏤᮶ࡢࢱࣥࣃࢡ㉁ࡢศᯒ࡟ࡣᑐᛂ࡛ࡁ࡞࠸ࡇ࡜ࡀከࡃࠊ࣐ࢫࢫ࣌ࢡࢺࣝ࠿ࡽ┤᥋ࢱࣥ
ࣃࢡ㉁ࡢ࢔࣑ࣀ㓟㓄ิࢆྠᐃࡍࡿ┠ⓗ࡛᪂ࡋ࠸ࣇࣛࢢ࣓ࣥࢸ࣮ࢩࣙࣥᡭἲࡢ㛤Ⓨࡶ⾜ࢃࢀ࡚࠸ࡿࠋṇ☜࡞ࢱࣥࣃࢡ㉁࢔࣑ࣀ㓟㓄ิྠᐃ࡟ࡣࠊࢱࣥࣃࢡ㉁ࢆつ๎ⓗ࡟ศゎࡍࡿᡭἲࡀᚲせ࡛࠶ࡾࠊࡇࢀࡣࢱࣥࣃࢡ㉁࢖࢜
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࢝ࣝศゎ཯ᛂ࡟ࡘ࠸࡚ࠊ᳨ウࢆ⾜ࡗࡓࠋ2ィ⟬᪉ἲ⌮ㄽィ⟬ࡣ *DXVVLDQ ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚⾜ࡗࡓࠋᐦᗘỗ㛵ᩘࡣ M062X-D3 ᇶᗏ㛵ᩘࡣ * GS ࢆ⏝࠸ᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ඲࡚ࡢ᭱㐺໬ᵓ㐀࡟ࡘ࠸࡚᣺ືゎᯒࢆ⾜࠸ࠊᏳᐃᵓ㐀࠾ࡼࡧ㑄⛣≧ែ࡛࠶ࡿࡇ࡜ࢆ
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⤊≧ែࡼࡾࠊ㑄⛣≧ែ⌮ㄽࢆ⏝࠸࡚཯ᛂ㏿ᗘᐃᩘࢆ⟬ฟࡋࡓࠋ3◊✲ᡂᯝ
ࢱࣥࣃࢡ㉁࠿ࡽࡢỈ⣲ࣛࢪ࢝ࣝ⬺㞳࡟ࡼࡗ࡚ࠊࢱࣥࣃࢡ㉁୺㙐ࡢ &Į& ⤖ྜࡀ㑅ᢥⓗ࡟ษ᩿ࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾࠊࡇࡢศゎ཯ᛂࡣࠊ)LJXUH D ࡟♧ࡍࡼ࠺࡟࢔࣑ࢻ❅⣲ཎᏊ࠿ࡽࡢỈ⣲ᘬࡁᢤࡁ࡟ࡼࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ୍᪉ࠊ࢔࣑ࢻ❅⣲ࡀ㸱⣭࡜࡞ࡗ࡚࠸ࡿࣉࣟࣜࣥṧᇶ 3UR ࡛ࡣ &Į& ⤖ྜࡢษ᩿ࡣ㉳ࡇࡽࡎࠊ௦ࢃࡾ࡟
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⤖ྜࡢษ᩿㐣⛬࡟ࡘ࠸࡚ࡼࡾヲ⣽࡟ゎᯒࡍࡿࡓࡵ࡟ࠊᐦᗘỗ㛵ᩘ⌮ㄽ࡟ࡼࡾ᳨ウࢆ⾜ࡗࡓࠋィ⟬࡟ࡣࠊࣔࢹࣝ࣌ࣉࢳࢻ࡜ࡋ࡚ Ala-Ala-Proࢆ⏝࠸ࡓࠋPro ṧᇶ࠿ࡽࡢỈ⣲ᘬࡁᢤࡁ࡟ࡼࡾ
⏕ᡂࡋࡓࣛࢪ࢝ࣝࠊ[M – H]•ࢆ Figure 2a ࡟♧ࡍࠋࡇࡢࣛࢪ࢝ࣝࡢ࣌ࣉࢳࢻ⤖ྜษ᩿࡟ᚲせ࡞άᛶ໬࢚ࢿࣝࢠ࣮ࡣ 159 kJ mol–1 ࡜ồࡲࡗ

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0$/',,6' ࡢᐇ㦂᮲௳࡛ࡣศゎ཯ᛂࡀ༑ศ࡟㐍⾜ࡋ࡞࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋᚑࡗ࡚ࠊࡇ
ࡢ࣌ࣉࢳࢻ⤖ྜࡢษ᩿ࡣỈ⣲ᘬࡁᢤࡁ࡟㉳ᅉࡍࡿࡶࡢ࡛ࡣ
࡞࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋ
࣌ࣉࢳࢻ⤖ྜࡢษ᩿ࢆㄝ᫂
ࡍࡿࡓࡵ࡟ࠊ࣌ࣉࢳࢻ࠿ࡽࡢ
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ࢳ࢜ࣥ>01@•ࢆ )LJXUHE ࡟♧ࡍࠋࡇࡢࣛࢪ࢝ࣝ࢝ࢳ࢜ࣥࡢ
࣌ࣉࢳࢻ⤖ྜࡢษ᩿࡟ᚲせ࡞άᛶ໬࢚ࢿࣝࢠ࣮ࡣࠊࢃࡎ࠿
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ࡁ࡟ࡼࡿࣛࢪ࢝ࣝศゎ཯ᛂࢆㄏ㉳ࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡓࠋ୍᪉࡛ࠊ௒ᅇ♧ࡉࢀࡓࡼ࠺࡟ࠊ3UR ṧᇶ࡟㞄᥋ࡍࡿ࣌ࣉࢳࢻ⤖ྜࡢษ᩿࡟ࡘ࠸࡚ࡣࠊỈ⣲ࣛࢪ࢝ࣝࡢᘬࡁᢤࡁ࡟ࡼࡿศゎ཯ᛂࣔࢹ࡛ࣝࡣㄝ᫂ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞
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4Ⓨ⾲ࠊฟ∧ᐇ⦼

‫ۻ‬㻌1. D. Asakawa, J. Am. Soc. Mass Spectrom. 30, 1491-1502 (2019)‫ۻ‬㻌2. D. Asakawa, H. Takahashi, S. Iwamoto, K. Tanaka, Phys. Chem. Chem. Phys. 21, 11633-11641(2019)‫ۻ‬㻌3. D. Asakawa, H. Takahashi, S. Iwamoto, K. Tanaka, Phys. Chem. Chem. Phys. 21, 26049-26057(2019)‫ۻ‬㻌4. D. Asakawa, H. Takahashi, S. Sekiya, S. Iwamoto, K. Tanaka, Anal. Chem. 16, 10549-10556(2019)‫ۻ‬㻌5. D. Asakawa, H. Takahashi, S. Iwamoto, K. Tanaka, J. Am. Soc. Mass Spectrom. 31, 450−457(2020)‫ۻ‬㻌6. D. Asakawa, N. Saito, E. Takahashi, J. Phys. Chem. A, 124, 2019−2028 (2020)- 293 -

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Fig. 2 (a) p(" logP "Çµa|Üa"®Ø, (b) pE"
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pKa "®Ø”, MRjzf 100 O:B5e_|k)#U{‫ۻ‬S. Onozawa, T. Matsui, Y. Nishimura, and K. Morihashi, "MAIM- É?[")x`HELAM±i!2o"Ji!Ø2ÆT", Journal of Computer Chemistry, Japan, 2019, 18, 254-256.
K. Tosaka, Y. Osaki, Y. Shigeta, and T. Matsui, “A Semi-empirical Improvement of Solvent Model by
MachineLearning Method”, to be submitted.



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.

T. Matsui, Y. Tanaka, T. Otsuka, M. Sumita, H. Izawa, and K. Morihashi, “A theoretical study on molecularclusterof citric acid”, to be submitted.

- 295 -

」ྜࢼࣀࢡࣛࢫࢱ࣮࣭ศᏊ」ྜయࡢᵓ㐀࠾ࡼࡧ㟁Ꮚ≧ែ࡟㛵ࡍࡿ◊✲
Study on geometric and electronic structure for supramolecularcomplexes of binarynanoclusters with organic molecules‫ۑ‬ゅᒣ ᐶつ㸦៞ᛂ⩏ሿ኱Ꮫ⌮ᕤᏛ㒊㸧

1◊✲┠ⓗࠊෆᐜ
ᩘಶ࠿ࡽᩘⓒಶ⛬ᗘࡢཎᏊ࡛ᵓᡂࡉࢀࡿࢼࣀࢡࣛࢫࢱ࣮ࡣࠊᵓᡂཎᏊᩘࡢࢃࡎ࠿࡞㐪࠸࡟ࡼࡗ࡚㟁Ꮚ࠾ࡼࡧࢫࣆࣥ≧ែࡀኚ໬ࡍࡿࡓࡵࠊࢧ࢖ࢬࢆไᚚᅉᏊ࡜ࡋࡓ≀㉁⛉ᏛࡢⓎᒎࡀᮇᚅ࡛ࡁࡿ≀㉁⩌࡛࠶ࡿࠋᡃࠎࡣࠊࢧ࢖ࢬไᚚࡋࡓ㑄⛣㔠ᒓࢼࣀࢡࣛࢫࢱ࣮
ࡸ㑄⛣㔠ᒓෆໟࢩࣜࢥࣥࢼࣀࢡࣛࢫࢱ࣮ࢆᇶᯈୖ࡟ᅛᐃ໬ࡋࠊࡑࡢ≀ᛶࡸゐ፹స⏝ࡢゎ᫂࡟ྥࡅ࡚◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Ⅳ⣲ᇶᯈୖ࡟ᅛᐃ໬ࡋࡓⓑ㔠 (Pt) ࢼࣀࢡࣛࢫࢱ࣮

ࡢᵓ㐀᭱㐺໬ィ⟬࡟ࡣࠊVASP ࣃࢵࢣ࣮ࢪ (ver. 5.4.1)
ࢆ฼⏝ࡋࠊGGA-PBE ỗ㛵ᩘࢆ⏝࠸ࡓ PAW ἲ࡟ࡼࡾ⾜ࡗࡓࠋⅣ⣲ᢸయࡣ 6x6 ࢫ࣮ࣃ࣮ࢭࣝ (72 ཎᏊ) ࡢࢢࣛࣇ࢙ࣥࢆ௬ᐃࡋࡓࠋ⌮ㄽィ⟬࡟ࡘ࠸࡚ࡣࠊศᏊ⛉Ꮫ◊✲ᡤ࣭Ụཎṇ༤ᩍᤵ࡜ࡢඹྠ◊✲࡛࠶ࡿࠋࢧ࢖ࢬࢆつᐃࡋࡓ Pt ࢼࣀࢡࣛࢫࢱ࣮ (Pt/GC) ࡣࠊẼ┦࣐ࢢࢿࢺࣟࣥࢫࣃࢵࢱࣜࣥࢢἲ࡜㉁㔞ศᯒჾࢆ⤌ࡳྜࢃࡏ࡚
Ẽ┦ྜᡂࡋࠊࢢࣛࢵࢩ࣮࣮࢝࣎ࣥᇶᯈୖ࡟ࢯࣇࢺࣛࣥ
ࢹ࢕ࣥࢢࡋࡓࠋPt/C ࡢ㓟⣲㑏ඖ཯ᛂ (ORR) ࡟ᑐࡍࡿゐ፹άᛶࢆࠊ㐣ሷ⣲㓟Ỉ⁐ᾮ୰ࠊ༢ࢭࣝἲ࡟ࡼࡗ࡚
ᐃࡋࠊᕷ㈍ࡢ Pt ࢼࣀ⢏Ꮚゐ፹࡜ẚ㍑ࡋࡓࠋᵓ㐀ྠᐃ
࡟ࡣࠊX ⥺྾཰ᚤ⣽ᵓ㐀 (XAFS) ἲࢆ⏝࠸ࡓࠋ ᐃࡋࡓ XAFS ࢫ࣌ࢡࢺࣝ࠿ࡽ F(k) ࣉࣟࣇ࢓࢖ࣝࢆᢳฟࡋࠊ
ୖグ DFT ィ⟬࡟ࡼࡗ࡚ồࡵࡓ 7 ࡘࡢ␗ᛶయ࡟ࡘ࠸࡚
ᵓ㐀᭱㐺໬ィ⟬࠿ࡽᚓࡽࢀࡓ 7 ✀㢮ࡢᵓ㐀␗ᛶయ࡟ࡘ࠸࡚ከ㔜ᩓ஘⌮ㄽ࡟ᇶ࡙ࡃ FEFF ࢥ࣮ࢻ⏝࠸࡚F(k)ࣉࣟࣇ࢓࢖ࣝࢆồࡵࠊᐇ࡜ẚ㍑ࡍࡿࡇ࡜࡛ᵓ㐀ࢆྠ

ᐃࡋࡓࠋ

3

◊✲ᡂᯝ
Ẽ┦ྜᡂ࡟ࡼࡾస〇ࡋࡓࢢࣛࢵࢩ࣮࣮࢝࣎ࣥᢸᣢ

ᅗ 1. ᐇ(㟷) ࠾ࡼࡧᵓ㐀᭱㐺໬ィ⟬࡟ᇶ࡙࠸Pt6 㔞య (Pt6/GC) ࡢ ORR ゐ፹άᛶࡣࠊ㧗ẚ⾲㠃✚Ⅳ

ࡓ FEFF ࢩ࣑࣮ࣗࣞࢩࣙ࡟ࡼࡗ࡚ᚓࡽࢀࡓ XAFS⣲ᮦᩱ࡟ᢸᣢࡋࡓ Pt/C ᶆ‽ゐ፹ (⢏Ꮚᚄ: ⣙ 2 nm) ࡟F(k) ࣉࣟࣇ࢓࢖ࣝࡢẚ㍑- 296 -

ẚ࡭࡚ࠊ㔜㔞࠶ࡓࡾ 1.7 ಸࠊゐ፹⾲㠃✚࠶ࡓࡾ 2.3 ಸ㧗࠸್ࢆ♧ࡋࡓࠋࡇࡢ㧗࠸άᛶࡀぢฟࡉࢀࡓ 6 㔞య࡟ࡘ
࠸࡚ࠊXAFS ศග࠾ࡼࡧ DFT ィ⟬࡟ࡼࡗ࡚ᵓ㐀ࢆホ౯ࡋࡓࠋᖹ㠃ᆺࡢ␗ᛶయ (3 ✀㢮, ᅗ 1 ࡢ␗ᛶయ 1) ࡟ࡘ࠸࡚ࡣࠊk = 3~12 Å ࡢ㡿ᇦ࡛ F(k) ࣉࣟࣇ࢓࢖ࣝࡀ୍⮴ࡏࡎೃ⿵࠿ࡽ㝖እࡉࢀࡓࠋᢡࢀ᭤ࡀࡗࡓ୕ゅᙧ≧ࡢ␗ᛶయ (2 ✀㢮, ᅗ 1 ࡢ␗ᛶయ 4) ࡟ࡘ࠸࡚ࡣࠊk > 8 Å ࡢ㡿ᇦ࡛ᐇ࡜ゎ㞳ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊೃ⿵࠿ࡽ㝖እࡉࢀࡿࠋ୍᪉࡛ࠊ࢚ࢿࣝࢠ࣮ⓗ࡟ࡣ᭱ࡶ㧗࠸཮ᅄ㠃యᆺࡢ␗ᛶయ (ᅗ 1 ␗ᛶయ 7) ࡣࠊk = 3~12 Å ࡢ㡿ᇦ࡛୧⪅ࡢࣉࣟࣇ࢓࢖ࣝࡀࡼࡃ୍⮴ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊPt6/GC ࡢᵓ㐀ࡣ␗ᛶయ 7 ࡛࠶ࡿ࡜⤖ㄽࡋࡓࠋ␗ᛶయ 7 ࡢ㟁Ⲵศᕸゎᯒ࠿ࡽࠊࡇࡢᵓ㐀࡟࠾࠸࡚ࡣࠊ㓄఩ᩘࡢᑠࡉ࠸ Pt ཎᏊୖࡢ㈇㟁Ⲵࡀቑ኱ࡋࠊᇶᯈ࠿ࡽ㞳ࢀࡓప఩㓄఩ᩘࡢ Pt ཎᏊୖࡢ d ㌶㐨ࡢ୰ᚰ࢚ࢿࣝࢠ࣮ (Hd) ࡀࣂࣝࢡࡢHd ࡟ẚ࡭࡚ୖ᪼ࡋ࡚࠸ࡓࠋ୍᪉࡛ࠊ⢏Ꮚᚄࡀ 2 nm
⛬ᗘ (300 㔞య⛬ᗘ) ࡢࢼࣀ⢏Ꮚ࡛ࡣࠊHd ࡀࣂࣝࢡ࡜ྠ⛬ᗘ࡛࠶ࡾࠊ⾲㠃࡟࠶ࡿ Pt ཎᏊࡢศᴟࡀᑠࡉ࠸ࡇ࡜ࡀ
▱ࡽࢀ࡚࠸ࡿࠋࣂࣝࢡ⣔ゐ፹࡟࠾ࡅࡿ d ࣂࣥࢻࡢ୰ᚰ࢚ࢿࣝࢠ࣮࡜άᛶࡢ㛵ಀࢆཧ⪃࡟ࡍࡿ࡜ࠊPt6 ࡢ㧗࠸άᛶࡣࠊGC ୖ࡬ࡢ྾╔࡟ࡼࡗ࡚㟁Ⲵศ㞳ࡀ⏕ࡌࠊ≉ᐃࡢࢧ࢖ࢺࡢ d ㌶㐨࢚ࢿࣝࢠ࣮ࡀࣂࣝࢡ≧ែ࡟ẚ࡭࡚ୖ᪼ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊศᏊ≧㓟⣲ࡢ྾╔άᛶ໬ࡀ᭷฼࡟㐍⾜ࡍࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ศᏊ⛉Ꮫウㄽ఍ 2019ࠕ༢୍ࢧ࢖ࢬᢸᣢⓑ㔠ࢼࣀࢡࣛࢫࢱ࣮ࡢࢧ࢖ࢬ≉␗ⓗゐ፹άᛶ࡜ࡑࡢᵓ㐀ᶵ⬟┦㛵ࠖゅᒣ ᐶつ㸪኱἟ ᫂㸪㧗ᶫ ຌ㍤㸪Archana Velloth㸪Ụཎ ṇ༤㸪୍ᅧ ఙஅ㸪୰ᔱ ᩔ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫“ ۻ‬Enhanced oxygen reduction activity of platinum subnanocluster catalysts through charge redistribution”
Hironori Tsunoyama, Akira Ohnuma, Koki Takahashi, Archana Velloth, Masahiro Ehara, Nobuyuki Ichikuni,
Masao Tabuchi, Atsushi Nakajima, Chem. Commun. 55, 12603-12606 (2019).

- 297 -

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¶ÌÆ
1.

“Development of Multiscale Method for Nano-Bio Materials Design Based on Statistical Mechanics Theory of- 298 -

Molecular Liquids”, International Conference on Materials Research and Innovation 2020, 2019  12  16 ,Centara Grand Central Plaza Ladprao and Kasetsart University, Norio Yoshida Ó¬2.“Understanding Biological Processes in Solution Based on the Statistical Mechanics Theory of Liquids”, The
10th Toyota RIKEN International Workshop on Science of Life Phenomena Woven by Water and Biomolecules,
2019  9  4 , Toyota Chemical and Physical Research Institute, Norio Yoshida Ó¬3.“Understanding Biological Processes in Solution Based on the Statistical Mechanics Theory of Liquids”, 10th
International Conference of the Asian Consortium on Computational Materials Science (ACCMS-10), 2019  6
 27 , City University of Hong Kong, Hong Kong, China, Norio Yoshida Ó¬4.“Understanding Biological Processes in Solution Based on the Statistical Mechanics Theory of Liquids”, The
23th international annual symposium on computational science and engineering (ANSCSE23), 2019  6  27 ,
Chiang-mai University, Chiang-mai, Thailand, Norio Yoshida Ó¬

a®Æ
1.

"Development of a solvent-polarizable three-dimensional reference interaction-site model theory ", Norio
Yoshida, Tsuyoshi Yamaguchi, J. Chem. Phys., (2020) 152, 114108 (doi.org/10.1063/5.0004173)

2.

"Distinct ionic adsorption sites in defective Prussian blue: a 3D-RISM study", Nirun Ruankaew, Norio Yoshida,
Yoshihiro Watanabe, Akira Nakayama, Haruyuki Nakano, Saree Phongphanphanee, Phys. Chem. Chem. Phys.,(2019) 21, 22569-22576 (DOI: 10.1039/C9CP04355A )3.

"Effects of Water Addition on a Catalytic Fluorination of Dienamine", Daiki Kuraoku, Tsunaki Yonamine, Genta
Koja, Norio Yoshida, Satoru Arimitsu, Masahiro Higashi, Molecules (2019) 24, 3428(1-8) ( DOI:
10.3390/molecules24193428 )4.

"Effect of Molecular Orientational Correlations on Solvation Free Energy Computed by Reference Interaction
Site Model Theory", Shoichi Tanimoto, Norio Yoshida, Tsuyoshi Yamaguchi, Seiichiro Ten-no, Haruyuki Nakano,
J. Chem. Info. Model (2019) 59, 3770-3781 ( DOI: 10.1021/acs.jcim.9b00330)- 299 - π 

Design and synthesis of novel π-electronic molecules which form
functional assemblies
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- 301 -

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# [1] J. Morimoto, et al., J. Am. Chem. Soc. 2020, 142, 2277–2284.
 [2] J. Morimoto, et al., J. Am. Chem. Soc. 2019, 141, 14612–14623.

>+2[1] J. M. Frisch et al. Gaussian, Inc., Wallingford CT, 2016.
[2] K. Vanommeslaeghe, et al. 2009, J. Comput. Chem. 30, 671–690.
[3] M. J. Abraham, et al. SoftwareX 2015, 1–2,19–25.

- 303 -

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Reaction analysis of transition metal clusters and organic compounds )1 #%"!0, - /,,  (. '#%$ )°³fm_¸Wno'x¹«YqP $º¹S` (CVD) 'Ug+H>F8:3CH=(SWCNT)Yq]zJ¦^°³fm_'¹O_'O¥ SWCNT 'q$º )2:HE'$ ¹´(Fe) -;E6(Co)¦^!$¸[«G¸X² SWCNT Yq  $ ¹WnA+90@©TO&º )2:HE°³f,D/2HWnq'«²O{¢bO{|¹Co ±S+3*F,
D/2H)2:HEWn H2)2:HE"¶,D/2HMQ$Wn ¤e %ºyWn¬'²_S`§v"$ '$º2 #%0+&Gaussian09 '¹diµtª]

~®w¯SGrRt§! IRC §'º

B3LYP µt¹6-31+G(d,p) ]hµt¹Co V_ LANL2DZ s?4F.BE'¹Co3O3 ,D/2H
+)2:HEWn'«²O{c·lWnq­¥{$º3 #%
\ 1. l"%Wn¬}£'ºc·¤e %WnWnj (a)º             q C2H4O ~®c·b  ¹(16(E5<7(CH3CHO) '­abwqpbº§|¹)2:HE OH ]! CH3 ]"I H V_ ¶ ,D/2HZ$¹   R(16(

E5<7 q$¬'lºc·q Co3O3H2+,D/2H)2:HEZWn¤e%#¹Lk§' Kb$º4*(¡5

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㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿගྜᡂỈศゎ཯ᛂࡢศᏊᶵᵓࡢゎ᫂
Quantum chemical calculation study on the molecular mechanism ofphotosynthetic water oxidation‫ۑ‬㔝ཱྀ ᕦࠊᒣᮏ ┿⏕㸦ྡྂᒇ኱㝔࣭⌮㸧

1◊✲┠ⓗࠊෆᐜ
ගྜᡂỈศゎ཯ᛂࡣࠊග໬Ꮫ⣔ II ࢱࣥࣃࢡ㉁㸦PSII㸧ࡢ㓟໬ഃ࡟ᏑᅾࡍࡿỈศゎ⣔࡟࠾࠸࡚⾜ࢃࢀࡿࠋỈศゎ⣔ࡣࠊゐ፹୰ᚰ࡛࠶ࡿ Mn4CaO5 ࢡࣛࢫࢱ࣮࡜ࡑࢀࢆྲྀࡾᅖࡴ࢔࣑ࣀ㓟ṧᇶ࠾ࡼࡧỈศᏊ࠿ࡽᡂࡾ㸦ᅗ㸯㸧ࠊ
5 ࡘࡢ୰㛫≧ែ㸦S0-S4㸧ࡢ཯ᛂࢧ࢖ࢡࣝࢆ୍࿘ࡍࡿࡈ࡜࡟ࠊ2 ࡘࡢỈศᏊࡀ㸯ࡘࡢ㓟⣲ศᏊ࡜ 4 ࡘࡢࣉࣟࢺࣥ
࡟ศゎࡉࢀࡿࠋࡇࡢ཯ᛂ࡟ࡼࡾࠊ஧㓟໬Ⅳ⣲㑏ඖ࡟ᚲせ࡞㟁Ꮚࡀ౪⤥ࡉࢀࠊࡲࡓ࿧྾⏕࿨ࡢ⏕Ꮡ࡟ᚲ㡲࡞㓟⣲ࡀ⏕ᡂࡉࢀࡿࠋPSII ࡢ X ⥺⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡾᬯ୰࡛Ᏻᐃ࡞ S1 ≧ែࡢᵓ㐀ࡀ♧ࡉࢀࠊࡲࡓ㐃⥆ࣇ࢙࣒ࢺ⛊⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡾ୰㛫≧ែࡢᵓ㐀ࡢゎ᫂ࡀ㐍ࡵࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊMn4CaO5 ࢡࣛࢫࢱ࣮ࡸ㏆ഐỈศᏊࡢࣉࣟࢺࣥ໬ᵓ㐀ࡣᮍࡔ୙࡛᫂࠶ࡾࠊ୰㛫≧ែࡢᵓ㐀࡟ࡘ࠸࡚ࡶ᫂☜࡞⤖ㄽࡣᚓࡽࢀ࡚࠸࡞࠸ࠋᡃࠎࡣࠊ㛝ගㄏ㉳㉥እᕪศගἲ࡟ࡼࡿィ࠾ࡼࡧ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿࢫ࣌ࢡࢺࣝゎᯒ࡟ࡼࡗ࡚ࠊỈศゎ⣔ࡢᵓ㐀࠾ࡼࡧ཯ᛂࡢ◊✲ࢆ⾜ࡗ࡚ࡁࡓࠋᮏ◊✲࡛ࡣࠊ㸱㛝ගᚋ࡟⏕ᡂࡍࡿ S0 ୰㛫≧ែ㸦S1 ≧ែࡢ㸯㟁Ꮚ㑏ඖ≧ែ㸧࡟ࡘ࠸࡚ࠊ
quantum mechanics/molecular mechanics㸦QM/MM㸧ィ⟬࡟ࡼࡿỈศゎ⣔ࡢᇶ‽᣺ືゎᯒࢆ⾜࠸ࠊᐇ㉥እࢫ࣌ࢡࢺࣝࢆ෌⌧ࡍࡿࡇ࡜࡟ࡼࡾࠊS0 ≧ែࡢࣉࣟࢺࣥ໬ᵓ㐀ࢆㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲึᮇᵓ㐀࡜ࡋ࡚ࠊS1 ≧ែࡢ X ⥺⤖ᬗᵓ㐀㸦PDB code 4UB6, Suga et al., Nature 2015㸧࡟࠾ࡅࡿ Mn4CaO5 ࢡࣛࢫࢱ࣮ࡢ࿘ᅖ 20 Å ௨ෆࡢ࢔࣑ࣀ㓟ṧᇶ࠾ࡼࡧỈศᏊࢆ⏝࠸ࠊGaussian09 ࡢ ONIOM ἲ࡟ࡼࡾ QM/MM ィ⟬ࢆᐇ⾜ࡋࡓࠋึࡵ࡟ࠊX ⥺⤖ᬗᵓ㐀࡟Ỉ⣲ཎᏊࢆ௜ຍࡋࠊAmber ຊሙ࡟ࡼࡾỈ⣲ཎᏊࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋ
Mn4CaO5 ࢡࣛࢫࢱ࣮ࠊ࠾ࡼࡧࡑࡢ࿘ᅖ࡟Ꮡᅾࡍࡿ࢔࣑ࣀ㓟࠾ࡼࡧỈศᏊࢆ QM 㡿ᇦ࡜ࡋࠊࡑࢀ௨እࢆ MM 㡿ᇦ࡟ᣦᐃࡋ࡚ࠊᵓ㐀᭱㐺໬࠾ࡼࡧᇶ‽᣺ືィ⟬ࢆ⾜ࡗࡓࠋᵓ㐀᭱㐺໬࡟࠾࠸࡚ࠊQM 㡿ᇦࡢཎᏊࡣࡍ࡭࡚ࣇ
࣮ࣜ࡜ࡋࠊMM 㡿ᇦࡢཎᏊ࡟ࡘ࠸࡚ࡣࡑࢀࡽࡢ఩⨨ࢆᅛᐃࡋࡓࠋࡲࡓࠊQM 㡿ᇦࡢィ⟬࡟ࡣ B3LYP 㛵ᩘ⣔ࢆ౑⏝ࡋࠊᇶᗏ⣔࡜ࡋ࡚ Ca ཬࡧ Mn ཎᏊ࡟ࡣ LANL2DZ ࢆࠊࡑࡢ௚ࡢཎᏊ࡟ࡣ 6-31G(d) ࢆ⏝࠸ࡓࠋMM 㡿ᇦࡢィ⟬࡟ࡣ Amber ຊሙࢆ᥇⏝ࡋࡓࠋS1 ≧ែ࡟ࡘ࠸࡚ࡣࠊMn4 ࡟㓄఩ࡍࡿỈศᏊ W2 ࡀ H2O ࡢሙྜ࡜ OH-ࡢሙྜ࡟ࡘ࠸࡚ィ⟬ࢆ⾜࠸ࠊ୍㟁Ꮚ㑏ඖࡉࢀࡓ S0 ≧ែ࡟ࡘ࠸࡚ࡣࠊࡉࡽ࡟ Mn4CaO5 ࢡࣛࢫࢱ࣮ࡢ O4 ࡀࣉࣟࢺࣥ
໬ࡉࢀࡓ O4H ᵓ㐀࡜ O5 ࡀࣉࣟࢺࣥ໬ࡉࢀࡓ O5H ᵓ㐀࡟ࡘ࠸࡚ィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝMn4CaO5 ࢡࣛࢫࢱ࣮ࡀ O4H ᵓ㐀࠾ࡼࡧ O5H ᵓ㐀ࢆᣢࡘ㸰ࡘࡢ S0 ≧ែࠊ࠾ࡼࡧࡑࢀࡽࡀ⬺ࣉࣟࢺࣥ໬ࡋࡓ

S1 ≧ែ࡟ࡘ࠸࡚ࠊQM/MM ἲ࡟ࡼࡿᇶ‽᣺ືゎᯒࢆ⾜࠸ࠊS1/S0 ㉥እᕪࢫ࣌ࢡࢺࣝࢆィ⟬ࡋࡓࠋW2=H2O ࠾ࡼࡧ OH-ࡢࡑࢀࡒࢀࡢᵓ㐀࡟ࡘ࠸࡚ࠊᚓࡽࢀࡓィ⟬ࢫ࣌ࢡࢺࣝࢆᐇ

ࡢ S0/S1 㛝ගㄏ㉳ࣇ࣮࢚ࣜኚ᥮㉥እᕪࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡋࡓࠋࡑࡢ⤖ᯝࠊO4H ᵓ㐀ࢆᣢࡕࠊW2 ࡀ H2O ࡢሙྜࡢィ⟬ࢫ࣌ࢡࢺࣝࡀ᭱ࡶࡼࡃᐇ

ࢆ෌⌧ࡋࡓ㸦ᅗ㸰㸧ࠋࡲࡓࠊO4H ࣔࢹࣝࡢ S0 ≧ែࡢ᭱㐺໬ᵓ㐀࡛ࡣࠊO4H ࡣỈศᏊ࡜ᴟࡵ࡚ᙉ࠸Ỉ⣲⤖ྜࢆᙧᡂࡋ
࡚࠾ࡾࠊMn ࡢ㓟໬࡟కࡗ࡚ࠊO4 ࠿ࡽ࣮࣓ࣝࣥഃ࡬࡜⥆ࡃỈศᏊ㙐࡬ࡢ㏿࠸ࣉࣟࢺࣥᨺฟࡀྍ⬟࡛࠶ࡿ࡜⪃- 305 -

࠼ࡽࢀࡿࠋࡇࡢ⤖ᯝࡣࠊS0ĺS1 㑄⛣࡟࠾࠸࡚~45 ȝs ࡢ㏿࠸ࣉࣟࢺࣥඹᙺ㟁Ꮚ⛣ື཯ᛂࡀ㉳ࡇࡿ࡜࠸࠺ᙜ◊✲ᐊࡢ᫬㛫ศゎ㉥እゎᯒࡢ⤖ᯝ࡜୍⮴ࡋ࡚࠸ࡿࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊỈศゎ⣔ࡢ S0 ≧ែࡣ W2 ࡀ H2O ࡛ O4 ࡀࣉࣟࢺࣥ໬ࡉࢀࡓᵓ㐀ࢆᣢࡕࠊS1 ࡬ࡢ㓟໬࡟ࡼࡗ࡚ࠊO4H ࡢࣉࣟࢺࣥࡀ O4 ࢳࣕࢿࣝࡢỈศᏊ㙐ࢆ௓ࡋ࡚ࣝ
࣮࣓ࣥഃ࡬ᨺฟࡉࢀࡿ࡜⤖ㄽࡋࡓࠋ

YZ
H190

W6
W5

W7

W4

W3

R357 E189
A344
D170 Ca
W15
W2
1
2
4
W13
5
4
W8
1 2
W1
D342
W11 3
3
W14
W9
E354
E333
W12 H332
H337
D61
W10

ᅗ 1. PSII ࡟࠾ࡅࡿỈศゎ⣔ S0 ≧ែ㸦O4H,
W2=H2O㸧ࡢ QM 㡿ᇦࡢ᭱㐺໬ᵓ㐀

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

ᅗ 2. QM/MM ィ⟬࡟ࡼࡾᚓࡽࢀࡓ S1/S0 ㉥እᕪࢫ࣌ࢡࢺࣝ㸦㉥⥺㸧࡜ᐇ FTIR ᕪࢫ࣌ࢡࢺࣝ㸦㯮⥺㸧ࠋィ⟬࡟ࡼࡿ⥺ࢫ࣌ࢡࢺࣝࢆ㟷⥺㸦S0㸧࠾ࡼࡧ⥳⥺㸦S1㸧࡛♧ࡍࠋ(a) O4H, W2=H2O; (b)O4H, W2=OH-; (c) O5H, W2=H2O; (d) O5H,
W2=OH-‫ۻ‬1. Takumi Noguchi, Infrared analyses of electron and proton transfer reactions in photosystem II, Annual Meeting of
the French Photosynthesis Society, Gif-sur-Yvette, France, May 9-10, 2019‫ۻ‬2. Masao Yamamoto, Shin Nakamura, and Takumi Noguchi, QM/MM analysis of the protonation structure of the S0state in the water-oxidizing Mn4CaO5 cluster, ೖຌਫ਼෼෼ཀྵָճ೧ճɼ‫࡜ٸ‬ɼ2019 ೧ 9 ݆ 24-26 ೖ‫ۻ‬3. Takumi Noguchi, Infrared detection of protons and water molecules in photosynthetic water oxidation, ೖຌਫ਼෼෼ཀྵָճ೧ճɼ‫࡜ٸ‬ɼ2019 ೧ 9 ݆ 24-26 ೖ‫ۻ‬4. Takumi Noguchi, Infrared studies on the water oxidation and electron transfer reactions in photosystem II, 3rdInternational Solar Fuels Conference/International Conference on Artificial Photosynthesis-2019, Hiroshima,
Japan, November 20-24, 2019.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬1. M. Yamamoto and T. Noguchi, Vibrational structure of the S0 state of the photosynthetic water oxidizing complex
as studied by quantum mechanics/molecular mechanics calculations, in preparation.

- 306 -

ࣞࢽ࣒࢘(I)ࣇࢱࣟࢩ࢔ࢽࣥ㘒య࡟ࡼࡿ㟁Ẽ໬Ꮫⓗ CO2 㑏ඖ཯ᛂ
Electrochemical CO2 Reduction
by a Rhenium(I) Phthalocyanine Complexࠐᮧ⏣ ្ࠊ▼஭ ࿴அ㸦ᮾி኱Ꮫ⏕⏘ᢏ⾡◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
஧㓟໬Ⅳ⣲㸦CO2㸧ࢆ㑏ඖࡋࠊ᭷⏝≀㉁࡬࡜ኚ᥮ࡍࡿᡭἲࡢ㛤ⓎࡣࠊCO2 ෌㈨※໬ࡢほⅬ࠿ࡽ㔜せ࡞ㄢ㢟࡛࠶ࡿࠋࡑࡢ࢔ࣉ࣮ࣟࢳࡢ୍ࡘ࡟ࠊ㑄⛣㔠ᒓゐ፹ࢆ⏝࠸ࡿ㟁Ẽ໬Ꮫⓗ㑏ඖࡀ࠶ࡿࡀࠊྠ཯ᛂࢆຠ⋡ⓗ࡟ᐇ⌧ࡍࡿࡓࡵ࡟ࡣࠊࡼࡾṇഃࡢ㟁఩࡟࠾࠸࡚㧗࠸άᛶࢆ♧ࡍゐ፹ศᏊࡢ㛤Ⓨࡀ㔜せ࡛࠶ࡿࠋᙜ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊ
௨๓ࠊ㟁Ẽ໬Ꮫⓗ CO2 㑏ඖࡢ཯ᛂ୰ᚰ࡜ࡋ࡚㧗࠸₯ᅾᛶࢆᣢࡘࣞࢽ࣒࢘㸦I㸧ࢺࣜ࢝ࣝ࣎ࢽࣝࣘࢽࢵࢺ࡜ࠊ㟁Ꮚཷᐜ⬟ࡢ㧗࠸ࣇࢱࣟࢩ࢔ࢽࣥ㓄఩Ꮚ࡜ࡢ」ྜ໬࡟ࡼࡾࠊ᪂つ஧᰾࠾ࡼࡧ༢᰾ࣞࢽ࣒࢘㸦I㸧ࣇࢱࣟࢩ࢔ࢽࣥ
㘒యࡢྜᡂ࡟ᡂຌࡋ࡚࠸ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊྠ㘒యࡢ㟁Ẽ໬Ꮫⓗᛶ㉁࠾ࡼࡧ㟁Ẽ໬Ꮫⓗ CO2 㑏ඖ࡟࠾ࡅࡿゐ፹⬟ࢆㄪ࡭ࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ❅⣲㸦N2㸧㞺ᅖẼୗ࠾ࡼࡧ CO2 㞺ᅖẼୗ࡟࠾ࡅࡿ஧᰾㸭༢᰾ࣞࢽ࣒࢘㸦I㸧ࣇࢱࣟࢩ࢔ࢽࣥ㘒యࡢࢧ࢖ࢡࣜ

ࢵࢡ࣎ࣝࢱ࣓ࣥࢺ࣮ࣜ

ᐃࢆ⾜࠸ࠊྠ㘒యࡢ㟁Ẽ໬Ꮫ≉ᛶ࠾ࡼࡧྛ✀཯ᛂ᮲௳ୗ࡟࠾ࡅࡿ㓟໬㑏ඖᣲືࢆㄪ

࡭ࡓࠋࡇࢀࡽ࡜୪⾜ࡋ࡚ࠊྠ㘒యࡢ㟁Ꮚ≧ែࢆᐦᗘỗ㛵ᩘἲ㸦DFT㸧࡟ࡼࡾゎᯒࡋࡓࠋィ⟬࡟ࡣࠊGaussian16ࣃࢵࢣ࣮ࢪࢆ⏝࠸ࠊB3LYP ỗ㛵ᩘ࠾ࡼࡧ LanL2DZ (Re), 6-31G(d,p) (H, C, N, O) ᇶᗏ㛵ᩘ⣔ࢆ㐺⏝ࡋࡓࠋ

3◊✲ᡂᯝ
N2 㞺ᅖẼୗ࡛ࣞࢽ࣒࢘ (I) ࣇࢱࣟࢩ࢔ࢽࣥ㘒యࡢࢧ࢖ࢡࣜࢵࢡ࣎ࣝࢱ࣓ࣥࢺ࣮ࣜ

᰾㘒య࡛ࡣྍ㏫ࠊ༢᰾㘒య࡛ࡣ‽ྍ㏫࡞㓟໬㑏ඖἼࡀࡑࢀࡒࢀ」ᩘほᐃࢆ⾜ࡗࡓ࡜ࡇࢁࠊ஧

ࡉࢀࡓࠋDFT ィ⟬࡟ᇶ࡙ࡃ㘒యࡢศᏊ㌶㐨ゎᯒࡼࡾࠊࡇࢀࡽࡣࡍ࡭࡚ࣇࢱࣟࢩ࢔ࢽࣥ⎔ࡢ㓟໬㑏ඖ㐣⛬࡟ᇶ࡙ࡃࢩࢢࢼ࡛ࣝ࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡲࡓࠊCO2 㞺ᅖẼୗ࡛༢᰾㘒యࡢࢧ࢖ࢡࣜࢵࢡ࣎ࣝࢱ࣓ࣥࢺ࣮ࣜ
㟁ὶ್ࡢ❧ࡕୖࡀࡾࡀほࡉࢀࡓࠋࡇࡢᣲືࡣࠊN2 㞺ᅖẼୗࡢᐃࢆ⾜ࡗࡓ࡜ࡇࢁࠊ㑏ඖഃ࡟㢧ⴭ࡞ᐃ࡛ࡣほࡉࢀ࡞࠿ࡗࡓࡇ࡜࠿ࡽࠊCO2 㑏ඖࡢゐ፹㟁ὶ࡟㉳ᅉࡍࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡇࡢゐ፹㟁ὶࡣࠊH2O ࡸ MeOH ࡜࠸ࡗࡓࣉࣟࢺࣥ※ࡢῧຍ࡟ࡼ
ࡾቑ኱ࡋࡓࠋ୍᪉ࠊ༢᰾㘒యࢆ㟁Ẽ໬Ꮫⓗ㓟໬᮲௳࡟࠾ࡃ࡜ࠊ཯ᛂ⣔ࡢẼ┦࠿ࡽ CO ࡀ᳨ฟࡉࢀࠊࣞࢽ࣒࢘
ୖࡢ࢝ࣝ࣎ࢽࣝ㓄఩Ꮚࡢ⬺㞳ࡀ㉳ࡇࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬M. Wang, Y. Koike, K. Murata, K. Ishii ➨ 31 ᅇ㓄఩໬ྜ≀ࡢග໬Ꮫウㄽ఍㸦ᐩᒣ㸧ࠊ2019  ௚ 8 ௳5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫ۻ‬I. Morichika, K. Murata, A. Sakurai, K. Ishii, S. Ashihara, Nat. Commun. 2019, 10, 3893.
K. Murata, H. Tanaka, K. Ishii, J. Phys. Chem. C 2019, 123, 12073.

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」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୰㇂ ెⴌࠊ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㸰㸧㔠ᒓ㓟໬≀࡟࠾ࡅࡿゐ፹཯ᛂ࣓࢝ࢽࢬ࣒ཬࡧ≀㉁྾ⶶ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࠊ㸱㸧ᑠศᏊࡢບ㉳≧ែࡢศᏊᵓ㐀࡜ᨃ࣮ࣖࣥࢸ࣮ࣛຠᯝࡢゎ᫂ࠊࢆ⾜ࡗࡓࠋࡇࡇ࡛ࡣ㸯) ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲศᏊ⣔ࡢィ⟬࡟ࡣ Gaussian 09/16 ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ SAC-CI ἲ࡜ DFT/TDDFT ཬࡧ MolCas ࡟ᐇ⿦ࡉࢀ࡚࠸

ࡿ CASSCF/CASPT2 ἲࢆ⏝࠸ࡓࠋ㓟໬≀ᅛయ⾲㠃ࡢィ⟬࡟ࡣࠊᖹ㠃Ἴᇶᗏ࡟ࡼࡿ࿘ᮇቃ⏺᮲௳ࡢ DFT ࢆ VASPࣉࣟࢢ࣒ࣛ࡟ࡼࡾ⾜ࡗࡓࠋOpenMP ཬࡧ MPI ࡟ࡼࡿ୪ิィ⟬ࢆ⾜ࡗࡓࠋ3◊✲ᡂᯝ
3.1. 」ྜ㔠ᒓཬࡧ」ྜ㔠ᒓ㓟໬≀⾲㠃ࡢ㟁Ꮚ≧ែ࡜ศᏊ྾╔ᶵᵓࡢゎ᫂㖡⣔ゐ፹ࡀ୍㓟໬❅⣲(NO)ࢆ㑏ඖศゎࡍࡿ஦ࡀ▱ࡽࢀ࡚࠾ࡾࠊඖ⣲ᡓ␎ⓗ࡞ほⅬ࠿ࡽࡑࡢᛶ⬟ྥୖࡀồࡵࡽࢀ࡚࠸ࡿࠋ㖡ࢆࣝࢸࢽ࣒࢘࡜」ྜ໬ࡍࡿࡇ࡜࡛ࠊNO 㑏ඖ⬟ຊࡢྥୖࢆᅗࡿࡇ࡜ࡀ᳨ウࡉࢀ࡚࠾ࡾࠊࡑࡢ
࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆ⾜ࡗ࡚࠸ࡿࠋࡇࡇ࡛ࡣࠊCu/Ru 」ྜ㔠ᒓ࡜ࡑࡢ㓟໬≀⾲㠃ࡀࠊCu ༢య࡜ẚ࡭୍࡚㓟໬Ⅳ⣲(CO)ࢆᙉࡃ྾╔ࡍࡿ஦ࢆ♧ࡋࡓࠋCO ࡣ NO ࡢ㑏ඖ๣࡜ࡋ࡚฼⏝࡛ࡁࡿࡓࡵࠊ⾲㠃ࡀ㓟໬ࡉࢀࡓ≧ែ࡛ࡶCO ࡢ྾╔⬟ຊࡀపୗࡋ࡞࠸࡞ࡽࡤࠊNO 㑏ඖ཯ᛂࡢάᛶⅬࡀಖᣢ࡛ࡁࡿࡓࡵࠊ⤖ᯝ࡜ࡋ࡚ゐ፹άᛶࡢྥୖ࡟
ᐤ୚ࡍࡿ࡜࠸࠺࣓࢝ࢽࢬ࣒ࢆぢฟࡋࡓࠋࣔࢹࣝࡢᵓ㐀࡜ィ⟬ࡉࢀࡓ CO ఙ⦰᣺ືࡢἼᩘࢆᅗ 1 ࡟♧ࡍࠋィ⟬ࡉࢀࡓ᣺ືࡣ Cu0 ୖ࡛ 2089 cm−1, CuI/Cuୖ࡛ 2130 cm−1, Ru0 ୖ࡛ 2033 cm−1 ࡛࠶ࡾࠊᐇ㦂್㸦ࡑࢀࡒࢀ 2095, 2120, 2041 cm−1㸧࡜Ⰻࡃ୍⮴ࡋࡓࠋCO ఙ⦰᣺ືࡣ CuI/Ru > CuI/Cu > Cu0/Ru > Cu0 > Ru0 ࡢ㡰ᗎ࡛పἼᩘࢩࣇࢺࡍࡿ࡜ண

ࡉࢀࡓࠋ✚ᒙᵓ㐀ࡢ㐪࠸ࡣᐃᛶⓗ࡞పἼᩘࢩࣇࢺഴྥ࡟ࡣᙳ㡪ࡋ࡞࠿ࡗࡓࠋ㟼㟁྾╔」ྜἲ࡟ࡼࡾྜᡂࡉࢀࡓ」ྜ㔠ᒓ⢏Ꮚ࡛ࡣࠊCuI ࡜
Cu0 ࡢ㛫࡛࠶ࡿ 2112 cm−1 ࡟㉥እ྾཰ࡀほࡉࢀ࡚࠾ࡾࠊࡇࢀࡀࠊ2093 cm−1 ࡜ 2096cm−1 ࡟ィ⟬ࡉࢀࡓ Cu0/Ru࡟྾╔ࡋࡓ CO ࡢఙ⦰᣺ື࡜ᖐᒓࡉࢀࡓࠋ
ࡲࡓࠊCu0 ࡬ࡢ CO ྾╔࢚ࢿࣝࢠ࣮ࡣ 15.8 kcal mol−1, CuI ࡬ࡢ྾╔࢚ࢿࣝࢠ࣮ࡣ 11.5 kcal mol−1 ࡜ィ⟬ࡉࢀࡓࠋࡘࡲࡾ Cu ࡀ㓟໬ࡉࢀࡿ࡜ CO ࡢ྾╔ࡀᙅࡲࡿࠋ୍᪉࡛ࠊCuI/Ru ࡬ࡢ CO ྾╔࢚ࢿࣝࢠ࣮ࡣ 21.8 kcal mol−1 ࡜ィ⟬ࡉࢀࠊCu0/Ru ࡬ࡢ྾╔࢚ࢿࣝࢠ࣮㸦⣙ 22 kcal mol−1㸧࡜࡯࡜ࢇ࡝ኚࢃࡽ࡞࠿ࡗࡓࠋCu ࢆ Ru ࡜」ྜ໬ࡍ
ࡿ࡜㓟໬ⓗ㞺ᅖẼୗ࡛ࡶ CO ྾╔ࡀಁ㐍ࡉࢀࠊCO 㓟໬άᛶࡀྥୖࡍࡿ஦ࢆ♧၀ࡍࡿ⤖ᯝ࡛࠶ࡿࠋCu/Ru 」ྜ

- 308 -

⣔࡟࠾࠸࡚ࠊ㓟໬཯ᛂࡀಁ㐍ࡉࢀࡿࡇ࡜ࡣࢡࣛࢫࢱ࣮ࣔࢹࣝ࡟ࡼࡿ཯ᛂ࢚ࢿࣝࢠ࣮ࡢィ⟬⤖ᯝ࡜ࡶ୍⮴ࡍࡿࠋᅗ 1㸬ィ⟬ࣔࢹࣝ㸦࿘ᮇቃ⏺ࢆㄢࡋࡓ㸧(a) Cu0/Cu, (b) Cu0/Ru (ABA ✚ᒙᵓ㐀), (c) Cu0/Ru (ABC ✚ᒙᵓ㐀), (d)CuI/Cu, (e) CuI/Ru (ABA ✚ᒙᵓ㐀), (f) CuI/Ru (ABC ✚ᒙᵓ㐀), (g) Ru on-top ྾╔, (h) Ru bridge ྾╔

4

Ⓨ⾲ᐇ⦼

‫ ۻ‬R. Fukuda “Quantum Chemistry for Confined Molecular and Electronic Structures with XP PCM“, Theoretical andComputational Chemistry of Complex Systems (July 18, 2019, Okazaki, Japan) (Invited)‫୍Ⰻ ⏣⚟ ۻ‬㸪ࠕ⌮ㄽィ⟬໬Ꮫࡢᇶ♏࠿ࡽゐ፹໬Ꮫ࡬ࠖ
㸪➨㸯㸱ᅇゐ፹㐨ሙ㸪2019 ᖺ 8 ᭶ 29-30 ᪥㸪⍇⍈†ࢢࣛࣥࢻ࣍ࢸࣝ㸦ᣍᚅㅮ₇㸧‫ ۻ‬R. Fukuda, K. Nakatani, N. Takagi, M. Ehara, S. Sakaki “Theoretical Study on the Electronic Origin and Reaction
Mechanism of Catalytic Nitric Oxide Reduction with Metal Clusters“, Materials Research Meeting 2019 (December
10–14, 2019, Yokohama, Japan)

5

ฟ∧ᐇ⦼

‫ ۻ‬N. Takagi, K. Ishimura, R. Fukuda, M. Ehara, S. Sakaki, “Reaction Behavior of the NO Molecule on the Surface ofan Mn Particle (M = Ru, Rh, Pd, and Ag; n = 13 and 55): Theoretical Study of Its Dependence on Transition-Metal
Element” Journal of Physical Chemistry A 123, 7921–7033 (2019).
‫ ۻ‬J. Ohyama, J. Shibano, A.Satsuma. R. Fukuda. Y. Yamamoto, S. Arai. T. Shishido, H, Asakura, S. Hsokawa, T.
Tanaka “Quantum Chemical Computation-Driven Development of Cu-Shell–Ru-Core Nanoparticle Catalyst for NO
Reduction Reaction” Journal of Physical Chemistry C 123, 20251–20256 (2019).
‫ ۻ‬K. Nakatani, H. Sato, R. Fukuda “Pseudo-Jahn-Teller effect on the lowest triplet state of para-benzoquinone
involving inequivalent carbonyl bonds” Chemical Physics Letters 741, 137072 (6 pages) (2020).

- 309 -







Elucidation of Organic Reaction Mechanism and Physical Properties by
Computational Approach '"

1 #&(µ× ±±`²bÉ²='DIE]bN±±`²bfÃÔk¢#ÄM &#]bM b¡!$#M ½o#M Ïy½oM ÍQpÖ¡$ }Ám qh#Jc¯±¹± ¯±¯±²bÉ² $]bÆzÈ]r]r^¶e]rZÎ§ $­]b b©® $#¯±¯±²bÉ² $c¯±¹±]bN¯±¯±`²bfÃÔk¢#Ä
M&#]bÙgÛAÚw)9H6*@I#1'28F*@I&Z[U=>

GIEn5(,0'@(0HUÙgÛBÚ  $!Ó#©®_Z ¯±¯±²bfÃÔk¢#ÄM &]bC3A]Ôk¯±¯±²bst}Óª¨ºjd $ ©®¯±¯±²bÉ² $ÄM ¹±]b«r
¤x&§i¦#M st}&! # &§¥YS¥³=+E;4IE 1ÙgÜÚC3A]):E-I¯±¯±²bÑ¸):E-I{&¾°uØ "st}&¿V
OH

(A)

(B)

R
Rotation

N

N

N

N

N

Me

N

Me
Me

H

N

N

N

N

R

R

(R)

Me

CO2H

H

CO2H
R

OH

CO2H

H

HO2C

(S)

H

HO2C

HO2C

HO

Dixiamycin A

HO

Dixiamycin B

gÛ

tBu

tBu

tBu

N

N

N

N

tBu

(R)-1

(S)-1

gÜ

2 %¾° Gaussian <7/I1?G.CB&T¡DFT [B3LYP/6-31G(d)]&¡³=+E;4I
E 1 a³+E;4IEC1+E 2 stÍ|aÌ¬ÈÈË]¾°\¾°&Õ

- 310 -

·uØ¥XrZ[ 1 C3A] ¯±¯±²bÑ¸ #Z¼& HPLC ÇÂst}&¿V

3 
=+E;4IE 1 ÐW£}SÒlÜ+E;4
cis Í³Ì¬~ trans Í³Ì¬~IE

!$ÙgÝÚ
³iQ³Ê !ßÌ¬~ 
!$ÙgÞÚ
trans Í³Ì¬~"RC3A]):E
cis transition state-I&167 kJ/mol [B3LYP/6-31G(d)]!$J¯

trans transition state図３±¯±²b Ñ¸C1+E 2•#):E-I& %135 kJ/mol   !=+E;4IE 1 ¯±¯±²bÑ¸ #Z¼PLC3A]  O $
tBu

tBu

N

tBu

tBu

tBu

N

N

N

N

N

N

tBu

(R)-cis-TS1
200.2 kJ/mol

tBu

cis-TS2
200.3 kJ/mol

tBu
tBu

(S)-cis-TS1
200.2 kJ/mol

N

N

tBu

×2

N
tBu

tBu

135.3 kJ/mol
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N

N

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2019  10 V 28 T(V)29 T(d)W<|EY<B

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1. Koichiro Mikami*
submitted
2. Hiroaki Hirano#, Hitoshi Hanamura#, Munenori Inoue, Saori Ueda, Makoto Watanabe, Masao Tanabiki,
Koichiro Mikami* (#Contributed equally)"Synthesis of soluble, air-stable fully conjugated ladder polymers "Polymer 2019, 177, 282-289.
3. Koji Takagi,* Hidetoshi Tanaka, Koichiro Mikami*" Ladderization of polystyrene derivatives by palladium-catalyzed polymer direct arylation"
Polym. Chem. 2019, 10, 2647-2652.
4. Koji Takagi,* Yuto Hirano, Koichiro Mikami,* Shoko Kikkawa, Isao Azumaya"Chiral non-planar oligophenylenes bridged by urea linkage: synthesis through intramolecular direct arylation,
chiroptical behavior, and theoretical investigation"
Eur. J. Org. Chem. 2019, 10, 2071-2080.

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27th International Society of Heterocyclic Chemistry CongressŧÃë!ixoxhzAŚ¤ÕAŖÜÖēČ@(-LŕġĊØčņAĝĴ!ħ  ¬ûPÝ&ñú ¼]zp^SsŧÃë! 
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ĈÀĵF6B¿1) Hiroaki Kurouchi, Tomohiko Ohwada, "Synthesis of Medium-Ring-Sized Benzolactams by Using Strong
Electrophiles and Quantitative Evaluation of Ring-Size Dependency of the Cyclization Reaction Rate. "
J. Org. Chem. 2020, 85, 876 - 901.

- 317 -

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◊✲᪉ἲࠊィ⟬᪉ἲ㔞Ꮚ໬Ꮫィ⟬⏝ࡢࢯࣇࢺ࢙࢘࢔࡜ࡋ࡚௨ୗࡢࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓࠋ (1) ࢭࣥࢱ࣮ᥦ౪ࡢࣉࣟࢢ࣒ࣛࣃࢵࢣ

࣮ࢪ: Gaussian 16 (rev. B.01, C.01)ࠊNBO (ver. 7.0)ࠊ (2) ࣮ࣘࢨ࣮࢖ࣥࢫࢺ࣮ࣝ: GRRM (developer’s version)ࠊ
PSI4 (ver. 1.3.2)ࠊOrca (ver. 4.2.1)ࠋࡲࡎࠊ᥎ᐃ཯ᛂᶵᵓ࠿ࡽண᝿ࡉࢀࡿ࢚ࢼࣥࢳ࢜㑅ᢥᛶࡢỴᐃࡍࡿ⣲㐣⛬ࡢィ⟬ࣔࢹࣝࢆసᡂࡋࠊ㔞Ꮚ໬Ꮫィ⟬ࢆ⏝࠸࡚㑄⛣≧ែ᥈⣴ࢆ⾜ࡗࡓࠋ⥆࠸࡚ࠊィ⟬࠿ࡽᚓࡽࢀࡿ⌮ㄽⓗ࡞㑅ᢥᛶ࡜ᐇ㦂ࡢ㑅ᢥᛶࢆẚ㍑ࡍࡿࡇ࡜࡛ィ⟬ࡢጇᙜᛶࢆホ౯ࡋࠊጇᙜ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ㑄⛣≧ែ࡟ᑐࡋ࡚ᵓ
㐀࡜㟁Ꮚ≧ែࡢゎᯒࢆ⾜ࡗࡓࠋࡲࡓࠊศᏊෆ┦஫స⏝ࢆᐃ㔞ⓗ࡟ホ౯࡛ࡁࡿ I-SAPT ࢆ⏝࠸࡚㑄⛣≧ែ࡟࠾ࡅࡿ⨨᥮ᇶྠኈࡢ┦஫స⏝ࢆㄪᰝࡋࡓࠋ

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᭱㏆ࠊᙜ◊✲ᐊࡣ㖡 , ゐ፹ࢆ⏝࠸ࡓභဨ⎔࢔ࣜࣝồ㟁Ꮚ๣ࡢ࢚ࢼࣥࢳ࢜㑅ᢥⓗ࡞࣍࢘⣲໬཯ᛂࢆ㛤Ⓨࡋࡓࠋࡲࡓࠊ୙ᩧ㓄఩Ꮚࡢ RR 4XLQR[3 ࡟ࢺ࣓ࣜࢳࣝࢩࣜࣝᇶࢆᑟධࡍࡿࡇ࡜࡛࢚ࢼࣥࢳ࢜㑅ᢥᛶࡀྥୖࡍࡿࡇ࡜ࢆぢฟࡋࡓ㸦ᅗ 㸧ࠋᮏ◊✲࡛ࡣࢺ࣓ࣜࢳࣝࢩࣜࣝᇶࡢຠᯝࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡟㑄⛣≧ែࡢࢥࣥࣇ࢛
࣓࣮ࢩࣙࣥ᥈⣴ࢆ⾜ࡗࡓࠋ᭱⤊ⓗ࡟ࠊᚓࡽࢀࡓ㑄⛣≧ែࡢ୰࡛᭱ࡶᏳᐃ࡞ᵓ㐀࡟ᑐࡋࠊI-SAPT ࢆ⏝࠸ࡓศᏊෆ┦஫స⏝ゎᯒࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊࢺ࣓ࣜࢳࣝࢩࣜࣝᇶ࡜ࣜࣥୖࡢ⨨᥮ᇶࡢ❧యⓗ┦஫స⏝ࡀ㓄఩Ꮚࢆ๛┤໬ࡋࠊ㑄⛣≧ែ࡟࠾ࡅࡿ㓄఩Ꮚࡢ୙ᩧሙࡀࡼࡾᇶ㉁ࡢ㠃㑅ᢥ࡟᭷฼࡞ᙧ࡟ኚ໬ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ

ᅗ 1. ࢚ࢼࣥࢳ࢜㑅ᢥᛶỴᐃࡢࡢ㑄⛣≧ែ᥈᥈⣴࡜᭱᭱Ᏻᐃ࡞࡞㑄⛣≧ែᵓ
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ࢩࣗ࢘ࢻ࢔ࢬࣜࣥࡢ➨஧㓄఩ᅪ࡟࠾ࡅࡿᙅ࠸┦஫స⏝ࡢຠᯝ
Effects on noncovalent weak interaction on the structural stability andreactivity of pseudoazurin‫ࠊࣛ࢕ࢸ࢔ ࢩࣟ࣎ࢱۑ‬㧗ጔ Ꮥග㸦Ⲉᇛ኱Ꮫ⌮ᕤᏛ◊✲⛉㸧

1◊✲┠ⓗࠊෆᐜ
ࢩࣗ࢘ࢻ࢔ࢬࣜࣥࡢ➨஧㓄఩ᅪ࡟࠾ࡅࡿᙅ࠸┦஫స⏝ࡀࠊ཯ᛂᛶ㸦㓟໬㑏ඖ㟁఩ࠊ㟁Ꮚ⛣ື཯ᛂ㏿ᗘ㸧࡟ཬࡰࡍᙳ㡪ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊMet16X ኚ␗య(X = Tyr, Trp Ala, Gly)ࡢ QM/MM ἲ࡟ࡼࡿᵓ㐀᭱㐺໬ࠊ᣺ືゎᯒࢆ⾜ࡗࡓࠋࡲࡓࠊࢩࣗ࢘ࢻ࢔ࢬࣜࣥ Met16Tyr, Met16Ile ኚ␗యࡢᵓ㐀Ᏻᐃᛶ࡜ኚᛶࣉࣟࢭࢫࢆ᳨ウࡍࡿࡓ
ࡵ࡟ࠊpH 3 ࡟࠾ࡅࡿ MD ィ⟬ࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ
2.1 ࢩࣗ࢘ࢻ࢔ࢬࣜࣥ Met16 ኚ␗యࡢ QM/MM ἲ
Gaussian 16 (rev A.03)ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࢆ౑⏝ࡋࠊB3LYP+D3/def2SVP ࡛ࣞ࣋ࣝ QM/MM ἲࡢᵓ㐀᭱㐺໬࡜᣺ືゎᯒ࡟ࡼࡿ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜ࡗࡓࠋࡲࡓࠊ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜࠺ࣔࢹࣝࢧ࢖ࢬࢆ᳨ウࡍࡿࡓࡵ࡟ࠊ
QM ࣔࢹࣝࠊQM/MM ࣔࢹࣝࠊ⁐፹Ỉࢆྵࡴ QM/MM ࣔࢹࣝࡢ᣺ືゎᯒࢆ⾜ࡗࡓࠋ
2.2 ࢩࣗ࢘ࢻ࢔ࢬࣜࣥ Met16 ኚ␗యࡢ CpHMD ἲ
Amber (version 18)ࢆ⏝࠸ࠊ࢔࣏ᆺࠊ࣍ࣟᆺࢩࣗ࢘ࢻ࢔ࢬࣜࣥࡢ pH 3ࠊ7 ࡟࠾ࡅࡿ 16ns ࡢືⓗᵓ㐀ࢆ Constant
pH molecular dynamics (CpHMD)ἲ࡟ࡼࡗ࡚ィ⟬ࡋࡓࠋ3◊✲ᡂᯝ
3.1 QM/MM ἲ࡟ࡼࡿ Met16 ኚ␗యࡢᵓ㐀ᙅ࠸┦஫స⏝ࢆᑟධࡋࡓ Met16yr, Met16Trp, Met16Ala, Met16Gly ࢩࣗ࢘ࢻ࢔ࢬࣜࣥࡢάᛶ୰ᚰᵓ㐀ࡣࠊ୺

࡜ࡋ࡚ Cu-S(Met86)ࡀኚ໬ࡋࠊCu-S(His40), Cu-N(Cys78), Cu-S(His81), Cu-S(Met86)ࡣ㔝⏕ᆺ࡜ྠᵝ࡛࠶ࡗࡓࠋ
ࡲࡓࠊ࢚ࢿࣝࢠ࣮ィ⟬ࢆ⾜࠺᣺ືゎᯒࡢࣔࢹࣝ࡟ࡣࠊ⁐፹Ỉࢆྵࡵࡓ QM/MM ᵓ㐀ࣔࢹࣝࡀ᭱㐺࡛࠶ࡿࡇ࡜
ࡀࢃ࠿ࡾࠊࡼࡾከࡃࡢィ⟬᫬㛫ࠊィ⟬㈨※ࡀᚲせ࡛࠶ࡗࡓࠋ

3.2 CpHMD ἲ࡟ࡼࡿ Met16 ኚ␗యࡢ࢔ࣥࣇ࢛࣮ࣝࢹ࢕ࣥࢢ
CpHMD ἲ࡟ࡼࡗ࡚ pH 3 ࡟࠾ࡅࡿ 16ns ࡢືⓗᵓ㐀ࢆィ⟬ࡋࡓ࡜ࡇࢁࠊ㔝⏕ᆺࠊMet16Phe, Met16Ile ࢩࣗ࢘ࢻ࢔ࢬࣜࣥࡢ࢔ࣥࣇ࢛࣮ࣝࢹ࢕ࣥࢢ㐣⛬࡟ഹ࠿࡞ᕪࡀぢฟࡉࢀࡓࠋࡲࡓࠊ࠸ࡎࢀࡢኚ␗య࡟࠾࠸࡚ࡶ࣍ࣟᆺ
ᵓ㐀ࡀ࢔࣏ᆺᵓ㐀ࡼࡾࡶᏳᐃ࡛࠶ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋ10 Å cut off, 16 ns ࡛ pH 7 ࡟࠾ࡅࡿືⓗᵓ㐀ኚ໬ࢆㄪ࡭
ࡓ࡜ࡇࢁࠊࢱࣥࣃࢡ㉁ࡀ࢔ࣥࣇ࢛࣮ࣝࢻࡋࡓࡇ࡜࠿ࡽࠊ30 Å ⛬ᗘࡢ኱ࡁ࠸ cut off ࡛ 100-200 ns ⛬ᗘࡢィ⟬ࡀᚲせ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

1.

‫ۻ‬Attila Taborosi, Takahide Yamaguchi, Seiji Mori, Takamitsu Kohzuma “Structural and energetic studies of S-π,
π-π, and CH-π noncovalent weak interactions in Met16X Pseudoazurin variants” ᪥ᮏ໬Ꮫ఍➨ 100 ᫓Ꮨᖺ఍,- 320 -

㸦2020 ᖺ 3 ᭶㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

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- 321 -

0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓከ๣᤼ฟࢺࣛࣥࢫ࣏࣮ࢱ࣮」ྜయࡢᇶ㉁᤼ฟ
࣓࢝ࢽࢬ࣒ࡢゎ᫂㸸⬡㉁ศᏊࡢᙳ㡪
(IIHFWRIOLSLGVRQWKHWUDQVSRUWPHFKDQLVPRIPXOWLGUXJHIIOX[SXPS$FU$%7RO&0ROHFXODUG\QDPLFVVWXG\‫ۑ‬⠛⏣ ᜨᏊࠊ⸨㇂ ⚽❶㸦ᮾ኱ඛ➃◊㸧

1◊✲┠ⓗࠊෆᐜ
ከ๣᤼ฟࢺࣛࣥࢫ࣏࣮ࢱ࣮」ྜయࡣ㏆ᖺ♫఍ၥ㢟࡜࡞ࡗ࡚࠸ࡿ㝔ෆឤᰁࡸᮎᮇࡀࢇࠊ෌Ⓨࡀࢇ࡟ࡳࡽࢀࡿࠊ

n⸆ࡀຠ࠿࡞࠸|࡜࠸࠺⸆๣⪏ᛶ໬࡟኱ࡁ࡞ᙺ๭ࢆᢸࡗ࡚࠸ࡿ⭷ࢱࣥࣃࢡ㉁࡛ࠊ」ᩘࡢࢥ࣏࣮ࣥࢿࣥࢺ ࣏ࣥࣉᶵ⬟ࢆᢸ࠺ $FU%ࠊእ㒊ࢳࣕࢿࣝࡢ 7RO&ࠊ$FU% ࡜ 7RO& ࢆࡘ࡞ࡄ $FU$ࠊࡑࡋ࡚ᇶ㉁ࡢ᤼ฟࢆㄪᩚࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ $FU= ࡛ᵓᡂࡉࢀࡿᕧ኱㉸ศᏊ࡛࠶ࡿࠋ᫖ᖺᗘࠊࡇࡢ⭷࡟ᇙࡵ㎸ࡲࢀࡓࢺࣛࣥࢫ࣏࣮ࢱ࣮」ྜ
యࡸ࣏ࣥࣉ㒊ศࡢࡳࡢ㸯࣐࢖ࢡࣟ⛊ࡢ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ㸱ᮏࡎࡘ⾜࠸ࠊ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥࡢᵓ㐀ኚ໬ࡢ㉳Ⅼ࡜ࡉࢀࡿ WUDQVPHPEUDQH 㡿ᇦ࡟࠶ࡿ࢔࣑ࣀ㓟ࡢࠊࣉࣟࢺࣥ໬࡟ᑟࡃࡼ࠺࡞ࢥࣥࣇ࢛࣓࣮ࢩࣙࣥኚ໬ࡀ
」ྜయ࡟࠾࠸࡚ຍ㏿ࡉࢀࡿࡇ࡜࡞࡝ࡀぢฟࡉࢀࡓࠋ
௒ᖺᗘࡣ㸰ࡘࡢ┦஫స⏝࡟↔Ⅼࢆ࠶࡚ࡓࠋ㸯ࡘࡵࡣ⬡㉁ศᏊ࡜ࢺࣛࣥࢫ࣏࣮ࢱ࣮࡜ࡢ┦஫స⏝ࠊࡶ࠺୍ࡘ
ࡣࠊ$FU% ࡢ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥ࡟⤖ྜࡋ࡚࠸ࡿ $FU= ࡜ $FU% ࡜ࡢ┦஫స⏝࡛࠶ࡿࠋ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥࡢᵓ㐀ኚ໬ࡣࣉࣟࢺࢿ࣮ࢩࣙࣥࡢኚ໬ࡔࡅ࡟ࡼࡿࡢ࡛࡞ࡃࠊ⬡㉁ศᏊ࡜ࡢ┦஫స⏝ࡶᙳ㡪ࢆ୚࠼ࡿࡇ࡜ࡣ᝿ീࡉࢀ
ࡿࠋ୍᪉ࠊᡃࠎࡢࢢ࣮ࣝࣉ࡛⾜ࡗ࡚࠸ࡓከᡂศ⭷ࡢィ⟬࡛ࡣࠊ⬡㉁ศᏊࡸỈࡢࢲ࢖ࢼ࣑ࢡࢫࡀ 323( ༢ᡂศ⭷ࡢࡑࢀ࡜ࡣ␗࡞ࡿࡇ࡜ࢆぢฟࡋ࡚࠸ࡓࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊ᫖ᖺᗘࡢィ⟬⤖ᯝࢆඖ࡟ࠊ᪂ࡓ࡟ᐇᅾࡍࡿ
኱⭠⳦⭷ࢆ࣑࣑ࢵࢡࡋࡓࣔࢹࣝ⭷ࢆᵓ⠏ࡋࠊ኱⭠⳦ࣔࢹࣝ⭷୰࡟࠾ࡅࡿከ๣᤼ฟࢺࣛࣥࢫ࣏࣮ࢱ࣮ࡢ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜ $FU%$FU=323( ⭷ࡢ 0' ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗ࡚ࠊࢺࣛࣥࢫ࣏࣮ࢱ࣮ࢆᵓᡂࡍࡿศ
Ꮚ㛫ࡢ┦஫స⏝ࡸࢲ࢖ࢼ࣑ࢡࢫࠊ࠾ࡼࡧ⬡㉁ศᏊ࡜ࢺࣛࣥࢫ࣏࣮ࢱ࣮࡜ࡢ┦஫స⏝ࡀࠊ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥࡢ
ᵓ㐀ኚ໬࡟࡝ࡢࡼ࠺࡟㛵ࢃࡿࡢ࠿ࢆㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ᭱ึ࡟ᐇᅾࡢ኱⭠⳦⭷ࢆᵓᡂࡍࡿ୺せ⬡㉁ศᏊ 303( ࡸ 303( ࢆྵࡴ⌧ᐇࡢ኱⭠⳦⭷ࡢᵓᡂẚ⋡ୖ఩㸶✀㢮㸦303(ࠊ393(ࠊ303*ࠊ403(ࠊ3<3(ࠊ9<3(ࠊ3<3*ࠊ393*㸧ࡢ⬡㉁ศᏊ࠿ࡽᡂࡿ㸰✀㢮ࡢࢧ࢖ࢬ㸦඲⬡㉁ศᏊᩘࡀ  ศᏊࡢ 0 ࢧ࢖ࢬ㸦 ୓ཎᏊ㸧࡜  ศᏊࡢ / ࢧ࢖ࢬ  ୓ཎᏊ 㸧ࡢ⬡㉁஧㔜ᒙ⭷ࢆᵓ⠏ࡋࡓࠋ⬡㉁ศᏊ࡜ࢱࣥࣃࢡ㉁ࡢຊሙࡣ IXML ຊሙࠊỈࡣ 7,33 ࣔࢹࣝࢆ⏝࠸ࠊ⬡㉁஧㔜ᒙ⭷ࡢᵓ⠏࡟ࡣ &+$500*8, ࢆ⏝࠸ࡓࠋ ᗘࡣ .ࠊẼᅽࡣ㸯Ẽᅽ࡛࠶ࡿࠋ$FU%$FU=323( ⭷ࠊ$FU%303( ⭷⣔ࠊ$FU%኱⭠⳦⭷⣔࡛ࡣ 0 ࢧ࢖ࢬࡢ⭷ࢆ⏝࠸ ODPEDGD ࣉࣟࢢ࣒ࣛ࡟ࡼࡾ⭷࡟ࢱࣥࣃࢡ㉁ࢆᇙࡵ㎸ࢇࡔࠋ0'εϝϣϪʖεϥϱͶͺ *520$&6 Ν༽͏ͪɽ੫ు૮‫༽ࡠޕ‬͹‫ࢋܯ‬Ͷͺ 3DUWLFOH 0HVK (ZDOG 30(  ๑ɼ
/HQQDUG-RQHV /- ૮‫༽ࡠޕ‬͹‫ࢋܯ‬Ͷͺɼຜ͹෈‫ۋ‬Ҳ͖ͯҡ๏੓͹੓࣯ͶΓͮͱໃࢻͲ͘͵͚͵ͮͪϓΟϱυϩ
ϭʖϩηྙΝ੠ౕΓ͚‫ٽ‬ΌΖͪΌ /-30( ๑Ν༽͏ͪɽ෾ׄͪ͢྘Үͺ 03, ด྽ɼ֦྘Ү಼͹ཽࢢؔΝ- 322 -

2SHQ03 ด྽Ͷͪ͢ύ΢ϔϨρφ๑ͶΓΕ‫ࢋܯ‬Νࣰߨͪ͢ɽεϝϣϪʖεϥϱͺ֦‫ͳܧ‬΍̏ИV ͹‫ࢋܯ‬Νɼॵ‫غ‬ӣಊྖΝร͓ͱ̑ຌࣰߨͪ͢ɽ

3◊✲ᡂᯝຌ‫Ͳڂݜ‬ͺΉͥߑ஛ͪ͢ຜ͹մੵΝߨͮͪɽͺͣΌͶ኱⭠⳦⭷ࡢ୺せ⬡㉁ศᏊ࡛࠶ࡿ 㻼㻹㻼㻱㸦ᅗ㸯㸧ࡢ⬡㉁஧㔜ᒙ⭷ࡢᛶ㉁ࡀ⏕యࣔࢹࣝ⬡㉁ศᏊ
࡛࠶ࡿ 㻼㻻㻼㻱 ࡢ⬡㉁஧㔜ᒙ⭷࡜ẚ࡭࡚࡝ࢇ࡞≉ᚩࡀ࠶ࡿࡢ࠿ࢆㄪ࡭ࡓࠋ㻼㻹㻼㻱 ࡣᅗ㸯࡟࠶ࡿࡼ࠺࡟㻝㻣 ఩ࡢ఩⨨࡟ 㼏㼥㼏㼘㼕㼏㻌 㼙㼛㼕㼑㼠㼥㻌 ࡀ࠶ࡿࡢࡀ≉ᚩ࡛࠶ࡿࠋ⭷ཌࢆẚ࡭ࡿ࡜ࠊ323( ⭷ࡣ sࠊ
303( ⭷ࡣ s ࡜࡞ࡾࠊ303( ⭷ࡢ᪉ࡀ⭷ཌࡣᑠࡉ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ $UHD SHU OLSLG ࡣ
323( ⭷ࡀ s 303( ⭷ࡀ s ࡜
303( ⭷ࡢ᪉ࡀ኱ࡁࡃ࡞ࡾ⭷ཌᅗ㸯 ኱⭠⳦⭷࡛⣙ ࢆ༨ࡵࡿ୺せ࡞⬡㉁ศᏊ
303( ࡜ࡑࡢࣔࢹࣝ⬡㉁ศᏊࡢ 323( ࡢᵓ㐀ࡢ⤖ᯝ࡜▩┪ࡋ࡞࠸ࡇ࡜ࡀࢃ࠿
ࡗࡓࠋᅗ㸰ࡣ 323( ⭷࡜ 303(⭷ࡢ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ 6&' ࢆ♧ࡍࠋ6&' ࡣࠊ⬡㉁ศᏊࡢ㸰ࡘࡢ࢔ࢩࣝ㙐 6Q 㙐ࠊ6Q 㙐 ࡢࡺࡽࡂලྜࢆ཯ᫎࡍࡿኚ㔞࡛ࠊᩘ್ࡀᑠࡉࡃ࡞ࡿ࡯࡝ࠊ࢔ࢩࣝ㙐ࡣࢹ࢕ࢫ࣮࢜ࢲࡋ࡚࠸ࡿࡇ࡜ࢆ
♧ࡍࠋ୧⭷࡜ࡶࠊ6Q 㙐ࡣࣜࣥ㓟ഃ㸦&㸰㸧࠿ࡽᮎ➃ࡲ࡛࡞ࡔࡽ
࠿࡟ῶᑡࡋ࡚࠸ࡿࡀࠊ6Q 㙐ࡣᅗ㸰 ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ㸦SCD㸧㸰ࡘࡢ⬡㉁ศᏊ࡛኱ࡁࡃ␗࡞ࡗ
࡚࠸ࡿࠋ323( ࡢ VQ 㙐ࡢ  ఩࡟ぢࡽࢀࡿࡼ࠺࡞஧㔜⤖ྜࡣ⬡㉁ศᏊࡢᒁᡤⓗ࡞ࢹ࢕ࢫ࣮࢜ࢲ࣮ࢆᘬࡁ㉳ࡇࡍࡇ࡜ࡣ▱ࡽࢀ࡚࠾ࡾ ఩ࢆ୰ᚰ࡟ 9 Ꮠᆺ࡟࡞ࡗ࡚࠸ࡿࠋ303( ศᏊࡶ VQ 㙐ࡢ  ఩ࡣᑠࡉࡃ࡞ࡗ࡚࠸ࡿࡀࠊ఩࡜  ఩ࡢ㛫࡟఩⨨ࡍࡿ  ఩㸦&㸧ࡢ್ࡀ኱ࡁࡃ࡞ࡗ࡚࠾ࡾࠊࡇࡢ㸱ࡘࡢ & ཎᏊ࡟ࡼࡿ
F\FOLF PRLHW\ ࡀ❧య㞀ᐖ࡜ࡋ࡚ᙳ㡪ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࡢࡇ࡜ࡣᣑᩓಀᩘ࡟ࡶ⌧ࢀ࡚࠾ࡾࠊ323( ⭷࡛ࡣ ʸ FPVᅗ㸱 ኱⭠⳦ࣔࢹࣝ⭷ࡢ⭷㠃࡟ᆶ┤࡞᪉ྥ࠿ࡽࡳࡓ㟁ᏊͶଲ͢ɼ303( ຜͺ ʸ  FPV ͳᐦᗘࠋ㉥Ⰽࡀ M ࢧ࢖ࢬࠊ㟷Ⰽࡀ L ࢧ࢖ࢬ࡛࠶ࡿࠋ

- 323 -

ঘ͚͠ɼ֨ࢆ͗ங͏͞ͳ͗Κ͖ͮͪࠋ኱⭠⳦ࣔࢹࣝ⭷࡛ࡣ㸰ࡘࡢࢧ࢖ࢬ࡟ࡘ࠸࡚ゎᯒࡋࡓࠋᅗ㸱ࡣ / ࢧ࢖ࢬ࡜ 0 ࢧ࢖ࢬࡢ඲㟁Ꮚᐦᗘ࡛࠶ࡿࠋ
ࣆ࣮ࢡ㛫㊥㞳㸦⭷ཌ㸧ࡣ୧ࢧ࢖ࢬ࡜ࡶ ʸ
QP Ͳࢧ࢖ࢬ࡟ࡼࡿᕪࡣぢࡽࢀ࡞࠸ࡀࠊࣆ࣮ࢡࡢ
ᙧ≧ࡣ / ࢧ࢖ࢬࡢ᪉ࡀࣆ࣮ࢡࡀࣈ࣮ࣟࢻ࡟࡞ࡗ
࡚࠸ࡿࡢࡀࢃ࠿ࡿࠋࡇࢀࡣ / ࢧ࢖ࢬ⭷ࡢ࠺ࡡࡾᅗ㸲኱⭠⳦ࣔࢹࣝ⭷ࢆ⭷㠃࡟ᆶ┤࡞᪉ྥ࠿ࡽぢࡓࢆ཯ᫎࡋࡓࡶࡢ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ㸦ᅗ㸲㸧ࠋᅗࠋୖࡀ M ࢧ࢖ࢬ࡛ୗࡀ L ࢧ࢖ࢬࠋL ࢧ࢖ࢬ⭷ࡢ⬡㉁ศᏊࡢᣑᩓಀᩘࡀ༢୍ᡂศ⭷ࠊከᡂศ⭷ࠊ᪉ࡀ࠺ࡡࡗ࡚࠸ࡿࡢࡀࢃ࠿ࡿࠋ

⭷ࢱࣥࣃࢡ㉁ࢆྵࡴ⣔࡛࡝ࡢ⛬ᗘ␗࡞ࡿ࠿ࢆࠊ
303( ศᏊ࡛ㄪ࡭ࡓࠋ኱⭠⳦ࣔࢹࣝ⭷ෆࡢ 303( ศᏊࡢᣑᩓಀᩘࡣ 303( ຜ಼Ͳ͹ 303( ෾ࢢ͹֨ࢆ‫਼ܐ‬ΓΕ΍ঘ͚͠ ʸ FPV ͳ͵Εɼ$FU%୉ௐۗϠυϩຜ‫ܧ‬Ͷ͕͏ͱͺɼʸFPV ͳ͠ΔͶঘ͚͠͵Ζ͞ͳ͗Κ͖ͮͪɽ͞Ηͺ $FU% ͗ଚࡑͤΖ͞ͳͶΓͮͱࢹ࣯෾ࢢ͗૮‫༽ࡠޕ‬Νण͜ɼಊ͘Ͷ͚͚͵ͮͱ͏Ζ͞ͳΝࣖ͢ͱ͏Ζɽਦ̓ͺ  झྪ͹ࢹ࣯෾ࢢͶͯ͏ͱͨΗͩΗ֨ࢆ‫਼ܐ‬Ν‫ͪ͢ࢋܯ‬΍͹Ͳ͍
Ζ͗ɼ୉ௐۗϠυϩຜ͹Ί͹‫Ͳܧ‬ͺɼࢹ࣯෾ࢢؔͲͺͨΗΆʹ֨ࢆ‫਼ܐ‬Ͷࠫ͗‫ݡ‬ΔΗ͵͏͹Ͷଲ͢ɼ$FU% ͗
ଚࡑͤΖͳಝͶ 3* Ν‫؜‬΋ࢹ࣯෾ࢢ͹֨ࢆ‫਼͗ܐ‬ঘ͚͠͵Ζ͞ͳ͗Κ͖Ζɽ3* ͺ Ճ͹ు՛Ν΍ͯͪΌ
$FU% ͳ͹૮‫͗༽ࡠޕ‬୉͚͘͵Εಊ͘Ͷ͚͚͵ͮͪ͞ͳ͗ࣖࠨ͠ΗΖɽ
ḟ࡟ࢺࣛࣥࢫ࣏࣮ࢱ࣮$FU% ࡜⭷࡜ࡢ┦஫స⏝ࢆㄪ࡭ࡓࠋ$FU% ࡣ࣍ࣔ㸱㔞య࡛࠶ࡿࠋ$FU%
323( ⭷ࠊ$FU%303( ⭷ࠊ$FU%኱⭠⳦ࣔࢹࣝ⭷࡛ࡣ $FU% ඲య࡜⭷඲య࡜ࡢ┦஫స⏝࡛ࡣ᭷ពᕪࡀ࡞࠿ࡗࡓࡀࠊ$FU% ࢆᵓᡂࡋ࡚࠸ࡿࣔ
ࣀ࣐࣮㛫ࡢ┦஫స⏝ࡢ኱ࡁࡉ࡟㐪࠸ࡀ࠶ࡾࠊ
323( ⭷ࡢʸ N-PRO ࡟ẚ࡭࡚ࠊ
303( ⭷ࡸ኱⭠⳦ࣔࢹࣝ⭷࡛ࡣʸࠊʸN-PRO ͳ͵Ε $FU% ࡢࣔࣀ࣐࣮
㛫ࡢ┦஫స⏝ࡀᑠࡉࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ
࠿ࡗࡓ㸦ᅗ㸴㸧ࠋ303( ⭷࡛ࡣ 303( ศᏊࡀࠊᅗ㸳 ⬡㉁ศᏊࡢᣑᩓಀᩘࠋ(ᕥ)㸸኱⭠⳦ࣔࢹࣝ⭷⣔ࠊ(ྑ)㸸

኱⭠⳦ࣔࢹࣝ⭷࡛ࡣ 3<3* ศᏊࡀ $FU% ࡜ᙉ

AcrB-኱⭠⳦ࣔࢹࣝ⭷⣔ࡃ┦஫స⏝ࡋࠊࣔࣀ࣐࣮⏺㠃ࡢ࢔࣑ࣀ㓟ࡢࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࢆኚ࠼࡚࠸ࡓࡇ࡜ࡀࢃ࠿

ᅗ㸴 AcrB ࢆᵓᡂࡍࡿࣔࣀ࣐࣮㛫ࡢ┦஫స⏝ࠋࡗࡓࠋ୍᪉ࠊ$FU%$FU=Ѹ323( ⭷⣔࡛ࡣࠊ$FU%$FU= ඲య࡜ 323( ⭷࡜ࡢ┦஫స⏝ࡣsN-PRO ࡛ࠊ$FU%Ѹ323( ⭷⣔ࡢsN-PROࡼࡾࡶᑠࡉࡃࠊࡲࡓ $FU% ࡢࣔࣀ࣐࣮㛫┦஫స⏝ࡶsN-PRO ࡜ᑠࡉ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ$FU= ࡣ࣏ࣥࣉࡢᙺ┠ࢆࡍࡿ $FU% ࡢ㸱ࡘࡢࣔࣀ࣐࣮ࡢ WUDQVPHPEUDQH ࢻ࣓࢖ࣥ࡟ࡑࢀࡒࢀ⤖ྜࡋ࡚࠸ࡿࡀࠊ$FU%$FU=
323( ⭷⣔࡛ࡣࠊࣔࣀ࣐࣮㛫ࡢ┦஫స⏝ࡢ኱㒊ศࢆᢸ࠺࢔࣑ࣀ㓟࣌࢔ࡢࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࡀኚ໬ࡋ࡚࠾ࡾࠊ
$FU= ࡀ┦஫స⏝ࡍࡿ $FU% ࡢ࢔࣑ࣀ㓟ࡢࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࡶኚ໬ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊ$FU= ࡣ┤᥋┦஫స

- 324 -

⏝ࡋ࡚࠸࡞࠸ࡀࠊ$FU= ࡀ┦஫స⏝ࡍࡿ $FU% ࡢ࢔࣑ࣀ㓟ࡀࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࢆኚ࠼ࡓࡇ࡜࡟ࡼࡾ⤖ᯝⓗ࡟⏺㠃ࡢ࢔࣑ࣀ㓟ࡢࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࢆኚ࠼ࠊࣔࣀ࣐࣮㛫ࡢ┦஫స⏝ࡀኚ໬ࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ
᭱ᚋ࡟ᇶ㉁᤼ฟ࡟㛵ࢃࡿ $FU% ࡢ࣏࣮ࢱ࣮㒊ศࡢࢲ࢖ࢼ࣑ࢡࢫ࡟ $FU= ࡀᙳ㡪ࢆ୚࠼ࡿ࠿࡝࠺࠿ࢆࡳࡿࡓ
ࡵ࡟ࠊ୺ᡂศゎᯒࢆ⾜ࡗࡓࠋ$FU= ࡣ WUDQVPHPEUDQH 㡿ᇦ࡟఩⨨ࡋ࡚࠾ࡾࠊ$FU% ࡢ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥ࠿ࡽࡣ
㞳ࢀ࡚࠸ࡿࠋᅗ㸵ࡣᕥ࠿ࡽ $FU%323( ⭷⣔ࠊ$FU%$FU=323( ⭷⣔ࠊ$FU$$FU%$FU=7RO&323( ⭷⣔ࡢ➨୍୺ᡂศࢆ㯮࠸▮༳࡛♧ࡋࡓᅗ࡛࠶ࡿࠋゎᯒࡣ QVȣV ࡢࢺࣛࢪ࢙ࢡࢺࣜ㸱ᮏ࡛⾜ࡗࡓࠋྛࢺࣛࢪ࢙
ࢡࢺࣜࡣ WUDQVPHPEUDQH 㡿ᇦࡢ EDFNERQH ཎᏊ࡟ࣇ࢕ࢵࢸࣥࢢࡋࡓᚋࠊ$FU% ࡢ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥࡢỈ⣲ཎᏊ௨እࡢཎᏊ࡟ᑐࡋ࡚ඹศᩓ⾜ิࢆィ⟬ࡋࡓࠋᅗ㸵ࢆぢࡿ࡜ࠊ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥࡢ୰ኸ㒊㸦㉥࠸୸࡛ᅖࡗࡓ㒊ศ㸧ࡢ▮༳ࡢᩘࡀ␗࡞ࡗ࡚࠾
ࡾࠊ$FU%323( ⭷⣔࡛ࡣ▮༳ࡀぢࡽࢀ࡞࠸ࡢ࡟ᑐࡋࠊ
$FU%$FU=323( ⭷ ⣔ ࠊ$FU$$FU%$FU=7RO&
323( ⭷⣔࡜ቑ࠼࡚࠸ࡿࡢ
ࡀࢃ࠿ࡿࠋࡇࢀࡣ $FU= ࡀ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥࡢࢲ࢖ࢼ࣑
ࢡࢫ࡟ᙳ㡪ࢆ୚࠼࡚࠾ࡾࠊࡉ
ࡽ࡟」ྜయ࡟࡞ࡿ࡜ $FU$ ࡸ
7RO& ࡶᙳ㡪ࢆ୚࠼ࡿࡇ࡜ࢆ

ᅗ㸵 AcrB ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥࡢ୺ᡂศゎᯒ⤖ᯝࠋ➨㸯୺ᡂศࡣ㯮▮༳࡛♧ࡉࢀࡿࠋࣔࣀ࣐࣮ࡢⰍࡣ㉥ࡀྲྀࡾ㎸ࡳᆺࠊ㟷ࡀ⤖ྜᆺࠊ⥳ࡀ᤼ฟᆺࢆ
♧ࡍࠋ㉥࠸୸࡛ᅖࡗࡓ㒊ศࡣ࣏࣮ࢱ࣮ࢻ࣓࢖ࣥࡢ୰ኸ㒊ࠋ♧၀ࡋ࡚࠸ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬⠛⏣ᜨᏊࠕከ๣᤼ฟࢺࣛࣥࢫ࣏࣮ࢱ࣮」ྜయ AcrA-AcrB-AcrZ-TolC ࡢ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࠖ
➨ 14 ᅇࢺࣛࣥࢫ࣏࣮ࢱ࣮◊✲఍ᖺ఍‫ ۻ‬⠛⏣ᜨᏊࠕከ๣᤼ฟࢺࣛࣥࢫ࣏࣮ࢱ࣮AcrABZ-TolC ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ㸸⭷-⭷ࢱࣥࣃࢡ㉁㛫┦஫స⏝ࡢホ౯ࠖ➨ 33 ᅇศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥウㄽ఍‫ ۻ‬Keiko Shinoda “Molecular Dynamics Study of Multidrug Efflux Transporter AcrA-AcrB-AcrA-TolC Complex
Embedded in Lipid Bilayer” 64th Annual Meeting of the Biophysical Society (2020)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ ۻ‬1 .DPL\D 0 .D\DQXPD+ )XMLWDQLDQG . 6KLQRGD n$ QHZ OLSLG IRUFH ILHOG )8-, | -

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chevron-type undulation ,Ď¨Ásinusoidal undulation /òď ³ = 0.36 Ñ

chevron ć½ĈyăS-ďĎ = 0.52 Ñ chevron ć½Ĉy +|Þ-ď| Ă ¨Á ÜÆçc !c = 50  60 Ñ,Ď¹¼
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GLØ« 1 ÈOß-ď ´¸È} +þhÈ chevron ¿Ď |%fÂ- +Ďgk{!,ĎbnE<I -}5BFJN5GL sÛď4
31st International Microprocesses and Nanotechnology Conference (MNC2018) rĉÇâ/àĎ2019 ¬îW áĄëñ¡/g¾ 1ďVĎPêí¥gbnik{/z±­Ù·/Å×åmk{ g/àĎ g·Āñ¡Ò/àT-ďoÚ¡À(1) M. Sakamoto and I. Hanasaki: Japanese Journal of Applied Physics 58 (SD) SDDC03(2019) .
(2) G. Tiberio, L. Muccioli, R. Berardi and C. Zannoni: Chem. Phys. Chem. 10 (1) 125(2009) .
(3) J. Jeong and M. W. Kim: Phys. rev. lett. 108 (20) 207802(2012) .

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+H'[mlF$'#{´b·Il+H C¯l ¤K('•.PÍbE)G `´Î)QXk][l¿±)¹ÍbEÚZeH`Àl Û'k¸_(ÍbE¿±´Â$&ÍbE$P´b`°PÎ£'C¯l ¤K(%,E:@G1$'XkÁ¿¿±)]|´ÎJP©LQ
`$ÖP =Ñ)ËNOV 19 ¦Ø =Ñ ­w©LQCGU_
ΔΔG )±W#¢., ° U£P)È(kql$&Q´]Ð SPR m)¹ ËNÂ``'·Il)F$'}\%Á¿Xk`Xk][l¿±)]|´Á¿U£P`´b'x% s 'k ¸_(•5P germline É6Â¾ %5PÁÕ 3 κ Õh λ Õm*­.C;6´b)a2C¯'%m(]Ð HER2 PÝtrastuzumabÞ)Y!'ZP<²J 6 P)

4CÈ(kql$&.C;6a2PU£P)Q´DSC m)¹´P[ml F$
'k ½%(º z¶[mlF$º' ¤K(~Xk][l¿±$&[mlF$)XkD<C¾')» ¿±$&6¦P4ÍY!UlÊ'ÖP

Ze.C;6´ba2$&Ul Ä('k ¸_(P[mlF$qD¾Ï&#q$ t35PÆ{ '[mlF$q!'® %('

4¥»]¬%m•ßj­, “Addressing the Benefits of Simulations in Computer-aided Antibody Engineering”,

Biologics Manufacturing Japan 2019, 2019 s 9  18 } Tokyo 
•ßj­, “,E:@G1ºQPlF¯%ÆÝ”, CBI l's', 2019s 10  22 } M •ßj­, e, “Computational modeling algorithm in antibody engineering: How precise are

they?”, ¨ 19 L}É®l's', 2019 s 6  24 }  
•W, ß j­, * <",,  , Kevin Entzminger, e, The effects

of protonation of a phosphorylated amino acid on the molecular recognition: comparative studies of- 330 -

generic proteins and an antibody, Mjl

®l-E>, Mjl, 2019/4/20,

VF.

1G
•

Í

, Ö×«, J~Å, ßj­, e, [lFÃu¾Q Shh P`´bg¾, ¨ 19 L }É®l's', ~ Ð'R(~d), 2019/6/24,

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 !, ß·Il}

j­, J~Å, e, _lmXk-=@DG-AE)P¥¾, ¨ 19 L }É®l's', ~Ð'R(~d), 2019/6/24,

VF.1G•,  , Kevin Entzminger, e, The efffects

W, ß j­, * <",of protonation pf a phosphorylated amino acid on the molecular recongnation:Comparative studies ofgeneric proteins and an antibody, 33rd The Protein Society Annual Symposium, Sheraton Grand Seattle
HotelÝUSA,Seattle), 2019/7/3,•

Í, Ö×«, ßVF.1Gj­, J~Å, *<" , e, Thermodynamic, kinetic

and computational analyses of the recognition mechanism of an antibody to a flexible protein antigen, CBIl' 2019 sj', 1GGC

5Ý~Þ, 2020/10/23,

VF.1GW]¬%m•

Kuroda D and Tsumoto K, “Engineering Stability, Viscosity, and Immunogenicity of Antibodies by
Computational Design“, Journal of Pharmaceutical Sciences, 109(5):1631-1651 (2020)•

Morimoto J, Kim J, Kuroda D, Nagatoishi S, Tsumoto K, and Sando S, “Per-residue Program ofMultiple Backbone Dihedral Angles of β-Peptoids via Backbone Substitutions”, Journal of the American
Chemical Society, 142(5):2277-2284 (2020)•

Kawade R, Kuroda D, and Tsumoto K, “How the protonation state of a phosphorylated amino acidgoverns molecular recognition: insights from classical molecular dynamics simulations”, FEBS Letters,594(5):903-912 (2020)•

Kondo HX, Kiribayashi R, Kuroda D, Kohda J, Kugimiya A, Nakano Y, Tsumoto K, and Takano Y,“Effects of a remote mutation from the contact paratope on the structure of CDR-H3 in the anti-HIV
neutralizing antibody PG16”, Scientific Reports, 9(1):19840 (2019)•

Morimoto J, Fukuda Y, Kuroda D, Watanabe T, Yoshida F, Asada M, Nakamura T, Senoo A, Nagatoishi
S, Tsumoto K, Sando S, “A Peptoid with Extended Shape in Water”, J. Am. Chem. Soc. 141:14612-14623(2019)•

Ishii et al. J.

•

Ikeuchi et al. %m.

•

Kawakami et al. %m.

•

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•

Kawade R et al. %m.

•

Kaneda et al. %m.

- 331 -

཯ᛂ⤒㊰⮬ື᥈⣴ἲࡢ㛤Ⓨ࡜ᛂ⏝'HYHORSPHQWDQG$SSOLFDWLRQRI$XWRPDWHG5HDFWLRQ3DWK6HDUFK0HWKRGV‫ۑ‬๓⏣⌮㸪ཎῲ♸㸪ᕷ㔝ᬛஓ㸪㛗㇂ᕝኴ♸, 㕥ᮌᮘ೔㸪ᮡᒣెዉ⨾㸪ఀ⸨⌶☻ୖ⏣୍㈗㸪ᒸ⏣ᣅ᫂ṇᮧ ኴ୍㸪Ṋෆ㑈♸㸪ྡ⏿ኍᚿ㸦໭ᾏ㐨኱Ꮫ㸧1◊✲┠ⓗ㸪ෆᐜ
ᮏ◊✲࡛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(AFIR)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⤒㊰ࢿࢵࢺ࣮࣡ࢡࢆ
⮬ື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⾜ิ⦰⣙(RCMC)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ᯒࢆ㏻ࡌ࡚ࡑࡢ㐺⏝ᛶࢆ᳨ドࡍࡿ㸬᫖ᖺᗘࡣ㸪௨ୗࡢ 5 ࡘࡢㄢ㢟࡟ࡘ࠸᳨࡚ウࡋࡓ㸬

2◊✲᪉ἲ㸪ィ⟬᪉ἲ㸪◊✲ᡂᯝ
2019 ᖺᗘࡣ㸪௨ୗࡢ 5 ࡘࡢㄢ㢟࡟ྲྀࡾ⤌ࢇࡔ㸬

2.1 ேᕤຊㄏ㉳཯ᛂἲࢆ⏝࠸ࡓ㙐≧㧗ศᏊࡢຊᏛ≉ᛶࡢゎ᫂
2.2 㑄⛣≧ែ࡟࠾ࡅࡿᏳᐃ㓄ᗙ⮬ື᥈⣴ἲࡢ㛤Ⓨ࡜ᛂ⏝
2.3 ศᒱ཯ᛂ࡟࠾ࡅࡿ AFIR ⤒㊰࡜ IRC ⤒㊰ࡢẚ㍑
2.4 ㉸㧗ᅽୗ࡟࠾ࡅࡿ 14 ᒓ஧㓟໬≀⤖ᬗᵓ㐀ࡢ⣔⤫ⓗ᥈⣴
2.5 ཯ᛂ⤒㊰⮬ື᥈⣴ἲࢆ⏝࠸ࡓ㉁㔞ࢫ࣌ࢡࢺࣝࡢண
2.6 㔠ᒓ㘒యࢆ⏝࠸ࡓ࢔࣑ࢻศゎ࡟㛵ࡍࡿ⌮ㄽ◊✲

2.1 ேᕤຊㄏ㉳཯ᛂἲࢆ⏝࠸ࡓ㙐≧㧗ศᏊࡢຊᏛ≉ᛶࡢゎ᫂࿘ᮇ⣔ࡢ཯ᛂ⤒㊰⮬ື᥈⣴࡟ࡼࡗ࡚ᮦᩱࡢຊᏛ≉ᛶࢆゎ᫂ࡍࡿヨࡳࢆ⾜ࡗࡓ㸬౛࡜ࡋ࡚࣏࢚ࣜࢳࣞࣥࢆ
C10H20 ࡢ┤㙐≧࣏࢚ࣜࢳࣞࣥࢆࣘࢽࢵࢺࢭࣝ࡜ࡍࡿ࿘ᮇⓗቃ⏺᮲௳࡛ࣔࢹࣝ໬ࡋ㸪༢ᡂศ(SC-)AFIR ἲࢆ㐺⏝ࡋࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࡢ␗࡞ࡿᵝࠎ࡞ᵓ㐀ࢆ⥙⨶ⓗ࡟᥈⣴ࡋࡓ㸬ࡲࡓ㸪እ㒊࠿ࡽࡢᶵᲔⓗᘬࡗᙇࡾ㸦࣓࢝- 332 -

ࣀࢫࢺࣞࢫ㸧ࡀ࠿ࡅࡽࢀࡓ≧ἣࢆ෌⌧ࡍࡿࡓࡵ࡟㸪⮬సࣉࣟࢢ࣒ࣛࢆసᡂࡋ㐺⏝ࡋࡓ㸬ᵓ㐀᭱㐺໬࡟ࡣ㸪GRRM
ࣉࣟࢢ࣒ࣛ㛤Ⓨ⪅∧ࢆ⏝࠸㸪㟁Ꮚ≧ែィ⟬ࡣ SIESTA (PBE-D2/DZP)࠾ࡼࡧ DFTB+ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓ㸬㛗㙐࣏࢚ࣜࢳࣞࣥ࡟ᑐࡍࡿᵓ㐀᥈⣴ࡢ⤖ᯝ㸪461 ಶࡢᵓ㐀࡜ 1059 ᮏࡢ཯ᛂ⤒㊰ࡀᚓࡽࢀࡓ㸬ࡑࡢ࠺ࡕ 㸪୍ᮏ㙐ࡢᵓ㐀ࢆ⥔ᣢࡋ࡚࠸ࡓࡶࡢࡣ 230 ᵓ㐀࠶ࡾ㸪ᚓࡽࢀࡓᵓ㐀ࡢ୰࡟ࡣࡽࡏࢇ≧ᵓ㐀ࡸᢡࡾ␚ࡳᵓ㐀ࡶྵࡲࢀ࡚࠸ࡓ㸬ᚓࡽࢀࡓ⤖ᯝ࡟ᑐࡋ࡚㸪⮬సࣉࣟࢢ࣒ࣛࢆ⏝࠸㸪࣓࢝ࣀࢫࢺࣞࢫࡢ኱ࡁࡉࢆኚ໬ࡉࡏ࡞ࡀࡽ⤒㊰ࢆ෌ィ⟬ࡍࡿࡇ࡜࡛㸪ࣘࢽࢵࢺࢭࣝࡢఙ㛗ࡢᵝᏊࢆㄪ࡭ࡓ㸬ࡲࡓ㸪෌ィ⟬๓ᚋ࡛ࡢᵓ㐀ࡢᩘࡢኚ໬࠿ࡽ㸪࣓࢝ࣀࢫࢺࣞࢫ࡟ࡼࡾࢥࣥࣇ࢛࣓࣮ࢩ࢚ࣙࣥࣥࢺࣟࣆ࣮ࡀῶᑡࡍࡿࡇ࡜ࡶ☜ㄆࡍࡿࡇ࡜ࡀ࡛ࡁࡓ㸬

2.2 㑄⛣≧ែ࡟࠾ࡅࡿᏳᐃ㓄ᗙ⮬ື᥈⣴ἲࡢ㛤Ⓨ࡜ᛂ⏝༢୍ࡢ㑄⛣≧ែࢆ୚࠼ࡿ࡜ࡑࡢᏳᐃ㓄ᗙࢆ⮬ື᥈⣴ࡋ㸪᭱ప࢚ࢿࣝࢠ࣮㑄⛣≧ែࢆỴᐃࡍࡿᡭἲࢆ㛤Ⓨࡋࡓ㸬ࡇࡢ࡜ࡁ㸪GRRM ࠾ࡼࡧ⮬సࣉࣟࢢ࣒ࣛࢆే⏝ࡋࡓ㸬ィ⟬ᑐ㇟ࡣ࢚ࣀ࣮ࣝᆺࡢ࢔ࣝࢻ࣮ࣝ཯ᛂ࠾ࡼࡧ୙
ᩧ࣐ࣥࢽࢵࣄ཯ᛂ࡜ࡋࡓ㸬㟁Ꮚ≧ែィ⟬ࡣ Gaussian16 ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓ(B97D/D95V ࣞ࣋ࣝ)㸬
࢔ࣝࢻ࣮ࣝ཯ᛂ࡛ࡣ 183 ಶࡢ㑄⛣≧ែࢥࣥࣇ࢛࣓࣮ࢩࣙࣥࢆ᥈⣴ࡍࡿࡇ࡜࡟ᡂຌࡋࡓ㸬ࡇࢀࡽࡢ㑄⛣≧ែ࡛ࡣ㸪⤖ྜ⤌ࡳ᥮࠼㒊఩ࡢཎᏊ㛫㊥㞳࡟ 0.1 Å ⛬ᗘࡢኚືᖜࡀぢࡽࢀࡓ㸬ࡋࡓࡀࡗ࡚㸪ࢥࣥࣇ࢛࣓࣮ࢩࣙࣥ࡟
ࡼࡗ࡚཯ᛂ୰ᚰ㸦㊥㞳㸧ࡀኚືࡍࡿ཯ᛂ⣔࡟ࡘ࠸࡚ࡶᮏᡭἲ࡛ࡣ㑄⛣≧ែࢧࣥࣉࣜࣥࢢࢆ⾜࠼ࡿࡇ࡜ࡀᮇᚅ
ࡉࢀࡿ㸬ࡲࡓ୙ᩧ࣐ࣥࢽࢵࣄ཯ᛂ࡛ࡣ㸪ሗ࿌ࡉࢀ࡚࠸ࡿ㑄⛣≧ែࡼࡾࡶప࢚ࢿࣝࢠ࣮ࡢ㑄⛣≧ែࢆ᥈⣴ࡍࡿࡇ࡜࡟ࡶᡂຌࡋࡓ㸬

2.3 ศᒱ཯ᛂ࡟࠾ࡅࡿ AFIR ⤒㊰࡜ IRC ⤒㊰ࡢẚ㍑
AFIR ἲ࡟ࡼࡗ࡚ᚓࡽࢀࡿ AFIR ⤒㊰࡜୍⯡ⓗ࡞ IRC ⤒㊰ࡢࡘ࡞ࡀࡾࢆẚ㍑ࡍࡿࡇ࡜࡛ືⓗ⤒㊰ศᒱ࡜࿧ࡤࢀࡿ⌧㇟ࢆ⮬ືⓎぢࡍࡿᡭἲࢆ㛤Ⓨࡋࡓ㸬ࡑࡢ㝿㸪AFIR ἲ࡟ࡼࡿ཯ᛂ⤒㊰᥈⣴ࡣ㛤Ⓨ⪅∧ࡢ GRRM ࣉࣟࢢ࣒ࣛ㸪㟁Ꮚ≧ែィ⟬ࡣ Gaussian16 ࢆ⏝࠸ࡓ㸬ᮏ᥈⣴ᡭἲࢆ㸪㐣ཤ࡟ศᒱ཯ᛂࡀ㉳ࡁࡿࡇ࡜ࡀሗ࿌ࡉࢀࡓ 2-ࣅࢽࣝࣇࣛࣥ࡜ 3-࣓ࢺ࢟ࢩ࢝ࣝ࣎ࢽࣝࢩࢡࣟ
࣌ࣥࢱࢪ࢚ࣀࣥࡢ Diels-Alder ཯ᛂ࡬࡜㐺⏝ࡋࡓ⤖ᯝ㸪㐣ཤሗ࿌ࡉࢀࡓศᒱ཯ᛂ㸪ཬࡧ 5 ࡘࡢ᪂つศᒱ཯ᛂࢆ
⮬ືⓗ࡟᥈⣴ࡍࡿࡇ࡜࡟ᡂຌࡋࡓ㸬᪂つศᒱ཯ᛂࡢ୰࡟ࡣ㸪௒ࡲ࡛࡟ࡣ▱ࡽࢀ࡚࠸࡞࠸ࢱ࢖ࣉࡢศᒱ཯ᛂࡶ
ྵࡲࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬

2.4 ㉸㧗ᅽୗ࡟࠾ࡅࡿ 14 ᒓ஧㓟໬≀⤖ᬗᵓ㐀ࡢ⣔⤫ⓗ᥈⣴㧗ᅽୗ࡛ࡢ⤖ᬗ┦㌿⛣⤒㊰⮬ື᥈⣴ࢆᐇ⿦ࡋ㸪㉸㧗ᅽୗ࡛ࡢ  ᪘஧㓟໬≀⤖ᬗᵓ㐀᥈⣴࡬ᛂ⏝ࡋࡓ㸬㟁Ꮚ≧ែィ⟬࡟ࡣ 6,(67$ ࣉࣟࢢ࣒ࣛ㸦YHU㸧ࢆ౑⏝ࡋ㸪**$3%( ỗ㛵ᩘ࠾ࡼࡧ '=3 ᇶᗏࢆ⏝࠸ࡓ㸬⤖ᬗᵓ㐀᥈⣴࡟ࡣ *550 ࣉࣟࢢ࣒ࣛ࡟ᐇ⿦ࡉࢀࡓ 3%&$),5 ἲࢆ⏝࠸㸪 Ẽᅽ㸦3   DWP㸧࠾ࡼࡧ  ୓Ẽᅽ㸦3 
DWP㸧ࡢྛ᮲௳ࢆ⪃៖ࡋ࡚⾜ࡗࡓ㸬⤖ᬗࡢ⤌ᡂࡣ㸯ࣘࢽࢵࢺࢭࣝ࠶ࡓࡾ  ༢఩࠾ࡼࡧ  ༢఩ࡢሙྜ㸦$2㸪$2㸦$ &6LRU*H㸧㸧ࢆ⪃៖ࡋ㸪⤖ᬗࡢ✵㛫⩌ࡢᑐ⛠ᛶ࡟ࡣไ㝈ࢆㄢࡉࡎ᥈⣴ࢆ⾜ࡗࡓ㸬ᚓࡽࢀࡓ඲࡚ࡢ
ᵓ㐀ࡣయ✚ࢆ  ಸ࡟ቑࡸࡋࡓࢫ࣮ࣃ࣮ࢭ࡛ࣝᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓ㸬᪂ወᵓ㐀ࢆྵࡴ  ಶ௨ୖࡢᏳᐃᵓ㐀ࡀᚓࡽࢀࡓ㸬&2 6L2 *H2 ࡢྛ⤌ᡂ࡟ࡘ࠸࡚㸪 Ẽᅽୗ࡛ࡣࡑࢀࡒࢀ  ಶ㸪 ಶ㸪 ಶ㸪 ୓Ẽᅽୗ࡛ࡣࡑࢀࡒࢀ  ಶ㸪 ಶ㸪 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  Ẽᅽ࠿ࡽ  ୓Ẽᅽࡢ㛫࡛Ẽᅽࢆ₞ቑῶࡉࡏࡓᵓ㐀᭱㐺໬ィ⟬ࢆ⾜࠸㸪୺せ࡞⤖ᬗᵓ㐀ࡢ࢚ࣥࢱࣝࣆ࣮ࡢ᥎⛣ࢆ- 333 -

㏣㊧ࡋࡓ ᅗ  㸬㧗ᅽ᮲௳࡛ࡣ㧗ᐦᗘ࣭㧗㓄఩ࡢ⤖ᬗᵓ㐀ࡀ┦ᑐⓗ࡟Ᏻᐃ࡜࡞ࡿഴྥࡀほᐹࡉࢀࡓ࡯࠿㸪㉸㧗ᅽࢆ᥃ࡅࡿࡇ࡜࡛ࡼࡾ㧗࿘ᮇࡢඖ⣲ࡢᛶ㉁ࢆⓎ⌧ࡍࡿࡼ࠺࡟࡞ࡿᵝᏊࡶほᐹࡉࢀࡓ㸬 ཯ᛂ⤒㊰⮬ື᥈⣴ἲࢆ⏝࠸ࡓ㉁㔞ࢫ࣌ࢡࢺࣝࡢண

໬Ꮫ࢖࢜ࣥ໬ἲ࡟ᇶ࡙ࡃ㉁㔞ศᯒࢫ࣌ࢡࢺࣝࢆ཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡࡢ㏿ᗘゎᯒ࠿ࡽྜᡂࡍࡿࣉࣟࢺࢥࣝ
ࢆ㛤Ⓨࡋࡓ㸬࢔࣑ࣀ㓟࣭࢔࣑ࣀ㓟ከ㔞య୍ศᏊ࡜ CI-MS ࡛ࡢ࢖࢜ࣥ※࡛࠶ࡿ CH5+࢖୍࢜ࣥศᏊ࠿ࡽ࡞ࡿ⣔࡟
ᑐࡋ࡚㸪GRRM ࣉࣟࢢ࣒ࣛ㛤Ⓨ⪅∧ࢆ౑⏝ࡋ࡚཯ᛂ⤒㊰᥈⣴ࢆᐇ᪋ࡋࡓ㸬㟁Ꮚ≧ែィ⟬࡟ࡣ Gaussian09 ෆࡢ
PM6 ࢆ౑⏝ࡋࡓ㸬᥈⣴࡟ࡼࡗ࡚ᚓࡽࢀࡓ཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡ࡟ᑐࡋ࡚㏿ᗘ⾜ิ⦰⣙(RCMC)ἲࢆ⏝࠸ࡓ㏿ᗘㄽࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋ࢖࢜ࣥࡢᏑᅾẚࢆ⟬ฟࡋࡓ㸬࢔ࢫࣃࣛࢠࣥ࡟ᑐࡋ࡚ GRRM ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࡓ཯ᛂ⤒㊰᥈⣴࡜ RCMC ἲࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ᪋ࡋ
ࡓ㸬ᐇ㦂࡛ᚓࡽࢀࡓࢫ࣌ࢡࢺࣝ࡟ࡣ࢖࢜ࣥ໬ࡋࡓ࢔ࢫࣃࣛࢠࣥ (MW=133)࠿ࡽࡑࢀࡒࢀ H2O(MW=18)࡜
COOH2(MW=46)ࡀ⬺㞳ࡋࡓ࢖࢜ࣥ(MW=115㸪MW=87)ࡢࣆ࣮ࢡࡀྵࡲࢀࡿ㸬RCMC ἲ࡟ࡼࡿ㏿ᗘㄽࢩ࣑ࣗࣞ
࣮ࢩࣙࣥࡢ⤖ᯝ㸪ᐇ㦂࡛ᚓࡽࢀ࡚࠸ࡿ࢖࢜ࣥࡢࣆ࣮ࢡࢆࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚෌⌧࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡗ
ࡓ㸬ࡲࡓ㸪㏿ᗘㄽ࡛ぢ✚ࡶࡗࡓᏑᅾẚࡀࣆ࣮ࢡᙉᗘẚ࡜ᐃᛶⓗ࡟୍⮴ࡍࡿࡇ࡜ࡶศ࠿ࡗࡓ㸬௚ࡢ࢔࣑ࣀ㓟࡟ࡘ࠸࡚ࡣ㸪᥈⣴࡟ࡼࡗ࡚ࣆ࣮ࢡ࡟ᑐᛂࡍࡿ࢖࢜ࣥࡀᚓࡽࢀࡓ୍᪉㸪ᐇ㦂࡛ᚓࡽࢀࡓࣆ࣮ࢡᙉᗘࢆ෌⌧࡛ࡁ࡞࠸࢔࣑ࣀ㓟ࡀ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬ࡑࡢ⌮⏤࡜ᨵၿἲ࡟ࡘ࠸࡚⌧ᅾ᳨ウ୰࡛࠶ࡿ㸬

2.6 㔠ᒓ㘒యࢆ⏝࠸ࡓ࢔࣑ࢻศゎ࡟㛵ࡍࡿ⌮ㄽ◊✲࢔࣑ࢻ⤖ྜࡣ㠀ᖖ࡟㔜せ࡞ᐁ⬟ᇶ࡛࠶ࡿࡀ㸪ࡑࡢศゎ࡟ࡣ㧗せ࡛࠶ࡿ㸬୍᪉㸪㓝⣲ࡣࡸᙉ࢔ࣝ࢝ࣜᛶ᮲௳࡞࡝ࡢ㐣㓞࡞᮲௳ࡀᚲ

࿴࡞᮲௳࡛࢔࣑ࢻ⤖ྜࢆศゎ࡛ࡁࡿ㸬ࡑࡇ࡛㸪ィ⟬୺ᑟࡢ཯ᛂタィ࡟ࡼࡗ࡚࢔࣑

ࢻ⤖ྜࢆຍỈศゎࡍࡿゐ፹ࢆ᥈⣴ࡋࡓ㸬ࣔࢹࣝゐ፹ᵓ㐀ࡣ㸪㓝⣲ࡢ཯ᛂ୰ᚰࢆᶍೌࡋࡓ཯ᛂ⣔ࢆᵓ⠏ࡋࡓ㸬ᵓ⠏ࡋࡓࣔࢹࣝ⣔࡟ᑐࡋ࡚㛤Ⓨ⪅∧ࡢ GRRM ࡟ᐇ⿦ࡉࢀ࡚࠸ࡿ AFIR ἲࢆ㐺⏝ࡋ㸪ィ⟬ࣉࣟࢢ࣒ࣛ࡟
Turbomole 7.3 ࠾ࡼࡧ Gaussian 09 ࢆ⏝࠸ࡓ DFT ィ⟬ࢆ⾜ࡗ࡚཯ᛂᛶࢆㄪ࡭ࡓ㸬ᵓ⠏ࡋࡓࣔࢹࣝᵓ㐀ࢆ⏝࠸ࡓຍỈศゎࡢ㞀ቨࡣ 120.4 kJ/mol ࡜㧗࠸ࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ḟ࡟㸪୰ᚰ㔠ᒓ࢖࡛࢜ࣥ࠶ࡿ Zn ࢖࢜ࣥࡢ㓄఩Ꮚ࡟ OH㸫࢖࢜ࣥࢆ⏝࠸ࡓ࡜ࡇࢁ㸪㞀ቨࡣ 102.3 kJ/mol ࡲ࡛ୗࡀࡗࡓ㸬ࡉࡽ࡟ Zn ࢖࢜ࣥࢆ Ni ࢖࢜ࣥ࡟⨨᥮ࡋࡓࣔࢹࣝ⣔࡛ࡣ㞀ቨࡣ 65.1 kJ/mol ࡲ࡛ᑠࡉࡃ࡞ࡗࡓ㸬ࡇࡢ⤖ᯝࡣ࿴᮲௳ୗ࡛ຍ

Ỉศゎࡀ㐍⾜ࡋ࠺ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿ㸬ୖグࡢィ⟬⤖ᯝࢆඹྠ◊✲ඛࡢᐇ㦂ࢢ࣮ࣝࣉ࡬ᥦ౪ࡋ㸪ᐇ㝿࡟࢔࣑ࢻ⤖ྜࢆຍỈศゎྍ⬟࠿᳨ド୰࡛࠶ࡿ㸬

3Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

>@ ★ᒸ⏣ᣅ᫂㸪ᕷ㔝ᬛஓ㸪ஂಖ⏣ᾈྖ㸪ఀ⸨⫕㸪๓⏣⌮㸪Ỉ⁐ᾮ୰࡛ࡢ࢔࣑ࢻຍỈศゎ࡟࠾ࡅࡿ㔠ᒓ࢖࢜ࣥ࡜ሷᇶࡢᙳ㡪')7 ィ⟬࡟ࡼࡿẚ㍑◊✲㸪᪥ᮏ໬Ꮫ఍➨  ᫓Ꮨᖺ఍
>@ ★7,WR<+DUDEXFKL60DHGD$Q([SORUDWLRQRI%LIXUFDWLRQRQD5HDFWLRQ5RXWH1HWZRUNRID'LHOV±$OGHU
5HDFWLRQ%DVHGRQWKH$),50HWKRG$3$7&&6\GQH\>@ ★+ 1DEDWD 07DNDJL . 6DLWD 6 0DHGD 6\VWHPDWLF 6HDUFK IRU &U\VWDO 6WUXFWXUHV RI 'LR[LGHV RI *URXS (OHPHQWV &26L2*H2 8QGHU8OWUDKLJK3UHVVXUH$3$7&&6\GQH\>@ ★ୖ⏣୍㈗㸪ᩧ⏣ㅬ୍㑻㸪๓⏣⌮㸪࣓࢝ࣀࢫࢺࣞࢫ࡟క࠺㙐≧ศᏊࡢ཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡࡢኚ໬㸪➨ ᅇศᏊ⛉Ꮫウㄽ఍  ྡྂᒇ- 334 -

>@ ★ఀ⸨⌶☻㸪ཎῲ♸㸪๓⏣⌮㸪$),5 ἲࢆ⏝࠸ࡓศᒱ཯ᛂ⮬ື᥈⣴㸸ࣅࢽࣝࣇࣛࣥ࡜ ࣓ࢺ࢟ࢩ࢝ࣝ࣎
ࢽࣝࢩࢡࣟ࣌ࣥࢱࢪ࢚ࣀࣥࡢ 'LHOV$OGHU ཯ᛂ࡬ࡢᛂ⏝㸪➨  ᅇศᏊ⛉Ꮫウㄽ఍  ྡྂᒇ>@ Ṋෆ㑈♸㸪㕥ᮌᮘ೔㸪๓⏣⌮㸪཯ᛂ⤒㊰⮬ື᥈⣴ἲ࡟ࡼࡿ໬Ꮫ࢖࢜ࣥ໬㉁㔞ࢫ࣌ࢡࢺࣝࡢ⌮ㄽⓗゎᯒ㸪➨  ᅇศᏊ⛉Ꮫウㄽ఍  ྡྂᒇ>@ ★ୖ⏣୍㈗㸪ᩧ⏣ㅬ୍㑻㸪๓⏣⌮㸪㙐≧ศᏊࡢ࣓࢝ࣀࢫࢺࣞࢫ࡟క࠺཯ᛂ⤒㊰ࢿࢵࢺ࣮࣡ࢡࡢኚ໬㸪ࢩ࣏ࣥࢪ࣒࢘ࠕ໬Ꮫ཯ᛂ⤒㊰᥈⣴ࡢࢽ࣮ࣗࣇࣟࣥࢸ࢕࢔ ࠖ㸪>@ ★7,WR<+DUDEXFKL60DHGD$),5SDWKVDQG,5&SDWKVLQDJOREDOUHDFWLRQURXWHQHWZRUNRI& +7KHWK
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㸪᪥ᮏ໬Ꮫ఍໭ᾏ㐨ᨭ㒊  ᖺኟᏘ◊✲Ⓨ⾲఍>@ ★ఀ⸨⌶☻㸪ཎῲ♸㸪๓⏣⌮㸪ศᒱ཯ᛂ࡟࠾ࡅࡿ $),5 ⤒㊰࡜ ,5& ⤒㊰ࡢẚ㍑㸸࣓ࢳࣞࣥࣅࢽࣜࢹ
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4ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

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   (! '#%")
DECB'1

RU_(Ñ'ÇP¥ÁÜ)±ÝÊ6""4 Ú)H¨$"¬Q"5 oS$"±\¶Â¾ \wÐ¿8×^ º')¤¯l'Le8a-0u°(}&YcÖ²$& "5 )´©t±v' P6¯#4Ë'F¹#50ÈM8×^5()À  " (ÈM×^')Ån& ÌV¡:=(ÅÈM#){NpO 1)¼\2*x9@D;'24j¿65ÅÈMTÆ6" x|¢h#q3652' x
9@D;(PUo|+(9@D;ÐX1Û«º#5 Zs(0(ÌgJlxÅ ®TÆ6" 63)fÙ½(['³"& ÙP') µb'ÓÍ&§Ii­8ÙÅ(TÆÚ#5 (V¡)]i­Å'É,ß5
(0 6.#']i­Å'!"®(¡·,36 Å24{V¡82'ØÅ`£¼ Å x¬W(ª/|7(»Py76" {V¡82'& ÚK)Õ3'& "&ÎÏ1®  " ®(r?>¦6"5]i­Å'!"mPUºÒ'24(8·~5$)Ú#5  PZsV¡8ABC<E

ÄG(81!   &%(  §Ii­) xO#¸Ô(zÞ^¯8k¢d PÃ81!0 xÅ$"Ù6" 
15²X[(ÐX'24i­«(\GD==¾¡8· # 3' { 

C:EG'

C:EG×¼«8Ù5$ i­«(ÅV¡(µO(tK$&5ÀÝ«PhÅ65$±36"5 . 
C:EG'15²X[)ÅV¡'³'Le5$Í6"4 

C:EG81!i­«)Ë'cÃ¡8Ä0xÅ$05  '    + )  Zs(0(°Æº&gJxÅ(J!5<VCDPDU9TGFC9>ID9TE|ØÅ¶(  «'25xÅ  Zs)  % 3'2 "  Â_¤'0"'Í6 (ÅA=EU#)  «)x¬W$Å(ÞÎ$"sÃ  )`£º&Zs$"sÃ5 &Zs¤¢É) #4 Ç¤¢
É$" &'$) «¤¢65 &3 V<HBU(¥Ø).4'Õ3'6"& 
 ZsÅe·(gÕ)<QEHYF[D8u50'

¤9@D;$"r¬6"5©(¤¢ K:;S=(ÔÙ&PUÉ+(ÐX&%(~vd²$Êy"4ª.6"5
d²(J!#5 ÝPUm3(Ú&})Å([Ïº¡8¼¯'[6"Õ3'5
$ 2*Åe·8t\OD#gÕ5$#5 ÏÂ¾) ¾'  «'25  3 - 336 -

+(xPUÐX2*  Øb¶'15  ,«'25  3; +(ÐX'¸8¹"~
v8y   L%

&).,6P0NB9( ?K+L%H-*42"M

AJB<3zÂ 2*«(ªO'"µÂ¾#Ûº'Ì§65$r#6$&%&#" # '&%) «¶o«$"|6´Ï«8Å$"Ù|#1$&%&#" #'&%) «|6"4(¤¢Û$$&%&#" # '&%) «(ªÛ'¢k¡lÁ6

È

M'15V¡#5$Ö¨6 f-) %3(Ål'" $&%&#" # '&%) «(¤¢e·8Õ3'5$$1' Åe·+(q×'!"Õ3'5$Óº$ :>=#    L%!K,6z  «'24  ; 'ÐX65$Í6 (ÈM#)9=?DAE
¼x×«$"Ù36 ØÅ)#5  «#)  ZHDFx¬W
$"sÃ ZHDFÅ$"º$7 "5  yÐ$' »2Å#"1ÔsØÅ$Øb#¤¢É`&5ÔsØÅ¶#)  ¤¢É#5 Í'25$/(£­¡#; ½36 Ç¤¢É$"  $  Ý½36"5  4 ÝÛ)  /#4ÔsØÅ¶#(xÅÈM$Ém"&4µÛ#5 Òj&8ØÅ$"Ù5$)Yc'$"Ë'Ú#5 Ï~v#); (¤¢e·8Õ3'5$$1'ÈMÛµÚK8¾¹5
$8Óº$ 

DE7;IF7;  L%

&).,6P0NB9( ?K+L%H-*42"MAJB<3¦»P)   Ãp Ò8Ù"y  ¦»P'"  t' ) ))')'(% 
[¶p 2*¿k¼t(0( )!*&' &)%)!# 8»Ù (7(t') [¶p 8Ù ØÅS8 Ý50  !$ #!!) (&#*)!&% W?D8»Ù 

PZsREEAXD)@DE=F'[6"m 

:>=#    L% ¦  » P )   Ã pÒ8Ù"y!K,6¦»P'" 

 2 *  t  ') ))')'(%[¶p 2*¿k¼t(0( )!*&' &)%)!# 8»Ù (7(t')  [¶p 8Ù ØÅS8 Ý50 !$ #!!)(&#*)!&% W?D8»Ù5$$1' ÈM+(p×d$ 0305)Õº' Ý 
 DE58  L%

&).,6P0NB9( ?K+L%H-*42"M

AJB<3

- 337 - «J¼Zs$N]FE6 

[Re(bpy)(CO)3Br]0* (S = 0) + TEOA (k¢V<HBU)rº'lÜ6(2) ISC[Re(bpy)(CO)3Br]0* (S = 1) + TEOA  Zs¤¢(5(ÈMV<HBU'!" Zs(&¤¢É)  #4  1  1xÅÈM)|6"&)Øb¶'N]FE

$"ª52(1) hν

"50

(3) Reductive
quenching[Re(bpy)(CO)3Br]– (S = 1/2) + TEOA

[Re(bpy)(CO)3Br]0 (S = 0) + TEOA"  ¤¢)_O(ÈM'¤¢65$¨65   → 
#)&4<$)x
&¤¢65$6"50Figure 3. 1 Schematic diagram of the formation of one-electron-.

reduced Re complex starting from the ground state of3^p'15(k¢(ÈM{ß8·~

[Re(bpy)(CO)3Br]0 via (1) photo absorption, (2) intersystem crossingm6Õ9@D;N]M8:D24(ISC), and (3) reductive quenching.

$&%&#" #'&%)«(¤¢'15Ú©°iJÎelectronic state.

 )`¡Pe·#5$7  xO#) ' ÄG«(J¼Zs¤¢650$&%&#" # '&%) «(k¢(ÈM{ß'!"1·~J¼Zs3.5

 V<HBU(n¸3$&%&#" #'&%) «(k¢'15Jz[¶¯{ß$J¼ZsÀz{ß(o'a)q36&

`¡P(ÈMË({24 Jz{ß8{Õ $&%&#" # '&%) «(k¢13$
7  3'f-)  (¤¢{ß2*Ç¤¢É#5 &'$) «(¤¢{ß1Õ3' &'$) «(¤¢{ß'") ,o|(ÈMË  ¤¢(Ú©°i#5  @:F+
OH

(a)

N

OH

O
+

HO

O

HO

N
O

+

CO
CO

O

H

Re

CO

N
N

Re

CO

CO

ΔG (kcal/mol)

12+

Br
N
N

Re

CO

CO

CO

110

+
2TEOA
+
0
CO2
+
[Br(TEOA)4]–
7.7(–34.4)

+
6TEOA
+
CO2

+
TEOA
+
CO2
+
[Br(TEOA)4]–
9.5(–45.0)

0

N

N

HO

H

HO

13+

O
CO

N

Re

N

N

OH
N

HO
O

CO
CO

CO

Re

N

N

CO

1TS-4a4b0

CO

14a0

150
+
+
14b0
+
CO2
CO2
CO2
+
+
+
–
+
CO2
]
[Br(TEOA)
4[Br(TEOA)4]–TEOAH++
5.7+[Br(TEOA)4]–(–66.9)[Br(TEOA)4]–
6.9
4.2(–65.5)(–67.9)2.6(–51.8)N+
TEOAH++[Br(TEOA)4]–

1TS-6a6b0+
TEOAH++[Br(TEOA)4]–
12.7(–55.5)16.2(–52.9)Proton abstraction

N
N

11.5
(–55.1)

O

N
N

Re
CO

CO2 binding

16.2

OH

N

O

CO

+
TEOAH++[Br(TEOA)4]–

CO

Isomerization

Figure 3. 2 (a) Free energy profile for forming monoalkyl carbonate complex in the
ground electronic state.

- 338 -

Re

CO
CO

N

OH

16c0

0

O

C O

CO

OH

12.7

OH

O
O

16b0

TEOA binding

COCO

1TS-6b6c0

0.0
(0.0)

Br– dissociation

Re
CO

CO

OH

HO

CO

Re

O

CO

HO

CO

N
N

C

HO

HO

N
N

O

N

C O

+
TEOAH++[Br(TEOA)4]–
2.3(–64.4)(  o|Ë241{0  ¤¢É$&5$¡Õ6

PZsREEAXD(m3) ¼I¿e·)Ë'È#5$6 :>=#    L%!K,6

¼Zs'(/  (o|cÃ#¯«(  «#)5   ´Ï#)2+¼Zs'"o|¤¢cÃ#5$7  ($3 ¯«(  «'É,5$N  «(  @:F)¼Ñ¾{$Ö¨6

N

N
N
N

Ru

Cl
N
N

N

  l'")  ÎG(xÞ^(¼Zs'24¼

CO
CO

Re
CO

  ÅÎG'I¿5$7 "5 ¼)9=?
DAE #4 m6 PZsREEAXD249=?

Figure 3. 3 Binuclear complexes of Ru

DAEand Re units functioning as®N]FEP1(3   «(Þ^'¼I¿^5$6   f-(moS#)

9=?DAE

photosensitizer and catalyst'25¼Zs'24  ( *')!# (!) (J]>EC

0



OH
O

:EGÙ®(5LGCG«¤¢
6

3'¼ZsÀP´©(´©

u¼º'LGCG$ . o|¤¢5
$6

!"P9=?DAE


HO

O



O

OH







0

OH
O

+(¼I¿'





–
OH
O

O

HO
OH

O

O





!"·,5 OHOO

3'((µÛ(ÚK'

O

O





¼Z

O

HO

OH

O

2–
OH

O

HO

HO

r'"xÅÛµÛÕ$"w36"5
s3

O

–

OH



0
OH
O

O

HO
O

O

O(@0G$/

Figure 3. 4 Redox states of ascorbic acids.

-,3 6)+%:%   1)',%2-67-' 678(< 32 61%00 130)'80) %'7-9%7-32 &< ,313+)2)386 '%7%0<67 > 267-787) 27)5)67
)1-2%5)5-)6<86,8!2-9)56-7< 45-0

-,36)+%:%)-.-+3=)0)'7-9);-(%7-32

3*%2(&<-53140); 1)',%2-67-'678(<> ,) 228%0))7-2+3*%4%23'-)7<*3530)'80%5'-)2')%+3<%   

-,36)+%:%> ,)30)3* -2,373'%7%0<7-'329)56-323*73&<)3140); 78(<267-787)27)5)67)1-2%5)5-)6<86,8!2-9)56-7< 39 -,36)+%:%= ,)530)3* -24,373'%7%0<7-''329)56-323*73&<)'3140); 78(<>
 27)52%7-32%0 "35/6,34 <86,8 !2-9)56-7<    -,3 6)+%:% =  78(< 32 7,)1)',%2-613*3;-(%7-32&<-3-264-5)(-28'0)%5%7%0<67> 7,27)52%7-32%032*)5)2')32%7%0<6-6%2(,)1-'%0
2+-2))5-2+)&  362+)0)6!-29-7)(

- 339 -

ḟୡ௦⇕㟁ኚ᥮ᮦᩱࡢࡓࡵࡢ⇕ఏᑟ⋡ไᚚ࡟㛵ࡍࡿ◊✲
Study on thermal conductivity control for next generation thermoelectric
conversion materials‫ۑ‬ᐑᓮ ⚽ಇ㸦ྡྂᒇᕤᴗ኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ
ࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ࡣ⇕㟁ᛶ⬟࡜ࡋ࡚㧗࠸㟁Ẽฟຊᐦᗘࢆ᭷ࡋ࡚࠸ࡿࡶࡢࡢࠊ㧗࠸⤖ᬗᑐ⛠ᛶ࡟㉳ᅉࡋࡓ㧗⇕ఏᑟ⋡ࡢపῶࡀᛶ⬟ྥୖࡢㄢ㢟࡜࡞ࡗ࡚࠸ࡿࠋࡑࡢࡓࡵࠊࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ࢆ⏝࠸ࡓ᭦࡞ࡿ᪂つ⇕㟁ኚ᥮ᮦᩱࢆᐇ⌧ࡍࡿ࡟ࡣࠊప࠸⇕ఏᑟ⋡ࢆ᭷ࡍࡿࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ࢆ୰ᚰ࡟⇕㟁ኚ᥮ᮦᩱࡢ
ྍ⬟ᛶࢆ᥈⣴ࡍࡿࡇ࡜ࡀᚲせ࡛࠶ࡿࠋ⇕㟁ኚ᥮ᮦᩱࡢᛶ⬟ࢆỴᐃࡍࡿ㔜せ࡞≀⌮ࣃ࣓࣮ࣛࢱ࡛࠶ࡿ⇕ఏᑟ⋡ࡢ⟬ฟ࡟ᚲせ࡞ࣇ࢛ࣀࣥィ⟬ࡣࠊ㏻ᖖࡢ DFT ィ⟬ࡢᩘ 100 ಸ⛬ᗘࡢィ⟬ࢥࢫࢺࡀᚲせ࡛࠶ࡿࠋࡶࡋࠊ⇕ఏᑟ⋡ࡢணࢆపィ⟬ࢥࢫࢺ࣭㧗⢭ᗘ࡛Ỵᐃྍ⬟࡞ᩘ⌮ⓗ࡞ࣔࢹࣝࢆᥦ᱌ࡍࡿࡇ࡜ࡀ࡛ࡁࢀࡤࠊ᪂つ⇕㟁ኚ᥮ᮦᩱࡢ㛤Ⓨ࡟࠶ࡓࡾࠊప౯᱁ࠊ▷᫬㛫ࡢ㛤Ⓨࡀྍ⬟࡟࡞ࡾࠊ⇕㟁ኚ᥮ᮦᩱࡢᮦᩱ᥈⣴࡟᪂ࡓ࡞ࣈ࣮ࣞࢡࢫ࣮ࣝ
ࡀᮇᚅ࡛ࡁࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊᵝࠎ࡞ࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀࡟࠾࠸࡚ࠊ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚⟬ฟࡉࢀࡓ⇕ఏᑟ⋡࡟ᑐࡋ࡚ࠊᵓᡂඖ⣲ࡢཎᏊ᝟ሗࡢࡳࢆࡶ࡜࡟ᶵᲔᏛ⩦࡟ࡼࡿ⇕ఏᑟ⋡ணࡀྍ⬟࠿ࢆ᳨ウࡋࡓࠋࡑࡢ⤖ᯝࠊࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛᆺ⤖ᬗᵓ㐀࡟࠾ࡅࡿྛࢧ࢖ࢺࡢཎᏊ༙ᚄ࠾ࡼࡧཎᏊ㉁㔞ࡢࡳࡢ᝟ሗ࠿ࡽ⇕ఏᑟ⋡ࢆ㧗⢭ᗘ࡛ண2࡛ࡁࡿᶵᲔᏛ⩦ࣔࢹࣝࡢᵓ⠏࡟ᡂຌࡋࡓࠋ

◊✲᪉ἲࠊィ⟬᪉ἲ➨ࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛᆺࡢ⤖ᬗᵓ㐀(C1b-type)࡟ࡣ 4a (0, 0, 0)ࠊ4b (0.5, 0, 0)ࠊ4c (0.25, 0.25, 0.25)ࢧ࢖ࢺࡢ 3 ✀㢮ࡢཎᏊࢧ࢖ࢺࡀ࠶ࡿࠋࡇࡢ࠺ࡕ 4a ࠾ࡼࡧ 4b ࢧ࢖ࢺࡣ⤖ᬗᏛⓗ࡟ࡣ➼౯࡞ࢧ࢖ࢺ࡛࠶ࡿࠋᵓᡂඖ⣲ࡢ 3 ✀㢮ࡢ࠺ࡕࠊᵓᡂඖ⣲ࡀࡑࢀࡒࢀ 4c ࢧ࢖ࢺࢆ༨ࡵࡿ࡜ࡋṧࡾࡢඖ⣲ࡀ 4a ࠾ࡼࡧ 4b ࢧ࢖ࢺࢆ༨ࡵࡿ࡜ࡋࠊ3 ࡘࡢሙྜࡢᵓ㐀ࣔࢹࣝࢆィ⟬ࡋࠊDFT ィ⟬࡟ࡼࡾ඲࢚ࢿࣝࢠ࣮࠾ࡼࡧ᱁Ꮚᐃᩘࢆྛᵓ㐀ࣔࢹࣝ࡟ᑐࡋ࡚ồࡵࡓࠋྛീࡢࣔࢹࣝࡢ᱁Ꮚᐃᩘࢆẚ㍑ࡋࠊ᭱ࡶᑠࡉ࠸඲࢚ࢿࣝࢠ࣮ࢆྲྀࡿᵓ㐀ࣔࢹࣝࢆ෌Ᏻᐃࡢᵓ㐀ࣔࢹ࡛ࣝ࠶ࡿ
࡜ỴᐃࡋࡓࠋDFT ィ⟬࡟ࡣࠊᨃ࣏ࢸࣥࢩࣕࣝἲ࠾ࡼࡧ PBE-sol ࡢ㟁Ꮚ┦㛵࣏ࢸࣥࢩࣕࣝࢆ౑⏝ࡋࡓ VASP ࣃࢵࢣ࣮ࢪࢆ⏝࠸ࡓࠋ࢝ࢵࢺ࢜ࣇ࢚ࢿࣝࢠ࣮࠾ࡼࡧ཰᮰࢚ࢿࣝࢠ࣮ࡣ 200 Ry ࠾ࡼࡧ 0.001 eV ࡟タᐃࡋࡓࠋ᱁Ꮚ⇕ఏᑟ⋡ࡢィ⟬࡟ࡣࠊࣇ࢛ࣀࣥࡢ㠀ㄪ࿴ᛶࢆィ⟬ྍ⬟࡞ Phon3py ࢆ౑⏝ࡋࡓࠋࣇ࢛ࣀࣥࡢ㠀ㄪ࿴ᛶࡢ᭱኱ᡂศ࡜࡞ࡿ 3 ḟࡢຊᐃᩘࢆồࡵࡿࡓࡵ࡟ࠊC1b ᵓ㐀ࡢ primitive cell ࢆ 2 x 2 x 2 ࡟ᣑᙇࡋࡓࢫ࣮ࣃ࣮ࢭࣝ
࡟ᑐࡋ࡚ࠊᵝࠎ࡞ཎᏊࡢ఩⨨ࢆኚ໬ࡉࡏࡓ㝿ࡢ DFT ィ⟬ࢆ⾜࠺ࠋࡇࡢィ⟬⤖ᯝࡼࡾࣇ࢛ࣀࣥᑑ࿨ࢆィ⟬ࡋࠊ࣎ࣝࢶ࣐ࣥ᪉⛬ᘧࢆ౑⏝ࡍࡿࡇ࡜࡛᱁Ꮚ⇕ఏᑟ⋡ࢆ⟬ฟࡋࡓࠋᶵᲔᏛ⩦ࡢࣔࢹࣝ࡟ࡣࠊ௨ୗࡢ 6 ࡘࡢࣔࢹࣝࢆ⏝࠸ࡓࠋ⥺ᙧࣔࢹࣝ࡜ࡋ࡚ࠊLinear regressionࠊBayesian linear
regressionࠊPoission regressionࠊ㠀⥺ᙧࣔࢹࣝ࡜ࡋ࡚ࠊNeural network regressionࠊDecision forest regressionࠊBoosted
decision tree regression ࢆ౑⏝ࡋࡓࠋᶵᲔᏛ⩦࡟ࡣࠊPython ࢆ⏝࠸ࡓࠋ- 340 -

3◊✲ᡂᯝ࠶➨୍ཎ⌮ィ⟬࠿ࡽィ⟬ࡉࢀࡓᵝࠎ࡞ࣁ࣮ࣇ࣍࢖ࢫ

࣮ࣛ໬ྜ≀ࡢ⇕ఏᑟ⋡ࡢᶵᲔᏛ⩦ࡢ⤖ᯝࢆᅗ 1 ࡟♧ࡍࠋ
6 ✀㢮ࡢᶵᲔᏛ⩦ࡢࣔࢹࣝࡢ⤖ᯝ࡛ࡣࠊBoosted decision
tree regression ࡢࣔࢹࣝࡢࡳࡀỴᐃಀᩘ 0.8 ࢆ㉸࠼࡚࠾ࡾࠊࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ࡢ⇕ఏᑟ⋡ࢆࡼࡃ෌⌧࡛ࡁ࡚࠸ࡿ(ᅗ 1(a))ࠋ༢⣧࡞⥺ᙧᅇᖐࡢࡼ࠺࡞ᶵᲔᏛ⩦ࡢࣔࢹ࡛ࣝࡣ⇕ఏᑟ⋡ࡢᶵᲔᏛ⩦ࢆ⾜࠺ࡇ࡜ࡣ࡛ࡁࡎࠊ
≉ᚩ㔞ࡢ᮲௳ศᒱ࡟ࡼࡾ᭱㐺࡞ண್᥈⣴ࢆ⾜࠺

decision tree regression ࡀ㧗࠸ᅇᖐ⢭ᗘࢆ♧ࡋࡓࠋࡇࡢ⤖ᯝࡣࠊ⇕ఏᑟ⋡ࡣᵝࠎ࡞≉ᚩ㔞ࡀ」㞧࡟స⏝ࡍࡿࡇ࡜࡟ࡼࡾࠊᶵᲔᏛ⩦ࢆ⾜࠸㧗࠸ᅇᖐ⢭ᗘࢆ♧ࡋ࡚࠸ࡿࡇ࡜ ࡀ ♧ ၀ ࡉ ࢀ ࡿ ࠋ ྛ ≉ ᚩ 㔞 ࡢ Permutation featureimportance ࢆィ⟬⤖ᯝࡣࠊୖ఩ 9 ಶࡢ≉ᚩ㔞࡛ࣁ࣮ࣇ࣍
࢖ࢫ࣮ࣛ໬ྜ≀ࡢ⇕ఏᑟ⋡ࢆᏛ⩦࡛ࡁ࡚࠸ࡿ(ᅗ 1(b))ࠋ
ࡼࡾᅇᖐ⢭ᗘࢆྥୖࡉࡏࡿࡓࡵ࡟ࠊྛ≉ᚩ㔞ࡢ࠺ࡕୖ఩ࡢ⤌ࡳྜࢃࡏࢆ」ᩘಶ⤌ࡳྜࢃࡏࡓ㝿ࡢỴᐃಀᩘࡢィ⟬ࢆ⾜ࡗࡓࠋୖ఩ 4 ࡘࡢ≉ᚩ㔞ࢆ⏝࠸࡚⇕ఏᑟ⋡ࡢᶵᲔᏛ⩦ࢆ⾜ࡗࡓ㝿ࡢỴᐃಀᩘࡣࠊ඲࡚ࡢ≉ᚩ㔞ࢆ⪃៖ࡋࡓ㝿ࡼࡾࡶỴᐃಀᩘࡀྥୖࡋࠊ0.84 ࡜᭱ࡶ㧗ࡃ࡞ࡗ࡚࠸ࡿ(ᅗ 1(c))ࠋࡑࡢ㝿ࡢ⇕ఏᑟ⋡ࡢண࡟ࡣ≉ᚩ㔞

x55 ࡢ᱁Ꮚᐃᩘࡀ᭱ࡶ኱ࡁࡃᐤ୚ࡋ࡚࠾ࡾࠊ⥆࠸࡚ᵓᡂඖ⣲ࡢཎᏊ༙ᚄࡢᖹᆒ್࡜ 4c ࢧ࢖ࢺࡢཎᏊ༙ᚄࡢ

ᅗ 2 6 ࡘࡢᶵᲔᏛ⩦ࣔࢹࣝࢆ⏝࠸࡚Ꮫ⩦ࡋࡓ⤖ᯝᕪࢆ⾲ࡍ x42 ࡜ᵓᡂඖ⣲ࡢཎᏊ㔞ࡢᖹᆒ್࡜ 4c ࢧ࢖࠿ࡽィ⟬ࡉࢀࡓ⇕ఏᑟ⋡ࡢணࢺࡢཎᏊ㔞ࡢᕪࢆ⾲ࡍ x33 ࡀᐤ୚ࡋ࡚࠸ࡿࠋᵝࠎ࡞≀Boosted decision tree regression ࡢᶵᲔᏛ⩦ࣔࢹࣝ࡟⌮ⓗ࡞せᅉࡀ」㞧࡟⤡ࢇ࡛Ⓨ⌧ࡍࡿ⇕ఏᑟ⋡ࡣᅗ 1(d)ࡼࡾᏛ⩦ࡋࡓ㝿ࡢྛ≉ᚩ㔞ࡢ Permutation feature࡟♧ࡍࡼ࠺࡟ࠊ඲యⓗ࡟ᶵᲔᏛ⩦ࡢண್࡜ࡼࡃ୍⮴

importance(b1ࠊb2)ࠋᐤ୚ᗘࡀ 0.1 ௨ୖࡢ≉ᚩ㔞ࡢࡳࡋ࡚࠾ࡾࠊࣁ࣮ࣇ࣍࢖ࢫ࣮ࣛ໬ྜ≀ࡢྛࢧ࢖ࢺ࡟࠾ࡅ

ࢆ♧ࡋ࡚࠸ࡿࠋྛ≉ᚩ㔞ࡢ࠺ࡕୖ఩ࡢ⤌ࡳྜࢃࡏࢆ

ࡿཎᏊ㔞࠾ࡼࡧཎᏊ༙ᚄࡢࡳࡢ᝟ሗࡢࡳ࡛࡯ࡰ෌⌧」ᩘಶ⤌ࡳྜࢃࡏࡓ㝿࡟ᚓࡽࢀࡓᶵᲔᏛ⩦ࣔࢹ࡛ࣝࡁ࡚࠸ࡿࠋ

࠿ࡽᚓࡽࢀࡓ⇕ఏᑟ⋡ࡢண್ࡢỴᐃಀᩘ(a)ࠋ

್࠿ࡽ⟬ฟࡉࢀࡓỴᐃಀᩘࡢ≉ᚩ㔞ࡢᩘࡢ౫Ꮡᛶ(c)ࠋୖ఩ 4 ࡘࡢ≉ᚩ㔞

4

Ⓨ⾲ᐇ⦼

‫ۻ‬

ᐑᓮ ⚽ಇ, Ώ㑔 ཌ௓, ⏣ᮧ ཭ᖾ, ୕ୖ ♸ྐ ,ࣔࢹࣝ࡟ࡼࡗ࡚ணす㔝 ὒ୍, “➨୍ཎ⌮ィ⟬࡟ࡼࡿࣁ࣮ࣇ࣍࢖ ࢫࣛఏᑟ⋡ࡢẚ㍑(d1, d2)ࠋࢆ⏝࠸࡚ Boosted decision tree regression ࡢᶵᲔᏛ⩦ࡉࢀࡓ⇕ఏᑟ⋡࡜ධຊ್ࡢ⇕࣮໬ྜ≀ࡢ᱁Ꮚ⇕ఏᑟ⋡ ゎᯒ” , 2019 ᖺᗘ᪥ᮏ⇕㟁Ꮫ఍Ꮫ⾡ㅮ₇఍, ྡྂᒇᕤᴗ኱Ꮫ
‫ۻ‬ᐑᓮ⚽ಇ, “ィ⟬⛉Ꮫࢆά⏝ࡋࡓప⇕ఏᑟ⋡࣍࢖ࢫ࣮ࣛᆺ⇕㟁ኚ᥮ᮦᩱࡢタィ࡜᥈⣴”, ➨ 29 ᅇ᪥ᮏ MRSᖺḟ኱఍, ᶓ὾᝟ሗᩥ໬ࢭࣥࢱ࣮

- 341 -



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

Mechanistic Investigations of Organic Reactions
by Experimental and Theoretical Combination○滝田良、渡邉 康平、金井 求、大井 未来、神崎 倭、永島 臨、真島
三ツ沼 治信、上村 祐伍、水本 真介、生長 幸之助（東大院薬）
熊谷 直哉、野田 秀俊（微生物化学研究所）

壮平、

1 研究目的、内容Íðö#­ ĝ¹î ÿ®¸´2§æ/)"È £ÞµÜ"ñø2ï»§Ĭ¤çĐċù"¢!,. Ô yû"ãµ2ÞêĎý £\;PE[2Ê- !/2 ?C&2JD&2
Íðö! / DFT ċù#Gaussian 16,$ GRRM 14Reaction PlusÉÜ#m!ωB97X-D, M06-2X úB3LYP

2têą ċù"ÛĤÆ2têĜóä· ,$ IRC ċù!,°-0úé¸ú "ÓĘ!ÓĘËě ,$¼ĊÏ2ą

3 ?C$,
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Y?QC7[ (MgI2)

Ar

THF, 100 °C-íéY?QC#anti ĝ¹î!SNcY?QC7[ ęą/

+7.9

H

Mg

thf

C7[õ#õ"Úħ£"´!,.øsĝ

H
H
+

Mg

thf

R

Ar

H

H

H
1.74

1.75

Mg 1.91
1.91 H
H 1.91 2.08thf
1.89
Mg

2.09

Mg 1.89
H
1.91
H 1.96 2.10 thf
1.90 Mg
1.75
H

thf

2.10

thf

ΔG‡ +23.6

2.48

1.81
1.26

INT1anti

1.75
2.10

/§Ĭî!úl

thf

1.90

Mg
1.91

H 1.92 2.08 thf
Mg
H 1.90 1.75
H

1.90

thf

1.10

1.35

H

INT2anti(–21.8)H 1.73 1.96
H 1.88Mg

1.92

H 1.89 thf
1.91
2.10
thf H1.90 Mg 1.81
2.45 H
2.60
1.79

2.09

ΔG‡ +25.9

2.14

1.80

1.74

Mg

thf
H 1.88 2.08
1.92 Mg

H

H(31.5)
H

+8.2

1.94

Mg

2.08

TSanti

(7.9)

H

INT0

H
1.74

–53.3

2.90

1.21

H

(0.0)

ĀÃ4a@d2j

E

E+

R

H
–for anti-hydromagnesiation2Ĉ~Į 1į
é4a@PaY?Q

Mg
Ar

anti-hydromagnesiation

7[SN`Nõ4`fa4a<dĒ"´¹î!

NaH (3 equiv)
MgI2 (3 equiv)

R

2.10

–52.9

thf

1.94

H 1.88 Mg

thf
2.10

H

2.14

1.09
1.35

1.21

–for syn-hydromagnesiationé¸/ MgH2 õ Þµõò0]La

1.25

INT1syn

TSsyn

INT2syn(8.2)(34.1)(–18.8)´ MgH2 H6Yfõ!,/DU8Pa4
F I b d " Ğ y Ě ô !    DFT ċ ùı. anti ĝ¹îSNcY?QC7["´ÕÓ(@ωB97X-D/6-311++G**/SMD(THF)//ωB97X-D/6-31++G**į2ąanti-SNcY?QC7[´#Ĝó
ä· TSanti 2þë4a<d%"SN`N"r*!Y?QC7[;I:d ĥÁ"áû%ó/ÒµÕÓ!,´ ęą/0#ĀÃ"Īă ħ£îÐ ,$øsîÐ2ò§ĬÿÐ2Äº/gÉsyn-s2j / TSsyn ! #Ē"¡

Ö( ³ć .anti-s2j /´þĔ!

×&i
-!é¸ ¶¦0/XKcbWK5J>

MgHI õ!Ô"ċù2ą
MgHI

õ"!# syn-ĝ¹î ´ /2Ĉ~MgHI õ Þµõ# 2§ĬÿÐ1Ćr'§Ĭî!#´WcU36a!,.çĐî!#ìµ!³ć Þµ9Qa=f Ĩ«!
¡  -é¸4a@PaY?QC7[õ" syn-anti ìµ ē- 342 -

2ñď

3.2 DIBAL čĄ!,/ N,N-D4a<a4ZN"Ğy´"ĝ¹µvia C–O cleavage
O
R

DIBAL čĄ!,/ N,N-D4a<a4ZN"Ğy´#©´
/4Zd2ĝ¹î!j /Į 2į´ÕÓ! DFT ċù(@ωB97X-D/6-311+G**/SMD(THF)//ωB97X-D/6-31+G*/SMD(THF))

N
R’amidesH O [Al]
R”
R
N
R’
I

via C–N cleavage

R”
N
R’
aminesR

R
OH
alcohols

C–O bond cleavage to afford the amine
H 1.75

1.77

Me2Al

AlMe2
O 1.87

1.88
1.46

1.43

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H

ΔG‡
+13.7

H

1.83

Me2Al

1.77

1.83

AlMe2
O 1.77

1.83

1.09

H

1.09

TS1dimer/C–O(13.7)

INT1dimer/C–O
(0.0)

NMe2

1.29

1.29

1.10

AlMe2

Me2Al 1.78 O 1.78

NMe2

2.84

NMe2

H

1.79

–1.9

H

INT2dimer/C–O(11.8)+0.6+ !ęą/ Ê-  čĄ"pġsÓĘ#Ġć
.Ñ"]La#zęą  1Í´! H"´µeĝ¹µ2±/ Ê-  

H

1.10
1.46

1.71

Al

–35.7

NMe2

1.70

1.77

1.70

1.09

Me
Al 1.68

1.79
ΔG‡+4.7 Me2Al 1.70 O

H
2.10

O

Me2Al

1.30

NMe2

H
NMe2

1.29

H
1.09
INT2’dimer/C–O(12.4)

H
TS2dimer/C–O(17.1)

INT3dimer/C–O(–18.6)

C–N bond scleavage to afford the alcohol
1.64

H

Me2Al

3.04

1.91

3.3 ¬ĩ£ģ"ĭėSN`Nó"´ÕÓĊÏO
1.41

èä6Zd DQ-Im•HCl !©/\IaTPa9fKa"Povarov è´! Ė«ĉà0/īlģs/KM
_ S N c < R ` d s THQ•HCl

1.11

O
AlMe2

pġsÓĘĭ Lewis ğµ2Ì/4aZP7[yû"ãµ

Me

Me Me

1.71

Me2Al

,$DSNc<R`ds

1.88

1.51

AlMe2
2.07

ΔG‡
+37.9

1.82

Me2 H 1.62
Al 2.78
AlMe2
O 1.98
Me 1.26
1.10 H

N
Me

N Me
1.10
H
Me
INT1dimer/C–N(–5.9)

TS1dimer/C–N(32.0)

Me2
Al

1.81

–1.3

Me

N
Me

H

O

1.62

AlMe2

3.18

1.97
1.25

1.10

H

INT2dimer/C–N(30.7)

 2. DIBAL čĄ!,/Ğy´

DHQ•HCl #z¾½0n¶!6Zd Ğy04Z
d DQ-Am•HCl " é*!¥ziīs/ TQ•HCl

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7.5 kcal mol–1 / 1 "Æw#Ė«¾½

0/DSNc<R`ds ĉà0´úlė+ !iī TQ•HCl !Ã0/"2Äº/"!/'éâ/ DQ-Am•HCl #÷ØĦØh!ğ0 DQ-Im•HCl!}Ã0/ §Ĭî!Ê .DQ-Im•HCl #Ē´"kĩ"¯2Ðĭå TQ•HCl !Îāß´ÕÓ2|æ/

4 :I6E 3. ¬ĩ£ģ"ĭėSN`Nó>@  Ong, D. Y.; Li, Y.; Pang, J. H.; Watanabe, K.; Takita, R.; Chiba, S. Chem. Sci. 2020, 11, 5267.
>@ Ong, D. Y.; Watanabe, K.; Takita, R.; Chiba, S. Helv. Chim. Acta 2019, 102, e1900166.
>@ Pang, J. H.; Ong, D. Y.; Watanabe, K.; Takita, R.; Chiba, S. Synthesis 2020, 52, 393.
>@ Hayashi, H.; Wang, B.; Wu, X.; Teo, S. J.; Kaga, A.; Watanabe, K.; Takita, R.; Yeow, E. K. L.; Chiba, S. Adv.
Synth. Catal. 2020, 362, 2223.
>@ Adachi, S.; Shibasaki, M.; Kumagai, N. Nat. Commun. 2019, 10, 3820.

- 343 -

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- 345 -

4 ßûõ'"W^ùìęĝÅ öÏĝÎ¾«¸ĝÑã¡Zĝí 57 }·¾Ü××Û[,  (2019).
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R. Sato, Y. Mori, R. Matsui, N. Okimoto, J. Yamamoto, M. Taiji. in preparation.
A. Morimoto, H. Miyamoto, R. Sato, S. Iwai, J. Yamamoto. in preparation.

- 346 -

 Electronic structure and properties of complexes and materials
W. M. C. SameeraInstitute of Low Temperature Science, Hokkaido University

1 Research purpose and contents
Chemical reactions are complex and difficult to characterize from experimental data alone.
Computational chemistry has been beneficial in the quantitative determination of the mechanismsof chemical processes. I use modern computational methods to study complex molecular systems
and their properties, such as reactivity and luminescence. The vast majority of my research has
been performed in collaborations with the well-established experimental research groups in Japan.

2 Computational methods
Calculations were performed using the density functional theory (DFT) or the two-layer ONIOM
method as implemented in Gaussian16 program. The SICTWO interface was used for
ONIOM(DFT:MM3) calculations. The multi-component artificial force induced reaction (MCAFIR) method, as implemented in the GRRM strategy, was used for systematic determination ofreaction paths. The ab-initio molecular dynamic simulation using the atom-centred density
matrix propagation (ADMP) method in the Gaussian16 program. The standard basis sets were
employed for DFT calculations. The polarizable continuum model (PCM) was used as theimplicit solvation model.

3 Results
OH anions in ice: Proton transfer in liquid water and ices,
gives rise to the positive current conductivity, can be
described by the Grotthuss mechanism. However, themechanism for the proton abstraction of OH anion fromneighbouring H2O, the so-called proton-hole transfer(PHT), is not established. In this direction, we havereported experimental evidence for the PHT, leading to
the negative current conductivity in ice (below 50 K).
Quantum chemical calculations, employing the ADMP
and ONIOM methods, confirmed that OH anions on ice
are unstable. As a result, OH anions drive toward ice bulk
though almost barrierless PHT (Figure 1). The kinetic
isotope effects were not observed, and therefore thequantum tunnelling would not affect the rate of the PHT- 347 -

Figure 1. Potential energy surface forthe initial PHT in amorphous ice.

process. At very low temperatures, we proposed that the PHT processes are faster than thethermal fluctuations of water molecules in the hydrogen bonding network.
Catalytic silylation of N2: We have developed two new hydride-bridged dinuclear Mo-Fe
complexes. The Mo-Fe distances of these complexes are shorter than that of the Mo-Fe
complexes in the literature. Calculated Mayer bond indices of 0.79 suggested a Mo-Fe single
bonding character, and the quantum theory of atoms in molecules (QTAIM) analysis indicated afairly ionic with modest covalent bonding. Our complexes can be used as the catalyst to performthe silylation of N2. Mechanism of theNcatalytic cycle was studied using theDFT (Figure 2). Further, the first stepof the mechanism is the reaction
between Me3Si· and the Mo-H moietyof the catalyst, 12b, which is abarrierless process. Then, N2 binding at
the Mo site gives the active
intermediate, 2I2. The reaction between
the Mo-N2 unit of the active
intermediate and Me3Si· radicals occur
in a stepwise manner to generate
N(SiMe3)3. Our computed reaction
mechanism goes through relatively low
free energy barriers.

N
N

N
Me3P
Mo

H
H

Me3P
Mo

Fe

H
H

Fe

H

H
52a (13.0)
32b (10.9)

NN

4TS1 (11.6)
4TS1 (-0.8)

12b (0.0)
6I1 (-1.6)

Me3P H H
H
Mo
Fe

Me3P

4I2 (1.1)Mo

2TS1' (-1.1)

2TS1 (-9.5)

H
H

Fe

H

2TS1'' (-7.3)

4I1 (-9.4)
4I2 (-13.8)

H
2I1 (-19.3)
+
N2
H
Me3P
+
H
SiMe3
Mo
Fe

H

2I2' (-20.7)
2I2 (-26.2)

Me3P

N
N H
H
Mo
Fe

Me3P

N
H N
H
Mo
Fe
H

H

Figure 2. Computed free energy profile for the formation of
the active intermediate.

Asymmetric preparation of enantioenriched β2-aryl amino acids: We have developed a Pdcatalyzed cross-coupling reaction of aziridine-2-carboxylates and arylboronic acids. In thisreaction,theregioselectiveandenantiospecific ring-opening, using thecommercial serine esters, gives rise to β2-arylamino acids. Mechanism of the full catalytic
cycle was rationalized from the DFT (Figure3). Further, the catalytic cycle consists ofaziridine ring-opening, reaction with water,transmetalation, and carbon-carbon bondformation. Based on the computed freeenergy profile, the ring-opening step is theselectivity determining step, while thecarbon-carbon bond formation is the ratedetermining step. Computed regioselectivity

Figure 3. Mechanism of the catalytic cycle.

- 348 -

of 100:0 is in agreement with the experimental results (100:0). An energy decomposition analysis(EDA) suggested that the interactions between the catalyst and the aziridine substrate play a vitalrole in the origin of the selectivity. The experimental results indicated that the NMe2IPr-Pd0 catalyst
shows a 97% yield, while SIPr-Pd0 catalyst gives only a 44% yield. DFT calculations indicatedthat the SIPr-Pd0 catalyst has a relatively high free energy barriers for the transmetalation andreductive elimination processes, leading to a poor yield. These results confirm that the NMe2SIPrPd0 catalyst is crucial for the enantiospecific and regioselective ring-opening Suzuki-Miyaura
arylation of aziridine-2-carboxylates.
Photophysical properties of transition metal complexes: We have developed three new Cucomplexes, [Cu(dmp)(xantphos)]+ (A) and [Cu2(dmp)2(μ-dppa)2]2+ (B), and [Cu2(Ph2dmp)2(μdppa)2]2+ (C) (Figure 4). TDDFT calculations suggested that the energy difference between the
optimized S1 and T1 states of complex A is very low. Thus, the luminescence of A comes fromthe thermally activated delayed fluorescence (TADF) from the singlet metal-to-ligand chargetransfer (1MLCT) excited state at the room temperature. In the case of complex B and C,
computed S1-T1 energy gap of the excited state optimized structures were relatively large.
Therefore, complex B and C
shows phosphorescence fromthe triplet metal-to-ligand
charge transfer (3MLCT)
excited state at room
temperature, which is inagreement with the lower
Figure 4. Luminescent Cu complexes A, B, and C.
radiative rate constants.
Calculations indicated that the dihedral angles between the N-Cu-N plane and the P- Cu-P planeof the complexes play a key role in their photophysical properties. Further, complex A shows thedihedral angle change from 900 (Franck Condon state) to 700 (S1 minima). Such structural
relaxation is not observed in complex B or C. As a result of this, computed S1-T1 energy gap of
the excited state optimized structures of A becomes small, leading to TADF.
We have developed luminescent Pt(II) complexes bearing a fluorine-substituted tridentate
ligand. The n-tetrabutylammonium salt of the complexes, (n-Bu4N)[Pt(dFphpy)(CN) and (nBu4N)[Pt(dFphpy)(Cl], show luminescence in the solidstate (Figure 5). The emission lifetime analysis and
TDDFT calculations confirmed that the complexes show
phosphorescence from metal-to-ligand charge transfer
state (3MLCT). The emissive triplet excited state has aplanar structure. Also, a low-lying non-emissive triplet
excited state is present and has a bent structure. The
activation energy to go from the emissive excited state- 349 -

Figure 5. Luminescent Pt(II) complexes.

(planar structure) to the non-emissive excited state (bent structure) is small, and this is the reason
for low emission efficiency in the solid-state.

4 Achievements
Invited Talks:() W. M. C. Sameera, Exploring mechanistic puzzles in Pd-catalyzed aziridine ring-opening
reactions. The Asia-Pacific Association of Theoretical and Computational Chemists (APATCC),
Sydney, Australia. (2019)() A. Miyasaki, W. M. C. Sameera, N. Watanabe, Behavior of OH radical on ice, Water in the
Universe in the ACS National Meeting, San Diego Convention Center, San Diego, USA. (2019)() A. Miyasaki, W. M. C. Sameera, N. Watanabe, Ortho-to-Para Ratios in water and H2desorbed from ice - Experimental view. Astrochemistry: From nanometers to megaparsecs - A
symposium in honour of John H. Black, Gothenburg, Sweden. (2019)() A. Miyasaki, W. M. C. Sameera, N. Watanabe, Behavior of OH Radical on an Ice Surface at
Low Temperatures. 35th Symposium on Chemical Kinetics and Dynamics, Higashi-Hiroshima,
Japan. (2019)() A. Miyasaki, W. M. C. Sameera, N. Watanabe, Detection of OH radicals on amorphous solid
water, IAU Symposium 350 Laboratory Astrophysics: From Observations to Interpretation,
Cambridge, UK. (2019)

Posters:() W. M. C. Sameera, A. Miyasaki, N. Watanabe, OH anions and OH radicals on amorphous
ice: a combined experimental and quantum chemical study. The 2nd ICReDD International
Symposium, Hokkaido University, Japan. (2019)() W. M. C. Sameera, F. Maseras, Combining modern force fields with ONIOM(QM:MM): The
SICTWO interface. The Asia-Pacific Association of Theoretical and Computational Chemists(APATCC), Sydney, Australia. (2019)() W. M. C. Sameera, On the reaction mechanisms: quantum mechanics/molecular mechanics(QM/MM) studies. International on Hybrid Catalysis for Enabling Molecular Synthesis on
Demand, Tokyo University, Japan. (2019)() W. M. C. Sameera, A. Miyazaki, N. Watanabe, OH radical on interstellar ices: a quantum
chemical study. IAU Symposium 350 Laboratory Astrophysics: from Observations to- 350 -

Interpretation. Jesus College, Cambridge, UK. (2019).
() A. Miyazaki, N. Watanabe, W. M. C. Sameera, T. Hama, H. Hidaka, A. Kouchi, Surface
diffusion of OH radical on amorphous solid water, IAU S350 Laboratory Astrophysics: From
Observations to Interpretation, Jesus College, Cambridge, UK. (2019)() A. Miyazaki, N. Watanabe, W. M. C. Sameera, T. Hama, H. Hidaka, A. Kouchi, Detectionof OH radicals on amorphous solid water, Astrochemistry: From nanometers to megaparsecs A symposium in honour of John H. Black, Gothenburg, Sweden. (2019)() A. Miyazaki, Naoki Watanabe, W. M. C. Sameera, T. Hama, H. Hidaka, A. Kouchi,
Activation energy of OH-radical diffusion on water ice surface, Water in the Universe in the ACS
National Meeting, San Diego Convention Center, San Diego, USA. (2019)5 Publications
1. () K. Ishihara, Y. Araki, M. Tada, T. Takayama, Y. Sakai, W. M. C. Sameera, Y. Ohki,
Chem. Eur. J. (Accepted) DOI: https://doi.org/10.1002/chem.202000104
2. () C. Wakasugi, M. Yoshida, W. M. C. Sameera, Y. Shigeta, A. Kobayashi, M. Kato,
Chem. Eur. J. 2020, 26, 5449-5458.
3. () T. Ogawa, W. M. C. Sameera, M. Yoshida, A. Kobayashi, M. Kato, Chem. Phy. Lett.
2020, 137024.
4. () N. Watanabe, W. M. C. Sameera, H. Hidaka, A. Miyazaki, A. Kouchi, Chem. Phys. Lett.
2019, 737, 136820.
5. () S. Yanagida, M. Yoshida, W. M. C. Sameera, A. Kobayashi, M. Kato, Masako, Bull.
Chem. Soc. Jpn. 2019, 92, 1684-1693.
6. () Y. Takeda, T. Matsuno, A. K. Sharma, W. M. C. Sameera, S. Minakata, Chem. Eur.
J. 2019, 25, 10226-10231.
7. () M. Yoshida, H, Shitama, W. M. C. Sameera, A. Kobayashi, M. Kato, Chem. Eur.
J. 2019, 25, 7669-7678.
8. () A. K. Sharma, W. M. C. Sameera, Y. Takeda, S. Minakata, ACS Catal. 2019, 9, 45824592.

- 351 -

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1.2 㠀᩿⇕㟁ᏊືຊᏛࡢィ⟬ࣉࣟࢢ࣒ࣛࡢ
⛣᳜࡜ࢳ࣮ࣗࢽࣥࢢ
ᡃࠎࡢィ⟬᪉ἲ࡛ࡣ㸪㟁Ꮚ㸫ཎᏊ᰾ࡢ㐠ື᪉⛬ᘧࢆཎᏊ᰾ࡢ⤒㊰࡟ἢࡗ࡚✚ศࡍࡿ㸬ᚲせ࡞⾜ิせ⣲ࡣྛ᫬้࡛ࡢ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ồࡵࡽࢀࡿ㸬ᡃࠎࡣࡇࢀࡲ࡛㸪ືຊᏛィ⟬࡟≉᭷ࡢ㒊ศ࡟㛵ࡍࡿࣉࣟࢢࣛ
࣒ࢆࢢ࣮ࣝࣉෆ࡛㛤Ⓨ࣭ᐇ⿦ࡋ࡚ࡁࡓ㸬ୖ
㏙ࡢ┠ⓗࢆ㐩ᡂࡍࡿࡓࡵ࡟㸪㛤Ⓨࡋ࡚ࡁࡓᅗ 1. ஧᰾ Mn 㘒య⣔ࡢບ㉳≧ែ㟁Ⲵศ㞳࡟㥑ືࡉࢀࡿỈࣉࣟࢢ࣒ࣛࢆࡼࡾ኱ࡁ࡞ศᏊ࡟㐺⏝ࡍࡿᚲศゎࢧ࢖ࢡࣝࡢ඲యീࡢᴫᛕᅗ㸬せࡀ⏕ࡌࡓࡀ㸪ࡍ࡛࡟୪ิ໬ࡸ㧗㏿໬࡞࡝ࡢᡭࢆᑾࡃࡋ࡚㝈⏺࡟㐩ࡋ࡚࠸ࡓ㸬ᮏࣉࣟࢪ࢙ࢡࢺ࡛ࡣࡲࡎ㸪ィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮ࡢࢩࢫࢸ࣒࡟㠀᩿⇕㟁ᏊືຊᏛࡢࣉࣟࢢ࣒ࣛࢆ⛣᳜ࡋ㸪ࢳ࣮ࣗࢽࣥࢢࡋࡓ㸬ࡑࡋ࡚㸪௨ୗ࡟♧ࡍ Mn ከ᰾㘒యࡢ⣔࡟ᑐࡋ࡚㸪୰つᶍ (250 core ⛬ᗘ) ィ⟬ࡀຠ⋡ⓗ࡟ᐇ⾜࡛ࡁࡿࡇ࡜ࢆ☜ㄆࡋࡓ.
1.3 Ỉศゎ཯ᛂ࡟࠾ࡅࡿᇶᮏⓗ࡞໬Ꮫⓗᶵᵓගゐ፹ⓗ࡞㟁Ⲵศ㞳ࡣ㸪ග࢚ࢿࣝࢠ࣮ࢆ໬Ꮫ࢚ࢿࣝࢠ࣮࡜ࡋ࡚ᤕᤊࡍࡿࡓࡵࡢᘬࡁ㔠࡜࡞ࡿ㔜せ࡞཯ᛂ࡛࠶ࡿ㸬ኳ↛ගྜᡂ⣔࡛ࡣ㸪ᘧ (1) ࡟♧ࡍࡼ࠺࡟㸪Ỉࡢගศゎ࡟ࡼࡗ࡚㟁Ⲵศ㞳≧ែࢆᐇ⌧ࡋ㸪ࡑࡢ๪⏕ᡂ≀࡜ࡋ࡚㓟⣲ศᏊࢆᨺฟࡍࡿ.

૛۶૛ ‫ ۽‬൅ ૝ࢎࣇ ՜ ૝۶ ା ൅ ૝‫ ି܍‬൅  ‫۽‬૛ ሺͳሻ⮬↛⏺࡛ࡇࡢ཯ᛂࢆᢸ࠺ࡢࡣගྜᡂ⣔࡟Ꮡᅾࡍࡿ photosystem II (PSII) ࡛࠶ࡾ㸪Ỉศゎࡣࡑࡢ୰ࡢ Mn ࢡࣛࢫࢱ࣮࡟ゐ፹ࡉࢀࡿ㸬ᐇ㦂ⓗ࡟ࡣ㸪㧗ᙉᗘ X ⥺࡟ࡼࡿືຊᏛࡢ㏣㊧ࡀྍ⬟࡟࡞ࡗ࡚ࡁ࡚࠾ࡾ㸪[2, 3] ࡑࡢ᫬㛫ศゎ⬟ࡣ㟁Ꮚࡸࣉࣟࢺࣥࡢ㐠ືࡢ᫬㛫ࢫࢣ࣮ࣝ (fs ࣮࢜ࢲ࣮) ࡟㐩ࡋ࡚࠸ࡿ㸬୍᪉࡛㸪⌮ㄽⓗ࡟ࡣ㸪ࣉࣟࢺࣥ࡜㟁Ꮚࡢ㐠ືࡀ஫࠸࡟ᙳ㡪ࡋ࠶࠺ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ࡟ࡶ࠿࠿ࢃࡽࡎ㸪୍㐃ࡢ཯ᛂࡢ⌮ゎࡣ࡯ࡰ㟼ⓗ࡞㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚࠸ࡿ. [4] ᮏ◊✲࡛ࡣ㸪ࣉࣟࢺࣥ࡜㟁Ꮚࡢ㠀᩿⇕┦஫స⏝ࢆ࠶ࡽࢃ࡟⪃៖ࡋࡓᇶᮏⓗ࡞໬- 352 -

Ꮫⓗᶵᵓࢆᥦ᱌ࡋ㸪Ỉศゎࢧ࢖ࢡࣝࢆࡇࢀ
ࡽࡢẚ㍑ⓗ༢⣧࡞⤌ࡳྜࢃࡏ࡜ࡋ࡚⾲⌧࡛ࡁࡿࡇ࡜ࢆ♧ࡍ㸬ᮏ◊✲࡛ࡣ Mn 㓟໬≀⣔࡟ὀ┠ࡋ㸪㸰✀㢮ࡢᇶᮏⓗ࡞㟁Ⲵศ㞳ࡢᶵᵓ㸪ࡍ࡞ࢃࡕᇶ
ᗏ≧ែࡢᶵᵓ [4] ࡜ ග ບ ㉳ ≧ ែ ࡢ ᶵ ᵓ[5] ࢆᇶ♏࡜ࡍࡿࢧ࢖ࢡࣝࢆ⪃࠼ࡿ㸬ᇶᗏ≧ែᆺࡣኳ↛ගྜᡂᆺ࡜ࡳ࡞ࡍࡇ࡜ࡀ࡛
ࡁࡿ㸬ኳ↛⣔࡛ࡣ㸪࢔ࣥࢸࢼ」ྜయࡀග㓟໬ࡉࢀ㸪Ỉศゎ཯ᛂࢆゐ፹ࡍࡿ Mn4CaO5 ࢡࣛࢫࢱ࣮ࡣගບ㉳≧ែ࡟࡞ࡽ࡞࠸࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸬୍᪉ගບ㉳≧ែᆺࡣேᕤගྜ

ᅗ 2. ᅄ᰾ Mn 㘒య⣔ࡢᇶᗏ≧ែ㟁Ⲵศ㞳࡟㥑ືࡉࢀࡿỈศᡂᆺ࡜ࡳ࡞ࡏࡿ㸬ࡑࡇ࡛ࡣ Mn ࡀ┤᥋ගບゎࢧ࢖ࢡࣝࡢ඲యീࡢᴫᛕᅗ㸬㉳ࡉࢀࡿࡓࡵ࡟㸪ᶵᵓࡣẚ㍑ⓗ༢⣧࡛࠶ࡿ㸬ࡑࡇ࡛㸪ࡲࡎࡣከ᰾ Mn 㘒య࡟ࡼࡿỈศゎࢧ࢖ࢡࣝᶵᵓ࡜ࡋ࡚᭱ࡶ༢⣧࡞ “஧᰾ Mn 㘒య⣔࡟࠾ࡅࡿບ
㉳≧ែᆺ” ࡢỈศゎࢧ࢖ࢡࣝࢆ⪃࠼ࡿ㸬ḟ࡟㸪஧᰾࡛ᚓࡽࢀࡓ▱ぢࢆά⏝ࡋࡘࡘ㸪ኳ↛ගྜᡂ⣔࡟ᑐᛂࡍࡿ
ࣔࢹࣝ⣔࡛࠶ࡿ “ᅄ᰾ Mn 㘒య⣔ࡢᇶᗏ≧ែᆺ͇ࡢỈศゎࢧ࢖ࢡࣝࢆ⪃࠼ࡿ㸬

2◊✲᪉ἲࠊィ⟬᪉ἲ

2.1 㠀᩿⇕㟁ᏊືຊᏛືຊᏛィ⟬ࡣ㸪path-branching representation ࡟ᇶ࡙ࡃ. [4] ࡇࡢ⌮ㄽ࡛ࡣ㸪㟁ᏊἼ᮰ȲሺRǡ rǡ ‫ݐ‬ሻ ൌσூ ‫ܥ‬ூ ሺ‫ݐ‬ሻȰூ ሺ‫ܚ‬Ǣ ‫܀‬ሺ‫ݐ‬ሻሻ ࡀ཯ᛂ⤒㊰࡟ἢࡗ࡚᫬㛫Ⓨᒎࡍࡿ㸬ࡇࡇ࡛㸪R, r, t ࡣࡑࢀࡒࢀཎᏊ᰾㸪㟁Ꮚ㸪᫬㛫ࡢᗙᶆ࡛࠶ࡿ㸬Ȱூ ሺ‫ܚ‬Ǣ ‫܀‬ሺ‫ݐ‬ሻሻࡣ᰾ᗙᶆ‫܀‬ሺ‫ݐ‬ሻࢆࣃ࣓࣮ࣛࢱ࡜ࡍࡿ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ồࡵࡽࢀࡿ㸬㟁Ꮚࡢ㐠ື᪉⛬ᘧࡣḟᘧ࡛⾲ࡉࢀࡿ㸬ሺࢋ࢒ሻ࢏԰࡯ሶࡵ ൌ ෍ሺࡴࡵࡶ െ ࢏԰ ෍ ࡾሶ࢑ ࢄ࢑ࡵࡶ െ
ࡶ

࢑

԰૛
‫כ‬
෍ሺࢅ࢑ࡵࡶ ൅ ࢅ࢑ࡶࡵ ሻሻ࡯ࡶ
૝
࢑

ሺ௘௟ሻ

௞
ࡇࡇ࡛㸪‫ܪ‬ூ௃ ࡣ㟁Ꮚࡢ Hamiltonian ࡛㸪ܺூ௃ൌ ‫ۃ‬Ȱூ ȁ߲Ȱ௃ Ȁ߲ܴ௞ ‫ۄ‬,ܻூ௃௞ ൌ ‫ۃ‬Ȱூ ȁ߲ ଶ Ȱ௃ Ȁ߲ܴ௞ଶ ‫ࡿ࠶࡛ۄ‬㸬ࡲࡓ㸪ཎᏊ᰾ࡣ force
matrix ‫ܨ‬ூ௃ ൌ ‫ۃ‬Ȱூ ห߲‫ ܪ‬ሺ௘௟ሻ Ȁ߲ܴ௞ หȰ௃ ‫࡟ۄ‬㥑ືࡉࢀࡿ㸬ࡓࡔࡋᮏ◊✲ࡣ▷᫬㛫ࡢ㠀᩿⇕㟁ᏊືຊᏛ࡟ὀ┠ࡍࡿࡓࡵ࡟㸪force matrix ࢆ㟁ᏊἼ᮰࡛ᖹᆒࡍࡿࡇ࡜࡛ᚓࡽࢀࡿ semiclassical Ehrenfest theory (SET) ἲࡢ path ࢆィ⟬ࡍࡿ㸬

2.2 ஧᰾ Mn 㘒య⣔࡟࠾ࡅࡿගບ㉳≧ែ㟁Ⲵศ㞳࡟㥑ືࡉࢀࡿỈศゎࢧ࢖ࢡࣝ
3 ✀㢮ࡢᇶᮏⓗ࡞໬Ꮫⓗࣉࣟࢭࢫ㸪ࡍ࡞ࢃࡕ charge-separation (CS), electron-proton reloading (RL), Mn reduction(MR) ࡟ࡼࡗ࡚㥑ືࡉࢀࡿỈศゎࢧ࢖ࢡࣝࢆ⪃࠼ࡿ㸬ࡇࡇ࡛ࡣ㸪࠸ࡃࡘ࠿᳨ウࡋࡓࡶࡢࡢ୰࠿ࡽ㸪࢚ࢿࣝࢠ࣮
ⓗ࡟᭷฼࡜⪃࠼ࡽࢀࡿࡶࡢ࡟ࡘ࠸࡚♧ࡍ㸬ศᏊ⣔࡛ࡢᐇ⌧ྍ⬟ᛶࢆㄪ࡭ࡿࡓࡵ࡟㸪ᅗ 1 ࡟♧ࡍࡼ࠺࡞஧᰾ Mn
㘒యࡢࣔࢹࣝ⣔ࢆ⏝࠸࡚㠀᩿⇕ືຊᏛࢆィ⟬ࡍࡿ㸬ࡇࡢࣔࢹࣝ⣔ࡣ㸪Mn2(OH)(HCOO)(H2O)2 㸦electron-proton
donor, EPD), ศᏊෆศᴟࡋࡓ 4-aminophenol (electron acceptor, EA), imidazole (proton acceptor, PA), ࡑࡋ࡚ 6H2O
(electron-proton resources, EPR) ࠿ࡽ࡞ࡿ㸬ࡇࡢ⣔ࡣ㸪ᡃࠎࡢ༢᰾ Mn 㘒యࡢࣔࢹࣝ⣔ [4] ࡢᣑᙇ࡛࠶ࡿ㸬- 353 -

2.3 ᅄ᰾ Mn 㘒య⣔࡟࠾ࡅࡿᇶᗏ≧ែ㟁Ⲵศ㞳࡟㥑ືࡉࢀࡿỈศゎࢧ࢖ࢡࣝ ஧᰾ࡢሙྜ࡜ྠᵝ࡟㸪㸱ࡘࡢᇶᮏⓗ࡞໬Ꮫⓗࣉࣟࢭࢫ (CS, RL, MR) ࡟㥑ືࡉࢀࡿỈศゎ཯ᛂࢆ⪃࠼ࡿ㸬F ᅗ㸰࡟♧ࡍࡼ࠺࡞ᅄ᰾ Mn 㘒యࡢࣔࢹࣝ⣔ࢆ⏝࠸࡚㸪ྛࣉࣟࢭࢫ࡟ᑐࡋ࡚㠀᩿⇕㟁ᏊືຊᏛࢆ
ィ⟬ࡍࡿ㸬ࡇࡢࣔࢹࣝ⣔ࡣ㸪Mn4CaO5(H2O)2 ࢆྵࡴ㘒య (EPD)㸪imidazole (PA) 4-aminophenol (EA),ࡑ
ࡋ࡚ 2H2O (EPR)࠿ࡽ࡞ࡿ㸬ࡓࡔࡋ㸪ᅗ࡛ࡣᅄ᰾ Mn
㘒యࡢᵓ㐀ࡸ㓟໬≧ែࢆㄪᩚࡍࡿ carboxy group ࡀ┬␎ࡉࢀ࡚࠸ࡿࡇ࡜࡟ὀពࡉࢀࡓ࠸㸬ࡇࡢࣔࢹࣝ⣔ࡣኳ↛ගྜᡂ⣔ࡢ photosystem II (PSII) ࡢ≧ἣࢆ࠶

ᅗ 3. ஧᰾㘒యࡢᇶᮏⓗ໬Ꮫࣉࣟࢭࢫࡢ࠺ࡕ㸪(a)㸯␒┠ࡢ CS㸪(b) 1 ␒┠ࡢ RL㸪ࡑࡋ࡚(c) 2 ␒┠ࡢCS ࡢ㟁Ꮚ࠾ࡼࡧࣉࣟࢺࣥࡢ⛣ື⤒㊰㸬㯤Ⰽࡢᢞ✏ࡽࢃ࡟཯ᫎࡋ࡚࠸ࡿ㸬≉࡟㸪Mn 㘒యࡀ࠸ࢃࡺࡿ

㠃ࡣ unpaired electron density ࡟ᑐᛂࡍࡿ㸬“3+1” ࡢ㠀ᑐ⛠࡞ᵓ㐀 (Ca ࢆྵࡴ 3 ᰾ cubane ᆺ Mn ࢜࢟ࢯ㘒య࡜㸪༢᰾ࡢ Mn 㘒యࡢ⤌ࡳྜࢃࡏ) ࡣ㸪ࡇࢀࡽࡢỈศゎࢧ࢖ࢡࣝ࡟࠾ࡅࡿᙺ๭ศᢸࢆ♧၀ࡋ࡚࠸ࡿ㸬ࡶࡋࡑࢀࡀ࠶ࡿ࡞ࡽ㸪᫂ࡽ࠿࡟ࡋࡓ࠸㸬

3

◊✲ᡂᯝ

3.1 ஧᰾ Mn 㘒య⣔࡟࠾ࡅࡿගບ㉳≧ែ㟁Ⲵศ㞳࡟㥑ືࡉࢀࡿỈศゎࢧ࢖ࢡࣝࡇࡢỈศゎࢧ࢖ࢡࣝࡢྛࣉࣟࢭࢫࡢ࠺ࡕ㸪Mn ࡢ㓟໬ࡲࡓࡣ㑏ඖࢆక࠺ࡶࡢ (CR ࡀ 4 ✀㸪RL ࡀ 2 ✀, MR
ࡀ 4 ✀) ࡟ࡘ࠸࡚㸪㠀᩿⇕㟁ᏊືຊᏛࢆィ⟬ࡋࡓ㸬ࡇࢀࡽ඲࡚࡟࠾࠸࡚ coupled proton electron-wavepacket
transfer (CPEWT) [1] ࡟ࡼࡗ࡚཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬ࡇࡇ࡛ࡣ㸪ࡇࡢࢧ࢖ࢡࣝࡢ᭱ึ࠿ࡽ 3 ࡘ㸪ࡍ࡞ࢃࡕ CS Ѝ RL Ѝ CS ࡟ࡘ࠸࡚♧ࡍ㸬ᅗ 3 ࡟㸪ࡇࢀࡽ 3 ࡘࡢ཯ᛂࡢ⤒㊰࡟ἢࡗࡓ୙ᑐ㟁Ꮚᐦᗘࡢ᫬㛫ኚ໬ࢆࡑࢀࡒࢀ♧ࡍ㸬᭱ึࡢ CR ࡛ࡣ㸪༢᰾ Mn 㘒యࡢሙྜ࡜ྠᵝ࡟, [4] Mn ࡢගບ㉳࡟కࡗ࡚ࣉࣟࢺࣥ࡜㟁Ꮚࡀูࠎࡢ⤒㊰ࢆ㏻ࡗู࡚ࠎࡢሙᡤ㸪ࡍ࡞ࢃࡕศᏊෆศᴟࡋࡓ 4-aminophenol ࡢ O ཎᏊ࡜ Rydberg-like states ࡟ࡑࢀࡒࢀ⛣ືࡍࡿ (ᅗ 3a)㸬ࡑࡋ࡚ RL ࡛ࡣ㸪Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࢆ௓ࡋࡓࣉࣟࢺ࣮ࣥࣜࣞ࡜࢝ࢵࣉࣝࡋ࡚㸪Mn 㘒యෆ࡛ࡢ㟁Ꮚ⛣ືࡀ㉳ࡇࡿ (ᅗ 3b)㸬ࡇࢀ࡟ࡼࡾ㸪2 ␒┠ࡢ CS ࡀ᭱ึࡢࡑࢀ࡜ྠࡌࡼ࠺࡟㉳ࡇࡿࡼ࠺࡟࡞ࡿ (ᅗ 3c)㸬ࡇࢀࡽࡢィ⟬⤖ᯝ࠿ࡽ㸪஧᰾ Mn 㘒య࡛ࡣ㸪እ㒊࠿ࡽ㟁Ꮚ࠾ࡼࡧࣉࣟࢺࣥࢆ⿵⤥ࡍࡿࡇ࡜࡞ࡃ
㸰ᅇ㐃⥆ࡢ㟁Ⲵศ㞳ࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸬௨ୖࡼࡾ㸪㸰ᅇࡢ㟁Ⲵศ㞳ࡢᚋ࡟ MR ࡟ࡼࡗ࡚㐣㓟໬Ỉ⣲ H2O2 ࡀ⏕ᡂࡋ㸪ࡉࡽ࡟㸰ᅇࡢ㟁Ⲵศ㞳ࡢᚋ࡟ྠᵝ࡟ O2 ࡀ⏕ᡂࡍࡿࡇ࡜࡟ࡼࡾ㸪ᘧ(1)ࡢỈศゎࢧ࢖ࢡࣝࡀ
୍࿘ࡍࡿ㸬
3.2 ᅄ᰾ Mn 㘒య⣔࡟࠾ࡅࡿᇶᗏ≧ែ㟁Ⲵศ㞳࡟㥑ືࡉࢀࡿỈศゎࢧ࢖ࢡࣝࡇࡢỈศゎࢧ࢖ࢡࣝࡢྛࣉࣟࢭࢫࡢ࠺ࡕ㸪Mn ࡢ㓟໬ࡲࡓࡣ㑏ඖࢆక࠺ࡶࡢ (CR ࡀ 4 ✀㸪RL ࡀ 3 ✀, MR ࡀ
4 ✀) ࡟ࡘ࠸࡚㸪㠀᩿⇕㟁ᏊືຊᏛࢆィ⟬ࡋࡓ㸬ࡇࢀࡽ඲࡚࡟࠾࠸࡚ CPEWT ࡟ࡼࡗ࡚཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜ࡀ
ࢃ࠿ࡗࡓ㸬ࡇࡇ࡛ࡣ㸪᭱ึ࠿ࡽ 3 ࡘ㸪ࡍ࡞ࢃࡕ CS Ѝ RL Ѝ CS ࡟ࡘ࠸࡚♧ࡍ㸬ᅗ㸲࡟㸪ࡇࢀࡽ 3 ࡘࡢ཯ᛂࡢ⤒㊰࡟ἢࡗࡓࣉࣟࢺࣥ࠾ࡼࡧ㟁Ꮚ⛣ື࡟ࡘ࠸࡚ࡑࢀࡒࢀ♧ࡍ㸬᭱ึࡢ CR ࡛ࡣ㸪Mn(4)࠿ࡽ phenoxy radical࡬ࡢ㟁Ꮚ࣭ࣉࣟࢺࣥ⛣ືࡢ⤖ᯝ phenol ࡟㑏ඖࡉࢀࡿ (ᅗ 4a) ࡑࡋ࡚ RL ࡛ࡣ㸪Ỉ⣲⤖ྜࢿࢵࢺ࣮࣡ࢡࢆ௓ࡋ

- 354 -

ࡓࣉࣟࢺ࣮ࣥࣜࣞ࡜࢝ࢵࣉࣝࡋ࡚㸪Mn 㘒యෆ࡛ࡢ㟁Ꮚ⛣ືࡀ㉳ࡇࡿ (ᅗ4b)㸬ࡇࢀ࡟ࡼࡾ㸪2 ␒┠ࡢ CS ࡀ᭱ึࡢࡑࢀ࡜ྠࡌࡼ࠺࡟㉳ࡇࡿࡼ࠺࡟࡞ࡿ (ᅗ 4c)㸬௚ࡢ㐣⛬࡟ࡘ࠸࡚ࡶྠᵝ࡟♧ࡍࡇ࡜ࡀ࡛ࡁࡿ㸬௨ୖࡼࡾ㸪㸲ᅇࡢ㟁Ⲵศ㞳ࡢᚋ࡟㸲ᅇࡢ MR ࡟ࡼࡗ࡚ O2 ࡀ⏕ᡂࡍࡿỈศゎࢧ࢖ࢡࣝࡀྍ
⬟࡞ࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸬
3.3 ⤖ㄽ
௨ୖࡢ⤖ᯝ࠿ࡽ㸪㠀ᖖ࡟」㞧࡟ぢ࠼

ᅗ 4. ᅄ᰾㘒యࡢᇶᮏⓗ࡞໬Ꮫⓗࣉࣟࢭࢫࡢ࠺ࡕ㸪(a) 㸯␒┠ࡢCS㸪(b) 1 ␒┠ࡢ RL㸪ࡑࡋ࡚(c) 2 ␒┠ࡢ CS ࡢ㟁Ꮚ࠾ࡼࡧࣉࣟࢺ
ࣥࡢ⛣ື⤒㊰㸬㯤Ⰽࡢᢞ✏㠃ࡣ unpaired electron density ࡟ᑐᛂࡍࡿࡿỈศゎࡢᶵᵓࡀ㸪㠀᩿⇕㟁ᏊືຊᏛࢆ⪃៖ࡍࡿࡇ࡜࡟ࡼࡾ㸪ᐇࡣ 3 ✀㢮ࡢ༢⣧࡞ᇶᮏⓗ໬Ꮫࣉࣟࢭࢫ (CS,RL, ࠾ࡼࡧ MR) ࡟ศゎࡋ࡚⪃࠼ࡽࢀࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬≉࡟⯆࿡῝࠸ࡢࡣ㸪ືຊᏛⓗゎᯒࡢ୰࡛㸪PSII ࡢᅄ᰾ Mn 㘒యࡢ࠸ࢃࡺࡿ ͆3+1͇ ࡢ㠀ᑐ⛠ᵓ㐀ࡢᙺ๭ศᢸࡀ㸪͆3͇ࡀ proton electron reloading (RL), ͆1͇ࡀ charge
separation (CS) ࡜ࡋ࡚⮬↛࡟ᑟࡁฟࡉࢀࡓࡇ࡜࡛࠶ࡿ. ࡇ࠺ࡋ࡚㸪PSII ࡢỈศゎ࡟࠾ࡅࡿᅄ᰾ Mn 㘒య࡟ࡼࡿゐ፹ࢧ࢖ࢡࣝࡢ໬ᏛືຊᏛⓗ඲యീ࡜ᇶᮏⓗ࡞ᶵᵓࢆ᫂ࡽ࠿࡟ࡋࡓ㸬

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] ‫ۑ‬Kentaro Yamamoto and Kazuo Takatsuka "A Chemical Mechanism of Unidirectional Proton Transfers Driven
by Coupled Proton and Electron-Wavepacket Transfers", Asia-Pacific Association of Theoretical and Computational
Chemists, Sydney, Australia, 2019/9/30-10/03, IC006 (invited talk).
‫[ۻ‬2] ‫ۑ‬ᒣᮏ᠇ኴ㑻㸪㧗ሯ࿴ኵ "஧᰾ Mn 㘒య࡟ゐ፹ࡉࢀࡿගỈศゎࢧ࢖ࢡࣝ࡟ࡘ࠸࡚: ㏣ຍࡢ Mn 㓟໬≀ࡢ㟁Ꮚ̾ࣉࣟࢺࣥࣂࢵࣇ࢓࡜ࡋ࡚ࡢᙺ๭", ➨ 13 ᅇศᏊᏛウㄽ఍, ྡྂᒇ 2019/9/17-20 3L07.
‫[ۻ‬3] ‫ۑ‬ᒣᮏ᠇ኴ㑻㸪㧗ሯ࿴ኵ "୍᪉ྥⓗ࡞ࣉࣟࢺࣥ⛣ືࡢ໬Ꮫⓗ࡞ᶵᵓ࡟ࡘ࠸࡚: 㠀᩿⇕㟁ᏊືຊᏛ࡟ࡼࡿ
◊✲", ➨ 22 ᅇ⌮ㄽ໬Ꮫウㄽ఍, ໭ᾏ㐨 2019/5/27-29 1L08.

5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] Kentaro Yamamoto and Kazuo Takatsuka “Binuclear Mn oxo complex as a self-contained photocatalyst in watersplitting cycle: Role of additional Mn oxides as a buffer of electrons and protons” J. Chem. Phys. 152, 024115 (2020)‫[ۻ‬2] Kentaro Yamamoto and Kazuo Takatuska “Charge separation and successive reconfigurations of electronic andprotonic states in a water-splitting catalytic cycle with the Mn4CaO5 cluster. On the mechanism of water splitting in PSII”
Phys. Chem. Chem. Phys. 22, 7912-7934 (2020).

ཧ⪃ᩥ⊩[1] T. Yonehara, K. Hanasaki, and K. Takatsuka, Chem. Rev., 112, 499 (2012).
[2] M. Suga et al., Nature, 543, 131 (2017).
[3] J. Kern et al., Nature, 563, 421 (2018).
[4] K. Yamamoto and K. Takatsuka, Phys. Chem. Chem. Phys., 20, 12229 (2018).
[5] K. Yamamoto and K. Takatsuka, Phys. Chem. Chem. Phys., 20, 6708 (2018).

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ศᏊືຊᏛィ⟬࡟ࡼࡿ㧗᥋╔⺮ⓑ㉁ࡢỈ୰᥋╔࣓࢝ࢽࢬ࣒ࡢゎ᫂Elucidation of adhesion mechanism of highly adhesive protein in waterby molecular dynamics simulation‫ۑ‬㕥ᮌ ῟ᕧࠊ➲ཎ ⣧ࠊᇼ ඞᩄ㸦ྡྂᒇ኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉㸧
1◊✲┠ⓗࠊෆᐜ
⣽⳦ $FLQHWREDFWHU6S7RO ࡣࠊ$WD$ ࡜࿧ࡤࢀࡿᕧ኱⧄⥔≧ࢱࣥࣃࢡ㉁  ṧᇶ㸱ࡢ࣍ࣔ  㔞య ࢆ⣽⬊⾲ᒙ࡟ᣢࡗ࡚࠾ࡾࠊࣉࣛࢫࢳࢵࢡࠊ㔠ᒓࠊ࢞ࣛࢫ➼ࡢᵝࠎ࡞≀㉁ࡢ⾲㠃࡟ᙉࡃ᥋╔ࡍࡿࠋ$WD$ ࡢ᥋╔ᛶࡣࠊࡑࡢඛ➃࡟࠶ࡿ 1KHDG ࢻ࣓࢖ࣥ ศᏊ㔞 N'D ࡀᢸࡗ࡚࠾ࡾࠊ1KHDG ༢⊂࡛ᵝࠎ࡞ᮦᩱ⾲㠃࡟ᙉࡃ᥋╔ࡍࡿࠋᮏ◊✲࡛ࡣࠊࡇ࠺ࡋࡓ᥋╔≉ᛶࡢ⫼ᬒ࡟࠶ࡿศᏊ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡓࡵ࡟ 1KHDG ࡀ࣏ࣜࢫࢳࣞࣥ㸦36㸧ࡢ⾲㠃࡟᥋╔ࡍࡿ㐣⛬ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦0' ィ⟬㸧ࢆ⾜࠸ࠊNhead ࡀ PS ⾲㠃࡟⤖ྜࡍࡿ㐣⛬ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢕࣮ࣝࢆ᫂ࡽ࠿࡟ࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲࡛ࡣࠊNhead ࡀ PS ⾲㠃࡟⤖ྜࡍࡿ㐣⛬ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢕࣮ࣝࢆ㸦㸯㸧࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥ
ࢢἲ࡜㸦㸰㸧⇕ຊᏛ✚ศἲ࡛ồࡵࡓࠋ⏝࠸ࡓ⣔ࡣࠊ12122.5nm3 ࡢṇ᪉ᙧࡢ PS ᇶ┙ࡢୖ࡟ 150mM ┦ᙜࡢ
NaCl ࢆྵࡴỈࡢᒙࢆ 20nm ࡢཌࡉ࡛ࡢࡏࠊࡇࡢ୰࡟ Nhead ࢻ࣓࢖ࣥࢆ⨨࠸ࡓࡶࡢ࡛ࠊィ 323,153 ಶࡢཎᏊࢆྵࡴࠋMD ィ⟬ࡣࠊ඲࡚ࣉࣟࢢ࣒ࣛ Gromacs ࢆ⏝࠸࡚⾜ࡗࡓࠋ࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢἲࡢ MD ィ⟬ࡣࠊ༢⢭ᗘ࡛⾜࠸ࠊ᫬㛫้ࡳ 2fs ࡛ 10ns ࡢ NPT ࢔ࣥࢧࣥࣈ࡛ࣝࡢィ⟬ࢆ Nhead ࢻ࣓࢖ࣥࡢ఩⨨࡜㓄ྥ࡟ㄪ࿴࣏ࢸࣥ
ࢩࣕࣝ࡟ࡼࡿ᮰⦡ࢆ࠿ࡅ࡚⾜ࡗࡓࠋィ⟬ࡣ PS ᇶ┙࡜ Nhead ࡢ㊥㞳ࢆ 0 ࠿ࡽ 7nm ࡲ࡛ 0.1nm 㛫㝸࡛ኚ࠼࡚⾜࠸ࠊNhead ࡜ PS ᇶ┙ࡢ㔜ᚰ㛫㊥㞳ࡢศᕸ࠿ࡽ WHAM ࢆ౑࠸⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋ୍᪉ࠊ⇕ຊᏛ✚ศἲࢆ⏝࠸ࡓ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡛ࡣࠊNhead ࢻ࣓࢖ࣥࡢ㔜ᚰ఩⨨࡜㓄ྥࢆᅛᐃࡋ࡚ 10ns ࡢ NPT ࢔ࣥࢧࣥࣈࣝ
࡛ࡢ MD ィ⟬ࢆ⾜࠸ࠊPS ᇶ┙࡜ Nhead ࢻ࣓࢖ࣥ㛫࡟ാࡃᖹᆒຊ(PMF)ࢆィ⟬ࡋࠊࡇࢀࢆ✚ศࡋ࡚ࠊ⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋ⇕ຊᏛ✚ศἲࡢ MD ィ⟬ࡣⓎᩓࡋࡸࡍࡃࠊ
᫬㛫้ࡳࢆ 0.5fs ࡲ࡛⣽࠿ࡃࡍࡿᚲせࡀ࠶ࡗࡓࠋ

3◊✲ᡂᯝ
Nhead ࡢ⧄⥔㍈ࡀ PS ᇶ┙࡟ᆶ┤㸦⦪㓄ྥ࡜࿧ࡪ㸧࡜ᖹ⾜㸦ᶓ㓄ྥ㸧ࡢ㸰ࡘࡢ㓄ྥ࡟ࡘ࠸࡚ࠊNhead ࡜PS ᇶ┙ࡢ㔜ᚰ㛫㊥㞳ࢆኚᩘ࡜ࡍࡿ⮬⏤࢚ࢿࣝࢠ࣮
ࣉࣟࣇ࢕࣮ࣝࢆィ⟬ࡋࡓࠋ࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥ
ࢢἲ࡟ࡼࡾ⟬ฟࡋࡓ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢕࣮࡛ࣝࡣࠊPS ᇶ┙࡟ᑐࡋ࡚⧄
⥔㍈ࢆᖹ⾜࡟ࡋ࡚ Nheadࢻ࣓࢖ࣥࡀ㏆࡙ࡃ࡯࠺ࡀࠊ

ᅗ㸯 ࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢἲ࡟ࡼࡾ⟬ฟࡋࡓ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢕࣮ࣝ

- 356 -

⧄⥔㍈ࢆᆶ┤࡟ࡋ࡚㏆࡙ࡃࡼࡾࡶ⮬⏤࢚ࢿࣝࢠ࣮ⓗ࡟᭷฼(༑ศ࡟㐲࠸㊥㞳࠿ࡽ Nhead ࢻ࣓࢖ࣥࢆ㏆࡙ࡅ࡚
PS ᇶ┙⾲㠃࡟᥋ࡍࡿࡲ࡛ࡢ⮬⏤࢚ࢿࣝࢠ࣮ኚ໬ࡀ኱ࡁ࠸)࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊ࢔ࣥࣈࣞ
ࣛࢧࣥࣉࣜࣥࢢἲ࡛ࡣࠊNhead ࢻ࣓࢖ࣥࡀ PS ᇶᯈ࠿ࡽ㐲ࡃ㞳ࢀࡓᆅⅬ࡛ࡢ┦஫స⏝࢚ࢿࣝࢠ࣮ࡀ 0(ࢮࣟ)࡟
཰᮰ࡋ࡟ࡃ࠸ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
୍᪉ࠊ⇕ຊᏛ✚ศἲ࡛ồࡵࡓࡢ⮬⏤࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢕࡛ࣝࡣࠊPS ᇶ┙࡟㏆࠸࡜ࡇࢁࡇ࡜࡛
ࡣࠊ࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢ࡜࡯ࡰྠࡌ࡛ࠊ࠿
ࡘࠊᇶ┙࠿ࡽ㐲࠸࡜ࡇࢁ࡛ࡣࢮࣟ࡟཰᮰ࡍࡿ᭤
⥺ࢆ୚࠼ࡓࠋࡲࡓࠊPS ᇶ┙࡜ Nhead ࢻ࣓࢖ࣥࡢ
㛫࡟ാࡃᖹᆒຊࡢ኱ࡁࡉࡶࠊཎᏊ㛫ຊ㢧ᚤ㙾࡟ࡼࡿᐇ㦂࡛࠼ࡽࢀࡓ್ 200pN(⌧ᅾᢞ✏‽ഛ୰)࡟㏆࠸್ࡀᚓࡽࢀࡓࠋࡑࡇ࡛ࠊ⇕ຊᏛ✚ศἲ࡛ࡢ⤖ᯝࢆᏛ఍࡛Ⓨ⾲(Ⓨ⾲ 1)ࡍࡿ࡜ඹ࡟ࠊㄽᩥ࡟
ࡲ࡜ࡵࡿ࡭ࡃࠊMD ィ⟬࡛ᚓࡽࢀࡓࢺࣛࢪ࢙ࢡ
ࢺ࣮ࣜࢆゎᯒࡋ࡚ࠊ᥋╔࡟࠾ࡅࡿ࢔࣑ࣀ㓟ṧᇶࡸỈ࡟ᙺ๭ࢆヲ⣽࡟ㄪ࡭࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ
ᅗ㸰 ⇕ຊᏛ✚ศἲ࡟ࡼࡾ⟬ฟࡋࡓ⮬⏤࢚ࢿࣝࢠ࣮
ࣉࣟࣇ࢕࣮ࣝ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫➲ۻ‬ཎ ⣧ࠊ㕥ᮌ῟ᕧࠊ⸨ᮏ࿴ኈࠊᒸᓮ 㐍ࠊᇼඞ ᩄࠊ➨ 9 ᅇ CSJ
໬Ꮫࣇ࢙ࢫࢱ 2019ࠊ2019 ᖺ 10
᭶5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
⌧ᅾࠊᢞ✏‽ഛࢆࡋ࡚࠾ࡾࠊ

ᖺෆࡢᢞ✏ࢆணᐃࡋ࡚࠸ࡿࠋ

ᅗ㸱 36 ᇶ┙࡜┦஫స⏝ࡋ࡚࠸ࡿ࢔࣑ࣀ㓟ṧᇶ

- 357 -

Computational innovation of nanocomposite materials using firstprinciples and molecular dynamics simulations
Pradeep R. Varadwaj
National Institute of Advanced Industrial Science and Technology, Tsukuba
Central 5, Ibaraki, Japan 305-8565
1. Introduction
Polymer networks are used in a variety of applications due to the wide rangeof beneficial molecular functionality they provide. Structural composites arepromising materials for increasing stiffness, reducing weight and consequently
reducing CO2 emissions from next-generation aircraft and vehicles called CFRP
(Carbon Fiber Reinforced Plastics). The three-dimensional structure of the polymer
and the resulting chemical interactions are thought to affect the structural hardness
and surface energy of the material.
The chemical interactions at the joints (interfacial regions) have been least
understood. They are feasible as covalent and noncovalent. Noncovalentinteractions are fundamental forces at the molecular and atomic level. They play avery important role in material design. They allow the material to function. Base

- 358 -

pairing in DNA and organic-inorganic perovskite solar cells are ideal examples
where noncovalent interactions play a major role. Epoxy polymers are a type of suchthermosetting materials. These are formed not only by the wonder of covalent crosslinking between chemicals of different nature, but also by noncovalent interactions.
The latter appear with different flavors, making the system behave like an adhesive.
They are the determinants of glass transition temperature and elastic properties ofthese materials. These innovative nanocomposites have many technical challenges,
especially in the field of aerospace engineering. For instance, epoxy resins arematerials for aerospace structural composites; a tiny version of the system modelledusing Gromacs and Materials studio simulation packages are shown in Figure 1.
Nevertheless, these polymeric adhesives have been shown to provide advantages
over more traditional methods of joining various types of materials. In this work, wehave modelled several very large-scale polymer network systems (viz. DGEBA44DDS, PEEK, o-PEEK and TGDDM-44-DDS, cf. Fig. 2) that are computationallyvery demanding and for understanding the of how noncovalent interactions canhelp maintain fragments of crosslinked epoxy polymer networks together. The
results obtained have highlighted the importance of simulation approaches tounderstanding these interactions at the molecular and polymer level using various
properties such elastic modulus, glass transition temperature and interfacial energy
landscapes. In addition, the stability preferences, geometric manifolds, and electron
density topologies were also analyzed, and presented in several conferences andinternational journals.

2. Computational details
Various Software codes were used for the calculation of structures and properties ofthe polymer network systems. These include Quantum Expresso, Gromacs, and
NWChem packages. The main aim of Gromacs simulation was to compare its resultswith those of Materials studio, and for a benchmark of the polymer network systems.
The geometries obtained from Gromacs and materials studies were chopped into
smaller fragments and manipulated. Several of these structures were geometry
optimized using Gaussian 16, together with vibrational frequency calculations.
The reason for these calculations were to assign the bonding features in themodelled structures, and calculate the energy strengths of these interactions.
Various tight convergence criteria were employed for accurate calculations. Since- 359 -

we were interested in the fundamental understanding of the energy strength of thenoncovalent interactions between molecular domains of the aforesaid polymer network
systems, several binary complex arrangements containing 600-900 atoms were extracted
from the various supercell geometries constructed using from the Materials Studiopackage optimized in the gas phase and were computed. The B97-D3 DFT functional,
together with several others and the Grimme-D3(BJ)Dispersion correction and cc-pVTZ
and aug-cc-pvTZ basis sets, were used. Tight and default algorithms for Self-ConsistentField convergence and ultrafine integration grid were used. The supermolecularmethod of Pople was used for the calculation of the stabilization energy, and wascorrected for the Basis Set Superposition Error (BSSE) using the counterpoise procedureof Boys and Bernardi. The Gaussian 16 code was used.
Simulation codes such Critic 2 and AIMPAC were extensively used for thedetermination of electron density topologies of bonding interactions. The MD
simulations were carried out on several systems.

3. Results
Whereas several model polymer network systems were modelled using Gromacs,
Materials studio and Gaussian 16 simulation packages, Figure 2 shows molecularversions of a few models examined.

- 360 -

Figure 3 shows the nature of cross-linking behavior for the DGEBA-44-DDS
polymer network system. Similar results were obtained when polymer systems
with 3000, 5000, 9000, 13000 atoms were modelled. The glass transition
temperatures were determined to be 192.2 K and were consistent withexperiment. Table 1 shows the details materials examined using materials studio,
which can be comparable with those of the results of Gromacs (not shown)obtained on range of temperatures 200 to 800 K.

Figure 3: Dependence of the nature of the a) rate of conversion on the number ofreaction cycle, b) reactive sites consumed on the number of reaction cycle, c) thereactive sites consumed on the rate of conversion, and d) density on the rate ofconversion/cycle.

- 361 -


Table 1: A comparison of the rate of cross-linking, young’s modulus and glasstransition temperature with literature data.
Figure 4 shows the relaxed models of the PEEK and o-PEEK systems, withthe glass transition temperatures. A very good agreement was found. Table 2
presents the details of the computed physical properties, which are compared withexperiment. Figure 5 shows the nature of various properties analyzed.


Figure 4: Example of DFT relaxed supercell models o-PEEK and PEEK.

- 362 -

Table 2: Comparision of selected DFT-PBESol and MD calculated unt-cell properties ofo-PEEK with experiment.a
Property

DFTb

MDb

Expt.c%Change(DFT)dUp(g/cm3) 1.395 1.364 1.328
V(cm3) 2744.5 2808.5 2884.6
N
272
272
272

+5.1
–4.9

%
Change(MD)d
+2.2
–2.6

–1.3
–1.3
–6.5
–2.6
–2.6
+2.8

–0.3
–0.3
–5.5
–2.4
–2.4
+1.9

Lattice constants
a/Å
b/Å
c/Å
D/deg
E/deg
J/deg
Tg/K

14.142 14.281 14.328
14.142 14.281 14.328
16.463 16.612 17.525
107.7 107.9 110.5
107.7 107.9 110.5
63.2
62.6
61.4

Glass Transition Temperaturec
424.4 418.2
r 22.3aProperties include the packing density (Up), the unit-cell volume (V), the number of atoms in the unit-cell(N), the lattice constants (a, b, c, D, E and J) and the glass transition temperature (Tg).
bThis work. The PBESol calculation was performed with 2u2u2 k-point mesh.
cExperimental values were taken from Ref. 18. Tg was calculated using MD simulation and the DFT relaxed
structure of o-PEEK was supplied.
d
The positive and negative signs indicate the percentage of increase and decrease of a specific calculated
property compared to experiment, respectively.

Figure 5: Dilatometric results of o-PEEK, where the equilibrium start- and end-temperatures were
700 K and 100 K, respectively, with the step size of 30 between them. a)-b) Specific volume vs.
Temperature and c)-d) Density vs. Temperature. The glass transition temperature (Tg) withstandard deviation is shown for each case.

- 363 -

The large stabilization energy for each of the two complexes in Figure 6 is not very
surprising, which are the largest compared to a bunch of model systems examined. The twooligomers in each system of o-PEEK are coupled with each other via multi-foldintermolecular interaction topologies. These are long-ranged and well-dispersed, as
demonstrated by the RDG isosurfaces shown at the bottom of Figure 6. The O···H(C),(C=C)S···H(C) and CS···H(C) contacts are common to both a) and b). However, the(C)H···H(C) contacts are prominent in the former and the (C=C)S···H(C) and (C6)S···H(C)contacts are prominent in the latter, in agreement with the spread in the isosurface topologythat appears in the intermolecular (interfacial) region.
Figure 6: a)-b) (Top) The intermoelcular contact geometries and (Bottom) the modified RDG
isosurface plots (0.005 a.u.) of two randomly selected binary complexes of o-PEEK. Selectedintermolecular distances are shown.

- 364 -

Fig. 7 illustrates the nature of chemical interactions in a model TGDDM44DDS polymer system containing 500 atoms (truncated), evaluated using AIMPAC
code.
Although several models were examined, the various noncovalentinteractions responsible for the stability of the aforementioned network system wereidentified to be N···H, O···H(C), (C=C)S···(C=C)S, (C=C)S···H(C), CS···H(C), and(C)H···H(C), among several others, whose energy strengths were ranging between 1 and -12 kcal mol-1, obtained using PSI4 code, thus demonstrating the fact that
weak-to-medium strength interactions play a vital role in determining the geometry,and materials properties (rigidity, transition temperature and gel features) of the
network systems examined. It should be noted that the appearance of an interactionin the interface region depends largely on the nature of the interfacial topology.
Changing the size of the system will change the topology of bonding, and the natureof the noncovalent interactions involved.

Figure 7: Illustration of molecular graphs of the TGDDM-44DDS polymer network
system (truncated). The (3,-1) critical points are shown as tiny blue spheres between
atoms (large spheres) and the bond paths are shown as red lines between atomic
basins.

- 365 -

Fig. 8 shows one of the large-scale polymer systems examined. A highest value ofcross-linking fraction of 88% was obtained for the TGDDM-44-DDS system, and was ranged
up to 97% for the DGEBA-44DDS system. The interfacial energy landscapes for this andseveral other model systems with different sizes were also analyzed. Table 1 shows the natureof dependence of the cross-linking radius on the percentage of cross-linking for the TGDDM44DDS cross-linked system. Fig. 9 shows the nature of energy contribution to the total energy,
as well as the interfacial energy for a model that had the 200/200 ratio mixture of the
TGDDM-44DDS and the DGEBA-44DDS cross-linked systems.


Figure 8. Illustration of uncross-linked a) TGDDM-44DDS and b) c) DGEBA-44DDS
systems. Shown in c) is the MD simulated epoxy-amine cross-linked TGDDM44DDS and epoxy-amine cross-linked DGEBA-44DDS polymer network systems inan amorphous cell.

- 366 -

Table 2: Example of a dependence of cross-linking fraction on the cross-linking
radius.
Cross-linking radius/Å
3.5
4
4.5
5
5.5

Iteration
1
1
1
1
1

Percent Conversion
70.55
75.25
79.4
82.95
88.05



Fig. 9: Illustration of the nature of energy components for MD simulated epoxy-amine crosslinked TGDDM-44DDS (ratio mixture 200/200) and epoxy-amine cross-linked DGEBA44DDS (ratio mixture 100/100) polymer network systems in an amorphous cell.

As presented above, the various properties of several polymer network
systems of different sizes modelled, analyzed, and compared with experiment were
presented different national and international conferences. In addition, a few papers
were prepared and submitted to international journals for possible publications.

- 367 -

Although all the computed results are yet to be fully analyzed, we expect that theresults obtained on the various model systems shall give any structure-function
relationship that will be useful for the prediction of similar properties of analogous
cross-linked polymer systems. The results of a few perovskite systems modelled are
yet to be examined. The outcome of our research is summarized below.

5. Conference presentations and publications

1- Study on Chemical Interactions at Interfaces in Structural Composite Joints,
Hasegawa K, Yamazaki N, Watari N, Kamo S, Takagi K,
Ohkubo M, Itoh H, Miura T, Funada M, Shimoi Y, Varadwaj P. R., Fons. P.,
Japan-US-Australia Composite Workshop, 2020, 3 Sep 2019 - 5
Sep 2019. Bristol, UK.
2- P. R. Varadwaj, Noncovalent interactions in novel epoxy polymers and related Slaminated systems: Importance of simulation in elucidating their physical andchemical properties, Plenary Lecture, Twenty-fourth International Workshop on
QUANTUM SYSTEMS IN CHEMISTRY, PHYSICS, AND BIOLOGY (QSCP-XXIV)
August 18-24, 2019 - Odessa, Ukraine.
3- Molecular Dynamics and DFT Simulation Study of the Properties of a Cyclic
Oligomer of o-PEEK, Varadwaj Pradeep R., Fons Paul, Takagi Kiyoka,
13th Symposium on Molecular Science, Nagoya University, September 17 through Friday, September 20, 2019.
4- Takagi
K, Hasegawa
K,
YamazakiN,
WatariN,
Kamo
S,
Ohkubo M, Itoh H, Miura T, Funada M, Shimoi Y, Varadwaj P. R., Fons. P., Studyon Chemical Interactions at Interfaces in Structural Composite Joints Japan-USAustralia Composite Workshop, 5th Composites Workshop, Japan-US-Australia
Composite Workshop, Defense Equipment Agency, Defense Equipment Agency,
Ichigaya, February 20-21, 2020, Japan.
5- Pradeep R. Varadwaj, Combined Molecular Dynamics and DFT Simulation Study of
the Molecular and Polymer Properties of a Catechol-Based Cyclic Oligomer ofPolyether Ether Ketone (manuscript submitted to a Wiley Journal).
6- Soft X-ray Absorption Spectroscopy Probes OH···π Interactions in Epoxy-Based
Polymers, H. Yamane, M. Oura, O. Takahashi, P. Fons, P. R. Varadwaj, Y. Shimoi, M.
Ohkubo, T. Ishikawa, N. Yamazaki, K. Hasegawa, K. Takagi, T. Hatsui, ((manuscript
submitted to an ACS Journal).

- 368 -

ᑠศᏊࡢኚ᥮཯ᛂࢆᣦྥࡋࡓ㑄⛣㔠ᒓゐ፹ྜᡂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical Study on the Synthesis of a Transition-metal Catalyst for Use
in the Transformation of Small Molecules‫ۑ‬㛗ᒸ ṇᏹ࣭㊊❧ ᾈ᫂㸦┦ᶍ୰ኸ໬Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
࣏࢚ࣜࢳࣞࣥࡣ㧗ỗ⏝ᛶࡢྜᡂᶞ⬡࡛࠶ࡾࠊ඲ྜᡂᶞ⬡⏕⏘㔞ࡢ⣙ 20% ࢆ༨ࡵࡿࠋ୰పᅽἲ࡟࠾ࡅࡿ࣏

࢚ࣜࢳࣞࣥ〇㐀ࣉࣟࢭࢫ࡛ࡣࠊZiegler ⣔ゐ፹ࡸ➨ 4 ᪘㔠ᒓ࣓ࢱࣟࢭࣥゐ፹࡜࠸ࡗࡓ㔠ᒓゐ፹ࡀ⏝࠸ࡽࢀ࡚࠾ࡾࠊ୰࡛ࡶ࣓ࢱࣟࢭࣥゐ፹ࡣࠊ㓄఩Ꮚ࡟ࡼࡗ࡚ᵓ㐀つไࡉࢀࡓ༢୍ࡢ཯ᛂࢧ࢖ࢺࢆ᭷ࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊ
ศᏊ㔞ศᕸࡢ⊃࠸࣏࢚ࣜࢳࣞࣥࢆ୚࠼ࡿࡇ࡜ࡀ≉ᚩ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊ㧗άᛶ࡞࣓ࢱࣟࢭࣥゐ፹ࡢタィ࡟㛵ࡍࡿ▱ぢࢆᚓࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࠊ࣓ࢱࣟࢭࣥゐ፹ࡢ⨨᥮ᇶࡢ㐪࠸ࡀ㔜ྜάᛶ࡟୚࠼ࡿᙳ㡪ࢆㄪᰝࡋࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 16 program ࢆ⏝࠸ࠊDFT ἲ࡟ࡼࡗ࡚ᵓ㐀᭱㐺໬࠾ࡼࡧ᣺ືィ⟬ࢆ⾜ࡗࡓࠋỗ㛵ᩘ࡜ࡋ࡚ࡣࠊ

B3LYP-D3 ࢆ᥇⏝ࡋࠊᇶᗏ㛵ᩘࡣ㔠ᒓඖ⣲ࡀ Lanl2DZࠊ඾ᆺඖ⣲ࡀ 6-31G++(d,p) ࡜ࡋࡓࠋ✀ࠎࡢ⨨᥮ᇶࢆࡶࡘࢪࣝࢥࣀࢭࣥゐ፹࡟ᑐࡋ࡚ࠊ࢚ࢳࣞࣥࡢ⏕㛗㐣⛬࡟ࡘ࠸࡚ゎᯒࡋࡓࠋ3◊✲ᡂᯝ࢖ࢯࣉࣟࣆࣝᇶࠊࢪ࣓ࢳࣝ࢔࣑ࣀᇶ࠾ࡼࡧࢺࣜࣇ

࣓ࣝ࢜ࣟࢳࣝᇶࢆ᭷ࡍࡿࢪࣝࢥࣀࢭࣥ 1–6 ࡟ࡘ࠸࡚࢚ࢳࣞࣥࡢᤄධ཯ᛂ࡟࠾ࡅࡿ࢚ࢿࣝࢠ࣮ኚ໬ࢆ
ゎᯒࡋࠊάᛶ໬࢚ࢿࣝࢠ࣮ ('G) ࢆ⟬ฟࡋࡓ (ᅗ)ࠋࡑࡢ⤖ᯝࠊࢪ࣓ࢳࣝ࢔࣑ࣀᇶࢆྵࡴࢪࣝࢥࣀࢭࣥ 2,
4, 6 ࡣࠊ࢖ࢯࣉࣟࣆࣝᇶࡲࡓࡣࢺࣜࣇ࣓ࣝ࢜ࣟࢳࣝ
ᇶࢆྵࡴࢪࣝࢥࣀࢭࣥ 1, 3, 5 ࡼࡾࡶάᛶ໬࢚ࢿࣝ
ࢠ࣮ࡀ㧗ࡃ࡞ࡿഴྥࡀぢࡽࢀࡓࠋ㟁Ꮚ౪୚ᛶᇶ࡛࠶
ࡿࢪ࣓ࢳࣝ࢔࣑ࣀᇶࡢᑟධ࡟ࡼࡗ࡚࢚ࢳࣞࣥ㘒య
B ࡀ୙Ᏻᐃ໬ࡉࢀࠊ⤖ᯝⓗ࡟ 'G ࡀᑠࡉࡃ࡞ࡿࡇ
࡜ࡀ᥎ᅗ㸬࢚ࢳࣞࣥᤄධ࡟࠾ࡅࡿάᛶ໬࢚ࢿࣝࢠ࣮

ࡉࢀࡓࡀࠊᐇ㝿࡟ࡣ㑄⛣≧ែ C ࡶ୙Ᏻᐃ໬ࡉࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࢪࣝࢥࢽ࣒࢘ୖࡢ㟁Ꮚᐦᗘࡀ㧗ࡃ࡞ࡿࡇ࡜࡛ࠊ㑄⛣≧ែ C ࡢȘ࢔ࢦࢫࢸ࢕ࢵࢡ┦஫స⏝࡟ࡼࡿᏳᐃ໬ࡀᚓࡽࢀ࡟ࡃࡃ࡞ࡗ࡚࠸ࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
ᮏ⤖ᯝ࡟ࡘ࠸࡚ࡣࠊᏛ఍࡟࡚Ⓨ⾲ணᐃ࡛࠶ࡿࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
ᮏ⤖ᯝ࡟ࡘ࠸࡚ࡣࠊ㛵㐃ࡍࡿ໬ྜ≀ࡢ≉チ࠾ࡼࡧㄽᩥࢆᇳ➹ணᐃ࡛࠶ࡿࠋ

- 369 -

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immersed in a liquid and the basic cell-size dependenceÇ Û÷ «£×ÿĂWvú» gyă1ÄËÁÀ_}
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1: Ken Tokunaga and Ryo Akiyama: Molecular dynamics study of a solvation motor in a Lennard-Jones solvent,Phys. Rev. E, 100, 062608-1-8 (2019); https://doi.org/10.1103/PhysRevE.100.062608.
2: Ayano Chiba, Akio Oshima, and Ryo Akiyama: Confined Space Enables Spontaneous Liquid Separation by
Molecular Size: Selective Absorption of Alkanes into a Polyolefin Cast Film, Langmuir, 35, 17177-17184 (2019);
https://pubs.acs.org/doi/full/10.1021/acs.langmuir.9b02509.
3: Yuka Nakamura, Shota Arai, Masahiro Kinoshita, Akira Yoshimori, and Ryo Akiyama: Reduced density profile ofsmall particles near a large particle: Results of an integral equation theory with an accurate bridge function and a Monte
Carlo simulation, J. Chem. Phys. 151, 044506-1-10 (2019); https://doi.org/10.1063/1.5100040.

- 370 -

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4°-~*"!V}Masatake Sugita (Oral, Invited), “Development of a Protocol for predicting the binding affinity by Combining

Statistical Mechanics Theory of Liquids and MD Simulation”, Pacifichem2020, 2020/12/15-20, Honolulu, (°-V})5

$~*"!V}1)*Masatake Sugita, Masataka Hamano, Kota Kasahara, Takeshi Kikuchi, and Fumio Hirata, New Protocol for

Predicting the Ligand-Binding Site and Mode Based on the 3D-RISM/KH Theory, Journal of Chemical Theory andComputation, 16, 2864-2876, (2020)- 372 -

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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
ࢩࣜ࢝ࡸ㓟໬ࢳࢱࣥ࡞࡝ࡢᛂ⏝ୖᴟࡵ࡚㔜せ࡞ᅛయ࡜Ỉ⁐ᾮ࡜ࡢ⏺㠃࡛ࡢศᏊᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࢆศᏊ

ືຊᏛ㸦MD㸧ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾゎ᫂ࡍࡿࠋ⾲㠃ศᏊ✀ࡸ㟁Ẽ஧㔜ᒙ࡞࡝ࡢศᏊᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࢆ
᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡛ࠊ཯ᛂᶵᵓࡀ㆟ㄽࢆ࿧ࢇ࡛࠸ࡿ㉸ぶỈᛶ࡞࡝ࡢ⏺㠃⌧㇟ࡢศᏊ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࠊMD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸ࡓⲴ㟁ࡋࡓᅛᾮ⏺㠃࡬ࡢᒎ㛤ࢆ┠ᣦࡍࠋᮏ◊✲ㄢ㢟࡛ࡣ࢔ࣔࣝ
ࣇ࢓ࢫࢩ࣭ࣜ࢝Ỉ⏺㠃࡜㓟໬ࢳࢱ࣭ࣥỈ⏺㠃ࢆࢱ࣮ࢤࢵࢺ࡜ࡍࡿࠋ
ࡇࢀࡲ࡛⏦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᭦࡟Ⓨᒎࡉࡏ࡚ࠊ࢔ࣔࣝࣇ࢓ࢫࢩࣜ࢝㸦࢞ࣛࢫ㸧࣭Ỉ⏺㠃࡛ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࣔࢹࣝࡢ᭦࡞ࡿ⢭ᗘྥୖࢆ㐍ࡵ࡚ࡁࡓࠋ㏻ᖖࡢྂ඾ MD ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥࡣ⏺㠃࡛ࡢ໬Ꮫ⤖ྜࡢ⏕ᡂ࣭㛤⿣ࢆᢅ࠼࡞࠸ࡓࡵࠊ
⏦ㄳ⪅ࡣ⌧ᅾ➨୍ཎ⌮ィ⟬࡛ึᮇᵓ㐀ࢆ⏕ᡂࡋࠊຊሙࣃ࣓࣮ࣛࢱ࣮ࢆỴᐃࡋ࡚࠸ࡿࠋࡼࡗ࡚ࠊィ⟬ᡭ㡰࡞࡝ࡣࡍ࡛࡟☜❧ࡋ࡚࠸ࡿࠋࡇࢀࡣ᪤Ꮡࡢィ⟬ᡭἲ࡜ࡣ␗࡞ࡾ᪂ࡋ࠸࢔ࣉ࣮ࣟࢳࡔࡀࠊࡑࡢ࢔࢖ࢹ࢕࢔ࡢጇᙜᛶ
ࡢ⌮ㄽⓗ࡞᳨ウࡣ⏦ㄳ⪅࡟ࡼࡗ࡚῭ࢇ࡛࠾ࡾࠊࢩ࣭ࣜ࢝Ỉ⏺㠃࡛ࡣ⏺㠃ᵓ㐀࡜ SFG ࢫ࣌ࢡࢺࣝࡀᐇ㦂ࢆ෌⌧ࡍࡿࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿࠋ
ձ᭱ึࡢࢱ࣮ࢤࢵࢺࡣ⏦ㄳ⪅ࡀࡇࢀࡲ࡛ྲྀࡾ⤌ࢇ࡛ࡁࡓ࢞ࣛࢫ࣭Ỉ⏺㠃࡜ࡍࡿࠋࡇࡢ⏺㠃ࡣ┒ࢇ࡟◊✲ࡉࢀ࡚࠾ࡾࠊᴟࡵ࡚୙ᆒ୍࡞ᇙࡶࢀࡓ⏺㠃࡜ࡋ࡚▱ࡽࢀࡿࡀࠊࢩࣛࣀ࣮ࣝᇶ࡞࡝ࡢᵓ㐀࡟ࡣᮍࡔ୙᫂ࡢ㒊ศࡀከ࠸ࠋࡑࡇ࡛ࠊᮏ◊✲࡟ࡼࡗ࡚Ỉ⏺㠃ࡢศᏊᵓ㐀ࡢ୙ᆒ୍ᛶࢆ᫂ࡽ࠿࡟ࡋࠊᅛᾮ⏺㠃࡬ࡢᒎ㛤ࡢᇶ♏࡜ࡍࡿࠋղḟ࡟ࠊගゐ፹࡜ࡋ࡚᭷ྡ࡞㓟໬ࢳࢱ࣭ࣥỈ⏺㠃࡟࠾ࡅࡿ⏺㠃ᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࢆゎᯒࡍࡿࠋ⏺㠃࡟ᩄឤ࡞ศගࢫ࣌ࢡࢺࣝࢆゎᯒࡍࡿࡇ࡜࡛⏺㠃ࡢᵓ㐀ࢆࢲ࢖ࣞࢡࢺ࡟ᐇ㦂࡜ẚ㍑ࡋࠊ㉸ぶỈᛶ࡞࡝ࡢศᏊ⛉Ꮫⓗ࡟ᮍ☜ᐃ࡞⏺㠃ࡢᵓ㐀ࢆ᫂ࡽ࠿࡟ࡍࡿࠋ⏺㠃㏆ഐ࡟ࡣࠊᵝࠎ࡞⾲㠃άᛶ✀ࡢᏑᅾࡀ♧၀ࡉࢀ࡚࠸ࡿࡓࡵගບ
㉳๓ᚋࡢ⏺㠃ᵓ㐀࡜ࢲ࢖ࢼ࣑ࢡࢫࢆ᫂ࡽ࠿࡟ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲձࢩ࣭ࣜ࢝Ỉ⏺㠃࡛ࡢ⬺ࣉࣟࢺࣥ໬ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࡢࡓࡵ࡟ࠊcp2k ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪࢆ⏝࠸ࡓ abinitio ศᏊືຊᏛ(MD)ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ㸦ฟ∧ᐇ⦼[4]㸧ࢣ࢖㓟Ỉ⁐ᾮࢆࢱ࣮ࢤࢵࢺ࡜ࡋࠊᣊ᮰ᐦᗘ
ỗ㛵ᩘ⌮ㄽ(CDFT)ࢆ⏝࠸࡚ࠊpKa ࡢ⡆༢࡞ィ⟬ࢫ࣮࣒࢟ࢆᥦ᱌ࡍࡿ࡜࡜ࡶ࡟ࠊືᚄศᕸ㛵ᩘࠊ᣺ືࢫ࣌ࢡࢺ
ࣝࠊ཯ᛂ⤒㊰࡞࡝ࡢᵓ㐀ࡸࢲ࢖ࢼ࣑ࢡࢫࡶゎᯒࡋࡓࠋղcp2k ࣉࣟࢢ࣒ࣛࣃࢵࢣ࣮ࢪ㸦MPI ୪ิ㸧ࢆ⏝࠸࡚㸪࢔ࢼࢱ࣮ࢮᆺ TiO2 ⾲㠃࡟࠾ࡅࡿගゐ፹཯ᛂᶵᵓࡢ◊- 377 -

✲ࢆ⾜ࡗࡓ㸦Ⓨ⾲ᐇ⦼[1]ࠊฟ∧ᐇ⦼[3]㸧ࠋ௒ᅇࡣ㸪࣮࣐࣍ࣝ࢖ࢢ࣮ࣞࢩࣙࣥ᫬ࡢ࢚ࢿࣝࢠ࣮࡜ᵓ㐀࡟╔┠ࡋࡓ㸬ຍ࠼࡚ࠊCuI ࢆ⏝࠸ࡓ Ru ᇶᯈ࡬ࡢ Cu ࡢపᅽ໬ᏛẼ┦ᡂ㛗ἲࢆ◊✲ࡋࡓࠋ
㸦Ⓨ⾲ᐇ⦼[2]ࠊฟ∧ᐇ⦼[1-2]㸧
ࡇࡇ࡛ࡣࠊ྾╔ࠊ࣐࢖ࢢ࣮ࣞࢩࣙࣥࠊ⬺㞳ࡢศᏊᶵᵓ࡟╔┠ࡋࡓࠋࡇࢀࡽࡣࠊLPCVD 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◊✲࡛࠶ࡿࠋ

3◊✲ᡂᯝィ⟬ࡉࢀࡓ⬺ࣉࣟࢺࣥ໬ࡢ཯ᛂ⮬⏤࢚ࢿࣝࢠ࣮ࡣᩘ kcal/mol ࡛ᐇ㦂⤖ᯝ࡜୍⮴ࡋࡓࠋỈ࿴ᵓ㐀ࡢゎᯒ࠿ࡽࠊ⬺ࣉࣟࢺࣥ໬ᚋࠊỈ⣲࢖࢜ࣥ D3O+ࡣ⬺ࣉࣟࢺࣥ໬ࡋࡓࢣ࢖㓟 SiO(OD)3-࡜Ᏻᐃ࡞᥋ゐ࢖࢜ࣥᑐࢆᙧᡂࡏࡎ࡟
཯Ⓨࡋ㞳ࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋィ⟬ࡉࢀࡓ᣺ືࢫ࣌ࢡࢺࣝࡣศගᏛⓗᐃ࡜୍⮴ࡋࠊ཯ᛂ⤒㊰ࡢືⓗゎᯒ࡟ࡼࡾࠊࢣ࢖㓟࡜Ỉࡢ OD ࢫࢺࣞࢵࢳ᣺ືࡢࣉࣟࢺࣥ཯ᛂ࡬ࡢ࢝ࢵࣉࣜࣥࢢࡀࠊ⁐㉁ᡂศ࡜⁐፹ᡂศࡢ୧᪉ࢆ
ྵࡴᆶ┤࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉᗙᶆࡢほⅬ࠿ࡽᐃ㔞໬ࡉࢀࡓࠋ
࢔ࢼࢱ࣮ࢮ㓟໬ࢳࢱࣥࡣ᭷ᶵ໬ྜ≀ࡢศゎ࡟㧗࠸ගゐ፹άᛶࢆ♧ࡋࠊ໬Ꮫࡸ≀⌮Ꮫࡢศ㔝࡛㔜せ࡞ᙺ๭ࢆᯝࡓࡍࠋගゐ፹άᛶࢆ㧗ࡵࡿࡓࡵ࡟ࡣࠊ⾲㠃≉ᛶࢆ㐺ษ࡟ไᚚࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡾࠊศᏊ࡛ࣞ࣋ࣝࡢ࣓࢝
ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊCDFT ἲࡸΰᡂỗ㛵ᩘࢆ⏝࠸ࡓᐦᗘỗ㛵ᩘἲィ⟬࡟ࡼࡾࠊ࢔ࢼࢱ࣮ࢮ㓟໬ࢳࢱࣥ⾲㠃࡟࠾ࡅࡿ࣮࣍ࣝࢺࣛࢵࣉࡢ㠃౫Ꮡᛶࢆ᫂ࡽ࠿࡟ࡋࡓࠋ࣓ࢳࣞࣥࣈ࣮ࣝỈ⁐ᾮ୰࡛ࡢ 365nm ௜㏆࡛ࡢ⣸እ⥺↷ᑕ࡟ࡼࡿගゐ፹άᛶࡣࠊከ㓄ྥ TiO2 ୖ࡛ࡢගゐ፹άᛶ࡟ẚ࡭࡚ 2 ᱆኱ࡁ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋDFT ィ⟬ࡢ⤖ᯝࠊ(112)㠃ࡣỈࡢ྾╔ࢆᏳᐃ໬ࡋࠊග࡟ࡼࡾ⏕ᡂࡋࡓ࣮࣍ࣝࡣ
(101)㠃࡛ࡣ࡞ࡃࠊ(001)㠃࡜(112)㠃ࡢ᪉ࡀỈ㓟໬㠃࡟ࢺࣛࢵࣉ
ࡉࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
㸦ྑᅗ:㸧ࡇࢀࡽࡢᐇ㦂⤖ᯝཬࡧ⌮ㄽⓗ▱ぢ࠿ࡽࠊ(112)㠃ࡣ௚ࡢ㠃࡟ẚ࡭࡚⾲㠃ࡢᵓ㐀⦆࿴ࡀ኱ࡁࡃࠊ྾╔ࡋࡓỈ࡜ࢺࣛࢵࣉࡉࢀࡓṇᏍࡢᏳᐃ໬ࡀ኱ࡁ࠸ࡇ
ᅗ 1 㸬 Molecular mechanism of hole࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

4

migration.

Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

‫[ۻ‬1] ࢔ࢼࢱ࣮ࢮᆺ TiO2 ⾲㠃ࡢ㟁Ꮚ≧ែィ⟬ ࠊ2019 ᖺ 12 ᭶ 20 ᪥ࠊ➨ 30 ᅇ ᪥ᮏ໬Ꮫ఍㛵ᮾᨭ㒊 Ⲉᇛᆅ༊◊✲஺ὶ఍ࠊྜྷᡂၨேࠊᇛሯ㐩ஓ[2] ࣚ࢘໬㖡ࢆ⏝࠸ࡓࣝࢸࢽ࣒࢘ୖ࡬ࡢ㖡ࡢ㑅ᢥ໬ᏛẼ┦ሁ✚ࠊ2019 ᖺ 9 ᭶ 18 ᪥ࠊ➨ 80 ᅇᛂ⏝≀⌮Ꮫ఍⛅ᏘᏛ⾡ㅮ₇఍ࠊᇼෆ೺భࠊᇛሯ㐩ஓࠊᒣෆᬛ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1] T. Joutsuka, S. Yamauchi: Chem. Phys. Lett. 741 (2020) 137108.
[2] T. Nishikawa, K. Horiuchi, T. Joutsuka and S. Yamauchi: submitted.
‫[ۻ‬3] T. Joutsuka, H. Yoshinari, K. Yamamoto and S. Yamauchi: in preparation for submission.
‫[ۻ‬4] T. Joutsuka, K. Ando: in preparation for submission.

- 378 -

࣏ࢫࢺ࣓ࢱࣟࢭࣥゐ፹࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜ཯ᛂ࠾ࡼࡧ㧗ศᏊ㙐⛣ື཯ᛂ࡟㛵ࡍࡿ⌮ㄽⓗ◊✲Theoretical analysis of olefin polymerization reactions and chain
shuttling reactions by post-metallocene catalysts‫ ⃝୕ۑ‬ዉࠎࠊ㕥ᮌ 㞝୍ࠊࢧࣁ ࢯ࣓࢘ࣥࠊ⏣୰ భ୍ࠊᏲᒇ ᏹ୍㸦ྡྂᒇ኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ
(pyridylamido)Hf(IV)ゐ፹㸦Hf ゐ፹࡜ࡍࡿ㸧࡟ࡼࡿ 1-࢜ࢡࢸࣥ㔜ྜ཯ᛂ࡟࠾࠸࡚ B(C6F5)4Ѹࢆ⏝࠸ࡓሙྜࡣMeB(C6F5)3Ѹࢆ⏝࠸ࡓሙྜࡼࡾࡶ㔜ྜ཯ᛂࡢ㐍⾜ࡀ㏿࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࡇ࡜࠿ࡽࠊ㧗άᛶ࡞ゐ፹⣔タィࡢᣦ㔪ࢆᚓࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࠊ࢔ࢽ࢜ࣥ㛫࡛ࡢ཯ᛂ㏿ᗘࡢ㐪࠸ࡢཎᅉ࡟ࡘ࠸࡚ィ⟬໬Ꮫⓗ࡞ゎᯒࢆ⾜ࡗࡓࠋ2◊✲᪉ἲࠊィ⟬᪉ἲ

Gaussian16 ࢆ⏝࠸࡚㑄⛣≧ែࡸ୰㛫యᵓ㐀ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࢆᚓࡓࠋィ⟬ࣞ࣋ࣝࡣࠊM06 (SCRF)/Lanl2dz+f(Hf)ࠊM06(SCRF)/6-31G(d,p) (Hf ௨እࡢඖ⣲) ࢆ⏝࠸ࡓࠋ3◊✲ᡂᯝ
Hf ゐ፹ࡢ㑄⛣≧ែᵓ㐀ࢆぢࡿ࡜ࠊMeB(C6F5)3Ѹࡣ Hf ཎᏊ࡟㓄఩ࡋ࡚ࠊ୙Ᏻ

ᐃ࡞ 6 㓄఩ࡢゐ፹ᵓ㐀ࢆᙧᡂࡍࡿࡢ࡟ᑐࡋࠊB(C6F5)4Ѹࡣ Hf ཎᏊ࡟㓄఩ࡏࡎࠊ ᅗ㸯. ᑐ࢔ࢽ࢜ࣥࡀ(a) B(C F ) Ѹ
6 5 4
Ᏻᐃ࡞ 5 㓄఩ࡢゐ፹ᵓ㐀࡛࠶ࡗࡓ㸦ᅗᅗ㸯㸧ࠋࡼࡗ࡚ࠊB(C6F5)4Ѹࢆ⏝࠸ࡓ㝿ࡢ᪉ ཬࡧ(b) MeB(C F ) Ѹࡢሙྜ࡟࠾ࡅ
6 5 3ࡀάᛶ໬⮬⏤࢚ࢿࣝࢠ࣮ࡣపࡃࠊ㔜ྜ㏿ᗘࡀ᪩࠸࡜࠸࠺஦ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ ࡿ 1-࢜ࢡࢸࣥᤄධ཯ᛂࡢ㑄⛣≧ែᵓ㐀.

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

➨ 22 ᅇ⌮ㄽ໬Ꮫウㄽ఍ࠊ㢟┠㸸͆(pyridylamido)Hf(IV)ゐ፹࡟ࡼࡿȘ-࢜ࣞࣇ࢕ࣥᤄධ཯ᛂ࡟࠾ࡅࡿᑐ࢔
ࢽ࢜ࣥࡢᙺ๭㸸㟁Ꮚⓗຠᯝ࡜ືⓗຠᯝ͇ࠊᙧᘧ㸸࣏ࢫࢱ࣮ࠊ᪥௜㸸5/28

➨ 35 ᅇ໬Ꮫ཯ᛂウㄽ఍ࠊ㢟┠㸹͆(ࣆࣜࢪࣝ࢔࣑ࢻ)Hf(IV) ゐ፹࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜ཯ᛂࡢ඲ཎᏊࢩ࣑
࣮ࣗࣞࢩ͇ࣙࣥ
ࠊᙧᘧ㸸࣏ࢫࢱ࣮ࠊ᪥௜㸹6/5



APATCC2019ࠊ㢟┠㸸͆Full atomistic simulation of ethylene/1-octene copolymerization reaction process by(pyridylamido)Hf(IV) catalyst͇ᙧᘧ㸸࣏ࢫࢱ࣮ࠊ᪥௜㸸10/1᪥ᮏ໬Ꮫ఍➨ 100 ᅇ᫓Ꮨᖺ఍͆(pyridylamido)Hf ゐ፹࡟ࡼࡿ࢜ࣞࣇ࢕ࣥ㔜ྜ཯ᛂ࡟㛵ࡍࡿィ⟬໬Ꮫⓗゎᯒ: ᑐ࢔ࢽ࢜ࣥࡀ཯ᛂ㏿ᗘ࡟ཬࡰࡍᙳ㡪͇ࠊᙧᘧ㸸ཱྀ㢌ࠊ᪥௜㸸3/22

5

ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
z

Nana Misawa, Yuichi Suzuki, Nobuaki Koga, and Masataka Nagaoka, ͆Computational chemical analysis ofolefin polymerization reaction by (pyridylamido)Hf catalyst: The influence of counteranions on reaction rates͇,Journal of Physical Chemistry B 㸦ᢞ✏ணᐃ㸧

- 379 -









Divelopment of synthetic reactions based on theoretical calculations£ç ÖÉĎ¬Põ±uyď, X jĎ¬PÄÑuyď

1 ÎÔÌË]~
Juglocombin AĐB2005

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O

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HO

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Juglocombin BOOhydration

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OH

HO

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OH

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O

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Juglocombin A

Juglomycin CÕVfy¹{OOH

oxidation

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CO2H

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Juglorescein

Figure 1. Juglorescein {ÅlÛô

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B3LYP -M¸Ą¢WÆ#¼wd®&ä§z{²÷eì­-è#3 ÎÔ®
Juglocombin AĐB'! Juglorescein=A;3?H²÷-¨*v½ÀJuglomycin C`xă−`x]

øÝD05FQch')OĀfÅ@<G3?H ÿf+*  Juglocombin A/B -
1C36f-Û JugloresceinÅ+*ÅlÛô n+#X(

Juglocombin Č\l  Juglomycin C ðV 1 -ÿØĉp·K74GGE9HL DBU -srÆ«T iÂ 73%©OĀV 2 -ÕVüË(+* -ê_# (Figure 1a) ĆaÅÀ(+ 2b ²÷')2a  2bªh

+*{h´²-RK'ä# (Figure 2b)% 1 mtsr'*`xă Michael h ùè 3a3bh')++ 4a4b(+`x] Michael

(+#§@<G3?H/>2H 4a4b- 380 -

++ÿØ`x-1C36f* ++ 2a2b -Å#1C36f

C2’  C9 *č[ĂċÕVć}^Ċ (ÊÅ*ä )ÃqÐ

3 µąÌÿfh Ãqí×öL )# čûÒÁ-ÛÇ*  N+%ªhü LăV 4a4b ¾byËz{óo*&ä #|ĆLăV 4a4b  DFT í×-è ,4a4b ¶" 1.4 kcal/mol U²÷Ï+# (B3LYP/6-31G+(d,p) level with the solvent model

density (SMD) for CH2Cl2)Ãqªāh\~ì¦%(*í×ì­-ù%* ,
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MOMO
O

DBU (3.0 equiv.), O2
H

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OTBS

MOMO
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73% (2a:2b = 5.4:1) MOMO

O

H O

O

MOMO

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OMOM

1

H O

O

OMOM

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O
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4a
(0 kcal/mol)

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OTBS

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4b
(+1.4 kcal/mol)

4aFigure 2. OĀfh'* 2 l{h´²4 _¿|á Kamo, S.; Saito, T.; Kusakabe, Y.; Tomoshige, S.; Uchiyama, M.; Tsubaki, K.; Kuramochi, K. “Synthetic andBiological Studies of Juglorubin and Related Naphthoquinones” J. Org. Chem. 2019, 81, 13967-13974

- 381 -

⣽⬊ෆ࣓ࢱ࣎ࣛ࢖ࢺ࡟ࡼࡿ㠀≉␗ⓗ┦஫స⏝ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
Molecular dynamics simulation of the non-specific interaction of
metabolites in cell‫ۑ‬ඃ எ▼㸦๓ᶫᕤ⛉኱Ꮫ㸧1◊✲┠ⓗࠊෆᐜ

⣽⬊ෆࡣࠊ࢔࣑ࣀ㓟ࡸࣜࣥ㓟࡞࡝ࡢ௦ㅰ≀㸦࣓ࢱ࣎ࣛ࢖ࢺ㸧ศᏊ࡛‶ࡕ⁄ࢀ࡚࠸ࡿ㸦ᅗ 1㸧ࠋ࣓ࢱ࣎ࣛ࢖ࢺࡣࠊ
⣽⬊ෆࡢ௦ㅰࢆᢸ࠺ᇶᮏศᏊ࡜ࡋ࡚඲⏕࿨య࡟ᬑ㐢ⓗ࡞ࡶࡢ࡛࠶ࡿࠋ୍᪉ࠊࡇࢀࡽࡢ࣓ࢱ࣎ࣛ࢖ࢺࡸྛ✀࢖࢜ࣥࡀࠕ⥲య࡜ࡋ࡚ࠖ⺮ⓑ㉁ࡢ≀ᛶ࣭ືែ࡟ཬࡰࡍᙳ㡪࡟ࡘ࠸࡚ㄪᰝࡀጞࡲࡗࡓࡢࡣࡈࡃ᭱㏆࡛࠶ࡿࠋ౛࠼
ࡤࠊ⺮ⓑ㉁⁐ᾮࡢ┦ศ㞳ࡸ⇕ኚᛶᐇ㦂࡟ࡼࡗ࡚ ATP ࡀ⺮ⓑ㉁ࡢྍ⁐ᛶࢆቑຍࡉࡏࠊจ㞟ࢆ㜵ࡄࡇ࡜ࡀ᫂ࡽ࠿
࡟࡞ࡾࠊኳ↛ࡢࣁ࢖ࢻࣟࢺ࣮ࣟࣉ㸦ྍ⁐໬๣㸧࡜ࡋ࡚ࡢ ATP ࡀ኱ࡁ࡞ὀ┠ࢆ㞟ࡵ࡚࠸ࡿ[A. Patel et al., Science(2017)]ࠋ
ࡋ࠿ࡋࠊ࣓ࢱ࣎ࣛ࢖ࢺࡀ⺮ⓑ㉁ࡢዴఱ࡞ࡿ㒊ศ࡟స⏝ࡋࠊ⺮ⓑ㉁ࡢ❧యᵓ㐀Ᏻᐃᛶࡸ⺮ⓑ㉁㛫┦஫స⏝ࢆ࡝ࢀ⛬ᨵኚࡋ࡚࠸ࡿࡢ࠿࡟ࡘ࠸࡚ࠊศᏊㄽⓗ࡞ゎ᫂ࡣ༑ศ࡟࡞ࡉࢀ࡚࠸࡞࠸ࠋࡲࡓࠊ⣽⬊ෆࡣ⏕య㧗ศᏊࡀయ✚ࡢ⣙ 3 ๭ࢆ༨ࡵࡿ㠀ᖖ࡟ΰࡳྜࡗࡓศᏊΰ㞧㸦ࢡࣛ࢘ࢹ࢕ࣥࢢ㸧⎔ቃ࡛࠶ࡿ㸦ᅗ 1㸧ࠋከᩘࡢ⏕య㧗ศᏊࡀ㧗⃰ᗘ࡛ඹᏑࡍࡿศᏊΰ㞧ୗࡢ࣓ࢱ࣎ࣛ࢖ࢺࡢືែ࡟ࡘ࠸࡚ࡶ୙᫂࡞Ⅼࡀከ࠸ࠋᮏ◊✲ࡣࠊATP ࢆ୰ᚰ࡜ࡋࡓ⣽⬊ෆ࣓ࢱ࣎ࣛ࢖ࢺࡸ࢖࢜ࣥࡢ㠀≉␗ⓗ┦஫స⏝ࡀ⺮ⓑ㉁ືែ࡟ཬࡰࡍᙳ㡪ࢆࠊ඲ཎᏊࣔࢹࣝࢆ⏝࠸ࡓศᏊືຊᏛ㸦Molecular Dynamics: MD㸧ἲ࡟ࡼࡿ⣽⬊⎔ቃࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ᚤどⓗ࡟ゎ᫂ࡍࡿࠋᅗ 1. ➹⪅ࡽࡢ MD ࢩ࣑࣮ࣗࣞࢩ࡛ࣙࣥᚓࡽࢀࡓ⣽⬊㉁୰ࡢ࣓ࢱ࣎ࣛ࢖ࢺ࣭࢖࢜ࣥࡢศ
ᕸࠋᵝࠎ࡞⺮ⓑ㉁㸦⅊Ⰽ㸧⾲㠃࡟㠀≉␗ⓗ࡟⤖ྜࡋ࡚࠸ࡿ㸦eLife 2016;5:e19274㸧
ࠋ- 382 -

2◊✲᪉ἲࠊィ⟬᪉ἲᮏ◊✲ィ⏬ࡣ୺࡟ ձ⺮ⓑ㉁㸦FUS㸧࡟ᑐࡍࡿ ATP ࡢ㠀≉␗ⓗ┦஫స⏝ ղATP Ỉ⁐ᾮࡢ⁐ゎᛶ ճ⣽⬊㉁ෆࡢ௦ㅰ≀࣭࢖࢜ࣥࡢ┦஫స⏝ゎᯒ࡟ࡘ࠸࡚ィ⟬㈨※ࢆ฼⏝ࡋࡓࠋࡑࢀࡒࢀ᪉ἲࠊィ⟬᪉ἲ࡞࡝ࢆグࡍࠋㄢ㢟 1㸸FUS-LC ࢻ࣓࢖ࣥ࡜ ATP ࡢ┦஫స⏝ᴫせ㸸⺮ⓑ㉁ 1 ศᏊ࡟ᑐࡋࠊATP ࡀ❧యᵓ㐀Ᏻᐃᛶࢆ࡝ࢀ࡯࡝ኚ໬ࡉࡏࡿ࠿ࢆศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩ
ࣙࣥ࡟ࡼࡗ࡚ゎ᫂ࡍࡿࠋ◊✲ᑐ㇟࡜ࡍࡿࢱࣥࣃࢡ㉁ࡣࠊ⣽⬊ෆ࡛ᾮ⁲ࡸจ㞟యࢆᙧᡂࡍࡿࡇ࡜࡛▱ࡽࢀࡿFUS㸦RNA ⤖ྜ⺮ⓑ㉁㸧ࡢࠊจ㞟యᙧᡂ࡟ᙉࡃ㛵ಀࡍࡿ㒊ศ㸦FUS-LC ࢻ࣓࢖ࣥ PDB id: 5w3n㸧ࢆ⏝࠸ࡓࠋATP Ỉ⁐ᾮ୰ࡢ FUS-LC ࢻ࣓࢖ࣥࡢᵓ㐀Ᏻᐃᛶࡸ ATP ࡜ࡢ┦஫స⏝ࢆ඲ཎᏊ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ
࡚ศᏊ࡛ࣞ࣋ࣝㄪᰝࡋࡓࠋୗᅗ 2 ࡟సᡂࡋࡓࣔࢹࣝࢆ♧ࡋࡓࠋィ⟬᪉ἲ㸸RCCS ࡟࡚ࢥࣥࣃ࢖ࣝࡉࢀࡓ AMBER18 ࡢ PMEMD ࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ࠊᖹ⾮໬ࡢᚋࠊ඲ཎ
Ꮚຊሙࢆ⏝࠸ࡓᐃMD ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦ᗘ 300K㸧ࢆ⣙ 500ns ᐇ⾜ࡋࡓࠋFUS-LC ࢻ࣓࢖ࣥࡢຊሙࣃࣛ ࣓ ࣮ ࢱ ࡣ AMBER ࡢ ff14SB ࢆ ౑ ⏝ ࡋ ࠊ ATP ࡟ ࡘ ࠸ ࡚ ࡣ Bryce ࡽ ࡢ ຊ ሙ ࣃ ࣛ ࣓ ࣮ ࢱ㸦http://research.bmh.manchester.ac.uk/bryce/amber㸧ࢆ⏝࠸ࡓࠋỈศᏊࣔࢹࣝࡣ tip3p ࢆ౑⏝ࡋࡓࠋィ⟬ࣀ࣮ࢻࡣ ccca㸦jobtype=gpu㸧ࢆ⏝࠸ࡓࠋ

ᅗ 2 ATP Ỉ⁐ᾮ୰ࡢ FUS-LC ࢻ࣓࢖ࣥࠋFUS-LC ࢻ࣓࢖ࣥ㸦㯤Ⰽ㸧ࡣ 50 ಶࡢ ATP㸦㉥ࠊⓑࠊ㟷ࠊỈⰍ㸧࡟ᅖࡲࢀ࡚࠸ࡿࠋ࿘ᮇቃ⏺⟽ࡢ୍㎶ࡣ⣙ 100X ࡛ࠊ⥲ཎᏊᩘࡣ 121294 ಶ࡜࡞ࡗࡓࠋ

ㄢ㢟 2㸸ATP Ỉ⁐ᾮࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥᴫせ㸸 ATP ศᏊࣔࢹࣝࡢỈ࿴≉ᛶࢆㄪᰝࡍࡿࡓࡵ࡟ ATP Ỉ⁐ᾮࡢ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ 2 ✀㢮ࡢATP ⃰ᗘ(0.33M,0.1M)ࠊ2 ✀㢮ࡢỈศᏊࣔࢹࣝ(tip3p, tip4pew)ࢆ⏝࠸࡚ᐇ⾜ࡋࡓࠋtip3p ࡣ᭱ࡶᗈࡃ⏝࠸ࡽࢀ࡚࠸ࡿỈศᏊࣔࢹ࡛ࣝ㓟⣲ཎᏊ 1 ಶ࡜Ỉ⣲ཎᏊ 2 ಶ࡛ᵓᡂࡉࢀࡿ 3 Ⅼ㟁Ⲵࣔࢹ࡛ࣝ࠶ࡿࠋtip4pew ࡣ 3 ཎᏊ࡟ຍ࠼࡚ࠊ௬᝿ࡢ┦஫స⏝Ⅼࢆ 1 ࡘᣢࡘ 4 Ⅼ㟁Ⲵࣔࢹ࡛ࣝ࠶ࡿࠋྛ ATP ࡟ࡣ࣐ࢢࢿࢩ࣒࢘࢖࢜ࣥ(Mg2+)ࢆ
1 ಶ௜ຍࡋࠊ㐣๫࡞㟁Ⲵࡣࢼࢺ࣒ࣜ࢘࢖࢜ࣥ(Na+)࡛୰࿴ࡋࡓࠋ࿘ᮇቃ⏺ࡢ኱ࡁࡉࡣ 100ύ࡜ࡋࠊATP ࡢಶᩘࡣ 0.33M ࣔࢹ࡛ࣝ 200 ಶࠊ0.1M ࣔࢹ࡛ࣝ 60 ಶ࡜࡞ࡗࡓࠋࡇࢀࡽࡢࣔࢹࣝ࡟ຍ࠼࡚ࠊ0.33M ࣔࢹࣝ࡟ࡘ࠸࡚ࡣࠊATP ࡜ỈศᏊ㛫ࡢࣇ࢓ࣥࢹ࢔࣮࣡ࣝࢫ㸦van der Waals: VDW㸧┦஫స⏝ࡢࣃ࣓࣮ࣛࢱ㸦Ȝ㸧ࢆ 1.1- 383 -

ಸ࡟ᙉࡵࡓࣔࢹࣝ㸦ࡇࡇ࡛ࡣ tip4pew_m ࡜⾲グࡍࡿ㸧࡟ࡘ࠸࡚ࡶู㏵సᡂࡋࡓࠋࡇࢀࡽ 5 ࡘࡢỈ⁐ᾮࣔࢹࣝ࡟ᑐࡋ࡚ࠊࡑࢀࡒࢀ 200ns ࡢᐃ 㸦300K㸧MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋィ⟬ࣉࣟࢢ࣒ࣛࡣࠊRCCS࡟࡚ࢥࣥࣃ࢖ࣝ῭ࡢ AMBER18 ࡢ PMEMD ࣉࣟࢢ࣒ࣛࢆ⏝࠸ࠊィ⟬ࣀ࣮ࢻࡣ ccca㸦jobtype=gpu㸧ࢆ⏝࠸ࡓࠋ3◊✲ᡂᯝㄢ㢟㸯࡟ࡘ࠸࡚ࡣࠊィ⟬⤖ᯝ࡟ၥ㢟ࡀⓎ⏕ࡋ୰᩿ࡋࡓࠋࡇࢀࡣࠊMD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ㐍⾜࡜࡜ࡶ࡟ ATPྠኈࡢ㐣๫࡞จ㞟ࡀⓎ⏕ࡋࠊ኱ࡁ࡞ ATP ከ㔞యࢆᙧᡂࡋ࡚ࡋࡲࡗࡓࡓࡵ࡛࠶ࡿࠋࡑࡢࡓࡵࠊ᪤Ꮡࡢ ATP ຊሙ࡟ࡼࡿỈ⁐ᾮ࡬ࡢ⁐ゎᛶࢆㄪᰝࡍࡿࡓࡵ࡟ࠊู㏵ㄢ㢟㸰ࢆ㐙⾜ࡋࡓࠋㄢ㢟㸰ࡢ◊✲ᡂᯝ㸸MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࠊ࡝ࡢỈ⁐ᾮ⣔ࡶ ATP ྠኈࡀ⤖ྜࡋࠊከ㔞యࢆᙧᡂࡋ࡚࠸ࡓ㸦ᅗ 3㸧ࠋࡇࢀࢆᐃ㔞ⓗ࡟ホ౯ࡍࡿࡓࡵ࡟ࠊATP ྠኈࡢࢥࣥࢱࢡࢺᩘ㸦5ύ௨ෆ࡟࠶ࡿཎᏊ࣌࢔ࡢ⥲ᩘ㸧ࢆゎᯒࡋࡓ㸦ᅗ 4㸧
ࠋ⃰ᗘ 0.1mol ࡛ࡣࠊỈࣔࢹࣝࡢ㐪࠸࡟ࡼࡗ࡚⤖ᯝ࡟኱ࡁ࡞ᕪ␗ࡣぢࡽࢀ࡞࠿ࡗࡓࠋ୍᪉࡛ࠊ⃰ᗘ 0.33mol ࣔࢹ࡛ࣝࡣ tip3p ࣔࢹࣝ࡟ẚ࡭࡚ࠊtip4pew ࣔࢹࣝࡢ࡯࠺ࡀᖖ࡟ࢥࣥࢱࢡࢺᩘࡀᑡ࡞ࡃࠊATP ྠኈࡢจ㞟ࡀᙅࡵࡽࢀ࡚࠸ࡿ஦ࡀ♧ࡉࢀࡓࠋࡇࡢせᅉ࡜ࡋ࡚ࠊATP ࢆྲྀࡾᅖࡴỈ࿴ᒙࡢ㐪࠸࡟╔┠ࡋࡓࠋᅗ 5 ࡣ ATP ࡢࣜࣥ㓟㒊ศࡢ㓟⣲ཎᏊ࿘ᅖࡢỈศᏊỈ⣲ཎᏊࡢືᚄศᕸ㛵ᩘ(radial distribution function: rdf)࡛࠶ࡿࠋᅗ 5 ࡛♧ࡉࢀࡿࡼ࠺࡟ࠊtip4pew ࣔࢹࣝࢆ౑⏝ࡋࡓሙྜࡣࡼࡾ㧗࠸ࣆ࣮ࢡࢆᣢࡕࠊATP ࿘ᅖ࡟ࡼࡾᙉᅛ࡞Ỉ࿴ᒙࢆᙧᡂࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࢀࡀ ATP ྠኈࡢจ㞟ࢆ tip3p ࣔࢹࣝࡼࡾᢚไࡋ࡚࠸ࡿ୍ᅉ࡜⪃࠼ࡽࢀࡿࠋ

ᅗ 3 ATP Ỉ⁐ᾮ㸦0.33mol㸧ࡢึᮇᵓ㐀㸦ᕥ㸧࡜ 200ns ᚋࡢᵓ㐀㸦ྑ㸧౑⏝ࡍࡿỈࣔࢹࣝ࡟ࡼࡗ࡚ከᑡࡢኚ໬ࡣ࠶ࡿࡶࡢࡢࠊ⤖ᯝ࡜ࡋ࡚඲࡚ࡢỈ⁐ᾮࣔࢹࣝ࡟࠾࠸࡚ ATP ࡀከ㔞యࢆᙧᡂࡋ࡚࠾ࡾࠊࡇࢀࡣ⃰ᗘ 0.1M ᮲௳ୗ࡛ࡶ ATP ࡀỈ࡟⁐ゎࡋ࡚࠸࡞࠸ࡇ࡜ࢆព࿡ࡋ࡚࠸ࡿࠋ୍᪉࡛ࠊ
ᐇ㦂ⓗ࡟ࡣ ATP ࡣ 0.1M ⛬ᗘ࡛ࡣᐜ᫆࡟Ỉ࡟⁐ࡅࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗ࡚࠸ࡿࠋࡘࡲࡾࢩ࣑࣮ࣗࣞࢩࣙࣥࡀ
ṇࡋࡃ ATP ࡢỈ⁐ᾮ≧ែࢆ෌⌧ฟ᮶࡚࠸࡞࠸ࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋࡇࢀࢆᨵၿࡍࡿࡓࡵ࡟ࠊࡍ࡛࡟㏙࡭ࡓࡼ࠺࡟ ATP ࡜ỈศᏊ㸦tip4pew㸧㛫ࡢ VDW ┦஫స⏝ࢆ 1.1 ಸ࡟ᙉࡵࡓࣔࢹࣝ㸦tip4pew_m_ATP200㸧࡟ࡘ࠸࡚ࡶู
㏵ MD ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࡀࠊከ㔞యᙧᡂࢆゎᾘࡍࡿࡼ࠺࡞ᨵၿࡣぢࡽࢀ࡞࠿ࡗࡓࠋ
ࡑࡇ࡛ᙧᡂࡉࢀࡓከ㔞యࡢ❧యᵓ㐀ࢆㄪᰝࡋࡓᡤࠊATP ࡢ࢔ࢹࢽࣥ⎔ࡀ㔜࡞ࡾྜ࠺ࡼ࠺࡟⤖ྜࡋ࡚࠸ࡿ஦㸦ࢫࢱࢵ࢟ࣥࢢ㸧ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ㸦ᅗ 6㸧
ࠋATP ྠኈࡀࡇࡢࡼ࠺࡞ᵓ㐀ࢆᙧᡂࡋᚓࡿ஦ࡣᐇ㦂ⓗ࡟ࡶ♧၀ࡉࢀ࡚࠸ࡿ㸦Weaver et.al., Biochemistry, 1988㸧ࡀࠊ᪤Ꮡࡢຊሙࣃ࣓࣮ࣛࢱ࡛ࡣࡇࢀࡀ㐣๫࡟ホ౯ࡉࢀ࡚࠸ࡿྍ⬟ᛶࡀ㧗࠸ࠋ௒ᚋࡣࠊࡇࡢ㒊ศࡢศᏊ㛫┦஫స⏝ࡢ⢭ᐦ໬࡟ྲྀࡾ⤌ࡴ஦ࢆㄢ㢟࡜ࡍࡿࠋ- 384 -

ᅗ 4 ATP 㛫ࢥࣥࢱࢡࢺᩘࡢ᫬㛫ኚ໬ࠋࡑࢀࡒࢀࡢィ⟬ࡣ౑⏝ࡋࡓỈࣔࢹࣝ࡜
ATP ࡢಶᩘࡢ࣌࢔࡛⾲グࡉࢀ࡚࠸ࡿࠋ

ᅗ 5 ATP ࡢ 3 ࣜࣥ㓟ࡢ㓟⣲ཎᏊ࿘ᅖࡢ
ỈศᏊỈ⣲ཎᏊࡢືᚄศᕸ㛵ᩘࠋ

ᅗ 6 ࢔ࢹࢽࣥ⎔ࡀ㔜࡞ࡾྜࡗ࡚ᙧᡂࡉ
ࢀࡓ ATP ከ㔞యࡢࢫࢼࢵࣉࢩࣙࢵࢺࠋ

ᅗ7ࣂࢡࢸࣜ࢔⣽⬊㉁ࡢ඲ཎᏊࣔࢹࣝ

ࡇࢀࡽㄢ㢟ࡢィ⟬ࡢ௚ࠊ⣽⬊ΰ㞧⎔ቃ࡟࠾ࡅࡿ௦ㅰ≀࣭࢖࢜ࣥࡢືែࢆㄪᰝࡍࡿࡓࡵ࡟ࠊࣂࢡࢸࣜ࢔⣽⬊㉁㸦ᅗ 7㸧ࡢᐃMD ィ⟬ࢆ⌮໬Ꮫ◊✲ᡤ⢏Ꮚ⣔⏕≀≀⌮◊✲ࢳ࣮࣒ࡢ㛤Ⓨࡋࡓ㉸୪ิศᏊືຊᏛࢯࣇࢺ

࢙࢘࢔ GENESIS㸦https://www.r-ccs.riken.jp/labs/cbrt/㸧ࢆ⏝࠸࡚ᐇ⾜ࡋࡓࠋࡇࡢ◊✲ィ⏬ࡣࡍ࡛࡟ูࡢィ⟬ࣜࢯ࣮ࢫ࡛኱㒊ศࢆ⤊஢ࡋ࡚࠾ࡾࠊRCCS ୖ࡛ࡢィ⟬ࡣࠊ⿵㊊ィ⟬࠾ࡼࡧ࣋ࣥࢳ࣐࣮ࢡ࡜ࡋ࡚ࡢព࿡ྜ࠸
ࡀᙉ࠸ࡢ࡛⤖ᯝࡢヲ⣽ࡣ๭ឡࡍࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
࡞ࡋࠋ- 385 -

⣽⬊ෆ࡟࠾ࡅࡿ⺮ⓑ㉁ࡢືែゎ᫂ࢆ┠ᣦࡋࡓศᏊືຊᏛィ⟬
Molecular Dynamics Simulations to Elucidate Protein Dynamics in Cells‫ۑ‬ᯇᓅ ኱㍜, George Pantelopulos, Hisham Dokainish, ᳃ ㈗἞, ඵᮌ Ύ, Weitong Ren㸦⌮໬Ꮫ◊✲ᡤ㸧
1

Introduction

In this project, we performed the following three simulations using IMS Molecular Simulator:(1) R-path sampling simulation of Phosphoglycerate kinase (PGK)(2) gREST simulation of Fibroblast Growth Factor Receptor 3 (FGFR3) transmembrane helix dimer(3) gREST simulation of C99 monomer and dimer.
In all simulations, we used GENESIS program package [1].

Among them, in simulations (1) and (2), analyses of the obtained trajectory are ongoing. In simulation (3), the analyses
were almost done, and we are now preparing a paper. Thus, in this report, we first outline the results of simulations (1)and (2), then we describe the results of simulation (3) in particular.

(1) R-path sampling simulation of Phosphoglycerate kinase (PGK)PGK is one of major enzymes in glycolysis, and is used in the first ATP-generating step of the glycolytic pathway.
PGK is present in all the living organisms and its sequence is highly conserved. PGK catalyzes the transfer of thephosphate group from 1,3-biphosphoglycerate (1,3-bPG) to MgADP generating 3-phosphoglycerate (3-PG) and MgATP.
The nucleotide substrates (MgADP or MgATP) binds to the C-terminal domain of the enzyme, and 1,3-bPG or 3PG
binds to the N-terminal domain, respectively. In apo state, the open state of PGK is more stable. The catalytic reaction
requires a large-amplitude conformational change so as to bring the two domains close to each other and so as toprovide the micro-environment for the phosphate group transfer [2]. To study the conformation transition mechanism of
PGK with and without substrate binding, we utilized replica path-sampling method.
From these simulations, we now obtained the results that PGK mainly shows the open conformation both in apo andin holo states. In the apo state, large inter-domain fluctuation was observed. Substrate binding stabilized the closed-like
conformation and suppressed the inter-domain fluctuation compared in the apo state.

(2) gREST simulation of FGFR3 transmembrane helix dimer
FGFR3 is one of the members of the Receptor Tyrosine Kinase, and it is involved in cell growth and migration.
Professor Sato (Kyoto Pharmaceutical Univ.) proposed the transmembrane (TM) helix tilt angle of FGFR3 would beclosely linked with FGFR3 activation through experiments using the constitutively active mutant G380R; in the active
mutant, the tilt angle was smaller than that of WT [3]. As the next stage of their research, to examine the relationshipbetween the tilt angle and activation, they made single mutants of Tyr residues at the N-terminal side of the TM helix
which serve as anchoring residues in membrane. They found the helix tilt angle of one of Tyr mutants was smaller thanthat of WT, and the tilt angle of the mutant was similar to that of G380R mutant.
To obtain structural insights about how the mutation affects the TM tilt angles, we performed gREST simulation for- 386 -

the WT and the Tyr mutants as in our previous study on FGFR3 TM helix dimer [4]. Currently, we obtained results thattilt angles of the Tyr mutants were smaller than that of WT.

(3) gREST simulation of C99 monomer and dimer
The amyloid hypothesis of Alzheimer’s disease (AD) describes the
production of the 42-residue amyloid beta (Aβ) congener, Aβ42, whichforms fibrils both outside cells and within the cell membrane and is
implicated as the disease agent in AD [5]. The 99-residue C-terminus ofamyloid precursor protein (APP), C99, is cleaved by γ-secretase in its
transmembrane domain (TMD) (Figure 1). The dependence of
mechanisms processing APP and the C99 domain by various secretaseson the molecular compositions of membranes has been well studied and isevidenced to be key to controlling the Aβ congeners produced by C99
cleavage by γ-secretase [6].
The C99 N-terminal domain, which contains the Aβ domain, likely has
an unqualified propensity for dimerization and oligomerization in themembrane via forming β-strands much like Aβ. Additionally, theC-terminal domain of C99 is involved in binding several cytoplasmic
proteins when structured as α-helices. Therefore the conformational
ensemble of both the dimer and the monomer are likely not only
complex, possibly featuring multiple metastable conformational states

Figure 1. Cartoon model of C99 monomer.
The secondary structure was predictedbased on solution NMR experiments.

that are sensitive to the local membrane environment [7], but the JMD and TMD conformations may also depend on theextra-membrane domain structure, ultimately changing the kinetics and mechanism of C99 processing and othersignaling interactions.
Recently, the group of Charles Sanders at Vanderbilt University has completely assigned chemical shifts of the fullC99 sequence in a membrane mimicking environment [8]. These experiments produced random coil chemical shifts inresidues outside of the TMD except the last 9 residues of the C-terminus forming helix (C-helix) as reported by NMR
experiments using micelles [9]. In addition, by using large hydrophilic and hydrophobic probes, they identified C99
regions that are water-exposed, membrane-embedded, or neither, implying frequent inter-protein interactions. However,through these experiments, we can’t interpret the underlying conformational states of C99, as the chemical shiftassignments in all regions except for the C-helix were near random coil. Thus, we performed molecular dynamic
simulations to elucidate conformation ensemble describing these experimental results.
In 2018, we published the first computational study of the full-length C99 monomer using an implicit solvent
membrane model to study the effect of membrane thickness on the conformational ensemble of C99 [10]. We found thatas membrane becomes thicker the helical character of the C99 ensemble is enhanced, implying a reduction in propensity
for C99 aggregation via β-strand formation between N- and C-terminal domains and implying an increase in interaction
propensity for other binding partners via structuring α-helices. We continued our work on the full C99 sequence using
more accurate explicit all-atom molecular dynamics simulations of both the C99 monomer, initiated from
conformational states of our past work, and new work on the C99 dimer.

- 387 -

2

Methods
Approximately the first half of these simulations were completed on the K computer and the last half was completed

on the IMS Molecular Simulator. We have utilized generalized Replica Exchange with Solute Tempering (gREST)
method [11]. Our gREST scheme employs 16 replicas and the “solute” temperature ranges from 310 K to 340 K. In
these simulations, we used CHARMM36m for peptide, CHARMM36 for lipid and TIP3P water molecules. To avoid the
TM helix dimer dissociation during the gREST simulation, we scaled lipid-peptide interactions down by the factor of
0.9 [4, 12]. We analyzed the conformations in the 310 K temperature system.

3

Results
Our main result is that the C99 monomer exhibits a truly intrinsically disordered ensemble in the residues outside of

the TMD, showing no metastable thermodynamic states, on the other hand, the C99 dimer exhibits 15 metastableconformational states (Figure 2A). The number of the conformation clusters was determined using the root meansquared difference of distances (dRMSD) between all D-carbons of the residues outside of the TMD.

Figure 2. (A) 6HFRQGDU\ VWUXFWXUH SURSHQVLWLHV REVHUYHG IRU HDFK & LQ WKH & GLPHU ZLWKLQ HDFK RI 
FRQIRUPDWLRQDO FOXVWHUV %  *G'73$ DTXHRXV SUREH  DQG '6$ OLSRSKLOLF SUREH   ± II RI 105 VLJQDO
LQWHQVLWLHVLQGLFDWLQJZKHUH&UHVLGXHVLQWHUDFWZLWKZDWHU SRVLWLYH OLSLGV QHJDWLYH RUQHLWKHU QHDU]HUR  & &ULFN DQJOH RI & GLPHU H[KLELWLQJ PDMRU SRSXODWLRQV DW *O\ ³LQ´ DQG *O\ ³RXW´ FRQIRUPDWLRQV DORQJ ZLWKYLVXDOL]DWLRQRIWKH&GLPHULQFOXVWHUDQGWKHODUJHVWFOXVWHUVEHORQJLQJWR HDFKRIWKHVH70'VWDWHV,QVHWGLVSOD\DQLOOXVWUDWLRQRIWKHWZR&ULFNDQJOHVRIWKH&KRPRGLPHU

7KHVH FRPSOH[ HQVHPEOHV RI FRQIRUPDWLRQV VXFK DV IRU WKH & GLPHU IRU ZKLFK VHFRQGDU\ VWUXFWXUHV IRU HDFKFOXVWHU DUH DVVLJQHG LQ )LJXUH $  DUH ZKDW DSSHDU WR RWKHUZLVH EH UDQGRP FRLO LQ 105 FKHPLFDO VKLIWV DQG LV DOVRUHVSRQVLEOHIRUPDQLIHVWLQJUHJLRQVZKHUHUHVLGXHVDSSHDUWREHQHLWKHUOLSLGHPEHGGHGRUZDWHUH[SRVHG )LJXUH% LQ

- 388 -

WKHPRQRPHULFDQGGLPHULFVWDWHVRI&GXHWRLQWUDDQGLQWHUSURWHLQLQWHUDFWLRQV ERWKWKHPRQRPHUDQGGLPHUDUH
SUHVHQW LQ WKH FRQFHQWUDWLRQV RI & XVHG LQ WKHVH H[SHULPHQWV >@  2XU VLPXODWLRQV RI & PRQRPHU DSSHDU WR
EHVWUHSUHVHQWWKHLUPHDVXUHVRIVLJQDOGDPSLQJVROYHQWH[SRVHGOLSLGHPEHGGHGSUREHV )LJXUH% 
The last key result observed in the dimer are the few different dimer interfaces in the TMD, which we define using
Crick angles of the TM helix dimer, defining the director vector between the two helices via the Gly33, the central
residue of the most frequently observed C99-C99 dimerization interface along a GxxxGxxxG motif in the sequence(Figure 2C). Each of these TMD conformational states correspond directly with extramembrane conformational states.
This leads to a key point: the C99 dimer motif depends directly on the C99 extra-membrane residues even though theseresidues appear to be intrinsically disordered via time-averaged experimental measurements.

4

Poster Presentation(listed only presentation relating to this project in FY2019)(1) Daisuke Matsuoka, Yuji Sugita “Dimer Conformation Sampling of transmembrane peptide dimer using MD

Simulation” The 5th International Conference on Molecular Simulation, Jeju, Korea, Nov. 2019.
‫(ۻ‬2) George A. Pantelopulos, James Hutchinson, Daisuke Matsuoka, Charles Sanders, Yuji Sugita, John E. Straub,“Exploring APP-C99 complexes in lipid bilayers and their role in Alzheimer's disease” ACS Spring 2020 National
Meeting & Expo, Philadelphia, USA, Apr. 2020

5

Publication(listed only papers relating to this project in FY2019)(3) D. Matsuoka, M. Kamiya, T. Sato, Y. Sugita, “Role of the N-Terminal Transmembrane Helix Contacts in the

Activation of FGFR3” J. Comput. Chem., 41, 561 (2020)
In addition, we are currently drafting the work about C99 for submission to peer review including additional
experiments from the Sanders group supporting us a co-authors in our work.

References[1] J. Jung et al, Wiley Interdiscip. Rev. Comput. Mol. Sci., 5, 310 (2015); C. Kobayashi, J et al, J. Comput. Chem.,
38, 2193 (2017)[2] M. W. Bowler, FEBS Letters 587 13 (2013)[3] H. Tamagaki et al, Biochemistry, 53, 5000 (2014)[4] D. Matsuoka et al, J. Comput. Chem., 41, 561 (2020)[5] &5HLW]Int. J. Alzheimers. Dis.2012  >@(:LQNOHUHWDOJ. Biol. Chem287  >@<6RQJ.)0LWWHQGRUI=/X&56DQGHUVJ. Am. Chem. Soc.,136  >@-+XWFKLVRQHWDOBiophys. J.,118D  >@$-%HHOHWDOBiochemistry47  >@*$3DQWHORSXORVHWDOBiochim. Biophys. Acta - Biomembr.1860  >@0.DPL\D<6XJLWDJ. Chem. Phys.149  >@-'RPDĆVNL0636DQVRP3-6WDQVIHOG5%%HVWJ. Chem. Theory Comput.14  - 389 -

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Membranes" Environ. Sci. Technol. 53, 6255 (2019).
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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኱㝔⸆㸧

1◊✲┠ⓗࠊෆᐜ
ᮏ◊✲ࡣ௨ୗࡢ஧ࡘࡢࣉࣟࢪ࢙ࢡࢺ࠿ࡽᡂࡿࠋ

(1) ᡃࠎࡣ᭱㏆ࠊࣛࢭ࣑యࡢࣉࣟࣃࣝࢠࣝ࢔ࣝࢥ࣮ࣝ 1 ࢆࠊ㧗ගᏛ⣧ᗘࡢ࢚ࢫࢸࣝ 2 ࡟㧗཰⋡࡛ኚ᥮ࡍࡿືⓗ㏿ᗘㄽⓗගᏛศ๭ (DKR) ἲࢆ㛤Ⓨࡋࡓ (Org. Lett., 2019, 21, 2978−2982)ࠋࡇࡢᡭἲࡣࠊࣛࢭ࣑య 1 ࡢࣜࣃ࣮ࢮゐ፹㏿ᗘㄽⓗගᏛศ๭ (KR) ࡜ࠊ࢜࢟ࢯࣂࢼࢪ࣒࢘ゐ፹ ࡟ࡼࡿ 1 ࡢࣛࢭ࣑໬ࡀྠ᫬㐍⾜ࡍࡿࡇ࡜࡛㐩ᡂࡉࢀࡓࠋࡓࡔࡋࠊୖグࣛࢭ࣑໬཯ᛂ࡛ࡣࠊ1 ࡢỈ㓟ᇶࡢ 1,3 ㌿఩(Meyer-Schuster ㌿఩) ࡟ࡼࡗ࡚࢚ࢼ࣮ࣝ 3 ࡀ㠀ྍ㏫ⓗ࡟๪⏕ࡋࠊ2 ࡢ཰⋡ࢆపୗࡉࡏࡿࡇ࡜ࡀၥ㢟࡜࡞ࡗࡓࠋ3 ࡣࠊࣂࢼࢪࣝ㓟࢚ࢫࢸࣝ B ࡢ[3,3]-ࢩࢢ࣐ࢺࣟࣆ࣮㌿఩ࡶࡋࡃࡣࠊࣛࢭ࣑໬㏵୰࡟⏕ࡌࡿࣉࣟࣃࣝࢠࣝ࢝ࢳ࢜ࣥ C ࡢ࢔ࢭࢳࣞࣥᮎ➃Ⅳ⣲࡟㓟⣲ࡀ෌⤖ྜࡍࡿࡇ࡜࡛⏕ᡂࡍࡿ࡜⪃࠼ࡽࢀࡿ (ᅗ 1)ࠋྛ✀ࡢ⁐፹୰࡛ࠊࣛࢭ࣑໬࡜ 3 ࡢ⏕ᡂࡢ⤒᫬ኚ໬ࢆㄪ࡭ࡓ⤖ᯝࠊࡇࢀࡽࡢ཯ᛂ㏿ᗘࡣ⁐፹࡟ࡼࡗ࡚኱ࡁࡃ␗࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡑࡇ࡛ࠊィ⟬⛉Ꮫⓗᡭἲ࡛ࠊࣛࢭ࣑໬୪ࡧ
࡟๪཯ᛂࡢᶵᵓ࡜⁐፹ຠᯝࡀゎ᫂ࡋࠊ3 ࡢ⏕ᡂࢆᢚ࠼ࡿ᪉⟇ࢆぢฟࡍࡇ࡜ࡀᮏ◊✲ࡢ┠ⓗ࡛࠶ࡿࠋᅗ 1. ࣉࣟࣃࣝࢠࣝ࢔ࣝࢥ࣮ࣝ 1 ࡢࣛࢭ࣑໬࣭␗ᛶ໬ཬࡧ DKR(2) ᮏ◊✲ࡢ௦⾲⪅࡛࠶ࡿ㉥஭ࡣ㸰㸮వᖺ࡟ࢃࡓࡾࠊBurkholderia cepacia lipase ࡸ Candida antarctica lipase Bࢆ➹㢌࡜ࡍࡿᵝࠎ࡞ࣜࣃ࣮ࢮࢆ⏝࠸ࠊ᭷ᶵ⁐፹୰ࠊࣛࢭ࣑య࢔ࣝࢥ࣮ࣝࡢ㏿ᗘㄽⓗගᏛศ๭ࠊ୙ᩧ㠀ᑐ⛠໬ࠊືⓗ㏿ᗘㄽⓗගᏛศ๭ࢆ⾜ࡗ࡚ࡁࡓࠋࡇࡢ㛫ࠊྠࡌࣜࣃ࣮ࢮࢆ⏝࠸࡚ࡶࠊᇶ㉁ࡢ⨨᥮ᇶࡀᑡࡋኚࢃࡿࡔࡅ࡛
཯ᛂᛶ࡜࢚ࢼࣥࢳ࢜㑅ᢥᛶࡀᩄឤ࡟ኚ໬ࡍࡿࡇ࡜ࢆᐇឤࡋࡓࠋࡇࢀࡽࡢ wet ᐇ㦂࡟ࡼࡗ࡚⵳✚ࡋࡓࣜࣃ࣮ࢮ
ࡢ཯ᛂᛶ࡜࢚ࢼࣥࢳ࢜㑅ᢥᛶࡢ⤖ᯝ࡟㛵ࡋࠊィ⟬⛉Ꮫⓗᡭἲ࡛ࠊศᏊᵓ㐀࡛ࣞ࣋ࣝࡢᶵᵓゎ᫂࡜ࠊ཯ᛂ⤖ᯝ࡟ᙳ㡪ࢆཬࡰࡍ✀ࠎࡢᅉᏊࢆ✲᫂ࡍࡿࡇ࡜ࡀᮏ◊✲ࡢ┠ⓗ࡛࠶ࡿࠋ- 392 -

2◊✲᪉ἲࠊィ⟬᪉ἲ(1) Gaussian09 ࡜ GRRM14 ࢆ⏝࠸࡚ࠊᅗ 1 ࡢࡑࢀࡒࢀࡢ཯ᛂ࡟ࡘ࠸࡚ᵓ㐀᭱㐺໬ࠊIRC ィ⟬ࠊ᣺ືゎᯒィ⟬ࢆ⾜࠸ࠊࣉࣟࣃࣝࢠࣝ࢔ࣝࢥ࣮ࣝࡢࣛࢭ࣑໬ཬࡧ␗ᛶ໬཯ᛂࡢྛࠎࡢࢫࢸࢵࣉ࡟࠾ࡅࡿ㑄⛣≧ែ࡜ࠊάᛶ໬
࢚ࢿࣝࢠ࣮ࢆồࡵࡓࠋ(2) ࡇࢀࡲ࡛ࡢ wet ᐇ㦂⤖ᯝࡢ࠺ࡕࡢ௦⾲ⓗ࡞཯ᛂ࡟ࡘ࠸࡚ࠊࣜࣃ࣮ࢮ࡜ᇶ㉁ࡢྛ㙾ീ␗ᛶయ࡜ࡢࢻࢵ࢟ࣥࢢ
ࢫࢱࢹ࢕࣮ࠊ཯ᛂ㑄⛣≧ែゎᯒࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋ≉࡟ࠊࣜࣃ࣮ࢮࡢ࡝ࡢ࢔࣑ࣀ㓟ṧᇶࡀ཯ᛂᛶ࡜࢚ࢼࣥࢳ࢜㑅ᢥᛶࡢⓎ⌧࡟኱ࡁࡃᐤ୚ࡋ࡚࠸ࡿࡢ࠿ࢆ≉ᐃࡍࡿࡓࡵ࡟ࠊGaussian09 ࢆ⏝࠸ࡓ㓝⣲㸫ᇶ㉁」ྜయࡢᵓ㐀᭱㐺໬ࠊIRC ィ⟬ࠊ᣺ືゎᯒࢆ⾜ࡗࡓࠋ

3

◊✲ᡂᯝ

(1) ๓㡯࡛♧ࡋࡓィ⟬᪉ἲ࡟ࡼࡾࠊୖᅗࡢ໬ྜ≀ B ⇆ D 㛫ࡢ[3,3]-ࢩࢢ࣐ࢺࣟࣆ࣮㌿఩ࡢ㑄⛣≧ែࢆྠᐃࡋࠊ
ࡑࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡲࡓࠊ໬ྜ≀ B ࡢศᏊෆ SN2 ཯ᛂࢆ௓ࡋࡓࣛࢭ࣑໬ࡢ㑄⛣≧ែࢆྠᐃࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ⌧ᅾࠊࣛࢭ࣑໬ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆồࡵࡿࡓࡵ࡟ㅖࠎࡢィ⟬ࢆᐇ⾜୰࡛࠶ࡿࠋ௒ᚋࡣࠊࡇࡢィ⟬ࢆ⤊஢ࡉࡏࠊPCM ࣔࢹࣝࢆ⏝࠸ࡓ⁐፹୰࡛ࡢάᛶ໬࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࠊᮏ◊✲ࡢ୺㢟࡛࠶ࡿ⁐፹ຠᯝ࡟ࡘ࠸࡚ゎ᫂ࢆ⾜ࡗ࡚࠸ࡃணᐃ࡛࠶ࡿࠋ
(2) ⌧ᅾࠊ㑄⛣≧ែࢆྠᐃࡍࡿࡓࡵ࡟ࠊ✀ࠎࡢィ⟬ᡭἲࡸࣃ࣓࣮ࣛࢱࢆ⏝࠸࡚◊✲ࢆ⥆⾜ࡋ࡚࠸ࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

(1)‫ ۻ‬᪥ᮏ⸆Ꮫ఍➨ 140 ᖺ఍㸦ி㒔㸧, 2020 ᖺ 3 ᭶ 25-28 ᪥㸦COVID-19 ࡟ࡼࡾ⣬ୖ㛤ദ࡜࡞ࡗࡓ㸧ගᏛάᛶࣉࣟࣃࢠࣝ࢔ࣝࢥ࣮ࣝࡢࣛࢭ࣑໬཯ᛂ࡟ཬࡰࡍ⁐፹ຠᯝࡢィ⟬⛉ᏛⓗゎᯒComputational Study of Solvent Effects on Racemization of Optically Pure Propargylࠐ∾㔝㞞⩏ࠊ㥖ᕝ᫴㍜ࠊ஭ᕝ㈗モࠊ㉥஭࿘ྖ(2) ⌧᫬Ⅼ࡛ࡣⓎ⾲ணᐃࡣ࡞࠸ࡀࠊ㸯ᖺ௨ෆ࡟Ⓨ⾲ࢆ⾜࠼ࡿࡼ࠺࡟㗦ពດຊࡋ࡚࠸ࡿࠋ

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

(1) ᮏ◊✲ࢸ࣮࣐࡟㛵ࡋ࡚ࠊᖺෆ࡟ㄽᩥᢞ✏ࡍࡿணᐃ࡛࠶ࡿࠋ
(2) ⌧᫬Ⅼ࡛ࡣⓎ⾲ணᐃࡣ࡞࠸ࡀࠊ㸯ᖺ௨ෆ࡟Ⓨ⾲ࢆ⾜࠼ࡿࡼ࠺࡟㗦ពດຊࡋ࡚࠸ࡿࠋ

- 393 -

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 ෽㸦ᮾ໭኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉໬Ꮫᑓᨷ㸧1◊✲┠ⓗࠊෆᐜ
2019 ᖺ 9 ᭶ࡼࡾ⮬↛⛉Ꮫ◊✲ᶵᵓᒸᓮඹ㏻◊✲᪋タィ⟬໬Ꮫ◊✲ࢭࣥࢱ࣮ࡢィ⟬ᶵࢆ฼⏝ࡉࡏ࡚࠸ࡓࡔࡁ

ࡣࡌࡵࡓࠋࡇࢀࡲ࡛ࠊᡃࠎࡢ◊✲┠ᶆࡢ୍ࡘ࡛࠶ࡿศᏊ㛫┦஫స⏝ࡸ໬Ꮫ཯ᛂ࡟࠾ࡅࡿ⁐፹࿴ࡢຠᯝࡢᚤどⓗ⌮ゎ࡟ྥࡅ࡚ࠊẼ┦ࢡࣛࢫࢱ࣮ࢆᑐ㇟࡜ࡋ࡚࣮ࣞࢨ࣮ศග࡜㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ◊✲ࢆ⾜ࡗ࡚ࡁࡓࠋẼ┦ࢡࣛࢫࢱ࣮ࡣࠊศᏊ㛫┦஫స⏝◊✲࡟࠾࠸࡚จ㞟⣔ࢆ⡆༢໬ࡋࡓ⌮᝿࡞ࣔࢹ࡛ࣝ࠶ࡿࠋࢡࣛࢫࢱ࣮ࡢ࢖࢜ࣥ
໬ㄏ㉳཯ᛂࡢ⌮ゎࡣࠊ㉁㔞ศᯒࡸᨺᑕ໬Ꮫศ㔝࡛㉳ࡇࡿ࢖࢜ࣥ໬㐣⛬࡟࠾ࡅࡿ␗ᛶ໬ࡸゎ㞳ࡢᚤどⓗ⌮ゎ࡟ࡘ࡞ࡀࡿࠋࡲࡓࡑࢀࡽࡣ࢖࢜ࣥ-ศᏊ཯ᛂࡢ༙⾪✺ࣔࢹࣝ࡜ࡳ࡞ࡍࡇ࡜ࡀ࡛ࡁࡿࠋ2019 ᖺ 9 ᭶௨㝆ࡢ༙ᖺ㛫ࠊ✀ࠎࡢẼ┦ศᏊࢡࣛࢫࢱ࣮ࡢศᏊᵓ㐀ゎᯒ࠾ࡼࡧ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬࡜ゎ㞳཯ᛂ࡟ࡘ࠸࡚ࠊ࣮ࣞࢨ࣮ศග◊✲ࢆ⾜࠺࡜࡜ࡶ࡟ࠊ⮬↛⛉Ꮫ◊✲ᶵᵓᒸᓮඹ㏻◊✲᪋タィ⟬ᶵࢆ฼⏝ࡋ࡚㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃࢡࣛࢫࢱ࣮
ࡢᵓ㐀᭱㐺໬ィ⟬ࠊㄪ࿴࠾ࡼࡧ㠀ㄪ࿴᣺ືィ⟬࡜ global reaction route mapping (GRRM)ἲ࡟ࡼࡿ཯ᛂ⤒㊰᥈⣴ィ⟬ࢆ⾜ࡗࡓࠋ ࡑࢀࡽ࡟ࡼࡾࠊ࣒࣍ࣝ࢔࣑ࢻࡢỈ࿴ࢡࣛࢫࢱ࣮ࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂࠊMcLafferty ㌿఩ࡢศගᏛⓗゎᯒࢆ┠ᶆ࡜ࡋࡓ 2-࣌ࣥࢱࣀࣥࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬࠾ࡼࡧゎ㞳཯ᛂࠊ࣌ࣥࢱࣥࢆྵࡴ࢔ࣝ࢝ࣥࡢ஧㔞యṇ࢖࢜ࣥࡢᵓ㐀࠾ࡼࡧศᏊ㛫┦஫స⏝࡟ࡘ࠸࡚◊✲ࢆ⾜ࡗ࡚ࡁࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
Gaussian 16 ࣉࣟࢢ࣒ࣛࢆ฼⏝ࡋ࡚ࠊPBE1PBE/6-31+G*ࠊ6-311++G(3df, 3pd), ZB97X-D/6-311++G(3df, 3pd)ࣞ࣋ࣝࡢ DFT ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬ࠊㄪ࿴࠾ࡼࡧ㠀ㄪ࿴᣺ືィ⟬ࠊNatural Bond Orbital (NBO)ィ⟬ࠊIntrinsic
Reaction Coordinate (IRC) ィ⟬ࢆ⾜ࡗࡓࠋࡲࡓ GRRM ἲ[1]ࢆ⏝࠸࡚ࠊ࢖࢜ࣥ໬ㄏ㉳཯ᛂࡢ཯ᛂ⤒㊰᥈⣴ࡸࢡࣛࢫࢱ࣮ࡢᏳᐃᵓ㐀ࡢ᥈⣴ࢆ⾜ࡗࡓࠋ࢖࢜ࣥ໬ㄏ㉳཯ᛂࡢ཯ᛂ⤒㊰᥈⣴࡟࠾࠸࡚ࠊࡲࡎᆶ┤࢖࢜ࣥ໬ᵓ㐀࡟ࡘ࠸࡚ IRC ィ⟬ࢆ⾜ࡗࡓࠋIRC ィ⟬࡛ᚓࡽࢀࡓṇ࢖࢜ࣥࡢᏳᐃᵓ㐀ࢆ㉳Ⅼ࡜ࡋ࡚ GRRM ἲ࡟ࡼࡿ཯ᛂ⤒㊰᥈⣴ࢆ⾜ࡗࡓࠋ
୰ᛶ࠾ࡼࡧṇ࢖࢜ࣥࡢศᏊࠊࢡࣛࢫࢱ࣮ࡢ㉥እࢫ࣌ࢡࢺࣝࡣࠊ118 nm ࡢ┿✵⣸እ(VUV)ග࡟ࡼࡿග࢖࢜ࣥ
໬᳨ฟ㉥እゎ㞳ศගἲ࡟ࡼࡾほࡋࡓࠋࡇࡢศගἲ࡛ࡣࠊVUV ග࢖࢜ࣥ໬࡟ࡼࡿ࢖࢜ࣥಙྕᙉᗘࢆ㉁㔞ศᯒィ࡟ࡼࡾࢧ࢖ࢬ㑅ูࡋ࡚ࣔࢽࢱ࣮ࡍࡿࠋ୰ᛶࡢ㉥እศගࡢሙྜࠊ㉥እගࢆ VUV ග࢖࢜ࣥ໬ࡼࡾ᫬㛫ⓗ࡟ඛ࡟↷ᑕࡍࡿࠋṇ࢖࢜ࣥࡢ㉥እศග࡟࠾࠸࡚ࡣࠊVUV ග࢖࢜ࣥ໬ࡼࡾ᫬㛫ⓗ࡟㐜ᘏࡉࡏ࡚㉥እගࢆ↷ᑕࡍࡿࠋ㉥እ྾཰࡟ࡼࡗ࡚ㄏ㉳ࡉࢀࡿ᣺ື๓ᮇゎ㞳࡟ࡼࡿศᕸᩘࡢኚ໬ࢆࠊࣔࢽࢱ࣮ࡍࡿ࢖࢜ࣥಙྕᙉᗘࡢኚ໬࡜ࡋ࡚
ほࡍࡿࡇ࡜࡟ࡼࡾࠊࢧ࢖ࢬ㑅ู㉥እࢫ࣌ࢡࢺࣝࢆ

ᐃࡍࡿࠋ- 394 -

㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ᣺ືィ⟬⤖ᯝ࡜ࠊᐇࡢ㉥እࢫ࣌ࢡࢺࣝࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊ୰ᛶ࠾ࡼࡧṇ࢖࢜ࣥࡢࢡࣛࢫࢱ࣮ࡢᗄఱᵓ㐀ࢆỴᐃࡋࡓࠋ

3

◊✲ᡂᯝ

1) ࣒࣍ࣝ࢔࣑ࢻࡢỈ࿴ࢡࣛࢫࢱ࣮ࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂࡢ࣮ࣞࢨ࣮ศග࠾ࡼࡧ⌮ㄽⓗ◊✲࣒࣍ࣝ࢔࣑ࢻࡣศᏊෆ࡟࢔࣑ࢻ⤖ྜࢆᣢࡘ᭱ࡶ⡆༢࡞ศᏊ࡛࠶ࡾࠊࡑࡢ࢖࢜ࣥ㐣⛬ࡣ⏕యศᏊࡢ࢖࢜ࣥ
໬㐣⛬ࡢࣔࢹࣝ࡜⪃࠼ࡽࢀࡿࠋ≉࡟࣒࣍ࣝ࢔࣑ࢻ(FA)ࡢỈ࿴ࢡࣛࢫࢱ࣮ࡢ࢖࢜ࣥ໬㐣⛬ࡢ⌮ゎࡣࠊMALDIࠊ࢚ࣞࢡࢺࣟࢫࣉ࣮ࣞἲ࡟࠾ࡅࡿ⏕యศᏊࡢ࢖࢜ࣥࡸࣉࣟࢺࣥ௜ຍయࡢ⏕ᡂ㐣⛬ࡸࠊᨺᑕ໬Ꮫ࡟࠾ࡅࡿࣛࢪ࢝
ࣝṇ࢖࢜ࣥ⏕ᡂᚋࡢࢲ࢖ࢼ࣑ࢡࢫࡢ⌮ゎ࡟ྥࡅࡓ㔜せ࡞᝟ሗࢆ୚࠼ࡿ࡜ᮇᚅࡉࢀࡿࠋᡃࠎࡣࠊࡇࢀࡲ࡛࣍ࣝ
࣒࢔࣑ࢻࡢ୍Ỉ࿴ࢡࣛࢫࢱ࣮(FA-H2O)ࡢග࢖࢜ࣥ໬࡟࠾࠸࡚ࠊ࣒࣍ࣝ࢔࣑ࢻṇ࢖࢜ࣥࡀࣉࣟࢺࣥ⛣ື࡟ࡼࡗ࡚␗ᛶ໬ࡍࡿ㝿࡟ࠊỈศᏊࡀ≉␗ⓗ࡞ゐ፹స⏝ࢆࡍࡿࡇ࡜ࢆぢฟࡋ࡚ࡁࡓࠋ[2] ᅗ 1 ࡟ࠊFA-H2O ࡢ࢖࢜ࣥ໬
ㄏ㉳␗ᛶ໬཯ᛂ๓ᚋࡢ୰ᛶ(๓㥑య)࠾ࡼࡧṇ࢖࢜ࣥ(⏕ᡂ≀)ࡢᵓ㐀ࢆ♧ࡍࠋFA-H2O ࡣ࢖࢜ࣥ໬ᚋࠊ࣒࣍ࣝ࢔࣑ࢻࡢ CH ࡢࣉࣟࢺࣥࡀ㓟⣲ཎᏊ࡟⛣ືࡋ࡚࢚ࣀ࣮ࣝ໬ࡋࠊỈศᏊ࡜ࡑࡢࣉࣟࢺࣥࢆ
ඹ᭷ࡋࡓᵓ㐀࡬࡜␗ᛶ໬ࡍࡿࠋࡇࡢ␗ᛶ໬཯ᛂ㐣⛬࡟࠾࠸࡚ࠊỈ
1 ศᏊࡀࠊCH ࠿ࡽࣉࣟࢺࣥࢆᘬࡁᢤ࠸࡚㓟⣲ཎᏊ࡬㍺㏦ࡍࡿ
catch & release ᆺࡢゐ፹స⏝ࢆࡍࡿࠋࡇࡢࡼ࠺࡞࣒࣍ࣝ࢔࣑ࢻࡢ

ᅗ 1 FA-H2O ࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂ࡟࠾࠸࡚ࠊỈศᏊᩘࡢቑຍ࡟ࡘࢀ࡚ࠊ௚
ࡢゐ፹ᶵᵓࡢⓎ⌧࡞࡝ỈศᏊࡢᙺ๭ࡀ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿ࠿⯆࿡ࡀᣢࡓࢀࡿࠋ
FA ࡢ Ỉ ࿴ ࢡ ࣛ ࢫ ࢱ ࣮ ࡢ ග ࢖ ࢜ ࣥ ໬ ㄏ ㉳ ␗ ᛶ ໬ ཯ ᛂ࡟ ࠾ ࡅ ࡿ ⁐ ፹ ᩘ ౫ Ꮡ ᛶ ࢆ ㄪ ࡭ ࡿ ࡓ ࡵ ࡟ ࠊFA+-(H2O)n, n=2,
3 ࡢ㉥እゎ㞳ศග࠾ࡼࡧᵓ㐀᭱㐺໬ࠊᇶ‽᣺ືィ⟬ࠊ࢖࢜ࣥ໬
ㄏ㉳␗ᛶ໬཯ᛂࡢ཯ᛂ⤒㊰᥈⣴ࢆ⾜ࡗࡓࠋᅗ 2(a)࡟ࠊ୰ᛶࡢ FA-(H2O)2 ࡢᵓ㐀ࢆ♧ࡍࠋFA-(H2O)2 ࡢᵓ㐀ࡣࠊ㉥እศග࡟ࡼࡾᅗࡢࡼ࠺࡞ cyclic ᆺࡢỈ⣲⤖ྜᵓ㐀ࢆᙧᡂࡍࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ[3]

ᅗ 2

FA-(H2O)2 ࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂ[FA-(H2O)2]+ࡢ(a)㉥እࢫ࣌ࢡ

ࢺࣝ࡜ZB97X-D/6-311++G(3df, 3pd)ࣞ࣋ࣝࡢ㔞Ꮚ໬Ꮫィ⟬࡛ᚓࡽࢀࡓ᭱Ᏻᐃᵓ㐀࡟ࡘ࠸࡚ࡢᇶ‽᣺ືィ⟬ࡢ⤖ᯝࢆ♧ࡍࠋᐇࡢ ㉥እ ࢫ ࣌ ࢡࢺ ࣝ ࡜᣺ ື ィ ⟬ࡢ ⤖ ᯝ ࡢẚ ㍑ ࡟ࡼ ࡾ ࠊ[FA-(H2O)2]+ࡀᅗ୰࡟♧ࡉࢀࡿ࢚ࣀ࣮ࣝ໬ࡋࡓ࣒࣍ࣝ࢔࣑ࢻṇ࢖࢜ࣥ࡜Ỉ஧㔞య㛫࡛ࠊ࣒࣍ࣝ࢔࣑ࢻṇ࢖࢜ࣥࡢࣉࣟࢺࣥࢆ
ඹ᭷ࡋࡓ࢚ࣀ࣮ࣝᆺࡢᵓ㐀ࢆᙧᡂࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡼࡗ
࡚ᅗ 2 ࡟♧ࡉࢀࡿࡼ࠺࡟ࠊFA-(H2O)2 ࡣග࢖࢜ࣥ໬࡟࠾࠸࡚ࠊ
FA-H2O ࡜ྠᵝ࡟ CH ⤖ྜࡢࣉࣟࢺࣥࡀ㓟⣲ཎᏊ࡟⛣ືࡍࡿ࢚ࣀ࣮ࣝ໬ࡀ㉳ࡇࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ

ᅗ 3 [FA-(H2O)2]+ ࡢᐇ໬཯ᛂࡢᶵᵓࢆ⌮ゎࡍࡿࡓࡵ࡟ࠊGRRM ἲ࡟ࡼࡾࠊᆶ┤࢖࢜ࢺࣝ࡜ࠊ[FA-(H2O)2]+ ࡢ᭱Ᏻᐃᵓ㐀࡜ࡑࣥ໬ᵓ㐀࠿ࡽࡢ␗ᛶ໬཯ᛂࡢ⤒㊰᥈⣴ࢆ⾜ࡗࡓࠋࢀ࡟ࡘ࠸࡚ࡢ᣺ືィ⟬ࡢ⤖ᯝ

- 395 -

ࡢ㉥እࢫ࣌ࢡ ᅗ 4 ࡟ FA-(H2O)2 ࡢග࢖࢜ࣥ໬ㄏ㉳␗ᛶ ໬ ཯ ᛂ ࡢ ཯ ᛂ ⤒ ㊰ ࢆ ♧ ࡍ ࠋ
PBE1PBE/6-31+G*ࣞ ࡛࣋ࣝ཯ᛂ⤒㊰᥈⣴ࢆ⾜࠸ࠊᚓࡽࢀࡓᏳᐃᵓ㐀࡜㑄⛣≧ែࡢᵓ㐀ࢆZB97X-D/6-311++G(3df, 3pd)࡛ࣞ࣋ࣝ
᭱㐺໬ࡋࡓࠋᅗ୰ࡢᩘᏐࡣࠊࡑࢀ࡟ࡼࡗ࡚
ᚓࡽࢀࡓ┦ᑐ࢚ࢿࣝࢠ࣮(kJ/mol)࡛࠶ࡿࠋ
EQ9 ࡜ EQ10 ࡀ᭱Ᏻᐃࡢ࢚ࣀ࣮ࣝᆺࡢᵓ㐀࡛࠶ࡾࠊᮎ➃ࡢỈศᏊࡢ㓄ྥࡀᑡࡋ␗࡞ࡿࠋ
ᆶ┤࢖࢜ࣥ໬ᚋ EQ1 ࡟␗ᛶ໬ࡋࠊࡑࡢᚋỈศᏊࡢ㛗㊥㞳⛣ື࡟కࡗ࡚ EQ3ࠊEQ14ࠊ

ᅗ 4 [FA-(H2O)2]+ࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂࡢ⤒㊰

EQ15 ࠿ࡽࠊEQ9 ࡜ EQ10 ࡬࢚ࣀ࣮ࣝ໬ࡍ
ࡿࠋࡇࡢ࢚ࣀ࣮ࣝ໬ࡣࠊỈ஧ศᏊࡀ㛵୚ࡍࡿࣉࣟࢺ࣮ࣥࣜࣞࡢᶵᵓ(ࢢࣟࢵࢱࢫᶵᵓ)࡛㉳ࡇࡿࠋỈศᏊࡀ࣍ࣝ
࣒࢔࣑ࢻṇ࢖࢜ࣥࡢ CH ࠿ࡽࣉࣟࢺࣥࢆᘬࡁᢤࡁ H3O+࡜ỈศᏊࡀ࢝ࣝ࣎ࢽࣝᇶ࡟⛣ືࡍࡿࡇ࡜࡟ࡼࡾࠊH2O
࡜࢝ࣝ࣎ࢽࣝ㓟⣲ࡢ㛫࡛ࣉࣟࢺࣥࡀඹ᭷ࡉࢀࡿࠋࡇࡢࡼ࠺࡟ࠊỈ஧ศᏊࡀゐ፹స⏝ࡍࡿ࣒࣍ࣝ࢔࣑ࢻṇ࢖࢜ࣥࡢ࢚ࣀ࣮ࣝ໬ࡢᶵᵓࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡇࡢ◊✲ࡣࠊ኱㔝බ୍ᮾ໭኱Ꮫྡ㄃ᩍᤵ(㔞Ꮚ໬Ꮫ᥈⣴◊✲ᡤᡤ㛗)ࠊ
๓⏣⌮໭ᾏ㐨኱Ꮫᩍᤵ࡜ࡢඹྠ◊✲࡜ࡋ࡚⾜ࢃࢀࡲࡋࡓࠋ[4][FA-(H2O)3]+࡟ࡘ࠸࡚ࡶྠᵝ࡟㉥እศග◊✲ࢆ⾜࠸ࠊ࣒࣍ࣝ࢔࣑ࢻṇ࢖࢜ࣥࡀ࢚ࣀ࣮ࣝᆺࡢᵓ㐀࡬␗ᛶ໬ࡍ
ࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋ⌧ᅾ GRRM ἲ࡟ࡼࡾࠊ࢖࢜ࣥ໬ࡉࢀࡓ FA-(H2O)3 ࡢ࢚ࣀ࣮ࣝᆺ࡬ࡢ␗ᛶ໬཯ᛂ⤒㊰ࡢ᥈⣴ࢆࡍࡍࡵ࡚࠸ࡿࠋࡑࡢ཯ᛂ⤒㊰᥈⣴࡟࠾࠸࡚ࠊ(FA-H2O)+ࡸ[FA-(H2O)2]+ࡢ␗ᛶ໬࡛ࡣぢࡽࢀ࡞࠸཯ᛂ⤒㊰ࡀぢࡘ࠿ࡗ࡚࠸ࡿࠋ

2) 2-࣌ࣥࢱࣀࣥࡢ࢖࢜ࣥ໬㐣⛬࡟࠾ࡅࡿ࣐ࢡࣛࣇ࢓ࢸ࢕㌿఩ࡢศගᏛⓗ◊✲࣐ࢡࣛࣇ࢓ࢸ࢕㌿఩ࡣࠊJ఩ࡢⅣ⣲(CJ)࡟Ỉ⣲ཎᏊࢆᣢࡘࢣࢺࣥࡢ࢖࢜ࣥ໬࡟࠾࠸࡚ほࡉࢀࡿࠊ࢚ࣀ࣮ࣝ

໬ࢆక࠺ゎ㞳ᶵᵓ࡛࠶ࡿࠋ[5] ࣐ࢡࣛࣇ࢓ࢸ࢕㌿఩࡟ࡘ࠸࡚ࠊࡇࢀࡲ࡛ከࡃࡢ㉁㔞ศᯒ◊✲ࡀ⾜ࢃࢀ࡚ࡁࡓࡀࠊ
ศගᏛⓗ࡞◊✲౛ࡣ࡞࠸ࠋᮏ◊✲࡛ࡣࠊ࣐ࢡࣛࣇ࢓ࢸ࢕㌿఩࡟࠾ࡅࡿ␗ᛶ໬཯ᛂࡢ⌮ゎࢆ┠ⓗ࡜ࡋ࡚ࠊCJH
ࢆᣢࡘ᭱ࡶ༢⣧࡞ࢣࢺ࡛ࣥ࠶ࡿ 2-࣌ࣥࢱࣀࣥࢆᑐ㇟࡜ࡋ࡚┿✵⣸እග࢖࢜ࣥ໬᳨ฟ㉥እゎ㞳ศගἲࢆ⏝࠸࡚ࠊ୰ᛶ࠾ࡼࡧṇ࢖࢜ࣥࡢ㉥እศග࡜㔞Ꮚ໬Ꮫィ⟬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ2-࣌ࣥࢱࣀࣥṇ࢖࢜ࣥࡢ㉥እࢫ࣌ࢡࢺࣝ࡟ CH ఙ⦰᣺ືࣂࣥࢻ࡜࡜ࡶ࡟ࠊ୰ᛶࡢ㉥እࢫ࣌ࢡࢺࣝ࡟ࡣほࡉࢀ࡞࠸ OH ఙ⦰᣺ືࣂࣥࢻࡀほࡉࢀࡓࠋࡇࡢ⤖ᯝࡣࠊ࢖࢜ࣥ໬ࡉࢀࡓ 2-࣌ࣥࢱࣀࣥ࡟࠾࠸࡚ࠊCJH ࠿ࡽࡢࣉࣟࢺࣥࡢ⛣ື࡟ࡼࡿ࢚ࣀ࣮ࣝ໬ࡀ㉳ࡁ࡚࠸ࡿࡇ࡜ࢆ♧ࡍࠋࡇࡢ⤖ᯝࡣ࣐ࢡࣛࣇ࢓ࢸ࢕㌿⛣࡟࠾࠸࡚⏕ᡂࡉࢀࡿ࢚ࣀ࣮ࣝయࢆศගᏛⓗ࡟ほࡋࡓࡣࡌࡵ࡚ࡢ⤖ᯝ࡛࠶ࡿࠋࡇࡢ㉥እศගࡢ⤖ᯝ࡜࡜ࡶ࡟ࠊ㔞Ꮚ໬Ꮫィ⟬࡟ᇶ࡙ࡃ཯ᛂ⤒㊰᥈⣴࡟ࡼࡾࠊ2-࣌ࣥࢱࣀࣥࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂࢆゎᯒࡋࡓࠋࡇࡢ 2-࣌ࣥࢱࣀࣥࡢ⤖ᯝࡢㄽᩥࡣࠊ⌧ᅾᢞ✏୰࡛࠶ࡿࠋ

3) ࡑࡢ௚
௚࡟㉥እศග࠾ࡼࡧ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡿ 1,3-ࣉࣟࣃࣥࢪ࣮࢜ࣝࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂࡸࠊ࣌ࣥࢱࣥࢆ
ྵࡴ࢔ࣝ࢝ࣥ஧㔞యṇ࢖࢜ࣥࡢᵓ㐀ゎᯒ࡞࡝ࡢ◊✲ࢆ᫖ᖺᗘࡼࡾ⾜ࡗ࡚࠸ࡿࠋ

- 396 -

ཧ⪃ᩥ⊩[1]

K. Ohno and S. Maeda, Chem. Phys. Lett. 384, 277, 2004. K. Ohno and S. Maeda, J. Phys.Chem. A, 110, 8933,
2006. S. Maeda and K. Ohno, J. Phys. Chem. A, 109, 5742, 2005.

[2]

S. Maeda, Y. Matsuda, S. Mizutani, A. Fujii, and K. Ohno, J. Phys. Chem. A, 114, 11896 (2010).

[3]

D. Sakai, Y. Matsuda, M. Hachiya, M. Mori, A. Fujii, N. Mikami, J. Phys. Chem. A, 112, 6840 (2008).

[4]

Y. Matsuda, Y. Hirano, S. Mizutani, D. Sakai, A. Fujii, S. Maeda, K. Ohno, J. Phys. Chem. A, 124, 2802 (2020).

[5]

N. M.M. Nibbering, Int. J. Am. Spectrom. 377, 10 (2015).

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

1) ࣒࣍ࣝ࢔࣑ࢻ-(H2O)3 ࡢ࢖࢜ࣥ໬ㄏ㉳␗ᛶ໬཯ᛂࡢ㉥እศග◊✲ࠊᯇ⏣Ḡஅࠊᖹ㔝⿱ኴ㑻ࠊ⸨஭ᮒ㫽ࠊ➨
13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019 ᖺ 9 ᭶2) ㉥እศග࡟ࡼࡿ࣌ࣥࢱࣀࣥ࢖࢜ࣥ࡟࠾ࡅࡿ࣐ࢡࣛࣇ࢓ࢸ࢕㌿఩ࡢほࠊᏳᮏ෽ࠊᯇ⏣Ḡஅࠊ⸨஭ᮒ㫽ࠊ

13 ᅇศᏊ⛉Ꮫウㄽ఍ࠊྡྂᒇࠊ2019 ᖺ 9 ᭶3) Infrared spectroscopy of intermediate in the MacLafferty rearrangement of ionized pentanoneࠊᏳᮏ෽ࠊᯇ⏣Ḡஅࠊ⸨஭ᮒ㫽ࠊ2019 ᖺᗘ໬Ꮫ⣔Ꮫ༠఍ᮾ໭኱఍ࠊᒣᙧࠊ2019 ᖺ 9 ᭶4) IR spectroscopic investigation of semi-covalent interaction in petane dimer cation, Y. Matsuda, 2020 Molecular andIonic Clusters, GRC, Ventura, USA, 2020 ᖺ 1 ᭶

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ

1) Migrations and catalytic action of water molecules in the ionized formamide-(H2O)2 cluster, Y. Matsuda, Y. Hirano,
S. Mizutani, D. Sakai, A. Fujii, S. Maeda, K. Ohno, J. Phys. Chem. A, 124, 2802-2807, (2020).
2) Infrared spectroscopic observation of the McLafferty rearrangement in ionized 2-pentanone, R. Yasumoto, Y.
Matsuda, A. Fujii, ᢞ✏୰3) Semi-covalent bonded pentane dimer cation, which is a reaction intermediate of coupling reactions, T. Endo, Y.
Matsuda, R. Yasumoto, A. Fujii, K. Takahashi, ᇳ➹୰4) Migrations and catalytic action of water molecules in the ionized formamide-(H2O)3 cluster (௬㢟), Y. Matsuda, Y.
Hirano, A. Fujii 㔞Ꮚ໬Ꮫィ⟬ࢆᐇ⾜୰5) IR spectroscopic investigation of 1,3-propandiol cation on its acidic CH bond (௬㢟) Y. Matsuda, A. Matsuura, H.
Harigaya, A. Fujii ◊✲ࡀ㐍⾜୰6) IR spectroscopic investigation of alkane dimer cations (௬㢟) R. Yasumoto, Y. Matsuda, A. Fujii㔞Ꮚ໬Ꮫィ⟬ࢆᐇ⾜୰- 397 -

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



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140 Å x 140 Å x 160 Å Ü¡*"ą¶Ôºe/đÒė
particle mesh Ewald ĦPMEħÇô LJ ØahÒ6CF5KĂĜ

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üßě*VLT6ę¶×É¡JSPY@/b®+ētáĔê{Ï×:XL
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6 ētáMOÅâd`ĠûğĞØahÒ LJ ġ/Ē©VLT6
É¡JSPY@

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30 ns üß3 #$
MO`ĕð[ª¯ íāª¯¹è,ñª¯k°

10-7 cm2/s 5YAY+, Åñª¯Ħ10-5 cm2/sħÄĆ 100 mÜ¡ďÐĀ*t;NQVY;RX(+:XL
TX9 ĝ+  gREST ÇÞ(+:XLTX9zċ ¤ø+gREST üß+MOFS<38FTĦ30 nsħ/ 1 ÛFS<38FT/&üßª¯k°
5YAY*³Úzċ ù), - 398 -

10-7 cm2/s

 1. gREST üß+MO

FS<38FTMO Fe
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õÛ+MOzċ/Đ§+%đuºe/¾ý+%@XJ8ā #à~ád\ 3  gREST üß/ô
1. ētáMOíā tail ēt`Ġû/LJ ġ/¬Ò
2. ētáMOíā tail ētLJ ġ/¬Ò
3. ētáMOíāog`Ġû/LJ ġ/¬Ò,,VLT6°

12 VLT6Â 30 ns üß/ô´&ĥÉ¡JSPY@ ,,412.4 K, 444.1 K, 366.0 K  b®§yÏ

0.25 Ü¡+

,,ºeª¯k°/üß-gREST üßđÒwÄĆ. zċ ù),&10-7 cm2/s 5YAY )}  [@XJ8ā/#á +üß ētá8YWXġ/% , 8YWX
ġ/$ gREST üßð ú,%+Z±Huang )üß 8YW
Xġ/$ REST üß(íāª¯/ 10-100 mzċ+§y+[2]»ÙÝ 8YWXġ/$ gREST üß/ô%ºe­ã/ô

4(&
Öõé – Ħ·pĘĤEY@/$%ħ
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sÌé – sÌ_ – *6'[1] Kamiya, M.; Sugita, Y., J. Chem. Phys., 2018, 149, 072304.
[2] Huang, K.; Garcia, A.E., J. Chem. Theory. Comput., 2014, 10, 4264–4272.

- 399 -

㧗ᴟᛶᾮᬗ໬ྜ≀ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
Molecular Dynamics Simulation of Highly Polar Liquid Crystalline
Compounds‫ۑ‬ዟᮧ Ὀᚿࠊ㐲⸨ ⪽ኴࠊ⳥ụ ⿱Ⴙ㸦஑ᕞ኱Ꮫඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
᭱㏆ࠊᡃࠎࡣࢪ࢜࢟ࢧࣥᇶࢆ᭷ࡍࡿࣇࢵ⣲⣔ᮦᩱ࡛࠶ࡿ DIO (Fig. 1)ࡀࠊ⣙ 10,000 ࡶࡢẚㄏ㟁⋡ࢆ♧ࡍᾮᬗ┦࡛࠶ࡿࠕMP ┦ࠖࢆⓎ⌧ࡍࡿࡇ࡜ࢆぢฟࡋࠊDSC
཯㌿㟁ὶ

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ᐃࠊ೫ග㢧ᚤ㙾ほᐹࠊXRD

ᐃࠊㄏ㟁⦆࿴

ᐃࠊศᴟᐃࢆ㥑౑ࡍࡿࡇ࡜࡛ࠊ୍ぢࢿ࣐ࢳࢵࢡ┦ࡢࡼ࠺࡟᣺ࡿ⯙࠺ MP ┦ࡀ㓄ྥ࣋ࢡࢺࣝ᪉ྥ࡟཯㌿ᑐ⛠ᛶࡢ◚ࢀࡓᴟᛶᵓ㐀ࢆࡶࡘ㧗ᴟᛶᾮᬗ࡛࠶ࡿ࡜ᥦၐࡋࡓ 1)ࠋ⌧ᅾࠊDIO ࡢᴟࡵ࡚㧗࠸ẚㄏ㟁⋡ࢆά⏝ࡋࡓᛂ⏝◊✲ࡶ㐍ࡵ࡚࠸ࡿࡀࠊ࡞ࡐ DIO ࡢศᏊᵓ㐀࡛࡞ࡅࢀࡤ㧗ᴟᛶࡀⓎ⌧ࡋ࡞࠸ࡢ࠿ࠊDIO ࡢ≉Ṧ࡞ศᏊᙧ≧࠿ࠊᒁᡤⓗ࡞ศᏊ㛫┦஫స⏝࠿ࠊࡲࡓࡣࡑࡢ୧᪉࡞ࡢ

F

࠿ゎ࡛᫂ࡁ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙ +Q&Q

Oࣥἲࢆ⏝࠸࡚MP┦ࢆィ⟬ᶵୖ࡟෌⌧ࡋࠊఱᨾDIOศᏊࡔ࡜ศ

O
F

O

F

F

O

F

Ꮚศᴟࡀᥞࡗ࡚ᕧどⓗ࡟཯㌿ᑐ⛠ᛶࡀ◚ࢀ࡚㧗ᴟᛶᾮᬗ≧ែ࡟
Fig. 1 CnDIO ࡢ໬Ꮫᵓ㐀࡞ࡿࡢ࠿ࠊࡑࡢᶵᵓࡢゎ᫂ࢆ┠ᣦࡍࠋ

2F◊✲᪉ἲࠊィ⟬᪉ἲࢪ࢜࢟ࢧࣥ⎔࠿ࡽఙࡧࡿ࢔ࣝ࢟ࣝ㙐㛗㸦n=1, 2, 3, 4㸧ࡀ␗࡞ࡿ㸲✀㢮ࡢDIOࡢ࠺ࡕࠊ₇⟬ᑐ㇟࡜ࡋ࡚ࡣ᭱ࡶᐇ㦂ⓗ࡞◊✲ࡀ㐍ࢇ࡛࠾ࡾࠊ࠿ࡘ315 K࠿ࡽ341 K࡜ᗈ࠸ᗘ⠊ᅖ࡛MP┦ࢆⓎ⌧ࡋࡓC3DIOࢆ㑅ࢇࡔࠋศᏊືຊᏛィ⟬ࡣࠊỗ⏝ࣉࣟࢢ࣒ࣛ
GROMACS 2018.7ࡢ඲ཎᏊࣔࢹࣝ࡟࡚ᐇ᪋ࡋࡓࠋᾮᬗศᏊࡢ㟁ⲴศᕸࡣAM1-BCC࡜࿧ࡤࢀࡿ㠀⤒㦂ⓗศᏊ㌶㐨ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡿRESP㟁Ⲵ࡟㏆࠸್ࢆ༙⤒㦂ⓗᡭἲ࡟ࡼࡗ࡚ィ⟬ࡍࡿ Fig. 2 ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ
࡚ィ⟬ࡉࢀࡓ DIO1728 ศᏊ࡛ᵓᡂࡉࢀࡿ
᪉ἲࢆ⏝࠸ࡓࠋC3DIO࡟ࡼࡿᾮᬗ≧ែࡢ෌⌧࡟ࡣࠊ໭㔛኱Ꮫࡢ ࢩࢫࢸ࣒࡟࠾ࡅࡿࠊ360 K ࡛ࡢ୍㍈㓄ྥࢆ཯ᫎࡍࡿ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(P2)࡜ࠊ⮬Ώ㎶㇦ඛ⏕ࡢᣦᑟࢆཷࡅࡓࠋ
Ⓨศᴟࢆ཯ᫎࡍࡿ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮
X ⥺༢⤖ᬗゎᯒࡼࡾᐇ㦂ⓗ࡟ᚓࡽࢀࡓ㸲ศᏊࡢ C3DIO ࠿ࡽ࡞
S(P1)ࡢ₇⟬᫬㛫౫Ꮡᛶࡿ༢఩᱁ᏊࢆᵓᡂࡍࡿศᏊࡢཎᏊ㛫㊥㞳ࢆఙᙇࡍࡿࡇ࡜࡞ࡃࠊ
༢఩᱁Ꮚࡢྛ㎶ࢆࡑࢀࡒࢀ 1.3 ಸ࡟ᗈࡆࡓ᱁Ꮚࢆྛ㎶ࡢ᪉ྥ࡟689 ಶ✚ᒙࡉࡏ࡚ࠊ1728 ศᏊࠊ⥲ཎᏊᩘ⣙ 10 ୓ಶࢆ㓄⨨ࡋࡓᵓ㐀ࢆึᮇᵓ㐀࡜ࡋࡓࠋࡑࡋ࡚ࠊ500 K ࡛ 1 ns ࡢึᮇᵓ㐀⦆࿴ィ⟬ࢆ⾜࠸ࠊศᏊ㓄ྥࢆ➼᪉ⓗ࡟ࡍࡿ࡜ྠ᫬࡟ᐦᗘࡢ᭱㐺໬ࢆ⾜ࡗࡓࠋࡑࡢᚋࠊ475ࠊ450ࠊ430ࠊ425ࠊ420ࠊ410ࠊ400ࠊ380ࠊ
360ࠊ300 K ࡛ࡢ 5 ns ࡢึᮇᵓ㐀⦆࿴ィ⟬ࢆ⾜ࡗࡓᚋࠊ200㹼800
ns ࡢᖹ⾮໬ィ⟬ࢆ⾜ࡗࡓࠋFig. 3 DIO ศᏊ 1728 ಶ࠿ࡽ࡞ࡿ➼᪉┦≧ែ(a)࡜ࠊࢿ࣐ࢳࢵࢡᾮᬗ≧ែ(b)- 400 -

3◊✲ᡂᯝ
ᖹ⾮໬ィ⟬ࡢ⤖ᯝࠊᾮᬗ┦ࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥᑐ㇟࡜ࡋ࡚ࡣ㞴ࡋ࠸኱ࡁ࡞ศᏊ(MW=510.4)࡛࠶

ࡿ࡟ࡶಀࢃࡽࡎࠊᐇ㦂ⓗ࡟ࢿ࣐ࢳࢵࢡ┦ࢆ♧ࡍᗘ㡿ᇦ࡟࠾࠸࡚ࠊ⣙ 400 nsec ࡢ㛫࡟ᾮᬗࡢ㓄ྥᗘࢆ⾲ࡍ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(P2)ࡀᐇ㝿ࡢᾮᬗ≧ែ࡜ྠ➼ࡢ⣙ 0.65 ࡬࡜ቑ኱ࡋࡓ(Fig. 2)ࠋᖹᆒࡢ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ
࣮࡛ࡣ⣔඲యࡢᆒ୍ᛶࡀ☜ㄆ࡛ࡁ࡞࠸ࡓࡵࠊDIO ศᏊࢆྍど໬ࡋ࡚☜ㄆࡋࡓ࡜ࡇࢁࠊ➼᪉┦≧ែ࡛ࡣ㓄ྥࡣ☜ㄆࡉࢀࡎࠊᾮᬗ≧ែ࡛ࡣ⣔඲య୍࡛᪉ྥ࡟㓄ྥࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ Fig. 3(b)ࠋᴫࡡ཰᮰ࡋࡓ࣮࢜ࢲ
࣮ࣃ࣓࣮ࣛࢱ࣮ࡢ

ᗘ౫Ꮡᛶࢆࣉࣟࢵࢺࡋࡓ⤖ᯝࠊ୍⯡ⓗ࡞ࢿ࣐ࢳࢵࢡ┦࡜ྠᵝ࡟᪼࡟ᑐࡋ࡚஧ḟ㌿⛣ⓗ࡟࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(P2)ࡀపୗࡋࡓ(Fig. 5)ࠋࡑࡢᚋࡢ୍ḟ㌿⛣ࡢ᭷↓ࡣ☜ㄆ࡛ࡁ࡞࠿ࡗࡓࡀࠊ࣮࢜ࢲ࣮
ࣃ࣓࣮ࣛࢱ࣮ࡢ್ࡀ 0.2~0.3 ࡢ⠊ᅖ࡛ࡣ኱ᖜ࡞ᦂࡽࡂࡀ☜ㄆࡉࢀ࡚࠾ࡾ(Fig. 4)ࠊప S(P2)≧ែࡢ୙Ᏻᐃᛶࡀ♧၀ࡉࢀࡓࠋᐇ㦂ⓗ࡞ᾮᬗ┦-➼᪉┦㌿⛣Ⅼ TNI ࡜ࡢᗘࡢࢬࣞࡀ 20Υ⛬ᗘ࡜ᑠࡉ࠸ㄗᕪ࡛ᾮᬗ┦-➼᪉┦㌿⛣Ⅼࢆィ⟬ᶵୖ࡛෌⌧ࡍࡿࡇ࡜࡟ᡂຌࡋࡓ࡜ゝ࠼ࡿ(Fig. 5)ࠋ
୍᪉࡛ࠊ₇⟬⤖ᯝ࠿ࡽᚓࡽࢀࡓᾮᬗ┦ࡣ DIO ࡢ MP ┦≉᭷ࡢ཯㌿ᑐ⛠ᛶࡢ◚ࢀ࡟ࡼࡿ⮬Ⓨศᴟࢆព࿡ࡍࡿ
࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(P1)ࡢቑ኱ࡣ☜ㄆࡉࢀ࡚࠾ࡽࡎ(Fig. 2)ࠊᙉㄏ㟁ࢿ࣐ࢳࢵࢡᾮᬗࢆィ⟬ᶵୖ࡟෌⌧ࡍࡿ࡜࠸࠺ᮏ◊✲ࡢ┠ᶆࡣᐇ⌧ࡉࢀ࡞࠿ࡗࡓࠋᮏィ⟬ࡢࡼ࠺࡟➼᪉┦≧ែ࠿ࡽ⮬Ⓨⓗ࡟཯㌿ᑐ⛠ᛶࡀ◚ࢀࡓ㧗ᴟᛶᾮᬗ≧ែࡢ෌⌧ࡀࠊ⌧ᐇⓗ࡞₇⟬⬟ຊ࡛ྍ⬟࠿ࢆ᳨ドࡍࡿ
ࡓࡵࠊ360 K ࡛ࡢࢿ࣐ࢳࢵࢡᾮᬗ≧ែ࡛ࡢ DIO ศᏊࡢྥࡁࡢ཯㌿㏿ᗘࡢᢳฟࢆヨࡳࡓࠋࡑࡢ⤖ᯝࠊ100 ศᏊࡢ㓄ྥࡢ཯㌿ࡢ㢖ᗘࢆ☜ㄆࡋࡓࠋࡑࡢ⤖ᯝࠊ600 nsec ࡢ㛫࡟⣙ 1 ๭ࡢศᏊࡢྥࡁࡀ཯㌿ࡍࡿࡇ࡜ࠊࡍ࡞ࢃࡕ 360 Υ࡛ࡢศᏊࡢྥࡁࡢᣢ⥆᫬㛫ࡀ⣙ 6,000 nsec ࡜ศᏊືຊᏛィ⟬ࡢ₇⟬᫬㛫ࡼࡾࡶ㛗࠸ࡇ࡜ࢆ☜ㄆࡋࡓࠋC3DIO ࡀ MP
┦ࢆⓎ⌧ࡍࡿ

ᗘࡣ 315 K ࠿ࡽ 341 K ࡜᭦࡟పFig. 4 ୍㍈㓄ྥࢆ཯ᫎࡍࡿ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(P2)ࡢ␗࡞ࡿ ᗘ࡛ࡢ₇⟬᫬㛫౫Ꮡᛶ࡛࠶ࡾࠊྥࡁࡢ཯㌿㏿ᗘࡣ᭦࡟㐜ࡃ࡞ࡿࡓࡵࠊࣛࣥࢲ࣒࡞≧ែ࠿ࡽ⮬Ⓨⓗ࡟ᙉㄏ㟁ࢿ࣐ࢳࢵࢡᾮᬗࢆ෌⌧ࡍࡿ࡟ࡣ₇⟬᫬㛫ࡀ㊊ࡾ࡞࠸ࡓࡵࠊMP ┦ࡢ㐺ษ࡞෌⌧࡟ࡣࠊ཯㌿ᑐ⛠ᛶࢆ◚ࡗࡓ₇⟬ࡢึᮇ≧ែࡢᑟධ࡜ࠊ⏕ᡂࡋࡓᾮᬗ┦ࡢ⇕ຊᏛⓗᏳᐃᛶࡢホ౯ࡀᚲせ࡜⪃࠼ࡽࢀࡿࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ

Fig. 5 ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚
ィ⟬ࡉࢀࡓ DIO1728 ศᏊ࡛ᵓᡂࡉࢀࡿࢩࢫࢸ
࣒ࡢ࣮࢜ࢲ࣮ࣃ࣓࣮ࣛࢱ࣮S(P2)ࡢ ᗘ౫Ꮡ
ᛶࠋTNI(exp.)ࡣᐇ㦂ⓗ࡟ ᐃࡉࢀࡓ DIO ࡢᾮᬗ┦-➼᪉┦㌿⛣Ⅼ࡞ࡋ5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ࡞ࡋཧ⪃ᩥ⊩1) H. Nishikawa, K. Shiroshita, H. Higuchi, Y. Okumura, Y. Haseba, S. Yamamoto, K. Sago, H. Kikuchi, Advanced
materials, 29, 43, 1702354 (2017).

- 401 -

จ⦰⣔࡟࠾ࡅࡿ⦆࿴࠾ࡼࡧ཯ᛂࢲ࢖ࢼ࣑ࢡࢫࡢ⌮ㄽ◊✲
7KHRUHWLFDOVWXGLHVRIUHOD[DWLRQVDQGUHDFWLRQG\QDPLFV LQFRQGHQVHGSKDVH‫ۑ‬ᩧ⸨ ┿ྖࠊ᳃ ಇᩥࠊ⏥⏣ ಙ୍ࠊ✄ᇉ Ὀ୍ࠊᯇᮧ ⚈ᏹࠊ0$85<$0DQLVKࠊ
.$/$7+,1*$/0DKURRIࠊ=+8=KH㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧 ◊✲┠ⓗࠊෆᐜᮏᖺᗘࡣࠊ 㓝⣲཯ᛂ࡟࠾ࡅࡿࢱࣥࣃࢡ㉁ࡢືⓗᶵᵓࠊ ᫬ィࢱࣥࣃࢡ .DL& ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࠊ จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎࡢゎ᫂ࠊ ᅛ┦จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿᵓ㐀⦆࿴㐣⛬ࠊ ࢖࢜ࣥࢳࣕࢿࣝศᏊࡢ⭷ᤄධᶵᵓࠊ ᅛయ⏺㠃ୖࡢỈ⁲ࡢᵓ㐀࣭ᦂࡽࡂࠊ 㧗➼᳜≀࡟࠾ࡅࡿບ㉳࢚ࢿࣝࢠ࣮
⛣ືᶵᵓ࡟㛵ࡍࡿ◊✲ࢆ⾜ࡗࡓࠋ⣬㠃ࡢ㛵ಀ࡛ࠊ㸫 ࡟ࡘ࠸࡚௨ୗ࡟⧳ࡵࡿࠋ
 㓝⣲཯ᛂ࡟࠾ࡅࡿ໬Ꮫ཯ᛂ࡜ࢱࣥࣃࢡ㉁ࢲ࢖ࢼ࣑ࢡࢫࡢືⓗᶵᵓࡢゎᯒ
ࢱࣥࣃࢡ㉁ࡢኳ↛≧ែ࡟࠾ࡅࡿᵓ㐀ᦂࡽࡂࡸ≧ែ㑄⛣࡞࡝ࡢᰂࡽ࠿࡞ᵓ㐀≉ᛶࡀࠊࢱࣥࣃࢡ㉁ࡢᶵ⬟࡟㔜せ࡛࠶ࡿࡇ࡜ࡀ㏆ᖺᐇ㦂ⓗ࡟᫂ࡽ࠿࡟࡞ࡗ࡚ࡁࡓࡀࠊࡑࡢヲ⣽࡞ᶵᵓࡣ⌮ゎࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊ≉࡟㓝⣲཯ᛂ࡟࠾࠸࡚ࢱࣥࣃࢡ㉁ࡢᵓ㐀ᦂࡽࡂࡀዴఱ࡟ᐤ୚ࡍࡿ࠿ㄪ࡭࡚࠸ࡿࠋࣉࣟࣜࣥ␗ᛶ໬㓝⣲ࡢ୍ࡘ࡛
࠶ࡿ 3LQ ࡣࠊࢱࣥࣃࢡ㉁ࡢࣇ࢛࣮ࣝࢹ࢕ࣥࢢࢆಁ㐍ࡋࠊࣜࣥ㓟໬࡜ᶵ⬟ࢆ⤖ࡧࡘࡅࡿࡀࠊ␗ᛶ໬࡟క࠺㓝⣲ࡢᵓ㐀ኚ໬ࡢ㐣⛬࡞࡝ࠊศᏊᶵᵓࡢヲ⣽ࡣᮍゎ࡛᫂࠶ࡿࠋᡃࠎࡣࠊศᏊືຊᏛ㸦0'㸧ィ⟬ࢆ⏝࠸࡚ 3LQ ࡛㉳ࡇࡿ࣌ࣉࢳࢻ⤖ྜࡢ FLVWUDQV ␗ᛶ໬㐣⛬ࢆㄪ࡭ࡿࡇ࡜࡛ࠊ≉࡟ࢲ࢖ࢼ࣑ࢡࢫࡢヲ⣽࡞ゎᯒࢆ⾜ࡗࡓࠋ ᫬ィࢱࣥࣃࢡ .DL& ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࡢゎᯒࢩ࢔ࣀࣂࢡࢸࣜ࢔ࡢᴫ᪥ࣜࢬ࣒ࡣ  ✀ࡢࢱࣥࣃࢡ㉁ .DL$.DL%.DL& ࡢ┦஫స⏝࡟ࡼࡗ࡚⏕ࡌࡿࠋࡇࡢᴫ

᪥ࣜࢬ࣒ࡣ .DL& භ㔞యࡢ୰࡛⏕ࡌࡿ $73 ࡢຍỈศゎ཯ᛂ࡛ᚓࡽࢀࡿ࢚ࢿࣝࢠ࣮࡟ࡼࡗ࡚㥑ືࡉࢀࡿࠋ୍᪉ࠊ
.DL& ୰ࡢ $73 ຍỈศゎ཯ᛂࡣࠊ0\RVLQ ࡸ .LQHVLQ ࡞࡝ࡢ࣮ࣔࢱ࣮ࢱࣥࣃࢡ㉁࡜ẚ㍑ࡍࡿ࡜㠀ᖖ࡟㐜ࡃ㐍⾜ࡍࡿࠋࡇࡢ㐜ࡉࡀ⣔඲యࡢ  ᫬㛫࡜࠸࠺㛗࿘ᮇࡢ᣺ື࡜ᐦ᥋࡟㛵ಀࡋ࡚࠸ࡿࡇ࡜ࡣ▱ࡽࢀ࡚࠸ࡿࡀࠊࡑࡢヲࡋ࠸ᶵᵓࡣᮍࡔ࡟୙࡛᫂࠶ࡿࠋᮏ◊✲࡛ࡣࠊ᣺ືᏊࡢ୰࡛ $73 ຍỈศゎ཯ᛂ࡟㛵㐃ࡍࡿ㐣⛬࡟╔┠ࡋࠊࡑࡢ㐣⛬ࡢᶵ⬟Ⓨ⌧࡟࠾ࡅࡿᙺ๭ࢆ཯ᛂࣔࢹࣝᵓ⠏࡟ࡼࡗ࡚ヲ⣽࡟᳨ウࡋࡓࠋ จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎ࡟㛵ࡍࡿ⌮ㄽ◊✲จ⦰ศᏊ⣔࡟࠾ࡅࡿᦂࡽࡂࡣືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎ࡜࿧ࡤࢀࠊ໬Ꮫ཯ᛂࡸᵓ㐀ኚ໬ࢆ⌮ゎࡍࡿୖ࡛㔜せ࡛࠶ࡿࠋࡇࢀࡲ࡛⡆༢࡞⌮ㄽࣔࢹࣝ࡟ࡼࡿ◊✲ࡀ⾜ࢃࢀ࡚ࡁࡓࡀࠊཎᏊ࣭ศᏊࣞ࣋ࣝࡢᥥീࡣᮍࡔࡼࡃࢃ࠿ࡗ
࡚࠸࡞࠸ࠋᮏ◊✲࡛ࡣࠊ☜⋡㐣⛬⌮ㄽ࡟ᇶ࡙ࡁࠊ0' ィ⟬࡞࡝࡛ᚓࡽࢀࡿ⣔ࡢ᫬⣔ิ᝟ሗࢆゎᯒࡍࡿᡭἲࢆ
㛤Ⓨࡋࠊจ⦰⣔ࡢ໬Ꮫ཯ᛂࡸᵓ㐀ኚ໬࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎࡢᙺ๭ࢆ୍ศᏊ㏿ᗘㄽࡢほⅬ࠿ࡽཎᏊ࣭
ศᏊ࡛ࣞ࣋ࣝ᫂ࡽ࠿࡟ࡍࡿࠋ௒ᖺᗘࡣ≉࡟ࠊࢱࣥࣃࢡ㉁୍ศᏊࡢᵓ㐀ࢲ࢖ࢼ࣑ࢡࢫࡢ◊✲ࢆ᥎㐍ࡋࡓࠋ ᅛ┦จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿᵓ㐀⦆࿴㐣⛬࡜ࡑࡢ཯ᛂ㏿ᗘㄽ࡟㛵ࡍࡿ⌮ㄽ◊✲≀㉁ࡢ⭉㣗ࡸ྾⬺Ỉ࡞࡝ࡢᅛయ⾲㠃ࡲࡓࡣᅛయ⮬㌟ࡀኚ໬ࡍࡿ໬Ꮫ཯ᛂ㸦ᅛ┦จ⦰⣔ࡢ໬Ꮫ཯ᛂ㸧ࡢ㐣⛬ࡣࠊ࣓ࢯࢫࢣ࣮ࣝࡢ᩿∦ⓗ࡞ᵓ㐀ኚ໬ࡸぢ࠿ࡅࡢάᛶ໬࢚ࢿࣝࢠ࣮࡟ࡼࡗ࡚ᐇ㦂ⓗ࡟⌮ゎࡉࢀࡿࡼ࠺࡟࡞ࡗ

- 402 -

࡚ࡁࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡑࡢࡼ࠺࡞཯ᛂ㐣⛬ࢆ」ᩘࡢ⣲཯ᛂࡀ」㞧࡟⤡ࡳྜࡗࡓከẁ㝵཯ᛂ࡜ࡳࢀࡤࠊࡑࡢ
⌮ゎࡣ㠀ᖖ࡟ஈࡋࡃࠊࡑࡢ⣲཯ᛂྠኈࡢ┦㛵ࡸࡑࢀࡽࡀ࣓ࢯࢫࢣ࣮ࣝࡢᵓ㐀ኚ໬ࢆᡂࡍᵝᘧ࡟ࡘ࠸࡚ࡣ඲ࡃ
ࢃ࠿ࡗ࡚࠸࡞࠸ࠋᮏ◊✲ࡣࡑࡢࡼ࠺࡞ᅛ┦จ⦰⣔ࡢ໬Ꮫ཯ᛂᶵᵓࢆศᏊࣞ࣋ࣝ࠿ࡘ᫬㛫ⓗ࡟࣐ࣝࢳࢫࢣ࣮ࣝ
࡞どⅬ࡛⌮ㄽⓗ࡟ゎᯒ࣭⌮ゎࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚࠸ࡿࠋ௧࿴ඖᖺᗘࡣࠊ」㞧࠿ࡘከẁ㝵࡞཯ᛂ㐣⛬ࢆ⇕ຊᏛⓗᖹ⾮≧ែ࡬⦆࿴ࡍࡿ㐣⛬࡜ࡳ࡞ࡍࡇ࡜࡛ࠊཎᏊ࣭ศᏊࡢᣑᩓ࡜໬Ꮫ⤖ྜࡢ⤌ࡳ᥮࠼࡟ࡼࡿ⣔ࡢ⦆࿴ࢆᨃఝⓗ࡟㏣㊧ࡍࡿࢩ࣑࣮ࣗࣞࢩࣙࣥ᪉ἲࡢ㛤Ⓨࢆヨࡳࡓࠋ ◊✲᪉ἲࠊィ⟬᪉ἲ 㓝⣲཯ᛂ࡟࠾ࡅࡿ໬Ꮫ཯ᛂ࡜ࢱࣥࣃࢡ㉁ࢲ࢖ࢼ࣑ࢡࢫࡢືⓗᶵᵓࡢゎᯒࡲࡎࠊࣞࣉࣜ࢝஺᥮࢔ࣥࣈࣞࣛࢧࣥࣉࣜࣥࢢἲ࡜㑄⛣⤒㊰ࢧࣥࣉࣜࣥࢢἲࢆ⏝࠸࡚ࠊ␗ᛶ໬཯ᛂࡢ⮬⏤࢚ࢿࣝࢠ࣮㠃࡜㑄⛣ࢺࣛࢪ࢙ࢡࢺࣜࡢࢧࣥࣉࣜࣥࢢࢆࡑࢀࡒࢀ⾜ࡗࡓࠋḟ࡟ࠊ㑄⛣≧ែ௜㏆ࡢᵓ㐀࠿ࡽ▷࠸ࢺࣛࢪ࢙ࢡࢺࣜࢆከᩘⓎ⏕ࡉࡏࠊྛᵓ㐀࠿ࡽࡢ⏕ᡂ≀࡟฿㐩ࡍࡿ☜⋡㸦FRPPLWWRU㸧ࢆィ⟬ࡋࡓࠋࡲࡓࠊFRPPLWWRUࡀ㑄⛣≧ែ௜㏆࡛  ࡜࡞ࡿࡇ࡜ࢆ฼⏝ࡋ࡚ࠊFRPPLWWRU ࡢศᕸ࠿ࡽ཯ᛂᗙᶆࢆỴᐃࡍࡿ᪉ἲࢆᑟࡁࠊࡇࢀࢆ
⏝࠸࡚␗ᛶ໬཯ᛂࡢ཯ᛂᗙᶆࢆㄪ࡭ࡓࠋ≉࡟ࠊ⮬⏤࢚ࢿࣝࢠ࣮㠃ୖ࡜㑄⛣ࢺࣛࢪ࢙ࢡࢺࣜ࠿ࡽࡑࢀࡒࢀ཯ᛂ
ᗙᶆࢆồࡵࠊ᭱ᑠ⮬⏤࢚ࢿࣝࢠ࣮⤒㊰࡜㑄⛣⤒㊰ࡢẚ㍑ࢆ⾜ࡗࡓࠋ ᫬ィࢱࣥࣃࢡ .DL& ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࡢゎᯒ
ࡲࡎ .DL$%& ᣺ືᏊࡢㅖࠎࡢ⣲㐣⛬ࢆ࠶ࡽࢃ࡟⤌ࡳ㎸ࢇࡔ཯ᛂࣔࢹࣝࢆᵓ⠏ࡋࡓࠋࡇࡇ࡛ࡣ≉࡟ .DL& ࡢᵝࠎ࡞ᵓ㐀ኚ໬ࢆヲ⣽࡟⤌ࡳ㎸ࢇࡔࠋࡑࡋ࡚ᩘ୓ಶࡢ≧ែ㛫ࡢ᫬㛫ኚ໬ࢆィ⟬ࡋࠊࡑࡢ᣺ࡿ⯙࠸ࡀ✀ࠎࡢᐇ㦂⤖ᯝ࡜୍⮴ࡍࡿࡼ࠺࡟཯ᛂ㏿ᗘᐃᩘ➼ࡢࣃ࣓ࣛࢱࢆ᭱㐺໬ࡋࡓࠋࡑࡋ࡚ࠊ᣺ືᏊࡢ᫬ィ࡜ࡋ࡚ࡢᶵ⬟ࡀ⣲㐣⛬ࡢ⤌ࡳྜࢃࡏ࠿ࡽዴఱ࡟⏕ࡌࡿ࠿ࢆヲ⣽࡟ศᯒࡋࡓࠋ୍᪉ࠊ.DL& ࡜ .DL% ࡢ⤖ྜ㐣⛬ࡢ㐜ࡉࡢ㉳※㸦ࡇ
ࢀࡣ .DL% ࡢᵓ㐀ኚ໬࠾ࡼࡧ $73 ຍỈศゎ࡟ᚊ㏿ࡉࢀࡿ .DL& ࡢᵓ㐀ኚ໬ࡢ㸰ㄝ࠶ࡿ㸧ࢆ᫂ࡽ࠿࡟ࡍ࡭ࡃࠊࡇ
ࡢ㐣⛬ࢆ≉࡟ヲ⣽࡟⾲⌧ࡋࡓࣔࢹࣝࢆู㏵సᡂࡋࠊࡑࡢ㏿ᗘㄽࢆヲ⣽࡟ศᯒࡋࡓࠋ
 จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎ࡟㛵ࡍࡿ⌮ㄽ◊✲௒ᖺᗘࡣࠊືⓗ୙ᆒ୍ᛶ࣭↓⛛ᗎࡢࡓࡵࡢ᪂ࡓ࡞ゎᯒᡭἲࢆ㛤Ⓨࡋࡓࠋᮏᡭἲ࡛ࡣࠊจ⦰ศᏊ⣔ࡢ཯ᛂ࣭㑄⛣㐣⛬࡟࠾ࡅࡿ」㞧㸦㠀࣐ࣝࢥࣇࠊ㠀࣏࢔ࢯࣥ㸧࡞ᦂࡽࡂࡢᙳ㡪ࢆࠊ0' ィ⟬ࡢ᫬⣔ิࢹ࣮ࢱࢆゎᯒࡍࡿࡇ࡜࡛ᚤどⓗ࡟᫂ࡽ࠿࡟ࡋࠊ㏿ᗘಀᩘࡢᦂࡽࡂࡢศᏊㄽⓗ㉳※ࢆゎ࡛᫂ࡁࡿࠋࡑࢀࢆᛂ⏝ࡋࠊ≀⌮໬Ꮫ◊✲ࡢࣔࢹࣝ⺮ⓑ㉁⣔࡛࠶ࡿỈ⁐ᾮ୰ࡢ࢘ࢩ⮅⮚ࢺࣜࣉࢩࣥ࢖ࣥࣄࣅࢱ࣮㸦%37,㸧ࢱࣥࣃࢡ㉁ࡢᵓ㐀ࢲ࢖ࢼ࣑ࢡ
ࢫࡢ 0' ィ⟬࡟ࡼࡿ㸯࣑ࣜ⛊ࡢ᫬⣔ิࢹ࣮ࢱࢆゎᯒࡋࡓࠋࡲࡓࠊࢱࣥࣃࢡ㉁஧ศᏊࡢ㞳ྜ㞟ᩓ㐣⛬ࡢ◊✲࡟㛵ࡋ࡚ࠊኳ↛ኚᛶࢱࣥࣃࢡ㉁࡛࠶ࡿ S.,' ࡢᵓ㐀ኚ໬࡜ᣑᩓࡢ㛵㐃ࢆㄪ࡭ࡿࡓࡵࡢ 0' ィ⟬ࢆ⾜ࡗࡓࠋ ᅛ┦จ⦰⣔ࡢ໬Ꮫ཯ᛂ࡟࠾ࡅࡿᵓ㐀⦆࿴㐣⛬࡜ࡑࡢ཯ᛂ㏿ᗘㄽ࡟㛵ࡍࡿ⌮ㄽ◊✲ࣔࣥࢸ࢝ࣝࣟἲ࡜ศᏊືຊᏛ㸦0'㸧ἲࢆ⤌ࡳྜࢃࡏ࡚㓄⨨✵㛫ࡢࢧࣥࣉࣜࣥࢢࢆ⾜࠺ࣁ࣑ࣝࢺࢽ࢔ࣥࣔࣥ

ࢸ࢝ࣝࣟἲࢆᇶ♏࡟ࠊከᓠᛶศᕸࡢຠ⋡ⓗ࡞ࢧࣥࣉࣜࣥࢢࢆ⾜࠼ࡿࡼ࠺ᨵⰋࡍࡿࡇ࡜ࢆ⪃࠼ࡓࠋලయⓗ࡟ࡣࠊ㧗࠸཯ᛂ㞀ቨࢆᣳࡴᒁᡤᏳᐃᵓ㐀ࡢ㛫ࡢ㑄⛣☜⋡ࢆ㧗ࡵࡿࡓࡵ࡟ࠊẖᅇࡢ 0' ィ⟬ࢫࢸࢵࣉ࡟࠾࠸࡚࣏ࢸࣥ
ࢩ࢚ࣕࣝࢿࣝࢠ࣮㠃ࡢ㠀≀⌮ⓗ࡞ࢫࢣ࣮ࣜࣥࢢࢆ⾜࠺᪉ἲࢆ⪃᱌ࡋࡓࠋࡇࡢ᪉ἲࢆᵝࠎ࡞ࢸࢫࢺ⣔࡟㐺⏝ࡍࡿࡇ࡜࡛ࠊࡑࡢ᭷ຠᛶࢆ᳨ドࡋࡓࠋィ⟬ࡣᮏᡭἲࢆ 0' ィ⟬ࣉࣟࢢ࣒࡛ࣛ࠶ࡿ /$0036 ࡟ᐇ⿦ࡋ࡚⾜ࡗࡓࠋ- 403 - ◊✲ᡂᯝ 㓝⣲཯ᛂ࡟࠾ࡅࡿ໬Ꮫ཯ᛂ࡜ࢱࣥࣃࢡ㉁ࢲ࢖ࢼ࣑ࢡࢫࡢືⓗᶵᵓࡢゎᯒ
FRPPLWWRU ศᕸࢆ᭱㐺໬ࡍࡿᗙᶆࡢゎᯒ࠿ࡽࠊ⮬⏤࢚ࢿࣝࢠ࣮㠃ୖࡢ㑄⛣≧ែ࡛ࡣᇶ㉁̿㓝⣲ࡢ㛫ࡢ┦஫స⏝ࡀᙉࡲࡿᗙᶆࡀ㔜せ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ୍᪉࡛ࠊ㑄⛣⤒㊰࡛ࡣࡇࢀࡽࡢ┦஫స⏝ࡣ࡯ࡰಖᏑࡉࢀ࡚࠾
ࡾࠊ௦ࢃࡾ࡟␗ᛶ໬ࡢᗙᶆ࡛࠶ࡿ࣌ࣉࢳࢻ⤖ྜࡢ஧㠃ゅࡸࡑࡢ࿘ࡾࡢᇶ㉁ࡢ஧㠃ゅࡢኚ໬ࡀ཯ᛂᗙᶆ࡟኱ࡁ
࡞ᐤ୚ࢆᯝࡓࡋ࡚࠸ࡓࠋࡇࢀࡽࡢ⤖ᯝࡣࠊ᭱ᑠ⮬⏤࢚ࢿࣝࢠ࣮⤒㊰࡛ࡣ࣌ࣉࢳࢻ⤖ྜࡢ஧㠃ゅࡢኚ໬࡟క࠸
ᚎࠎ࡟ᇶ㉁̿㓝⣲㛫ࡢ┦஫స⏝ࡀᙧᡂࡉࢀࠊ㑄⛣≧ែࡀᏳᐃ໬ࡉࢀࡿࡢ࡟ᑐࡋࠊᐇ㝿ࡢ㑄⛣㐣⛬㸦㑄⛣ࢺࣛࢪ࢙ࢡࢺࣜ㸧࡛ࡣࠊᇶ㉁̿㓝⣲㛫ࡢᙉ࠸┦஫స⏝ࡣ࠶ࡽ࠿ࡌࡵᙧᡂࡉࢀ࡚࠾ࡾࠊࡑࡢࡼ࠺࡞ࠕᵓ㐀ບ㉳≧ែࠖ࠿ࡽ▷࠸᫬㛫㸦ᩘ SV ⛬ᗘ㸧ࡢ㛫࡟␗ᛶ໬཯ᛂࡀ᏶஢ࡍࡿࠊ࡜࠸࠺ࡇ࡜ࢆ⾲ࡍࠋࡇࢀࡽࡢ⤖ᯝࡣࠊࢱࣥࣃࢡ㉁ࡢᵓ㐀ᦂࡽࡂࡀᵓ㐀ບ㉳≧ែࢆᙧᡂࡍࡿࡇ࡜࡛㓝⣲཯ᛂࡢಁ㐍࡟ᐤ୚ࡋ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋ
 ᫬ィࢱࣥࣃࢡ .DL& ࡢᴫ᪥ࣜࢬ࣒ࡢᶵᵓࡢゎᯒ᣺ືᏊ඲యࡢ཯ᛂࣔࢹ࡛ࣝࡣ௨ୗࡢ⤖ᯝࢆᚓࡓࠋ.DL$ ࡜ .DL& ࡢ⤖ྜࡀࠊ.DL& ࡢᵓ㐀ኚ໬ࢆㄏ㉳ࡋࠊ࢔ࣟࢫࢸࣜࢵࢡ࡟ .DL% ࡜ .DL& ࡢ⤖ྜࢆ㜼ᐖࡍࡿ࡜࠸࠺ࡇ࡜ࡀᐇ㦂ⓗ࡟▱ࡽࢀ࡚࠸ࡓࡀࠊࡇࡢ㐣⛬ࡀ᣺ືᏊࡢ࿘
ᮇࡢ㡹೺ᛶ㸦ᑐᗘኚ໬࠾ࡼࡧᑐࢱࣥࣃࢡ㉁⃰ᗘኚ໬㸧ࡢⓎ⌧࡟࠾࠸࡚୺せ࡞ᙺ๭ࢆᢸࡗ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ

࠿࡟࡞ࡗࡓࠋࡲࡓࠊ.DL%.DL& ࡢ⤖ྜࡢ཯ᛂࣔࢹ࡛ࣝࡣࠊ」ྜయ୰ࡢ .DL%.DL% 㛫ࡢ┦஫స⏝ࢆ⪃៖ࡍࡿࡇ࡜࡛ࠊࡇࢀࡲ࡛ࡢྛ✀ࡢᐇ㦂⤖ᯝࢆ⤫୍ⓗ࡟ㄝ࡛᫂ࡁࡿࡇ࡜ࡀࢃ࠿ࡾࠊ⤖ᯝ࡜ࡋ࡚ .DL%.DL& ⤖ྜࡢ㐜ࡉࡣ
.DL& ࡢ $73 ຍỈศゎࡢ㐜ࡉ࡟㉳ᅉࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ
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Theoretical Calculations of Electronic Structure andElectron Dynamics in Nanostructures‫ۑ‬㣤⏣ ೺஧㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧ࠊ㔝⏣ ┿ྐ㸦⟃Ἴ኱Ꮫ㸧ࠊ➉ෆ ᓫ㸦⟃Ἴ኱Ꮫ㸧

1◊✲┠ⓗࠊෆᐜ
ᩘࢼࣀ࣓࣮ࢺࣝ⛬ᗘࡢ኱ࡁࡉࢆ᭷ࡍࡿࢼࣀᵓ㐀యࡣࠊග࡜ࡢ┦஫స⏝࡟ࡼࡗ࡚ከᙬ࡞ග㟁Ꮚᶵ⬟ࢆⓎ⌧ࡍࡿࡓࡵ࡟ࠊᇶ♏࣭ᛂ⏝ࡢ୧ほⅬ࠿ࡽ┒ࢇ࡟◊✲ࡀ⾜ࢃࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊᐇ㦂◊✲ࡸ⏘ᴗ㛤Ⓨࡢ㐍ᒎ࡟ẚࡋ࡚⌮ㄽ◊✲ࡣ㐜ࢀ࡚࠾ࡾࠊࢼࣀᵓ㐀యࡢࡈࡃ୍㒊ࢆษࡾฟࡋࡓ㒊ศ⣔ࢆᑐ㇟࡜ࡋ࡚➨୍ཎ⌮ィ⟬ࢆ⾜ࡗ࡚㟁Ꮚ≧ែࡢゎᯒࢆࡍࡿ࠿ࠊᴟᗘ࡟⡆༢໬ࡉࢀࡓᩘ⌮ィ⟬ࣔࢹࣝࢆ౑ࡗ࡚ᐃᛶⓗ㆟ㄽࢆ⾜ࡗ࡚࠸ࡿ◊✲ࡀከ࠸ࠋࡑࡢࡓࡵࠊࢼࣀᵓ㐀య࠿ࡽ࡞ࡿග࣭㟁Ꮚᶵ⬟ᛶ≀㉁ࡢ㛤Ⓨ࡟㈨ࡍࡿ⌮ㄽⓗ▱ぢࡣᴟࡵ࡚㝈ࡽࢀ࡚࠸ࡿࠋ
ᡃࠎࡣࠊࢼࣀᵓ㐀యࡢගບ㉳㟁Ꮚࢲ࢖ࢼ࣑ࢡࢫࢆ➨୍ཎ⌮࡟❧⬮ࡋ࡚ཎᏊ࣭㟁Ꮚࡢ࡛ࣞ࣋ࣝ᫂ࡽ࠿࡟ࡋࠊ
ග࢚ࢿࣝࢠ࣮ኚ᥮ࠊග࢚ࢿࣝࢠ࣮ఏᦙࠊගゐ፹➼ࡢග࣭㟁Ꮚᶵ⬟ࢆ᭷ࡍࡿ≀㉁ࢆ⌮ㄽタィࡍࡿࡇ࡜ࢆ┠ᶆ࡟◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋࡑࡢࡓࡵ࡟ࠊගບ㉳㟁Ꮚࢲ࢖ࢼ࣑ࢡࢫࡢィ⟬ࣉࣟࢢ࣒ࣛ SALMON[1]ࢆ⏝࠸࡚ࢼࣀᵓ㐀యࡢගᏛᛂ⟅ࡢ◊✲ࢆ㐍ࡵ࡚ࡁࡓࠋࡇࢀࡲ࡛࡟ࠊᵝࠎ࡞Ꮩ❧⣔(㔠ᒓࢡࣛࢫࢱ࣮ࠊ㔠-ࢳ࣮࢜ࣛࢺࢡࣛࢫࢱ࣮)ཬ
ࡧ࿘ᮇ⣔(஧ḟඖᒙ≧≀㉁ࠊ㈗㔠ᒓࢼࣀ⢏Ꮚ/ࢩࣜࢥࣥ⣔)ࢆᑐ㇟࡜ࡋ࡚ࠊගᏛᛂ⟅ࡢᶵᵓࢆ᫂ࡽ࠿࡟ࡋ࡚ࡁࡓࠋ
2019 ᖺᗘࡣࠊ᭷ᶵ㔠ᒓ㘒యࡢ㏆᥋ሙගບ㉳ࡸ㖟ࢼࣀ⢏Ꮚ/㓟໬ࢳࢱࣥ࣊ࢸࣟᵓ㐀࡟࠾ࡅࡿගㄏ㉳㟁Ꮚ⛣ື࡟ࡘ࠸࡚◊✲ࢆ⾜ࡗࡓ[5, 6]ࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲᡃࠎࡣࠊᩘࢼࣀ࣓࣮ࢺࣝ⛬ᗘࡢ኱ࡁࡉࢆ᭷ࡍࡿ≀㉁⣔ࢆᑐ㇟࡜ࡋ࡚ࠊගࡸ㟁ᅽ࡟ᑐࡍࡿᛂ⟅ᶵᵓࢆཎᏊ࣭

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㛫࣭ᐇ✵㛫࡛グ㏙ࡍࡿ➨୍ཎ⌮ィ⟬ࣉࣟࢢ࣒ࣛ SALMON ࢆ⏝࠸࡚◊✲ࢆ㐍ࡵ࡚ࡁࡓࠋ6$/021 ࡛ࡣࠊග࡜
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㖟ࢼࣀࢡࣛࢫࢱ࣮㓟໬ࢳࢱࣥ࣊ࢸࣟᵓ㐀࡟࠾ࡅࡿගㄏ㉳㟁Ꮚ⛣ື㈗㔠ᒓࢼࣀ⢏Ꮚ࡜༙ᑟయࡢ㛫ࡢගㄏ㉳㟁Ꮚ⛣ືࡣࠊཷග
⣲ᏊࡸỈศゎගゐ፹ࡢ㛤Ⓨ࡟㛵㐃ࡋ࡚┒ࢇ࡟◊✲ࡀ㐍ࡵࡽࢀ࡚ࡁࡓࠋࡇࢀࡲ࡛ࡢ◊✲࠿ࡽࠊ㈗㔠ᒓࢼࣀ⢏Ꮚࡢᒁᅾ⾲㠃ࣉࣛࢬࣔࣥඹ㬆 /635 ࡟ࡼࡗ࡚ບ㉳ࡋࡓ㟁Ꮚࡀ⛣ືࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ୍᪉࡛ࠊ/635 ࡛ᙉ࠸ගㄏ㉳㟁ሙࡀ⏕ࡌࡿࡇ࡜ࡣࡼࡃ▱ࡽࢀ࡚࠸ࡿࡀࠊ㟁Ꮚ⛣ື࡟࠾ࡅࡿࡑࡢᙺ๭
ࡣ᫂ࡽ࠿࡟࡞ࡗ࡚࠸࡞࠸ࠋᡃࠎࡣࠊ㖟ࢼࣀ⢏Ꮚ±㓟໬ࢳࢱࣥ- 406 -

ᅗ 1. (a)Ag20-TiO2 ࣊ࢸࣟᵓ㐀࡜(b)Ag20 ࡜
TiO2 ࢆࡑࢀࡒࢀಶู࡟᭱㐺໬ࡋࡓཧ↷⣔.

࣊ࢸࣟᵓ㐀ࡢගບ㉳㟁Ꮚࢲ࢖ࢼ࣑ࢡࢫࡢ➨୍ཎ⌮ィ⟬࡟ࡼࡗ࡚ࠊගᏛᛂ⟅ࡢᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿ࡭ࡃ◊✲ࢆ⾜ࡗ࡚ࡁࡓࠋࡇࢀࡲ࡛࡟ࠊAg20-TiO2 ࣊ࢸࣟᵓ㐀(ᅗ 1(a))ࡢィ⟬⤖ᯝ࠿ࡽࠊ㖟ࡢఏᑟᖏࢆ⤒ࡿࡇ࡜࡞ࡃ㖟࠿ࡽ㓟໬ࢳࢱࣥ࡬࡜㟁Ꮚࡀ┤᥋⛣ືࡍࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ࡚࠸ࡿࠋࡑࡇ࡛ࠊගㄏ㉳㟁Ꮚ⛣ືࡢᶵᵓ࡟ࡘ࠸࡚ゎᯒࢆ㐍ࡵࡓࠋ
ᅗ 2 ࡣࠊAg20 ࡜ TiO2 ⷧ⭷ࢆಶู࡟᭱㐺໬ࡋ࡚᥋ྜࡋࡓ⣔(ᅗ 1(b))ࡢගບ㉳࡟ࡼࡿ㟁Ꮚ༨᭷ᩘࡢኚ໬࡛࠶ࡿࠋAg-O ⤖ྜࡢ㊥㞳ࡣ 3.0-3.3 Å ࡛࠶ࡾࠊࣇ࢓ࣥࢹ࢔࣮༙࣡ࣝᚄࡢ࿴
(~3.7 Å)ࡼࡾࡶ▷ࡃࡋ࡚࠸ࡿࠋ᭱㐺໬ࡋࡓ Ag20-TiO2 ࣊ࢸࣟᵓ㐀(ᅗ 1(a))࡜ྠᵝ࡟ࠊAg20 ࡢఏᑟᖏ࡟ບ㉳㟁ᏊࡀṤ࡝⏕ࡌ࡚࠾ࡽࡎࠊ㟁Ꮚࡣ Ag20 ࠿ࡽ TiO2 ࡬࡜┤᥋⛣ືࡋ࡚࠸ࡿࠋ
ࡇࡢ⤖ᯝ࠿ࡽࠊAg20 ࠿ࡽ TiO2 ࡬ࡢ┤᥋㟁Ꮚ⛣ືࡣࠊAg-O
㛫ࡢ໬Ꮫ⤖ྜࡢヲ⣽࡟౫ᏑࡏࡎⓎ⌧ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞
ࡗࡓࠋ᭦࡟ $J ࢆ⏝࠸ࡓィ⟬ࢆ⾜ࡗࡓࡀࠊྠᵝ࡟ࠊ$J࠿ࡽ 7L2 ࡬࡜㟁Ꮚࡀ┤᥋⛣ືࡋ࡚࠸ࡓࠋࡑࡇ࡛ࠊගບ㉳ࡢᶵᵓࢆゎᯒࡋࡓ࡜ࡇࢁࠊ㖟ࢼࣀ⢏Ꮚ㓟໬ࢳࢱࣥ⏺㠃࡟࠾࠸࡚ගㄏ㉳㟁ሙ࡟ࡼࡗ࡚ᙉ࠸㟁Ꮚⓗ┦஫స⏝ࡀㄏ㉳ࡉࢀࡿࡓᅗ 2. ཧ↷⣔(ᅗ 1(b))ࡢගບ㉳࡟ࡼࡿ㟁Ꮚ༨᭷ᩘࡢኚ໬.

ࡵ࡟ࠊບ㉳㟁Ꮚࡀ㖟ࡢఏᑟయࢆ⤒ࡿࡇ࡜࡞ࡃ㓟໬ࢳࢱࣥ࡬
࡜┤᥋⛣ືࡍࡿ࡜࠸࠺ࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓ >@ࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ‫[ ۻ‬1] Kenji Iida, “Massively Parallel Calculations for Photoexcited Electron Dynamics in
Nanostructures”, ஧ ᅜ 㛫 ඹ ྠ ◊ ✲ ࢜ ࣮ ࣉ ࣥ ࢭ ࣑ ࢼ ࣮ ࠕ Theoretical and Computational
Chemistry of Complex Systemsࠖ, 2019 ᖺ 7 ᭶ 18 ᪥, ᒸᓮ [ᣍᚅㅮ₇].
‫[ ۻ‬2] Kenji Iida, “First-Principles Study of Heterostructures Consisting of Two-Dimensional
Layered Materials under Light and Voltage Bias”, 17th Japan-Korea Symposium on
Molecular Science ࠕAdvances in Materials and Molecular Sciencesࠖ, 2019 ᖺ 7 ᭶ 29-31 ᪥, ྡྂᒇ [ᣍᚅㅮ₇],‫[ۻ‬3] 㣤⏣೺஧ࠊ㔝⏣┿ྐࠊ“㈗㔠ᒓࢼࣀ⢏Ꮚ࡜༙ᑟయⷧ⭷ࡢ㛫ࡢගບ㉳㟁Ꮚ⛣ືࢲ࢖ࢼ࣑ࢡࢫ” ➨ 13ᅇศᏊ⛉Ꮫウㄽ఍ࠊ2019 ᖺ 9 ᭶ 17-20 ᪥ࠊྡྂᒇ.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ‫ @> ۻ‬7 7DNHXFKL 0 1RGD . <DEDQD ³2SHUDWLRQ RI 4XDQWXP 3ODVPRQLF 0HWDVXUIDFHV 8VLQJ (OHFWURQ

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npj Comput. Mater.6  - 407 -

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 theories‫ۑ‬Ụཎṇ༤ࠊVignesh K.R.ࠊPei Zhaoࠊ㔠⃝ᝆ⣖ࠊⓑ⏨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) ගᏛ≀ᛶ࡟㛵ࡍࡿศᏊ㞟ྜయࡢ⌮ㄽⓗ㏫タィἲࡢ㛤Ⓨ࡜ᛂ⏝ࠊ2) ༢ᒙ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ໬Ꮫಟ㣭࡟ࡼࡿ㔞ᏊḞᦆࡢ⏕ᡂ࡜㏆㉥እⓎගἼ㛗ไᚚࠊ3) 㻼㼠 Ⓨග㘒య䛾⇕⪏ᛶ⇥ගⓎගไᚚ䠖ⰾ㤶᪘ᛶ䛚䜘䜃䃟ඹᙺᵓ㐀࡜Ⓨගᛶ⬟ࡢ┦㛵ࠊ4) ከ㓄⨨㟁Ꮚ┦㛵⌮ㄽ࡟ᇶ࡙ࡃ㟁Ꮚඹ㬆≧ែ⌮ㄽࡢ㛤Ⓨ࡜㟁Ꮚ௜ຍ⤖ྜゎ㞳⣔࡬ࡢᛂ⏝ࠊ5) ᢸᣢⓑ㔠ࢧࣈࢼࣀࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜㓟⣲㑏ඖ཯ᛂ࡟ᑐࡍࡿ
㧗࠸ゐ፹άᛶࡢせᅉࠊ6) 㔠ᒓᚤ⢏Ꮚゐ፹ࡢ⌮ㄽゎᯒ㸸పNO 㑏ඖ཯ᛂࡢ཯ᛂᶵᵓ࠾ࡼࡧ㔠ᒓࢼࣀ⢏Ꮚࡢ⣔⤫ⓗศ㢮ࠊ7) ࣟࢪ࣒࢘ࢼࣀࢩ࣮ࢺ࡟ࡼࡿ CO-NO ཯ᛂࡢ㧗࠸ゐ፹άᛶࡢゎ᫂࡟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. ගᏛ≀ᛶ࡟㛵ࡍࡿศᏊ㞟ྜయࡢ⌮ㄽⓗ㏫タィἲࡢ㛤Ⓨ࡜ᛂ⏝ศᏊ㞟ྜయ䛾ගᏛ≀ᛶ䛿䠈ศᏊ⤌ᡂ䛸㞟ྜయ䛾ᵓ㐀䛻䜘䜚኱䛝䛟ኚ໬䛩䜛䛣䛸䛜▱䜙䜜䛶䛚䜚䠈᪂ወගᏛ≀㉁䛾㛤

Ⓨ䜢┠ᣦ䛧䛶䠈ᵝ䚻䛺ศᏊ㞟ྜయ䛜㛤Ⓨ䛥䜜䛶䛔䜛䚹◊✲㛤Ⓨ䛻䛚䛔䛶䛿䚸ගᶵ⬟䌦ᵓ㐀䛾㛵ಀ䛾ゎ᫂䛸タィᣦ㔪䛜ᚲせ䛸䛥䜜䜛䚹ᮏᖺᗘ䠈ගᏛ≀ᛶ䛾ィ⟬䛾㏫ၥ㢟䛻ᇶ䛵䛟ගᶵ⬟ᛶศᏊ㞟ྜయ䛾タィἲ䜢㛤Ⓨ䛧䛯䚹ᮏ᪉ἲ䛿䠈ೃ⿵ศᏊ㞟ྜయ䜢⾲䛩䝝䝭䝹䝖䝙䜰䞁䜢ᑟධ䛧䠈඲᥈⣴䛜ᅔ㞴䛷䛒䜛Ⳙ኱䛺ೃ⿵ศᏊ㞟ྜయ⩌䛻䛚䛔䛶᭱㐺໬䛻䜘䜛ྜ⌮ⓗ䛛䛴ຠ⋡ⓗ䛺タィ䜢ྍ⬟䛻䛧䛯䚹䛣䛾᪉ἲ䜢」ᩘ䛾ೃ⿵ศᏊ✀䛸ೃ⿵✵㛫㓄⨨䜢䜒䛴୍ḟඖศᏊ㞟ྜయ䛾タィ䛻㐺⏝䛧䠈ᙉ䛔ග྾཰䞉෇஧Ⰽᛶ䠄㻯㻰䠅䜢䜒䛴㞟ྜయ䛾ศᏊ⤌ᡂ䞉ᵓ㐀䜢ᥦ᱌䛧䛯䚹䜎䛯䚸㐺ษ䛺ศᏊ㞟ྜయ䛾タィ䞉ᙧᡂ䛸ᵓᡂศᏊᩘ䛾ቑ኱䛻䜘䜚䠈㠀⥺ᙧⓗ䛻 㻯㻰 䜢ቑ኱ྍ⬟䛷䛒䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹㧗䛔ගᶵ⬟䜢ᚓ䜛䛯䜑䛻タィἲ䛻䜘䜛ᥦ᱌䛸⢭ᐦ䛺ศᏊ✀䞉ศᏊ㓄ྥไᚚ䛜㔜せ䛷䛒䜛䛣䛸䜢♧䛧䛯䚹
3.2. ༢ᒙ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢ໬Ꮫಟ㣭࡟ࡼࡿ㔞ᏊḞᦆࡢ⏕ᡂ࡜㏆㉥እⓎගἼ㛗ไᚚ༢ᒙ䜹䞊䝪䞁䝘䝜䝏䝳䞊䝤䠄SWCNT䠅䛷䛿䠈໬Ꮫಟ㣭䛻䜘䜛ศᏊኚ᥮䛚䜘䜃Ⓨගᛶ㔞ᏊḞ㝗䛜ὀ┠䛥䜜䛶䛔䜛䚹ᐇ㦂䛸༠ຊ䛧䠈SWCNT 䛾໬Ꮫಟ㣭䛻䜘䜛㔞ᏊḞᦆ䛾⏕ᡂ䛸㏆㉥እⓎග䛾Ἴ㛗ไᚚ䜢◊✲䛧䛯䚹➨䠍䠉➨䠏ୡ௦䛾䝕䞁䝗䝻䞁䜢⨨᥮ᇶ䛻⏝䛔䠈⨨᥮ᇶ䛾❧యຠᯝ䛻䜘䛳䛶௜ຍ఩⨨䜢ไᚚ䛧䠈Ⓨග≉ᛶ䜢ไᚚ䛩䜛䛣䛸䛻ᡂຌ䛧䛯䚹䜎䛯䠈ศᒱ䞉⎔≧䜰䝹䜻䝹ᇶ䛾໬Ꮫಟ㣭䛻䜘䜛௜ຍ఩⨨ไᚚ䛚䜘䜃⇕ฎ⌮䛻䜘䜛ⓎගἼ㛗ไᚚ䛻䜒ᡂຌ䛧䠈䛭䛾ไᚚᶵᵓ䜢⌮ㄽィ⟬䛻䜘䛳䛶᫂䜙䛛䛻䛧䛯䚹䛥䜙䛻ᵝ䚻䛺ᚄ䛸䜹䜲䝷䝹ᣦᩘ䛾 SWCNT(m,n)䛾⣔⤫ⓗ䛺⌮ㄽィ⟬䜢ᐇ᪋䛧䠈ᒁᡤⓗ Clar ᵓ㐀䛾භဨ⎔䛜᭱኱ᩘ䛻䛺䜛䜘䛖䛻⨨᥮䛥䜜䠈ⓎගἼ㛗䜢⌮ㄽண- 408 -

䛷䛝䜛䛣䛸䜢ぢฟ䛧䛯䚹䛣䛾ᇶ♏ཎ⌮䛻ᇶ䛵䛔䛶䠈ᚄ䛾␗䛺䜛 SWCNT 䛾㏆㉥እ㡿ᇦ䛾ⓎගἼ㛗ไᚚ䛜ྍ⬟䛷䛒䜛䛣䛸䜢♧䛧䛯䚹
3.3. 㻼㼠 Ⓨග㘒య䛾⇕⪏ᛶ⇥ගⓎගไᚚ䠖ⰾ㤶᪘ᛶ䛚䜘䜃䃟ඹᙺᵓ㐀࡜Ⓨගᛶ⬟ࡢ┦㛵䝦䝔䝻⎔≧㓄఩Ꮚ䜢᭷䛩䜛 Pt, Ir 㘒య䛿䠈㔠ᒓ䠉㓄఩Ꮚ㟁Ⲵ⛣ືບ㉳≧ែ(3MLCT)䛛䜙ᙉ䛔⇥ගⓎග䜢♧䛩䚹ᮏ◊✲䛷䛿䠈trans-Bis[(b-iminomethyl)aryloxy]Pt(II)ศᏊ⩌䜢タィ䞉ྜᡂ䛧䠈77K 䛾ప⇥ගⓎග䜢♧䛩䛣䛸䜢ぢฟ䛧䛯䚹୍㒊䛾㘒య䛷䛿㧗䛻䛚䛔䛶㧗䛔㔞Ꮚ཰⋡䛷ᙉ䛔䛷ᾘග䛩䜛䛜䠈↓㍽ᑕኻά䛿 3MLCT 䛾཯ᛂ㠃䛛䜙᭱ప䜶䝛䝹䜼䞊஺ᕪⅬ䠄MECP䠅䜢⤒⏤䛧䛶ᇶᗏ≧ែ䛻⦆࿴䛩䜛䛣䛸䜢⌮ㄽⓗ䛻᫂䜙䛛䛻䛧䛯䚹䛥䜙䛻⇥ගⓎග䛾⇕⪏ᛶ䛿䠈
3

MLCT 䛾Ᏻᐃᵓ㐀䛸 MECP 䛾䜶䝛䝹䜼䞊ᕪ䛻┦㛵䛧䛶䛔䜛䛣䛸䜢♧䛧䛯䚹䜎䛯䠈MECP 䛾┦ᑐ䜶䝛䝹䜼䞊఩⨨䛿䠈

MECP ㏆ഐ䛷 Pt dσ*㌶㐨䛜㓄఩Ꮚ䛾 π*㌶㐨䛸┦஫స⏝䛩䜛ᙉ䛥䛻䜘䜛䛣䛸䜢᫂䜙䛛䛻䛧䠈㓄఩Ꮚ䛾䝦䝔䝻⎔䛾ⰾ㤶᪘ᛶ䛻䜘䜚ไᚚ䛷䛝䜛䛣䛸䜢♧䛧䛯䚹㻌
3.4. ከ㓄⨨㟁Ꮚ┦㛵⌮ㄽ࡟ᇶ࡙ࡃ㟁Ꮚඹ㬆≧ែ⌮ㄽࡢ㛤Ⓨ࡜㟁Ꮚ௜ຍ⤖ྜゎ㞳⣔࡬ࡢᛂ⏝ඹ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≧ែ䛜䛒䜛䚹ᡃ䚻䛿䠈㟁Ꮚඹ㬆≧ែ䛾ィ⟬ἲ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Ⓨ䛧䠈௵ព䛾ᙧ≧䛾ศᏊ䛻㐺⏝䛷䛝䜛䝪䝻䝜䜲䞉䝫䝔䞁䝅䝱䝹䜢㛤Ⓨ䛧䛯䚹ᮏᖺᗘ䛿䠈ከ㓄⨨㟁Ꮚ┦㛵⌮ㄽ䛷䛒䜛 㼄㻹㻿㻙㻯㻭㻿㻼㼀㻞 ἲ䛻」⣲྾཰䝫䝔䞁䝅䝱䝹䜢ᑟධ䛧䠈ከ㓄⨨ᛶ䛜㔜せ䛸䛺䜛⤖ྜゎ㞳㡿ᇦ䜔䝣䜵䝑䝅䝳䝞䝑䝝ඹ㬆䛻㐺⏝䛷䛝䜛 㻯㻭㻼㻛㼄㻹㻿㻙㻯㻭㻿㻼㼀㻞 ἲ䜢㛤Ⓨ䞉ᐇ⿦䛧䛯䚹䛣䛾᪉ἲ䜢 㻴㻞㻯㻻 ศᏊ䜔 㻯㻴㻞㻯㻴㻙㻯㼘 ศᏊ䛾⤖ྜゎ㞳㸪N2 ศᏊࡢ⤖ྜゎ㞳࡟㐺⏝ࡋ㸪䛻㐺⏝䛧䠈᪉ἲ䛾ಙ㢗ᛶ䛸᭷ຠᛶ䜢᳨ド䛧䛯䚹㻯㻴㻞㻯㻴㻙㻯㼘 ⣔䛷䛿䠈㟁Ꮚ௜ຍඹ㬆≧ែ䃟㻖䛛䜙䃢㻖䜈䛸⦆࿴䛧䠈㻯㻙㻯㼘 ⤖ྜゎ㞳䛜ㄏ㉳䛥䜜䜛཯ᛂ⤒㊰䜢᫂䜙䛛䛻䛧䛯䚹㻌
3.5. ᢸᣢⓑ㔠ࢧࣈࢼࣀࢡࣛࢫࢱ࣮ࡢᵓ㐀࡜㓟⣲㑏ඖ཯ᛂ࡟ᑐࡍࡿ㧗࠸ゐ፹άᛶࡢせᅉ⇞ᩱ㟁ụ䛻䛿ⓑ㔠䛜฼⏝䛥䜜䛶䛔䜛䛜䠈ⓑ㔠䛿ᕼᑡඖ⣲䛷䛒䜚䠈౑⏝㔞䛾పῶ䛜ồ䜑䜙䜜䛶䛔䜛䚹≉䛻䠈ṇᴟ䛻䛚䛡䜛㓟⣲㑏ඖ཯ᛂ㻔㻻㻾㻾㻕䛻䛚䛔䛶䠈㧗άᛶ䛺ⓑ㔠䝘䝜䜽䝷䝇䝍䞊䛾㟁ᴟゐ፹䜈䛾฼⏝䛜ᮇᚅ䛥䜜䛶䛔䜛䚹៞᠕⩏ሿ኱Ꮫ䞉୰ᔱ䜾䝹䞊䝥䛷䛿⊂⮬䛾䝟䝹䝇䝬䜾䝛䝖䝻䞁䝇䝟䝑䝍䝸䞁䜾ἲ䛻䜘䜚䠈ཎᏊᩘ䛜ᩘಶ䛛䜙ᩘⓒಶ䛾䝘䝜䜽䝷䝇䝍䞊䜢ᅛయᇶᯈୖ䛻ᢸᣢ䛥䛫䜛᪉ἲ䜢㛤Ⓨ䛧䚸☜❧䛧䛶䛔䜛䚹᭱㏆䠈䛣䛾ᡭἲ䜢⏝䛔䛶䠈ᢸᣢⓑ㔠 㻢 㔞య䛜⌧⾜䛾ⓑ㔠ᶆ‽ゐ፹䛻ẚ䜉䛶 㻻㻾㻾 䛜 㻝㻚㻣 ಸ⛬ᗘ㧗䛔㉁㔞άᛶ䜢♧䛩䛣䛸䜢ぢฟ䛧䛯䚹ᮏ◊✲䛷䛿䠈䜾䝷䝣䜵䞁ᢸᣢⓑ㔠 㻢 㔞య䛾ᒁᡤᏳᐃᵓ㐀䜢 㻰㻲㼀 ィ⟬䛻䜘䛳䛶⢭ᰝ䛧䠈㻱㼄㻭㻲㻿 䛾ィ ⤖ᯝ䛸ẚ㍑䛩䜛䛣䛸䛻䜘䜚䠈㻢 㔞య䛾ᵓ㐀䛜཮ᅄ㠃యᵓ㐀䛷䛒䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹䛥䜙䛻ⓑ㔠 㻢 㔞య䛾 㼐 ㌶㐨䜶䝛䝹䜼䞊䝺䝧䝹䜔㟁Ⲵศᕸ䛛䜙ⓑ㔠䝃䝤䝘䝜䜽䝷䝇䝍䞊䛾ゐ፹άᛶ䛾㉳※䜢㆟ㄽ䛧䛯䚹㻌
3.6. 㔠ᒓᚤ⢏Ꮚゐ፹ࡢ⌮ㄽゎᯒ㸸పNO 㑏ඖ཯ᛂࡢ཯ᛂᶵᵓ࠾ࡼࡧ㔠ᒓࢼࣀ⢏Ꮚࡢ⣔⤫ⓗศ㢮୕ඖゐ፹䛾◊✲㛤Ⓨ䛷䛿䠈ᕼᑡඖ⣲䛷䛒䜛 㻼㻳㻹 ඖ⣲䛾పῶ䜔䝴䝡䜻䝍䝇ඖ⣲䜈䛾㌿᥮䛜ᮇᚅ䛥䜜䛶䛔䜛䚹㻺㻻㑏ඖ཯ᛂ䛿≉䛻㔜せ䛷䛒䜚䠈ᵝ䚻䛺ᢸᣢᚤ⢏Ꮚゐ፹䛜᳨ウ䛥䜜䛶䛔䜛䚹ᡃ䚻䛿䠈㖡ඖ⣲䛻╔┠䛧䛯◊✲㛤Ⓨ䜢ᐇ᪋䛧䛶䛔䜛䚹㻯㼡 䜽䝷䝇䝍䞊䛷䛿䠈㻺㻻㻙㻯㻻 ཯ᛂ䛻䛚䛔䛶ప䛷䛿 㻺㻻 䛾஧㔞໬䛜㉳䛣䜚䠈㻺㻞㻻 䜢⤒⏤䛩䜛཯ᛂᶵᵓ䛜㐍⾜䛩䜛䛣䛸䜢ᥦ᱌䛧䛯䚹䛥䜙䛻 㻾㼡㻘㻌㻾㼔㻘㻌㻼㼐㻘㻌㻭㼓 䜽䝷䝇䝍䞊䛻䛴䛔䛶䠈㔠ᒓ䜽䝷䝇䝍䞊䠄㻹㻝㻟㻘㻌㻹㻡㻡䠅䛾⌮ㄽィ⟬䝰䝕䝹䜢⏝䛔䛶᳨ウ䛧䠈㻹㻩㻾㼡㻘㻌㻾㼔 䛷䛿 㻺㻻 䛾྾╔ゎ㞳䛜㉳䛣䜚䠈ཎᏊ≧ 㻺 䛛䜙཯ᛂ䛜㐍⾜䛩䜛䛣䛸䠈㻹㻩㻼㼐 䛷䛿 㻺㻻 䛾ศᏊ≧྾╔䛜㉳䛣䜛䛣䛸䠈㻹㻩㻭㼓 䛷䛿 㻺㻻 䛾஧㔞໬䛛䜙཯ᛂ䛜㐍⾜䛩䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹䜎䛯䛣䜜䜙䛾཯ᛂᶵᵓ䛜㔠ᒓ䛾 㼐 ㌶
㐨䛸 㼟 ㌶㐨䛾䜶䝛䝹䜼䞊䝺䝧䝹䛸┦㛵䛩䜛䛣䛸䠈㔠ᒓ䛾㟁Ꮚᵓ㐀䛷ศ㢮䛥䜜䜛䛣䛸䜢♧䛧䛯䚹㻌
3.7. ࣟࢪ࣒࢘ࢼࣀࢩ࣮ࢺ࡟ࡼࡿ CO-NO ཯ᛂࡢ㧗࠸ゐ፹άᛶࡢゎ᫂㻾㼔 䛿୕ඖゐ፹䛻ᐇ⿦䛥䜜䛶䛚䜚䠈㧗άᛶ䛷䛒䜛䛜ᕼᑡඖ⣲䛷䛒䜚䠈䛭䛾ῶ㔞䛜ᮃ䜎䜜䛶䛔䜛䚹᭱㏆䠈⇃ᮏ኱䞉⏫⏣- 409 -

䜾䝹䞊䝥䛾⊂⮬䛾䜰䞊䜽䝥䝷䝈䝬ἲ䛻䜘䜚䠈㻾㼔 䝘䝜䝅䞊䝖䛜 㻾㼔 䝘䝜⢏Ꮚ䜘䜚䜒 㻺㻻 㑏ඖ཯ᛂ䛷㧗䛔ゐ፹άᛶ䜢♧䛩䛣䛸䛜ぢฟ䛥䜜䠈㻾㼔 䛾኱ᖜ䛺ῶ㔞䛾᪉ἲ䛜㛤Ⓨ䛥䜜䛯䚹ᮏ◊✲䛷䛿䠈➨୍ཎ⌮ศᏊືຊᏛ䝅䝭䝳䝺䞊䝅䝵䞁䛾㑄⛣≧ែ᥈⣴䛻䜘䜚䠈㻺㻻 㑏ඖ཯ᛂ䛻䛴䛔䛶 㻾㼔 䝘䝜䝅䞊䝖䛸 㻾㼔 䝘䝜⢏Ꮚ䛾ゐ፹άᛶ䛻䛴䛔䛶ẚ㍑䞉᳨ウ䛧䛯䚹㻾㼔㻡㻡 䜽䝷䝇䝍䞊䠄㻝㻌㼚㼙 ⛬ᗘ䛾┤ᚄ䠅䛷䛿䠈ᵓ㐀䜢ᰂ㌾䛻⦆࿴䛷䛝䜛䛯䜑䛻 㻺 ཎᏊ䛾㓄⨨䛻ྜ䜟䛫䛶ᵓ㐀䛜ṍ䜏䠈୰㛫య䜢Ᏻᐃ໬䛧䠈䜶䝛䝹䜼䞊㞀ቨ䛜㧗䛟䛺䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹୍᪉䠈㻾㼔㻔㻝㻝㻝㻕㠃䛾䝘䝜䝅䞊䝖䛿๛┤䛺ᙧ≧䜢ᣢ䛱䠈㻺 ཎᏊ䛾䝩䝑䝢䞁䜾䛜ᐜ᫆䛻䛺䜚䠈Ᏻᐃ䛺୰㛫య䜢⏕ᡂ䛧䛺䛔䛣䛸䛛䜙䠈㻾㼔 䝘䝜⢏Ꮚ䜘䜚䜒㧗άᛶ䛷䛒䜛䛣䛸䜢᫂䜙䛛䛻䛧䛯䚹㻌

4

Ⓨ⾲ᐇ⦼

䖩㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 䇾㻾㼑㼍㼏㼠㼕㼛㼚㻌 㼍㼚㼐㻌 㻰㼥㼚㼍㼙㼕㼏㼟㻌 㼍㼠㻌 㻵㼚㼠㼑㼞㼒㼍㼏㼑㻌 㻾㼑㼓㼕㼛㼚㻌 㼛㼒㻌 㻯㼛㼚㼐㼑㼚㼟㼑㼐㻙㼜㼔㼍㼟㼑㻌 㻭㼡㻙㻼㼐㻌 㻺㼍㼚㼛㼏㼘㼡㼟㼠㼑㼞㻌 㻯㼍㼠㼍㼘㼥㼟㼠㼟㻘䇿㻌㻶㼍㼜㼍㼚㻙㻵㼚㼐㼕㼍㻌㻹㼕㼚㼕㻌㼃㼛㼞㼗㼟㼔㼛㼜㻘㻌㻷㼛㼎㼑㻌㻔㻶㼍㼜㼍㼚㻕㻘㻌㻻㼏㼠㼛㼎㼑㼞㻌㻞㻜㻝㻥㻚㻌䖩㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 䇾 㻯㼛㼛㼞㼐㼕㼚㼍㼠㼕㼛㼚㻌 㻭㼟㼥㼙㼙㼑㼠㼞㼥㻦㻌 㻲㼞㼑㼚㼗㼑㼘㻙㻱㼤㼏㼕㼠㼛㼚㻌 㻰㼑㼏㼛㼙㼜㼛㼟㼕㼠㼕㼛㼚㻌 㻭㼚㼍㼘㼥㼟㼕㼟㻌 㼛㼒㻌 㻯㼕㼞㼏㼡㼘㼍㼞㻌 㻰㼕㼏㼔㼞㼛㼕㼟㼙㻌 㼍㼚㼐㻌㻯㼕㼞㼏㼡㼘㼍㼞㼘㼥㻌 㻼㼛㼘㼍㼞㼕㼦㼑㼐㻌 㻸㼡㼙㼕㼚㼑㼟㼏㼑㼚㼏㼑㻌 㼒㼛㼞㻌 㻹㼡㼘㼠㼕㼏㼔㼞㼛㼙㼛㼜㼔㼛㼞㼕㼏㻌 㻿㼥㼟㼠㼑㼙㼟㻘 䇿 㻌 㼀㼔㼑㻌 㻥㼠㼔㻌 㻯㼛㼚㼒㼑㼞㼑㼚㼏㼑㻌 㼛㼒㻌 㼠㼔㼑㻌 㻭㼟㼕㼍㻙㻼㼍㼏㼕㼒㼕㼏㻌㻭㼟㼟㼛㼏㼕㼍㼠㼕㼛㼚㻌㼛㼒㻌㼀㼔㼑㼛㼞㼑㼠㼕㼏㼍㼘㻌㼍㼚㼐㻌㻯㼛㼙㼜㼡㼠㼍㼠㼕㼛㼚㼍㼘㻌㻯㼔㼑㼙㼕㼟㼠㼟㻌㻔㻭㻼㻭㼀㻯㻯㻌㻞㻜㻝㻥㻕㻘㻌㻿㼥㼐㼚㼑㼥㻌㻔㻭㼡㼟㼠㼞㼍㼘㼕㼍㻕㻘㻌㻿㼑㼜㼠㼑㼙㼎㼑㼞㻌㻞㻜㻝㻥㻚㻌䖩㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 䇾㼀㼔㼑㼛㼞㼑㼠㼕㼏㼍㼘㻌 㻭㼜㼜㼞㼛㼍㼏㼔㼑㼟㻌 㼒㼛㼞㻌 㻯㼛㼛㼞㼐㼕㼚㼍㼠㼕㼛㼚㻌 㻭㼟㼥㼙㼙㼑㼠㼞㼥㻦㻌 㻼㼔㼛㼠㼛㼞㼑㼍㼏㼠㼕㼛㼚㻌 㼕㼚㻌 㻹㻹㻲㻌 㼍㼚㼐㻌 㻯㼔㼕㼞㼛㼜㼠㼕㼏㼍㼘㻌㻿㼜㼑㼏㼠㼞㼛㼟㼏㼛㼜㼥㻘䇿㻌 㻯㼛㼙㼎㼕㼚㼍㼠㼕㼛㼚㻌 㼛㼒㻌 㼀㼔㼑㼛㼞㼑㼠㼕㼏㼍㼘㻛㻯㼛㼙㼜㼡㼠㼍㼠㼕㼛㼚㼍㼘㻌 㻿㼠㼡㼐㼕㼑㼟㻌 㼍㼚㼐㻌 㻱㼤㼜㼑㼞㼕㼙㼑㼚㼠㼟㻌 㼠㼛㼣㼍㼞㼐㻌 㻼㼛㼞㼛㼡㼟㻌 㻯㼛㼛㼞㼐㼕㼚㼍㼠㼕㼛㼚㻌㻼㼛㼘㼥㼙㼑㼞㼟㻛㻌㻹㼑㼠㼍㼘㻌㻻㼞㼓㼍㼚㼕㼏㻌㻲㼞㼍㼙㼑㼣㼛㼞㼗㼟㻘㻌㻻㼟㼘㼛㻌㻔㻺㼛㼞㼣㼍㼥㻕㻘㻌㻭㼡㼓㼡㼟㼠㻌㻞㻜㻝㻥㻚㻌䖩Ụཎṇ༤㻘㻌 䡞ྜ㔠ᚤ⢏Ꮚゐ፹䛾ᵓ㐀䛸ᶵ⬟䛻㛵䛩䜛⌮ㄽ◊✲䡟㻘㻌 ゐ፹Ꮫ఍ⱝᡭ఍㻌 ➨ 㻠㻜 ᅇኟ䛾◊ಟ఍㻘㻌 ឡ▱㻘㻌㻞㻜㻝㻥 ᖺ 㻣 ᭶㻚㻌

5

ฟ∧ᐇ⦼

䖩㼆㻚㻌㻮㼛㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㻿㻚㻌㻿㼍㼗㼍㼗㼕㻘㻌 䇾㻼㼞㼛㼜㼑㼚㼑㻌㻻㼤㼕㼐㼍㼠㼕㼛㼚㻌㻯㼍㼠㼍㼘㼥㼟㼕㼟㻌㼍㼚㼐㻌㻱㼘㼑㼏㼠㼞㼛㼚㼕㼏㻌㻿㼠㼞㼡㼏㼠㼡㼞㼑㻌㼛㼒㻌㻹㻡㻡㻌㻼㼍㼞㼠㼕㼏㼘㼑㻌㻔㻹㻩㻌㻼㼐㻌㼛㼞㻌㻾㼔㻕㻦㻌㻰㼕㼒㼒㼑㼞㼑㼚㼏㼑㼟㻌㼍㼚㼐㻌㻿㼕㼙㼕㼘㼍㼞㼕㼠㼕㼑㼟㻌㼎㼑㼠㼣㼑㼑㼚㻌㻼㼐㻡㻡㻌㼍㼚㼐㻌㻾㼔㻡㻡㻘䇿㻌 㻼㼔㼥㼟㻚㻌㻯㼔㼑㼙㻚㻌㻯㼔㼑㼙㻚㻌㻼㼔㼥㼟㻚㻌㼕㼚㻌㼜㼞㼑㼟㼟㻌㻔㻞㻜㻞㻜㻕㻚㻌 㻌䖩㻽㻚㻌㻹㻚㻌㻼㼔㼡㼚㼓㻘㻌㼅㻚㻌㻷㼛㼙㼛㼞㼕㻘㻌㼀㻚㻌㼅㼍㼚㼍㼕㻘㻌㼀㻚㻌㻿㼛㼙㼙㼑㼞㼒㼑㼘㼐㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌 䇾㻯㼛㼙㼎㼕㼚㼍㼠㼕㼛㼚㻌㼛㼒㻌㼍㻌㼂㼛㼞㼛㼚㼛㼕㻙㼠㼥㼜㼑㻌㻯㼛㼙㼜㼘㼑㼤㻌㻭㼎㼟㼛㼞㼎㼕㼚㼓㻌㻼㼛㼠㼑㼚㼠㼕㼍㼘㻌㼣㼕㼠㼔㻌㼠㼔㼑㻌㼄㻹㻿㻙㻯㻭㻿㻼㼀㻞㻌㻹㼑㼠㼔㼛㼐㻌㼍㼚㼐㻌㻼㼕㼘㼛㼠㻌㻭㼜㼜㼘㼕㼏㼍㼠㼕㼛㼚㼟㻘䇿㻌 㻶㻚㻌㻯㼔㼑㼙㻚㻌㼀㼔㼑㼛㼞㼥㻌㻯㼛㼙㼜㼡㼠㻚㻌㼕㼚㻌㼜㼞㼑㼟㼟㻌㻔㻞㻜㻞㻜㻕㻚㻌㻹㻚㻌 㻼㼞㼛㼙㼗㼍㼠㼗㼍㼑㼣㻘㻌 㻿㻚㻌 㻿㼡㼞㼍㼙㼕㼠㼞㻘㻌 㼀㻚㻌 㻷㼍㼞㼜㼗㼕㼞㼐㻘㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 㻿㻚㻌 㻴㼍㼚㼚㼛㼚㼓㼎㼡㼍㻘㻌 䇾㻰㻲㼀㻛㼀㻰㻙㻰㻲㼀㻌 㻵㼚㼢㼑㼟㼠㼕㼓㼍㼠㼕㼛㼚㻌 㼛㼚㻌 㼠㼔㼑㻌㻼㼔㼛㼠㼛㼕㼚㼐㼡㼏㼑㼐㻌㻱㼘㼑㼏㼠㼞㼛㼚㻌㼀㼞㼍㼚㼟㼒㼑㼞㻌㼛㼒㻌㻰㼕㼞㼡㼠㼔㼑㼚㼕㼡㼙㻌㼍㼚㼐㻌㼂㼕㼛㼘㼛㼓㼑㼚㻌㻯㼛㼙㼜㼘㼑㼤㼑㼟㻘䇿㻌 㻶㻚㻌㻸㼡㼙㼕㼚㻚㻌㻞㻞㻞㻞㻘㻌㻝㻝㻣㻝㻞㻝㻙㻝㻙㻥㻌㻔㻞㻜㻞㻜㻕㻚㻌 㻌㻹㻚㻙㼅㻚㻌 㻸㼕㻘㻌 㼆㻚㻙㻮㻚㻌 㻳㼍㼛㻘㻌 㼅㻚㻙㻮㻚㻌 㻴㼍㼚㻘㻌 㼅㻚㻙㼄㻚㻌 㼆㼔㼍㼛㻘㻌 㻷㻚㻌 㼅㼡㼍㼚㻘㻌 㻿㻚㻌 㻺㼍㼓㼍㼟㼑㻘㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 㼄㻚㻌 㼆㼔㼍㼛㻘㻌 䇾㻼㼛㼠㼑㼚㼠㼕㼍㼘㻌 㻹㼛㼘㼑㼏㼡㼘㼍㼞㻌㻿㼑㼙㼕㼏㼛㼚㼐㼡㼏㼠㼛㼞㻌 㻰㼑㼢㼕㼏㼑㼟㻦㻌 㻯㼥㼏㼘㼛㻙㻯㼚㻌 㻔㼚㻌 㻩㻌 㻝㻜㻌 㼍㼚㼐㻌 㻝㻠㻕㻌 㼣㼕㼠㼔㻌 㻴㼕㼓㼔㼑㼞㻌 㻿㼠㼍㼎㼕㼘㼕㼠㼕㼑㼟㻌 㼍㼚㼐㻌 㻭㼞㼛㼙㼍㼠㼕㼏㼕㼠㼕㼑㼟㻌 㼠㼔㼍㼚㻌 㻭㼏㼗㼚㼛㼣㼘㼑㼐㼓㼑㼐㻌㻯㼥㼏㼘㼛㻙㻯㻝㻤㻘䇿㻌㻼㼔㼥㼟㻚㻌㻯㼔㼑㼙㻚㻌㻯㼔㼑㼙㻚㻌㻼㼔㼥㼟㻌㻘㻌㻞㻞㻞㻘㻌㻠㻤㻞㻟㻙㻠㻤㻟㻝㻌㻔㻞㻜㻞㻜㻕㻚㻌䖩㼀㻚㻌㻿㼍㼐㼔㼡㼗㼔㼍㼚㻘㻌㻭㻚㻌㻶㼡㼚㼗㼍㼑㼣㻘㻌㻼㻚㻌㼆㼔㼍㼛㻘㻌㻴㻚㻌㻹㼕㼡㼞㼍㻘㻌㼀㻚㻌㻿㼔㼕㼟㼔㼕㼐㼛㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌 䇾㻵㼙㼜㼛㼞㼠㼍㼚㼏㼑㻌㼛㼒㻌㼠㼔㼑㻌㻼㼐㻌㼍㼚㼐㻌㻿㼡㼞㼞㼛㼡㼚㼐㼕㼚㼓㻌㻿㼕㼠㼑㻌㼕㼚㻌 㻴㼥㼐㼞㼛㼟㼕㼘㼥㼘㼍㼠㼕㼛㼚㻌 㼛㼒㻌 㻵㼚㼠㼑㼞㼚㼍㼘㻌 㻭㼘㼗㼥㼚㼑㼟㻌 㼎㼥㻌 㻼㼍㼘㼘㼍㼐㼕㼡㼙㻙㻳㼛㼘㼐㻌 㻭㼘㼘㼛㼥㻌 㻯㼍㼠㼍㼘㼥㼟㼠㻘䇿㻌 㻻㼞㼓㼍㼚㼛㼙㼑㼠㼍㼘㼘㼕㼏㼟㻘㻌 㻟㻥㻘㻌 㻡㻞㻤㻙㻡㻟㻣㻌 㻔㻞㻜㻝㻥㻕㻚㻌㻔㻿㼡㼜㼜㼘㼑㼙㼑㼚㼠㼍㼞㼥㻌㻶㼛㼡㼞㼚㼍㼘㻌㻯㼛㼢㼑㼞㻕㻌䖩㻿㻚㻌 㻿㼍㼞㼠㼥㼛㼡㼚㼓㼗㼡㼘㻘㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 㻴㻚㻌 㻿㼍㼗㼡㼞㼍㼕㻘㻌 䇾㼀㼕㼙㼑㻙㻰㼑㼜㼑㼚㼐㼑㼚㼠㻌 㻰㼑㼚㼟㼕㼠㼥㻌 㻲㼡㼚㼏㼠㼕㼛㼚㼍㼘㻌 㼀㼔㼑㼛㼞㼥㻌 㻵㼚㼢㼑㼟㼠㼕㼓㼍㼠㼕㼛㼚㻌 㼛㼒㻌 㻱㼤㼏㼕㼠㼑㼐㻌㻿㼠㼍㼠㼑㻌㻵㼚㼠㼞㼍㼙㼛㼘㼑㼏㼡㼘㼍㼞㻌㻼㼞㼛㼠㼛㼚㻌㼀㼞㼍㼚㼟㼒㼑㼞㻌㼕㼚㻌㼀㼞㼕㼟㻔㻞㻙㼔㼥㼐㼞㼛㼤㼥㼜㼔㼑㼚㼥㼘㻕㼠㼞㼕㼍㼦㼍㼟㼡㼙㼍㼚㼑㼚㼑㻘䇿㻌 㻶㻚㻌㻼㼔㼥㼟㻚㻌㻯㼔㼑㼙㻚㻌㻭㻘㻌㻝㻝㻞㻠㻘㻌㻝㻞㻞㻣㻙㻝㻞㻟㻠㻌㻔㻞㻜㻞㻜㻕㻚㻌
㻴㻚㻌㼅㼛㼟㼔㼕㼐㼍㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㼁㻚㻌㻰㼑㼢㼍㻌㻼㼞㼕㼥㼍㼗㼡㼙㼍㼞㻘㻌㼀㻚㻌㻷㼍㼣㼍㼕㻘㻌㼀㻚㻌㻺㼍㼗㼍㼟㼔㼕㼙㼍㻘㻌䇾㻱㼚㼍㼚㼠㼕㼛㼟㼑㼜㼍㼞㼍㼠㼕㼛㼚㻌㼍㼚㼐㻌㻯㼔㼕㼞㼍㼘㻌㻵㼚㼐㼡㼏㼠㼕㼛㼚㻌㼕㼚㻌㻭㼓 㻞㻥㻌㻝㻝㻘㻌㻞㻟㻥㻠㻙㻞㻠㻜㻜㻌㻔㻞㻜㻞㻜㻕㻚㻌㻺㼍㼚㼛㼏㼘㼡㼟㼠㼑㼞㼟㻌㼣㼕㼠㼔㻌㻵㼚㼠㼞㼕㼚㼟㼕㼏㻌㻯㼔㼕㼞㼍㼘㼕㼠㼥㻘䇿㻌㻯㼔㼑㼙㻚㻌㻿㼏㼕㻚㻌㻝㻿㻚㻌㻴㼡㻘㻌㻼㻚㻌㼆㼔㼍㼛㻘㻌㼃㻚㻌㻿㼔㼑㼚㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㼅㻚㻌㼄㼕㼑㻘㻌㼀㻚㻌㻭㼗㼍㼟㼍㼗㼍㻘㻌㼄㻚㻌㻸㼡㻘㻌䇾㻯㼞㼥㼟㼠㼍㼘㼘㼛㼓㼞㼍㼜㼔㼕㼏㻌㻯㼔㼍㼞㼍㼏㼠㼑㼞㼕㼦㼍㼠㼕㼛㼚㻌㼛㼒㻌㻱㼞㻞㻯㻞㻬㻯㻤㻜㻙㻤㻤㻦㻌㻯㼘㼡㼟㼠㼑㼞㻌㻿㼠㼞㼑㼠㼏㼔㼕㼚㼓㻌㼣㼕㼠㼔㻌㻯㼍㼓㼑㻌㻱㼘㼛㼚㼓㼍㼠㼕㼛㼚㻘䇿㻌㻵㼚㼛㼞㼓㻚㻌㻯㼔㼑㼙㻚㻌㻡㻡㻥㻘㻌㻝㻥㻠㻜㻙㻝㻥㻠㻢㻌 㻌 㻔㻞㻜㻞㻜㻕㻚㻌㻹㻚㻙㼅㻚㻌㻸㼕㻘㻌㼅㻚㻙㼄㻚㻌㼆㼔㼍㼛㻘㻌㼅㻚㻙㻮㻚㻌㻴㼍㼚㻘㻌㻷㻚㻌㼅㼡㼍㼚㻘㻌㻿㻚㻌㻺㼍㼓㼍㼟㼑㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㼄㻚㻌㼆㼔㼍㼛㻘㻌㻎㼀㼔㼑㼛㼞㼑㼠㼕㼏㼍㼘㻌㻵㼚㼢㼑㼟㼠㼕㼓㼍㼠㼕㼛㼚㻌㼛㼒㻌㼠㼔㼑㻌㻷㼑㼥㻌㻾㼛㼘㼑㼟㻌 㼕㼚㻌 㻲㼡㼘㼘㼑㼞㼑㼚㼑㻙㻲㼛㼞㼙㼍㼠㼕㼛㼚㻌 㻹㼑㼏㼔㼍㼚㼕㼟㼙㼟㻦㻌 㻱㼚㼍㼚㼠㼕㼛㼙㼑㼞㻌 㼍㼚㼐㻌 㻱㼚㼠㼔㼍㼘㼜㼥㻎㻘㻌 㻭㻯㻿㻌㻭㼜㼜㼘㼕㼑㼐㻌 㻺㼍㼚㼛㻌㻹㼍㼠㼑㼞㼕㼍㼘㼟㻌 㻘㻌 㻟㻘㻌 㻡㻠㻣㻙㻡㻡㻠㻌㻔㻞㻜㻞㻜㻕㻌

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䖩㻼㻚㻌㼆㼔㼍㼛㻘㻌㻮㻚㻌㻮㼛㼑㼗㼒㼍㻘㻌㼀㻚㻌㻺㼕㼟㼔㼕㼠㼛㼎㼍㻘㻌㻺㻚㻌㼀㼟㼡㼚㼛㼖㼕㻘㻌㼀㻚㻌㻿㼍㼚㼛㻘㻌㼀㻚㻌㼅㼛㼗㼛㼕㻘㻌㻹㻚㻌㻻㼓㼡㼞㼍㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㻎㼀㼔㼑㼛㼞㼑㼠㼕㼏㼍㼘㻌㻿㼠㼡㼐㼥㻌㼛㼚㻌 㻟㻝㻼㻌㻺㻹㻾㻌㻯㼔㼑㼙㼕㼏㼍㼘㻌㻿㼔㼕㼒㼠㼟㻌㼛㼒㻌㻼㼔㼛㼟㼜㼔㼛㼞㼡㼟㻙㻹㼛㼐㼕㼒㼕㼑㼐㻌㻯㻴㻭㻌㼆㼑㼛㼘㼕㼠㼑㼟㻎㻘㻌㻹㼕㼏㼞㼛㼜㼛㼞㻚㻌㻹㼑㼟㼛㼜㼛㼞㻚㻌㻹㼍㼠㻚㻌㻞㻞㻥㻠㻘㻌㻝㻜㻥㻥㻜㻤㻌㻔㻞㻜㻞㻜㻕㻌䖩㼀㻚㻌㼅㼍㼚㼓㻘㻌㻯㻚㻌㻷㼛㼚㼓㻘㻌㻿㻚㻌㼅㼍㼚㼓㻘㻌㼆㻚㻌㼅㼍㼚㼓㻘㻌㻿㻚㻌㼅㼍㼚㼓㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㻎㻾㼑㼍㼏㼠㼕㼛㼚㻌㻹㼑㼏㼔㼍㼚㼕㼟㼙㻘㻌㻺㼛㼞㼎㼛㼞㼚㼑㼚㼑㻌㼍㼚㼐㻌㻸㼕㼓㼍㼚㼐㻌㻱㼒㼒㼑㼏㼠㼟㻘㻌㼍㼚㼐㻌㻻㼞㼕㼓㼕㼚㼟㻌㼛㼒㻌㻹㼑㼠㼍㻙㻿㼑㼘㼑㼏㼠㼕㼢㼕㼠㼥㻌㼛㼒㻌㻼㼐㻛㻺㼛㼞㼎㼛㼞㼚㼑㼚㼑㻙㻯㼍㼠㼍㼘㼥㼦㼑㼐㻌㻯䇵㻴㻌㻭㼏㼠㼕㼢㼍㼠㼕㼛㼚㻎㻘㻌㻯㼔㼑㼙㻚㻌㻿㼏㼕㻚㻌㻝㻝㻝㻘㻌㻝㻝㻟㻙㻝㻞㻡㻌㻔㻞㻜㻞㻜㻕㻌㼅㻚㻌 㻹㼍㼑㼐㼍㻘㻌 㻴㻚㻌 㻹㼡㼞㼍㼗㼛㼟㼔㼕㻘㻌 㻴㻚㻌 㼀㼍㼙㼎㼛㻘㻌 㻼㻚㻌 㼆㼔㼍㼛㻘㻌 㻷㻚㻌 㻷㼡㼞㼛㼐㼍㻘㻌 㻹㻚㻌 㼅㼍㼙㼍㼐㼍㻘㻌 㼄㻚㻌 㼆㼔㼍㼛㻘㻌 㻿㻚㻌 㻺㼍㼓㼍㼟㼑㻘㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌㻎㼀㼔㼑㼞㼙㼛㼐㼥㼚㼍㼙㼕㼏㻌 㻯㼛㼚㼠㼞㼛㼘㻌 㼛㼒㻌 㻽㼡㼍㼚㼠㼡㼙㻌 㻰㼑㼒㼑㼏㼠㼟㻌 㼛㼚㻌 㻿㼕㼚㼓㼘㼑㻙㼃㼍㼘㼘㼑㼐㻌 㻯㼍㼞㼎㼛㼚㻌 㻺㼍㼚㼛㼠㼡㼎㼑㼟㻎㻘㻌 㻯㼔㼑㼙㻚㻌 㻯㼛㼙㼙㼡㼚㻌 㻡㻡㻘㻌㻝㻟㻣㻡㻣㻙㻝㻟㻣㻢㻜㻌㻔㻞㻜㻝㻥㻕㻌㼅㻚㻙㼄㻚㻌㼆㼔㼍㼛㻘㻌㻹㻚㻙㼅㻚㻌㻸㼕㻘㻌㻼㻚㻌㼆㼔㼍㼛㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㼄㻚㻌㼆㼔㼍㼛㻘㻌㻎㻺㼑㼣㻌㻵㼚㼟㼕㼓㼔㼠㻌㼕㼚㼠㼛㻌㼁㻬㻯㻤㻜㻦㻌㻹㼕㼟㼟㼕㼚㼓㻌㼁㻬㻰㻟㻔㻟㻝㻥㻞㻝㻕㻙㻯㻤㻜㻌㼍㼚㼐㻌㻺㼡㼍㼚㼏㼑㼐㻌㻡㻤㻘㻌㻝㻠㻝㻡㻥㻙㻝㻠㻝㻢㻢㻌㻔㻞㻜㻝㻥㻕㻌㻱㼚㼍㼚㼠㼕㼛㼙㼑㼞㼟㻌㼛㼒㻌㼁㻬㻯㻝㻔㻞㻤㻟㻞㻠㻕㻙㻯㻤㻜㻎㻘㻌㻵㼚㼛㼞㼓㻚㻌㻯㼔㼑㼙㻚㻌㻡㻴㻚㻌㼀㼟㼡㼚㼛㼥㼍㼙㼍㻘㻌㻭㻚㻌㻻㼔㼚㼡㼙㼍㻘㻌㻷㻚㻌㼀㼍㼗㼍㼔㼍㼟㼔㼕㻘㻌㻭㻚㻌㼂㼑㼘㼘㼛㼠㼔㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㻺㻚㻌㻵㼏㼔㼕㼗㼡㼚㼕㻘㻌㻹㻚㻌㼀㼍㼎㼡㼏㼔㼕㻘㻌㻭㻚㻌㻺㼍㼗㼍㼖㼕㼙㼍㻘㻌㻎㻱㼚㼔㼍㼚㼏㼑㼐㻌㻻㼤㼥㼓㼑㼚㻌㻾㼑㼐㼡㼏㼠㼕㼛㼚㻌㻭㼏㼠㼕㼢㼕㼠㼥㻌㼛㼒㻌㻼㼘㼍㼠㼕㼚㼡㼙㻌㻿㼡㼎㼚㼍㼚㼛㼏㼘㼡㼟㼠㼑㼞㻌㻯㼍㼠㼍㼘㼥㼟㼠㼟㻌㼠㼔㼞㼛㼡㼓㼔㻌㻯㼔㼍㼞㼓㼑㻌㻾㼑㼐㼕㼟㼠㼞㼕㼎㼡㼠㼕㼛㼚㻎㻘㻌 㻯㼔㼑㼙㻚㻌㻯㼛㼙㼙㼡㼚㻚㻌㻡㻡㻘㻌㻝㻞㻢㻜㻟㻙㻝㻞㻢㻜㻢㻌㻔㻞㻜㻝㻥㻕㻌㻿㻚㻌 㻴㼡㻘㻌 㼃㻚㻌 㻿㼔㼑㼚㻘㻌 㻼㻚㻌 㼆㼔㼍㼛㻘㻌 㼀㻚㻌 㼄㼡㻘㻌 㼆㻚㻌 㻿㼘㼍㼚㼕㼚㼍㻘㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 㼄㻚㻌 㼆㼔㼍㼛㻘㻌 㼅㻚㻌 㼄㼕㼑㻘㻌 㼀㻚㻌 㻭㼗㼍㼟㼍㼗㼍㻘㻌 㼄㻚㻌 㻸㼡㻘㻌 㻎㻯㼞㼥㼟㼠㼍㼘㼘㼛㼓㼞㼍㼜㼔㼕㼏㻌㻯㼔㼍㼞㼍㼏㼠㼑㼞㼕㼦㼍㼠㼕㼛㼚㻌 㼛㼒㻌 㻱㼞㻞㻯㻞㻬㻯㻞㻔㻠㻟㻕㻙㻯㻥㻜㻘㻌 㻱㼞㻞㻯㻞㻬㻯㻞㻔㻠㻜㻕㻙㻯㻥㻜㻘㻌 㻱㼞㻞㻯㻞㻬㻯㻞㻔㻠㻠㻕㻙㻯㻥㻜㻘㻌 㼍㼚㼐㻌 㻱㼞㻞㻯㻞㻬㻯㻝㻔㻞㻝㻕㻙㻯㻥㻜㻦㻌 㼀㼔㼑㻌 㻾㼛㼘㼑㻌 㼛㼒㻌㻝㻝㻘㻌㻝㻣㻟㻝㻥㻙㻝㻣㻟㻞㻢㻌㻔㻞㻜㻝㻥㻕㻌㻯㼍㼓㼑㻙㻿㼔㼍㼜㼑㻌㼛㼚㻌㻯㼘㼡㼟㼠㼑㼞㻌㻯㼛㼚㼒㼕㼓㼡㼞㼍㼠㼕㼛㼚㻎㻘㻌㻺㼍㼚㼛㼟㼏㼍㼘㼑㻌㻝㼅㻚㻙㼄㻚㻌㼆㼔㼍㼛㻘㻌㻹㻚㻙㼅㻚㻌㻸㼕㻘㻌㻾㻙㻿㻚㻌㼆㼔㼍㼛㻘㻌㻷㻚㻌㼅㼡㼍㼚㻘㻌㻼㻚㻌㼆㼔㼍㼛㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㻿㻚㻌㻺㼍㼓㼍㼟㼑㻘㻌㼄㻚㻌㼆㼔㼍㼛㻘㻌㻎㻼㼕㼢㼛㼠㼍㼘㻌㻾㼛㼘㼑㻌㼛㼒㻌㻺㼛㼚㼙㼑㼠㼍㼘㻌㻭㼠㼛㼙㼟㻌㼕㼚㻌㼠㼔㼑㻌㻿㼠㼍㼎㼕㼘㼕㼠㼕㼑㼟㻘㻌㻳㼑㼛㼙㼑㼠㼞㼕㼑㼟㻘㻌㻱㼘㼑㼏㼠㼞㼛㼚㼕㼏㻌㻿㼠㼞㼡㼏㼠㼡㼞㼑㼟㻌㼍㼚㼐㻌㻵㼟㼛㼑㼘㼑㼏㼠㼞㼛㼚㼕㼏㻌㻯㼔㼑㼙㼕㼟㼠㼞㼥㻌㼛㼒㻌㻿㼏 㻟㼄㻬㻯㻤㻜㻌㻔㼄㻩㻯㻘㻌㻺㻌㼍㼚㼐㻌㻻㻕㻎㻘㻌 㻶㻚㻌㻯㼛㼙㼜㼡㼠㻚㻌㻯㼔㼑㼙㻚㻌㻠㻠㻜㻘㻌㻞㻣㻟㻜㻙㻞㻣㻟㻤㻌㻔㻞㻜㻝㻥㻕㻌㼅㻚㻙㼄㻚㻌 㼆㼔㼍㼛㻘㻌 㻷㻚㻌 㼅㼡㼍㼚㻘㻌 㻹㻚㻙㼅㻚㻌 㻸㼕㻘㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 㼄㻚㻌 㼆㼔㼍㼛㻘㻌 㻎㻵㼚㻙㻰㼑㼜㼠㼔㻌 㼀㼔㼑㼛㼞㼑㼠㼕㼏㼍㼘㻌 㻼㼞㼛㼎㼑㻌 㼕㼚㼠㼛㻌 㻺㼛㼢㼑㼘㻌 㻹㼕㼤㼑㼐㻙㻹㼑㼠㼍㼘㻌㼁㼞㼍㼚㼕㼡㼙㻙㻮㼍㼟㼑㼐㻌 㻱㼚㼐㼛㼔㼑㼐㼞㼍㼘㻌 㻯㼘㼡㼟㼠㼑㼞㼒㼡㼘㼘㼑㼞㼑㼚㼑㼟㻌 㻿㼏㻞㼁㼄㻬㻵㼔㻔㻟㻝㻥㻞㻠㻕㻙㻯㻤㻜㻌 㻔㼄㻌 㻩㻌 㻯㻘㻌 㻺㻕㻎㻘㻌 㻵㼚㼛㼞㼓㻚㻌 㻯㼔㼑㼙㻚㻌 㻡㻤㻘㻌 㻝㻜㻣㻢㻥㻙㻝㻜㻣㻣㻣㻌㻔㻞㻜㻝㻥㻕㻌
䖩㻺㻚㻌㼀㼍㼗㼍㼓㼕㻘㻌㻷㻚㻌㻵㼟㼔㼕㼙㼡㼞㼍㻘㻌㻾㻚㻌㻲㼡㼗㼡㼐㼍㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㻿㻚㻌㻿㼍㼗㼍㼗㼕㻘㻌㻎㻾㼑㼍㼏㼠㼕㼛㼚㻌㻮㼑㼔㼍㼢㼕㼛㼞㻌㼛㼒㻌㼠㼔㼑㻌㻺㻻㻌㻹㼛㼘㼑㼏㼡㼘㼑㻌㼛㼚㻌㼠㼔㼑㻌㻿㼡㼞㼒㼍㼏㼑㻌㼛㼒㻌㼍㼚㻌㻹㼚㻌㻼㼍㼞㼠㼕㼏㼘㼑㻌㻔㻹㻌㻩㻌㻾㼡㻘㻌㻾㼔㻘㻌㻼㼐㻘㻌㼍㼚㼐㻌㻭㼓㻧㻌㼚㻌㻩㻌㻝㻟㻌㼍㼚㼐㻌㻡㻡㻕㻦㻌㼀㼔㼑㼛㼞㼑㼠㼕㼏㼍㼘㻌㻿㼠㼡㼐㼥㻌㼛㼒㻌㻵㼠㼟㻌㻰㼑㼜㼑㼚㼐㼑㼚㼏㼑㻌㼛㼚㻌㼀㼞㼍㼚㼟㼕㼠㼕㼛㼚㻙㻹㼑㼠㼍㼘㻌㻱㼘㼑㼙㼑㼚㼠㻎㻘㻌㻶㻚㻌㻼㼔㼥㼟㻌㻯㼔㼑㼙㻚㻌㻭㻌㻝㻝㻞㻟㻘㻌㻣㻜㻞㻝㻙㻣㻜㻟㻟㻌㻔㻞㻜㻝㻥㻕㻌㻼㻚㻌㼆㼔㼍㼛㻘㻌㼅㻚㻌㻹㼍㼑㼐㼍㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㻎㼀㼔㼑㼛㼞㼑㼠㼕㼏㼍㼘㻌㻵㼚㼟㼕㼓㼔㼠㻌㼕㼚㼠㼛㻌㻯㼛㼚㼒㼕㼓㼡㼞㼍㼠㼕㼛㼚㼍㼘㻌㻿㼑㼘㼑㼏㼠㼕㼢㼕㼠㼥㻌㼛㼒㻌㻲㼡㼚㼏㼠㼕㼛㼚㼍㼘㼕㼦㼑㼐㻌㻿㼕㼚㼓㼘㼑㻙㼃㼍㼘㼘㼑㼐㻌㻯㼍㼞㼎㼛㼚㻌㻺㼍㼚㼛㼠㼡㼎㼑㼟㻌㻮㼍㼟㼑㼐㻌㼛㼚㻌㼠㼔㼑㻌㻯㼘㼍㼞㻌㻿㼑㼤㼠㼑㼠㻌㼀㼔㼑㼛㼞㼥㻎㻘㻌㻶㻚㻌㻼㼔㼥㼟㻌㻯㼔㼑㼙㻚㻌㻯㻌㻝㻝㻞㻟㻘㻌㻝㻤㻢㻞㻥㻙㻝㻤㻢㻟㻣㻌㻔㻞㻜㻝㻥㻕㻌㻿㻚㻌㻷㼕㼚㼛㼟㼔㼕㼠㼍㻘㻌㼅㻚㻌㻵㼚㼛㼗㼡㼏㼔㼕㻘㻌㼅㻚㻌㻻㼚㼕㼠㼟㼡㼗㼍㻘㻌㻴㻚㻌㻷㼛㼔㼓㼡㼏㼔㼕㻘㻌㻺㻚㻌㻭㼗㼍㼕㻘㻌㼀㻚㻌㻿㼔㼕㼞㼍㼛㼓㼍㼣㼍㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㻷㻚㻌㼅㼍㼙㼍㼦㼍㼗㼕㻘㻌㼅㻚㻌㻴㼍㼞㼍㼎㼡㼏㼔㼕㻘㻌㻿㻚㻌㻹㼍㼑㼐㼍㻘㻌㼀㻚㻌㻱㼎㼍㼠㼍㻘㻌㻎㼀㼔㼑㻌㻰㼕㼞㼑㼏㼠㻌㻻㼎㼟㼑㼞㼢㼍㼠㼕㼛㼚㻌㼛㼒㻌㼠㼔㼑㻌㻰㼛㼛㼞㼣㼍㼥 㻌㻝㼚䃟㻖㻌㻿㼠㼍㼠㼑㻌㼛㼒㻌㻹㼑㼠㼔㼥㼘㼏㼕㼚㼚㼍㼙㼍㼠㼑㻌㼍㼚㼐㻌㻴㼥㼐㼞㼛㼓㼑㼚㻙㻮㼛㼚㼐㼕㼚㼓㻌㻱㼒㼒㼑㼏㼠㼟㻌㼛㼚㻌㼠㼔㼑㻌㻼㼔㼛㼠㼛㼏㼔㼑㼙㼕㼟㼠㼞㼥㻌㼛㼒㻌㻯㼕㼚㼚㼍㼙㼍㼠㼑㻙㻮㼍㼟㼑㼐㻌㻿㼡㼚㼟㼏㼞㼑㼑㼚㼟㻎㻘㻌㻼㼔㼥㼟㻚㻌㻯㼔㼑㼙㻚㻌㻯㼔㼑㼙㻚㻌㻼㼔㼥㼟㻌㻞㻝㻘㻌㻝㻥㻣㻡㻡㻙㻝㻥㻣㻢㻟㻌㻔㻞㻜㻝㻥㻕㻌㻿㻚㻌㻴㼡㻘㻌㻼㻚㻌㼆㼔㼍㼛㻘㻌㼃㻚㻌㻿㼔㼑㼚㻘㻌㻼㻚㻌㼅㼡㻘㻌㼃㻚㻌㻴㼡㼍㼚㼓㻘㻌㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㼅㻚㻌㼄㼕㼑㻘㻌㼀㻚㻌㻭㼗㼍㼟㼍㼗㼍㻘㻌㼄㻚㻌㻸㼡㻘㻌㻎㻯㼞㼥㼟㼠㼍㼘㼘㼛㼓㼞㼍㼜㼔㼕㼏㻌㻯㼔㼍㼞㼍㼏㼠㼑㼞㼕㼦㼍㼠㼕㼛㼚㻌㼛㼒㻌㻱㼞㻟㻺㻬㻯㻞㼚㻌㻔㻞㼚㻌㻩㻌㻤㻜㻘㻌㻤㻞㻘㻌㻤㻠㻘㻌㻤㻤㻕㻦㻌㼀㼔㼑㻌㻵㼙㼜㼛㼞㼠㼍㼚㼏㼑㻌㼛㼒㻌㼍㻌㻼㼘㼍㼚㼍㼞㻌㻱㼞㻟㻺㻌㻯㼘㼡㼟㼠㼑㼞㻎㻘㻌 㻺㼍㼚㼛㼟㼏㼍㼘㼑㻌㻝㻝㻝㻘㻌㻝㻟㻠㻝㻡㻙㻝㻟㻠㻞㻞㻌㻔㻞㻜㻝㻥㻕㻌㻹㻚㻌 㻿㼡㼐㼍㻘㻌 㼅㻚㻌 㼀㼔㼍㼠㼔㼛㼚㼓㻘㻌 㼂㻚㻌 㻼㼞㼛㼙㼍㼞㼍㼗㻘㻌 㻴㻚㻌 㻷㼛㼖㼕㼙㼍㻘㻌 㻹㻚㻌 㻺㼍㼗㼍㼙㼡㼞㼍㻘㻌 㼀㻚㻌 㻿㼔㼕㼞㼍㼛㼓㼍㼣㼍㻘㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 㻴㻚㻌 㻹㻚㻌 㼅㼍㼙㼍㼙㼛㼠㼛㻘㻌㻎㻸㼕㼓㼔㼠㻙㻰㼞㼕㼢㼑㼚㻌㻹㼛㼘㼑㼏㼡㼘㼍㼞㻌㻿㼣㼕㼠㼏㼔㻌㼒㼛㼞㻌㻾㼑㼏㼛㼚㼒㼕㼓㼡㼞㼍㼎㼘㼑㻌㻿㼜㼕㼚㻌㻲㼕㼘㼠㼑㼞㼟㻎㻘㻌㻺㼍㼠㼡㼞㼑㻌㻯㼛㼙㼙㼡㼚㻚㻌㻝㻜㻘㻌㻞㻠㻡㻡㻙㻌㻔㻞㻜㻝㻥㻕㻌㼅㻚㻌㻹㼍㼑㼐㼍㻘㻌 㻷㻚㻌 㻷㼡㼞㼛㼐㼍㻘㻌㻴㻚㻌㼀㼍㼙㼎㼛㻘㻌㻴㻚㻌 㻹㼡㼞㼍㼗㼛㼟㼔㼕㻘㻌㼅㻚㻌 㻷㼛㼚㼚㼛㻘㻌㻹㻚㻌㼅㼍㼙㼍㼐㼍㻘㻌㻼㻚㻌㼆㼔㼍㼛㻘㻌㼄㻚㻌㼆㼔㼍㼛㻘㻌㻿㻚㻌㻺㼍㼓㼍㼟㼑㻘㻌 㻹㻚㻌㻱㼔㼍㼞㼍㻘㻌㻎㻵㼚㼒㼘㼡㼑㼚㼏㼑㻌㼛㼒㻌㻸㼛㼏㼍㼘㻌㻿㼠㼞㼍㼕㼚㻌㻯㼍㼡㼟㼑㼐㻌㼎㼥㻌㻯㼥㼏㼘㼛㼍㼐㼐㼕㼠㼕㼛㼚㻌㼛㼚㻌㼠㼔㼑㻌㻮㼍㼚㼐㻌㻳㼍㼜㻌㻯㼛㼚㼠㼞㼛㼘㻌㼛㼒㻌㻲㼡㼚㼏㼠㼕㼛㼚㼍㼘㼕㼦㼑㼐㻌㻿㼕㼚㼓㼘㼑㻙㼃㼍㼘㼘㼑㼐㻌㻯㼍㼞㼎㼛㼚㻌㻺㼍㼚㼛㼠㼡㼎㼑㼟㻎㻘㻌㻾㻿㻯㻌㻭㼐㼢㻚㻌㻥㻥㻘㻌㻝㻟㻥㻥㻤㻙㻝㻠㻜㻜㻟㻌㻔㻞㻜㻝㻥㻕㻌䖩 㻳㻚㻌 㻴㼍㼙㼍㼟㼍㼗㼍㻘㻌 㻴㻚㻌 㼀㼟㼡㼖㼕㻘㻌 㻹㻚㻌 㻱㼔㼍㼞㼍㻘㻌 㼅㻚㻌 㼁㼛㼦㼡㼙㼕㻘㻌 㻎㻹㼑㼏㼔㼍㼚㼕㼟㼠㼕㼏㻌 㻵㼚㼟㼕㼓㼔㼠㻌 㼕㼚㼠㼛㻌 㼠㼔㼑㻌 㻯㼍㼠㼍㼘㼥㼠㼕㼏㻌 㻴㼥㼐㼞㼛㼓㼑㼚㼍㼠㼕㼛㼚㻌 㼛㼒㻌㻺㼛㼚㼍㼏㼠㼕㼢㼍㼠㼑㼐㻌㻭㼘㼐㼑㼔㼥㼐㼑㼟㻌㼣㼕㼠㼔㻌㼍㻌㻴㼍㼚㼠㼦㼟㼏㼔㻌㻱㼟㼠㼑㼞㻌㼕㼚㻌㼠㼔㼑㻌㻼㼞㼑㼟㼑㼚㼏㼑㻌㼛㼒㻌㼍㻌㻿㼑㼞㼕㼑㼟㻌㼛㼒㻌㻻㼞㼓㼍㼚㼛㼎㼛㼞㼍㼚㼑㼟㻦㻌㻺㻹㻾㻌㼍㼚㼐㻌㻰㻲㼀㻌㻿㼠㼡㼐㼕㼑㼟㻎㻘㻌㻾㻿㻯㻌㻭㼐㼢㻚㻌㻥㻥㻘㻌㻝㻜㻞㻜㻝㻙㻝㻜㻞㻝㻜㻌㻔㻞㻜㻝㻥㻕㻌- 411 -

ࢱࣥࣃࢡ㉁จ㞟ࡢศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ
0ROHFXODUVLPXODWLRQRISURWHLQDJJUHJDWLRQ‫ۑ‬ዟᮧஂኈ㸪ఀ⸨ᬡ㸪ᒣෆோႛ㸪ᐑ⃝࿴ஂ㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧 ◊✲┠ⓗ㸪ෆᐜ࢔࣑ࣟ࢖ࢻ⥺⥔ࡣࢱࣥࣃࢡ㉁ࡀ⥺⥔≧࡟จ㞟ࡋࡓ୙⁐ᛶ≀㉁࡛࢔ࣝࢶࣁ࢖࣐࣮⑓࡞࡝  ✀㢮௨ୖࡢ⑓Ẽ࡜㛵㐃ࡋ࡚࠸ࡿ࡜ゝࢃࢀ࡚࠸ࡿࠋ౛࠼ࡤ࢔࣑ࣟ࢖ࢻ ȕ㸦$ȕ㸧࣌ࣉࢳࢻࡣ࢔ࣝࢶࣁ࢖࣐࣮⑓ࡢཎᅉ࡜ゝࢃࢀ࡚࠸ࡿࠋᡃࠎࡣࡇࢀࡲ࡛ $ȕ ࣌ࣉࢳࢻจ㞟యࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺࡜࡜ࡶ࡟ࠊࡑࡢࡼ࠺࡞ࢩ࣑
࣮ࣗࣞࢩࣙࣥࢆຠ⋡ⓗ࡟ᐇ⾜ࡍࡿࡓࡵࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲࡢ㛤Ⓨ࡟ྲྀࡾ⤌ࢇ࡛ࡁࡓࠋ Ẽᾮ⏺㠃࡛ࡢ࢔࣑ࣟ࢖ࢻ ȕ ࣇࣛࢢ࣓ࣥࢺࡢจ㞟ࢩ࣑࣮ࣗࣞࢩࣙࣥ
㏆ᖺࡢ◊✲࡛ࠊ$ȕ ࡢ࢔࣑ࣟ࢖ࢻ⥺⥔ᙧᡂࡣ⢾㙐࡜⬡㉁⭷ࡢ⏺㠃ࠊ࠶ࡿ࠸ࡣỈ࡜✵Ẽࡢ⏺㠃࡜࠸ࡗࡓぶỈᛶ␯Ỉᛶ⏺㠃࡛ಁ㐍ࡉࢀࡿ࡜࠸࠺ࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡑࡇ࡛ᡃࠎࡣẼᾮ⏺㠃ࢆྵࡴ⣔࡟ $ȕ ࣌ࣉࢳࢻࡢ୍
㒊ศ࡛࠶ࡿ $ȕ  ࢆ  ᮏධࢀจ㞟ࡉࡏࡿศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋᅗ  ࡢࡼ࠺࡟ 
ಶࡢỈศᏊ࡜  ᮏࡢ $ȕ  ࢆྵࡳࠊぶỈᛶ␯Ỉᛶ⏺㠃ࢆᣢࡘ⣔ࢆ⏝ពࡋࡓࠋࢱࣥࣃࢡ㉁ࡢຊሙ࡟ࡣ
$0%(5SDUP6% ࢆࠊỈ࡟ࡣ 7,33 ࢆ⏝࠸ࡓࠋ㟼㟁┦஫స⏝ࡢィ⟬ࡣࣃ࣮ࢸ࢕ࢡ࣓ࣝࢵࢩ࢚ࣗ࣡ࣝࢻἲ࡛⾜ࡗࡓࠋ᫬㛫ࢫࢸࢵࣉᖜࡣࢱࣥࣃࢡ㉁࡟ࡘ࠸࡚ࡣ  IV ࡟ࠊỈศᏊ࡟ࡘ࠸࡚ࡣ  IV ࡟タᐃࡋࡓࠋỈศᏊࡣ๛య
࡜ࡋ࡚ᢅ࠸ࠊ ᗘࡣ⬟ໃ࣭ࣇ࣮ࣂ࣮⇕ᾎࢆ౑ࡗ࡚ไᚚࡋࡓࠋ ࡘࡢ␗࡞ࡿึᮇ᮲௳࠿ࡽ QV ࡢࢩ࣑࣮ࣗࣞࢩ
ࣙࣥࢆ⾜ࡗࡓࠋࣉࣟࢢ࣒ࣛࡣ⊂⮬࡟㛤Ⓨࡋࡓ *(0%㸦*HQHUDOL]HG(QVHPEOH0ROHFXODU%LRSK\VLFV㸧ࣉࣟࢢ࣒ࣛ
ࢆ⏝࠸ࡓࠋ
ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝࠊ᫬㛫ࡀ⤒ࡘ࡟ࡘࢀࣂ
ࣝࢡࡢỈ୰࠿ࡽ⏺㠃࡟ $ȕ  ࣌ࣉࢳࢻࡀ⛣ືࡋࠊ⏺㠃࡛ࡢ $ȕ  ࣌ࣉࢳࢻ⃰ᗘࡀୖ᪼ࡋࡓ㸦ᅗ 㸧ࠋࡉࡽ࡟⏺㠃㏆ࡃ࡛ࡶ⃰ᗘࡢ㧗࠸㡿ᇦ࡜ⷧ࠸㡿ᇦࡀ࡛ࡁࠊ㧗⃰ᗘ㡿ᇦ࡛⏺㠃࡟ἢࡗ࡚཯ᖹ⾜ศᏊ㛫 ȕ ࢩ࣮ࢺᵓ㐀ࢆᣢࡘจ㞟యࡀ⏕ᡂࡉࢀࡓࠋ
ࡇࢀࡽࡢจ㞟యࡣ  ᒙ࡟ศ࠿ࢀ࡚࠾ࡾࠊ⏺㠃࡟㏆࠸୍ᒙ┠࡛ࡣẚ㍑ⓗ ȕ ࣈࣜࢵࢪࡢᑡ࡞࠸࢜ࣜࢦ࣐
࣮ࡀከࡃᏑᅾࡋ࡚࠸ࡓࠋ୍᪉ࠊẚ㍑ⓗ ȕ ࣈࣜࢵࢪࢆከࡃᣢࡘ࢜ࣜࢦ࣐࣮⏺㠃࠿ࡽ✺ࡁฟ࡚Ỉ୰࡟ࡼࡾከࡃᏑᅾࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࢀࡽ⏕ᡂࡉࢀࡓศᏊ㛫 ȕ ࢩ࣮ࢺᵓ㐀ࡢ඾ᆺ౛ࢆᅗ  ࡟♧ࡍࠋࡇࡢ⌧㇟ࡣ࢔࣑ࣟ࢖ࢻ⥺⥔ࡢᙧᡂึᮇ㐣⛬࡟࠾࠸࡚ぶỈᛶ␯Ỉᛶ⏺㠃࠿ࡽ࢜ࣜࢦ࣐࣮ࡀⱆࡢ
ࡼ࠺࡟ఙࡧ࡚ࡃࡿⓎⱆ⌧㇟࡟ఝ࡚࠸ࡿࠋᅗ  ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓ⣔ࠋ- 412 -

ࡇࡢ⌧㇟ࡣ࢜ࣜࢦ࣐࣮ࡢᵓ㐀࠿ࡽㄝ࡛᫂ࡁࡿࠋ࢜ࣜࢦ࣐࣮ࡢ඾ᆺⓗ࡞ࢫࢼࢵࣉࢩࣙࢵࢺࢆᅗ  ࡟♧ࡍࠋᅗ  D ࡣࠊ ࡘࡢ ȕ ࣈࣜࢵࢪࢆᣢࡘ 㔞య࡛࠶ࡿࠋࡇࡢࡼ࠺࡞࢜ࣜࢦ࣐
࣮ࡣ✵Ẽ࡜Ỉࡢ㛫ࡢ⏺㠃ୖ࡛ᗈࡀࡗ࡚࠸ࡓࠋ ᅗ  E ࡜  F ࡣ࡜ࡶ࡟⏺㠃࠿ࡽ ࠥc 㞳ࢀࡓỈ୰࡟Ꮡᅾࡋ࡚࠸ࡓ࢜ࣜࢦ࣐࣮࡛࠶ࡿࠋỈ࡟✺ࡁฟࡓ࢜ࣜࢦ࣐࣮ࡣከࡃࡢșࣈࣜࢵࢪ࡜㛗࠸ ȕ ࢫࢺࣛࣥࢻࢆᙧᡂࡋ ᅗ  จ㞟ࡋࡓ $ȕ ±  ࣌ࣉࢳࢻࡢഃ㠃ᅗࠋỈศᏊࡣ⾲♧ࡋ࡚࠸࡞࠸ࠋ㟷ᯟࡣẼᾮ⏺㠃ࢆ⾲ࡍࠋ࡚࠸ࡿࠋࡑࡢࡓࡵࠊࡇࢀࡽࡢ࢜ࣜࢦ
࣐࣮࡛ࡣࠊ␯Ỉᛶṧᇶࡣ࢜ࣜࢦ࣐࣮
ࡢෆഃ࡛࠾஫࠸࡟จ㞟ࡋ࡚࠸ࡿ୍᪉ࠊぶỈᛶṧᇶࡣᅗ  E ࡜  F ࡢ㟷୸ࡢࡼ࠺࡟࢜ࣜࢦ࣐࣮ࡢ➃࡟ἢࡗ࡚ᩚิࡋ␯Ỉᛶṧᇶࢆそࡗ࡚࠸ࡿࠋ
ࡇࡢࡼ࠺࡟ぶỈᛶṧᇶ࡛そࢃࢀࡓ࢜ࣜࢦ࣐࣮ࡣࠊỈ⁐ᾮ୰࡟ᐜ᫆࡟Ꮡ
ᅾ࡛ࡁࡿࠋࡋ࠿ࡋࠊ⏺㠃ࡢ࢜ࣜࢦ࣐
࣮࡛ࡣࠊᅗ  E ࡢࡼ࠺࡟ぶỈᛶṧᇶᅗ  จ㞟ࡋࡓ $ȕ ±  ࣌ࣉࢳࢻࡢࢫࢼࢵࣉࢩࣙࢵࢺࠋ⏺㠃࡟ࡣ ȕࣈࣜࢵࢪࡢᑡ࡞࠸࢜ࣜࢦ࣐࣮㸦㟷ࡢࣁ࢖ࣛ࢖ࢺ㸧ࡀ㞟ࡲࡾࠊࡑࡇ࠿ࡽከࡃࡢ ȕ ࣈࣜࢵࢪࢆᣢࡘ࢜ࣜࢦ࣐࣮㸦㉥ࡢࣁ࢖ࣛ࢖ࢺ㸧ỈᛶṧᇶࡣぶỈᛶṧᇶ࡛そࢃࢀ࡚ࡀỈ୰࡟✺ࡁฟࡋ࡚࠸ࡿࠋ
࠸࡞࠸ࠋࡑࡢࡓࡵỈ୰࡟Ꮡᅾ࡛ࡁࡎࠊ
ࡀࡁࢀ࠸࡟ᩚิࡋ࡚࠸࡞࠸ࡓࡵࠊ␯

Ẽᾮ⏺㠃࡟Ꮡᅾࡍࡿࡢ࡛࠶ࡿࠋ
⏺㠃࡟㏆࠸୍ᒙ┠࡟Ꮡᅾࡋ࡚࠸ࡿ  㔞య࡜ᑡࡋ㞳ࢀࡓ஧ᒙ┠࡟Ꮡᅾࡋ࡚࠸ࡿ  㔞యࡢ⁐፹࿴⮬⏤࢚ࢿࣝࢠ࣮ࢆィ⟬ࡋࡓࠋࡑࡢ⤖ᯝࠊ୍ᒙ┠࡛ࡣí  NFDOPRO ࡛࠶ࡗࡓࡢ࡟ ᑐ ࡋ ࠊ ஧ ᒙ ┠ ࡛ ࡣ í 
NFDOPRO ࡛࠶ࡗࡓࠋࡇࡢࡇ࡜ࡣ஧
ᒙ┠ࡢ࢜ࣜࢦ࣐࣮ࡣࡼࡾከࡃࡢ ȕ ࢫࢺࣛࣥࢻࢆᙧᡂࡋぶỈᛶṧᇶ࡛そࢃࢀ࡚࠸ࡿࡓࡵỈ࡬ࡢ⁐ゎᛶࡀ㧗࠸ࡢ࡟ᑐࡋࠊ୍ᒙ┠ࡢ࢜ࣜࢦ࣐࣮ࡣᅗ  $ȕ ±  ࣌ࣉࢳࢻࡢ࢜ࣜࢦ࣐࣮ࡢ඾ᆺⓗ࡞ᵓ㐀ࠋ⏺㠃࡟ᙧᡂࡉࢀࡓࡶࡢࡣșࣈࣜࢵࢪࡀᑡ࡞࠸ࡢ࡟ᑐࡋࠊỈ୰࡟✺ࡁฟ࡚࠸ࡿ࢜ࣜࢦ࣐࣮࡟ࡣከࡃࡢ ȕ ࣈࣜࢵࢪࡀᙧᡂࡉࢀ࡚࠸ࡿࠋ
ࡵỈ࡬ࡢ⁐ゎᛶࡀప࠸ࡇ࡜ࢆព࿡
␯Ỉᛶṧᇶࡀ୍㒊㟢ฟࡋ࡚࠸ࡿࡓ

ࡋ࡚࠸ࡿࠋ

- 413 - ㉸ศᏊୖࡢ *0 ࢡࣛࢫࢱ࣮࡜ $ȕ ࣌ࣉࢳࢻࡢศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ
⣽⬊⾲㠃ୖ࡟࠶ࡿࣔࣀࢩ࢔ࣟࢸࢺࣛ࣊࢟ࢯࢩࣝ
࢞ࣥࢢࣜ࢜ࢩࢻ㸦*0㸧ࢡࣛࢫࢱ࣮ࡣ $ȕ ࣌ࣉࢳࢻࡢจ㞟ࢆಁ㐍ࡍࡿࡇ࡜ࡀࡇࢀࡲ࡛࡟♧ࡉࢀ࡚࠸ࡿࠋ
ࡋ࠿ࡋࠊ*0 ࢡࣛࢫࢱ࣮ࡀ $ȕ ࣌ࣉࢳࢻࡢᵓ㐀࡟ཬࡰࡍᙳ㡪ࡣࡲࡔゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋ$ȕ ࣌ࣉࢳࢻ࡜
*0 ࢡࣛࢫࢱ࣮㛫ࡢ┦஫స⏝ࡣࠊ*0 ࢡࣛࢫࢱ࣮
࡛ࡢจ㞟ࡢึᮇẁ㝵ࢆ⌮ゎࡍࡿࡓࡵ࡟㔜せ࡛࠶ࡿࠋࡲࡓࠊ*0 ⢾㙐ࢆ  ᮏ⛣᳜ࡋࡓ㉸ศᏊࡣࠊ⢾㙐ࢡࣛࢫࢱ࣮࡜ࢱࣥࣃࢡ㉁࡜ࡢ┦஫స⏝ࢆゎᯒࡍࡿࢶ࣮ࣝ࡜ࡋ࡚⏝࠸ࡽࢀ࡚࠾ࡾࠊ$ȕ ࣌ࣉࢳࢻࢆㄆ㆑࡛
ࡁࡿࡇ࡜ࡀᐇ㦂ⓗ࡟♧ࡉࢀ࡚࠸ࡿࠋࡑࡇ࡛ *0 ⢾㙐ࢆ⛣᳜ࡋࡓ㉸ศᏊ࡟ $ȕ ࣌ࣉࢳࢻࢆ⤖ྜࡉࡏࡿศ
ᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋࡑࡢึᮇᵓ㐀ࢆᅗ  ࡟♧ࡍࠋᅗ  *0 ⢾㙐ࢆ⛣᳜ࡋࡓ㉸ศᏊ࡟ $ȕ ࢆ⤖ྜࡉࡏࡿࢩ࣑࣮ࣗࣞࢩࣙࣥࡢึᮇ᮲௳ࠋ

ࢩ࣑࣮ࣗࣞࢩࣙࣥࡢ⤖ᯝ *0 ࢡࣛࢫࢱ࣮࡬ࡢ $ȕ
࣌ࣉࢳࢻࡢ⤖ྜࢆほᐹࡍࡿࡇ࡜࡟ᡂຌࡋࡓࠋࡲࡓ $ȕ
࣌ࣉࢳࢻࡣᅗ  ࡢࡼ࠺࡟ *0 ࢡࣛࢫࢱ࣮ୖ࡛ & ᮎഃ࡟࣊ࣜࢵࢡࢫᵓ㐀ࢆᙧᡂࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ࣊
ࣜࢵࢡࢫᙧᡂࡣจ㞟ࡢึᮇẁ㝵࡜ࡋ࡚ࡼࡃぢࡽࢀࡿ⌧㇟࡛࠶ࡿࠋࡇࡢ࣊ࣜࢵࢡࢫᵓ㐀ࡀᙧᡂࡉࢀࡿ㐣⛬ࡣ௨ୗࡢ㏻ࡾ࡛࠶ࡗࡓࠋࡲࡎỈ୰࡛ $ȕ ࣌ࣉࢳࢻ
ࡢ /\V ࡣ & ᮎࡢ࢝ࣝ࣎࢟ࢩࣝᇶ࡜㟼㟁┦஫స⏝࡛ࢥࣥࢱࢡࢺࡋ࡚࠸ࡿࡀࠊ*0 ࢡࣛࢫࢱ࣮ୖ࡛ࡣ
*0 ࡢࣀ࢖࣑ࣛࣥ㓟㸦1HX㸧࡜┦஫స⏝ࡍࡿࠋࡑࡢ
ࡓࡵ /\V ࡜ & ᮎࡣゎ㞳ࡋࠊ/\V ௨㝆ࡢ & ᮎഃࡢ࢔࣑ࣀ㓟ṧᇶࡣ␯Ỉᛶṧᇶࡀከ࠸ࡢ࡛ࡑࡢ㒊ศࡀ࣊ࣜࢵࢡࢫࢆᙧᡂࡍࡿࠋࡲࡓࠊࡇࡢࡇ࡜ࡣ $ȕ ࣌ࣉࢳࢻࡢ࣊ࣜࢵࢡࢫᙧᡂࡀ *0 ࢡࣛࢫࢱ࣮ࡢ⬡㉁ࢭ ᅗ  ㉸ศᏊୖࡢ $ȕ ࡢ඾ᆺⓗ࡞ࢫࢼࢵࣉࢩࣙࢵࢺࠋ
ࠥ ␒┠ࡢṧᇶ࡛࣊ࣜࢵࢡࢫᵓ㐀ࡀᙧᡂࡉࢀ
࣑ࣛࢻ㒊ศ࡛ࡣ࡞ࡃ⢾㙐㒊ศ࡛㉳ࡁࡿࡇ࡜ࢆ♧၀࡚࠸ࡿࠋ⥳ⰍࡢศᏊࡣ *0 ࢡࣛࢫࢱ࣮࡛࠶ࡿࠋ
ࡋ࡚࠸ࡿࠋ
ࡉࡽ࡟ࡇࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࠿ࡽ *0 ࢡࣛࢫࢱ࣮ㄆ㆑ࡢࡓࡵ࡟㔜せ࡞ࡢࡣ $ȕ ࣌ࣉࢳࢻࡢ  ␒┠ࡢṧ
ᇶ ++4 ࢭࢢ࣓ࣥࢺ࡛࠶ࡿࡇ࡜ࡶ᫂ࡽ࠿࡟ࡋࡓࠋࡇࡢ⤖ᯝࡣ $ȕ ࣌ࣉࢳࢻࡢ⢾㙐ㄆ㆑࡟㛵ࡍࡿࡇࢀࡲ࡛ࡢᐇ㦂◊✲࡜୍⮴ࡋ࡚࠸ࡿࠋ++4 ࢭࢢ࣓ࣥࢺࡀ⢾㙐ࢆㄆ㆑ࡍࡿ⌮⏤ࡣࣄࢫࢳࢪࣥࡢഃ㙐ࡢ஬ဨ⎔࡜⢾㙐ࡢභဨ⎔ࡢ㛫࡛┦஫స⏝ࡋࢫࢱࢵ࢟ࣥࢢࡍࡿ࠿ࡽ࡛࠶ࡿ࡜࠸࠺ࡇ࡜ࡶゎ᫂ࡋࡓࠋ

- 414 -

 Ⓨ⾲㸪ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
‫ۻ‬+2NXPXUDDQG6*,WRK³0ROHFXODUG\QDPLFVVLPXODWLRQVRIDP\ORLGȕ  SHSWLGHDJJUHJDWLRQDWDLUZDWHU
LQWHUIDFHV´-&KHP3K\V   SDJHV ‫ۻ‬10XUDNL.,VKLL68FKL\DPD6*,WRK+2NXPXUD6$RQR³6WUXFWXUDOFKDUDFWHUL]DWLRQRI+\S;UHVSRQVLEOH
IRU&2ELRV\QWKHVLVLQWKHPDWXUDWLRQRI1L)HK\GURJHQDVH´&RPPXQ%LRO   SDJHV ‫ۻ‬0 <DPDXFKL DQG + 2NXPXUD ͆5HSOLFD VXESHUPXWDWLRQ PHWKRG IRU PROHFXODU G\QDPLFV DQG 0RQWH &DUORVLPXODWLRQV͇-&RPSXW&KHP   
6<DQDND5<RJR5,QRXH06XJL\DPD6*,WRK+2NXPXUD<0L\DQRLUL+<DJL76DWRK7<DPDJXFKL
DQG..DWR³'\QDPLFYLHZVRIWKH)FUHJLRQRILPPXQRJOREXOLQ*SURYLGHGE\H[SHULPHQWDODQGFRPSXWDWLRQDOREVHUYDWLRQV´$QWLERGLHV   SDJHV - 415 -

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◊✲┠ⓗࠊෆᐜ
ᡃࠎࡣᾮయ୰ࡢศᏊ㛫┦஫స⏝ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊศᏊ◊ UVSOR-III ࡟࠾࠸࡚ᾮయࡢ㌾ X ⥺྾཰ศගᐃࢆ⾜ࡗ࡚ࡁࡓࠋࡇࡇ࡛ᚓࡽࢀࡓࣆ࣮ࢡࡢ໬ᏛࢩࣇࢺࡣศᏊ㛫┦஫స⏝࡟⏤᮶ࡍࡿࡓࡵࠊᾮయࡢศᏊືຊ

Ꮫ(MD)ィ⟬࡜㔞Ꮚ໬Ꮫ࡟ᇶ࡙ࡃෆẆບ㉳ィ⟬ࢆ⾜࠸ࠊᐇ㦂⤖ᯝ࡜ẚ㍑ࡍࡿࡇ࡜࡛ࠊࡑࡢᒁᡤᵓ㐀ࢆ᫂ࡽ࠿࡟
ࡍࡿࡇ࡜ࢆᮏ◊✲ࡢ┠ⓗ࡜ࡍࡿࠋᮏᖺᗘࡣ࢔ࢭࢺࢽࢺࣜࣝỈ⁐ᾮࡢศᏊ㛫┦஫స⏝ࢆㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲMD ィ⟬ࡣ GROMACS 5.1.4 ࢆ⏝࠸࡚⾜ࡗࡓࠋᇶᮏⓗ࡞࣏ࢸࣥࢩࣕࣝ࡟ࡣ OPLSAA ࢆ⏝࠸࡚࠸ࡿࠋ ᗘไᚚࡣ Nosé-Hoover ἲࢆ⏝࠸࡚ࠊᅽຊไᚚࡣ Parrinello-Rahman ἲࢆ⏝࠸ࡓࠋMD ィ⟬୰ࡢศᏊ㓄⨨࠿ࡽ⮬సࡢゎᯒࣉࣟࢢ࣒ࣛࢆ⏝࠸࡚ືᚄศᕸ㛵ᩘ(RDF)ࢆồࡵࡓࠋ

3◊✲ᡂᯝ࢔ࢭࢺࢽࢺࣜࣝỈ⁐ᾮ(ࣔࣝẚ⋡ x = 0.001)ࡢ MD ィ⟬ࢆ⾜ࡗࡓࠋ2 ḟඖࡢ RDF ࢆồࡵࡓ࡜ࡇࢁࠊ࢔ࢭࢺࢽ

ࢺࣜࣝศᏊࡢ CŁN ᇶࡢ❅⣲ཎᏊ࡜ỈࡢỈ⣲⤖ྜ࡜ඹ࡟ࠊCŁN ᇶ࡟཮ᴟᏊ┦஫స⏝࡛⤖ྜࡍࡿỈࡀᏑᅾࡍࡿࡇ
࡜ࢆ᫂ࡽ࠿࡟ࡋࡓࠋ㓄఩ᩘࡢゎᯒࡢ⤖ᯝࠊỈࡢỈ⣲⤖ྜࡼࡾࡶ཮ᴟᏊ┦஫స⏝ࡢ᪉ࡀࠊࡑࡢᏑᅾ☜⋡ࡀ㧗࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡇ࠿ࡽࠊ࢔ࢭࢺࢽࢺࣜࣝỈ⁐ᾮࡢᚤᑠ୙ᆒ୍ᛶ࡟ࡘ࠸࡚㆟ㄽࡋࡓ(ㄽᩥ[1])ࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫“ ۻ‬Soft X-ray Absorption Spectroscopy of Liquid for Understanding Chemical Processes in Solution”, M.

Nagasaka, Japan-Korea Molecular Science Symposium “Advances in Materials and Molecular Sciences”, Nagoya(Japan), 2019/7/30. (ᣍᚅㅮ₇)[2] ‫“ ۻ‬ᾮయࡢ㌾ X ⥺྾཰ศග ᐃࡢ⌧≧࡜௒ᚋࡢᒎᮃ”, 㛗ᆏᑗᡂ, ➨ 25 ᅇ HiSOR ◊✲఍ࠕᑠᆺᨺᑕග
ࣜࣥࢢ࡟ࡼࡿከᙬ࡞㔞Ꮚࣅ࣮࣒ࡢⓎ⏕࡜ᛂ⏝ࠖ, ᗈᓥ኱Ꮫ(ᗈᓥ), 2019/10/16. (ᣍᚅㅮ₇)[3] ‫“ ۻ‬㌾ X ⥺྾཰ศගἲ࡟ࡼࡿ⁐ᾮ཯ᛂࡢ࢜࣌ࣛࣥࢻほ ”, 㛗ᆏᑗᡂ, ᪥ᮏ⾲㠃┿✵Ꮫ఍ ᨺᑕග⾲㠃⛉Ꮫ◊✲㒊఍ࠕᨺᑕගࢆ฼⏝ࡋࡓ࢜࣌ࣛࣥࢻ⾲㠃⏺㠃ほࡢ᭱ඛ➃㸸ᵓ㐀࠿ࡽᶵ⬟࣭཯ᛂ࡬ࠖ, ࡘࡃࡤᅜ㝿఍㆟ሙ(Ⲉᇛ), 2019/10/28. (ᣍᚅㅮ₇)5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
[1] ‫“ ۻ‬Microheterogeneity in Aqueous Acetonitrile Solution Probed by Soft X-ray Absorption Spectroscopy”, M.

Nagasaka, H. Yuzawa, and N. Kosugi, J. Phys. Chem. B 124, 1259-1265 (2020).
[2] ‫“ ۻ‬Soft X-ray Absorption Spectroscopy of Liquids for Understanding Chemical Processes in Solution”, M.
Nagasaka, H. Yuzawa, and N. Kosugi, Anal. Sci. 36, 95-105 (2020).

- 416 -

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[1] ŔÀMlXAŕ­(¡ĒŉŇųKk5(Ì$«ċĎ(ÚśŤĬ¼¯Ġĥ ħ  ¦őĉ|Ţ2019 ¾ 4 ç[2] · ì œ ă  Design of Allosteric Site to Regulate Rotary Molecular Motor V1-ATPase, Frontier
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[3] ŔÀ }¼MlXAŕõśg=Zghn(ħ 71 ¦ãëĔĎ¼¯ª»º2019 ¾ 9ç[4] ·ìœă Allosteric Regulation of V1-ATPase by Designing Walker Motif in Non-catalytic Interface, 2ndTokyo ATPase Workshop, í|, 2019 ¾ 9 ç
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[1] R. Koga and N. Koga (2019). "Consistency principle for protein design" Biophys. & Physicobiol. 16, 304-309.
[2] H. Murakoshi, H. Horiuchi, T. Kosugi, M. Onda, A. Sato, N. Koga and J. Nabekura (2019). "ShadowR: a novel

chromoprotein with reduced non-specific binding and improved expression in living cells" Scientific Reports, 9, 12072.

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࡟࡞ࡗ࡚࠸࡞࠸ࠋࡇࡢ౛ࡣࠊ࢖࢜ࣥ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࡜࡞ࡾ࠺ࡿ
஦ࢆ♧၀ࡋ࡚࠸ࡿࠋ᫖ᖺᗘࡢィ⟬⛉Ꮫ◊✲ࢭࣥࢱ࣮࡛ࡢィ⟬ᶵ฼⏝࡟ࡼࡿศᏊືຊᏛἲࢆ⏝࠸ࡓ◊✲࠿ࡽࠊ㧗ศᏊࢭ࣮ࣝࣟࢫ㛫࡟ാࡃࢭ࣮ࣝࣟࢫ㛫Ỉ⣲⤖ྜᙉᗘࡣỈ୰࡟㍑࡭࡚࢖࢜ࣥᾮయ୰࡛ࡣࢭ࣮ࣝࣟࢫ㛫Ỉ⣲⤖ྜࡀᙅࡵࡽࢀࡿ⤖ᯝࡀᚓࡽࢀࠊࡇࡢࡇ࡜ࡀ࢖࢜ࣥᾮయ୰࡛ࢭ࣮ࣝࣟࢫࡢศゎࡀಁ㐍ࡉࢀࡸࡍ࠸ཎᅉࡢ㸯ࡘ࡛࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊศᏊෆỈ⣲⤖ྜࡢゎ㞳ࡀศᏊ㛫Ỉ⣲⤖ྜࡢゎ㞳ࡼࡾࡶඃඛࡋ࡚࠾ࡇࡿࡇ࡜ࡀィ⟬⤖ᯝࡼࡾ♧ࡉࢀࠊᐇ㦂◊✲࡟ࡼࡿᣦ᦬࡜ࡶ୍⮴ࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋ௒ᖺᗘࡣ◊✲ࢆࡉࡽ࡟㐍ࡵ࡚ࢭࣝࣟ
࣮ࢫࡢᣲື࡜࢖࢜ࣥᾮయ࡜ࡢ┦஫స⏝ࢆゎᯒࡋࠊຍ࠼࡚ከᒙᵓ㐀ࢆᣢࡘ኱つᶍ࡞㧗ศᏊࢭ࣮ࣝࣟࢫࡢ⣔࡟ࡘ࠸࡚ࡶศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࠊᐇ㝿ࡢ⣔࡟㏆࠸ᵓ㐀ࢆᣢࡘ⣔࡟࡛ࡢ࢖࢜ࣥᾮయ࡟ࡼࡿ⁐ゎ࣭ศゎࣉࣟࢭࢫࡢゎᯒࢆ⾜ࡗࡓࠋ㸰 ࢖࢜ࣥᾮయࡣ㝧࢖࢜ࣥ࡜㝜࢖࢜ࣥࡢ࣌࢔ࢆኚ࠼ࡿࡇ࡜࡛ከ✀ከᵝ࡞≀ᛶࡸ≀⌮໬Ꮫⓗᣲືࡀほᐹࡉࢀࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ≉࡟  ୡ⣖ึ㢌࠿ࡽከࡃࡢᐇ㦂◊✲࡟ࡼࡿሗ࿌ࡀ⾜ࢃࢀ࡚ࡁࡓࠋ⌮ㄽ◊✲ࡢほⅬ࠿ࡽࡣከࡃࡢ࢖࢜ࣥᾮయࡀ♧ࡍ≀ᛶࡸ≀⌮໬Ꮫⓗᣲື࡟ඹ㏻ࡍࡿᛶ㉁ࢆぢฟࡋࠊ⣔⤫ⓗ࡟ゎᯒࡍࡿࡇ࡜ࡀᮇᚅ
ࡉࢀ࡚࠸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฼⏝ࡋࠊศᏊືຊᏛἲ࡟ࡼࡿ◊✲ࢆ㐍ࡵࡓࠋ◊✲⤖ᯝࡼࡾࠊ࢖࢜ࣥᾮయࡢ㟼ⓗᵓ㐀ࡀ࢖࢜ࣥᾮయࡢ୙ᆒ୍ᛶ࡟ࡼࡗ࡚኱ࡁࡃᙳ㡪ࡉࢀ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊཎᅉࡢ୍ࡘ࡜ࡋ࡚ࠊ㝧࣭㝜࢖࢜ࣥ⮬㌟ࡢ✵㛫ⓗ࡞ศᕸ࡜୧࢖࢜ࣥࡢ㓄ྥࡀ኱ࡁࡃ㛵ಀࡋ࡚࠸ࡿࡇ࡜ࡀゎࡗࡓࠋ௒ᖺᗘࡣࠊ࢖࢜ࣥศᏊ

- 423 -

⮬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࢖࢜ࣥ

ᾮయ࡜Ỉ୰࡟࠾ࡅࡿ㧗ศᏊࢭ࣮ࣝࣟࢫࡢศゎ࣭⁐ゎ㐣⛬ࡢゎᯒࢆ⾜ࡗࡓࠋලయⓗ࡟ࡣ࢖࢜ࣥᾮయ࡜ࡋ࡚཯ᛂ
ຠ⋡ࡢࡼ࠸ࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ࣓ࢳࣝளࣜࣥ㓟࢔ࢽ࢜ࣥྵ᭷ࡢ࢖࢜ࣥᾮయ㸦>&PLP@> &+2

+ 32@㸧㑅ࡧࠊ㧗ศᏊࢭ࣮ࣝࣟࢫࢆ⁐㉁࡜ࡋ࡚ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࡓࠋィ⟬⤖ᯝࡼࡾࠊࢭ࣮ࣝࣟࢫ㛫Ỉ⣲⤖ྜࡢᙉࡉࡢኚ໬ࢆᐃᛶⓗ࡟ホ౯ࡋࠊࡉࡽ࡟࢖࢜ࣥᾮయ୰࡛ศゎࡀᐜ᫆࡟࡞ࡿཎᅉࢆㄪ࡭ࡓࠋ
୍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ⓗ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◊✲ᡂᯝࡣࠊ࢖࢜ࣥᾮయࡢࡼ࠺࡞͆᪂ࡋ࠸ᾮయ͇࡟㛵ࡋ࡚ᐇ㦂࣭⌮ㄽ◊✲཮᪉࡬ࡢ㔜せ࡞ᶫΏࡋ࡜࡞ࡾ࠺ࡿࠋ௒ᚋ
ࡉࡽ࡟ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࢭ࣮ࣝࣟࢫศᏊࡢ⁐ゎ࣭ศゎ㐣⛬ࡢゎᯒࢆ㐍ࡵࡿணᐃ࡛࠶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ⓗ࡞࢖࢜ࣥࡢศᕸࡣ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- 424 -

4

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‫“ۻ‬Theoretical Investigation of Dissolution and Decomposition Mechanisms of a Cellulose Fiber in Ionic Liquids”,
Tateki Ishida, J. Phys. Chem. B 2020, 124, 3090-3102.

- 425 -

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E. Minamitani, Theory of single spin spectroscopy at surfaces: from Kondo singlet to spin-orbit interaction”,
Exploring the Limits of Nanoscience with Scanning Probe Methods, 2019 ¥ 10 Å, Physikzentrum Bad Honnef,
Germany2.

E. Minamitani, “Ab-initio simulation of phonon related transport phenomena: inelastic electron tunnelingspectroscopy & thermal conductivity”, Electron-phonon coupling: Computational methods for electronictransport in nanostructures and in bulk materials, 2019 ¥ 10 Å, Lugano, Switzerland4 
1.



Hiromu Gamou, Koki Shimose, Ryoto Enoki, Emi Minamitani, Akitoshi Shiotari, Yoshinori Kotani, Kentaro
Toyoki, Tetsuya Nakamura, Yoshiaki Sugimoto, Makoto Kohda, Junsaku Nitta, and Shinji Miwa, "Detection of
spin-transfer from metal to molecule by magnetoresistance measurement", Nano letters, 2020, 20, 75-80.

2.

 Nao. H. Shimada, E. Minamitani, S. Watanabe, ´ýc- 427 -

㉸ᙉ⤖ྜ㡿ᇦ࡟࠾ࡅࡿศᏊ᣺ື࣏ࣛࣜࢺࣥࡢ⌮ㄽ◊✲
Theoretical study of molecular vibrational polariton in the ultrastrong
coupling regime‫ۑ‬Nguyen Thanh Phuc㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
Controlling chemical reactions has always been an important goal in the field of chemistry. Over the last century,

synthetic chemists have developed various kinds of catalysts to modify chemical reactions. There are also physicalmethods to control chemical reactivity by using intense laser fields to excite nuclear vibration to overcome the barrier ofreaction. However, these approaches often require cryogenic temperature as the excitation energy can be redistributed toother vibrational degrees of freedom. One way to overcome this challenge is to control the chemical reaction bystrongly coupling the molecular vibration to the vacuum field of a cavity mode. Strong coupling of both electronic andvibrational degrees of freedom of molecules to an optical cavity has been realized in various experimental platforms
involving both an ensemble of molecules as well as a single molecule. It gave rise to a variety of interesting phenomena
and important applications including the control of chemical reactivity, enhancement of transports, nonlinear opticalproperties with applications to optoelectronic devices, polariton lasing and condensate, and precise measurement ofmolecular excitation energies.
In particular, the interaction of the zero-point energy fluctuations of the cavity mode with the molecular vibration is
expected to modify the chemical reactivity, which has recently been demonstrated experimentally. Theoreticalinvestigations of the effect of the coupling between molecular vibrations and the optical cavity mode on the chemical
reaction rate have also been done for the ab initio model of a simple molecule and the model of electron-transfer
reaction. However, the physical mechanism underlying the modification of the chemical reactivity induced by themolecule-cavity coupling is not fully understood. In particular, the change of the ground state of the total system by themolecule-cavity coupling has been ignored when applying the rotating-wave approximation. The mixing of ground andexcited states of molecular vibration in the ground state of the hybrid system can, in principle, significantly affect thechemical reactivity in a way similar to the excitation of nuclear vibrations done by an intense laser. The only differenceis that here the excitation is induced by the quantum fluctuation in the vacuum field of the cavity rather than by a strong
laser field.
In this study, we extend the investigation of the effect of vibrational polariton on the chemical reaction rate to theso-called ultrastrong coupling regime, where the molecule-cavity coupling strength is comparable in magnitude withboth the vibrational and the cavity frequencies. The ultrastrong coupling has already been realized in various kinds ofsystems including intersubband polaritons, superconducting circuits, Landau polaritons, optomechanics as well asorganic molecules. In the ultrastrong coupling regime, the rotating-wave approximation is no longer valid and theoptical diamagnetic term cannot be neglected. As a result, the ground state of the total system can be strongly modified
as it now involves virtual photons and molecule’s vibrational excitations.

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2◊✲᪉ἲࠊィ⟬᪉ἲIn this study, we developed a theoretical model for the coupled system of molecules and an optical cavity. We

considered an electron-transfer chemical reaction in a system of N identical molecules, whose nuclear vibrations arecoupled to an optical cavity. As described by the Marcus-Levich-Jortner model, the reactant and product electronic
states of each molecule are coupled to a single high-frequency vibrational mode, which is further coupled to a single
mode of the optical cavity. The molecule’s electronic states are also coupled to a continuum of low-frequency
vibrational modes, which stem from the inter-molecular vibrations of the surrounding molecular environment such as
the solvent.
We then used the RCCS computers to find the energy eigenstates of the molecule-plus-cavity hybrid system, fromwhich we computed the electron-transfer reaction rate as a function of the coupling strength between molecules and thecavity. The computation was done for different number of molecules in the system.

3◊✲ᡂᯝ
We investigated how the ultrastrong coupling between molecular vibrations and an optical cavity can affect theelectron-transfer reaction rate. We found that there exist both regions of parameters for which the reaction rate increases
or decreases by coupling the molecular vibration to the cavity field. The modification of the reaction rate by themolecule-cavity coupling is determined by two factors: the relative shifts of the energy levels induced by the coupling,
and the mixing of ground and excited states of molecular vibration in the ground state of the hybrid system throughwhich the Franck-Condon factor between the initial and final states of the transition is altered. The former is thedominant factor if the molecule-cavity coupling strengths for the reactant and product states differ significantly fromeach other. It increases the reaction rate over a wide range of system’s parameters. Conversely, the latter dominates if
the coupling strengths and energy levels of the reactant and product states are close to each other, and it
counterintuitively leads to a decrease in the reaction rate. This is in contrast to the normal expectation that the reaction
rate would increase due to the molecule’s vibrational excitations. The result, however, can be understood as aconsequence of the minus sign of the coefficient of the molecular vibration’s excited state induced by coupling with thecavity. We also investigated how the effect of vibrational polariton on the reaction rate changes for a variable number ofmolecules coupled to the cavity. The effect of mixing of vibrational excitations on the reaction rate is suppressed in asystem containing a large number of molecules due to the collective nature of the resulting polariton, while the effect of
the relative shifts of the energy levels is essentially independent of the number of molecules.

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
㸦‫ۻ‬㸧Nguyen Thanh Phuc, Control of electron-transfer-like reaction rate through molecular-vibration polariton in theultrastrong coupling regime. ᪥ᮏ≀⌮Ꮫ఍ ➨ 75 ᅇᖺḟ኱఍㸦2020 ᖺ㸧

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
㸦‫ۻ‬㸧N. T. Phuc, P. Q. Trung, A. Ishizaki, Controlling the nonadiabatic electron-transfer reaction rate throughmolecular-vibration polaritons in the ultrastrong coupling regime. Scientific Reports 10, 7318 (2020).

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5;§t¤&#Ts

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4ďŃ®ĵ)%d­ áÝĭ¼ĠñŶæÝ÷śŞ³¦Š[ösZŪ´ąĖ¦çąs§Ū³çĽŭ«ūô§¬ąĆĿŀÝĶ×©µŀī©ĊŅİøũbĦf÷ĐíÝh§ DTI #-0¦ĻđŜ$Ƃż/ÇüÄ$Őq Ğmîĺ$Íë $tÖů$ŰŤƄ2019.9.6-7ƅ ħ 3 HEĻ6PY=W9ĚĤmƄàgƅ çąs§Ū[ösZŪŀÝĶ×©³çĽ¬ąĆĿµŀī©ĊŅİ´ąĖ¦Ş³§ŠĠñŶøũbĦf÷ĐòąªíÝh§ İ¨ŕĎ*.10ĘāťÿÀ$ğĮ¡
Ĕ$èŌƄ2019.9.6-7ƅ ħ 3 HEĻ6PY=W9ĚĤmƄàgƅ
 Masaki Fukunaga, International neuroimaging big data collaborations: ENIGMA and COCORO, (2019.10.11-13)
Discussant, 6th Congress of Asian College of Neuropsychopharmacology (Fukuoka, Japan)
 Ryota HASHIMOTO, Yota UNO, Junya MATSUMOTO, Chika SUMIYOSHI, Kentaro MORITA, Daisuke
KOSHIYAMA, Naohiro OKADA, Haruo FUJINO, Kazutaka OHI, Michiko FUJIMOTO, Yuka YASUDA,
Hidenaga YAMAMORI, Tomiki SUMIYOSHI, Kiyotaka NEMOTO, Masaki FUKUNAGA, Kenichiro MIURA,
Overview of biotype in psychiatry, (2019.10.11-13) 6th Congress of Asian College of Neuropsychopharmacology(Fukuoka, Japan)
 Junya MATSUMOTO, Masaki FUKUNAGA, Kiyotaka NEMOTO, Daisuke KOSHIYAMA, Kenichiro MIURA,
Yota UNO, Naohiro OKADA, Kentaro MORITA, Hidenaga YAMAMORI, Yuka YASUDA, Michiko FUJIMOTO,
Noriko KUDO, Hirotsugu AZECHI, Kiyoto KASAI, Yoshiyuki WATANABE, Ryota HASHIMOTO, Maturity of
cerebral white matter is associated with individual working hours indicating social function, (2019.10.11-13) 6th
Congress of Asian College of Neuropsychopharmacology (Fukuoka, Japan)5|ý®ĵ)%d­ Yasuda Y, Okada N, Nemoto K, Fukunaga M, Yamamori H, Ohi K, Koshiyama D, Kudo N, Shiino T, Morita S,
Morita K, Azechi H, Fujimoto M, Miura K, Watanabe Y, Kasai K, Hashimoto R. Brain morphological andfunctional features in cognitive subgroups of schizophrenia. Psychiatry Clin Neurosci. 2019 Dec 2. doi:
10.1111/pcn.12963.
 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, Nakataki
M, Onitsuka T, Holleran L, Jahanshad N, van Erp TGM, Turner J, Donohoe G, Thompson PM, Kasai K,
Hashimoto R; COCORO. White matter microstructural alterations across four major psychiatric disorders:mega-analysis study in 2937 individuals. Mol Psychiatry. 2019 Nov 29. doi: 10.1038/s41380-019-0553-7.

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࣮ࣛࣝ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⬟ⓗ 05, ࡟ࡼࡗ࡚ィ ࡋࡓࠋసᡂࡋࡓேᕤ▱⬟࡟ᶵ⬟ⓗ 05, 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&KLND]RHHWDO 1DWXUH 1HXURVFLHQFH㸧ࢆ㐺⏝ࡍࡿࡇ࡜࡟ࡼࡾࠊேᕤ▱⬟ࡢྛ㝵ᒙࡀ⬻ෆࡢ࡝ࡢ㡿ᇦ࡟ᑐᛂࡍࡿ࠿ࢆྠᐃ
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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⬟ⓗ 05, ࡟ࡼࡗ࡚ィ ࡋࡓࠋࡉࡽ࡟ࠊసᡂࡋࡓேᕤ⚄⤒ᅇ㊰࡟ᶵ⬟ⓗ 05, 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⤖ᯝࠊ9 ࡸ 9࡜࠸ࡗࡓึᮇどぬ㔝ࡣ⏬ീධຊ࡟㏆࠸ேᕤ⚄⤒ᅇ㊰ࡢపḟᒙ࡜ᑐᛂࡍࡿ୍᪉࡛ࠊGHIDXOWPRGHQHWZRUN ࡣ౯್
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ሗ࡟⮳ࡿ㝵ᒙⓗ᝟ሗฎ⌮ᵓ㐀ࡣࠊ㏆ᖺᥦၐࡉࢀ࡚࠸ࡿ⓶㉁ୖࡢᶵ⬟໙㓄㸦3ULQFLSDO*UDGLHQW㸧㸦0DUJXOLHVHWDO㸧࡟ἢࡗࡓࡶࡢ࡛࠶ࡿࡇ࡜ࡀ♧ࡉࢀࡓ㸦ᅗ㸯㸧ࠋᅗ㸯㸸㌿⛣Ꮫ⩦㸦ಶே᭱㐺໬㸧࡟ࡼࡿ⬻άື࡜ேᕤ⚄⤒ᅇ㊰ࡢྛ㝵ᒙࡢᑐᛂ㛵ಀࡢኚ໬

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㟁ᴟ㒊ࡢᵓ㐀ཬࡧ཯ᛂ࡟ࡣỈ⣲⛣ືࢆక࠺㓟໬㑏ඖ཯ᛂࡀ㛵୚ࡍࡿࠋỈ⣲ཎᏊࡣྂ඾⢏Ꮚ࡜ࡋ࡚ᢅࢃࢀ࡚
ࡁࡓࡀࠊ㔞Ꮚຠᯝࡀᙉ࠸ࡓࡵ⢭ᗘࡀฟ࡞࠸ࡔࡅ࡛࡞ࡃᐇ㦂࡜ᩚྜᛶࡢ࡞࠸⤖ᯝ࡜࡞ࡿࡇ࡜ࡀࡋࡤࡋࡤ࠶ࡿࠋⓑ㔠  ⾲㠃ࡣࡑࡢ඾ᆺ౛࡛࠶ࡾࠊྂࡃ࠿ࡽࡇࡢၥ㢟ࡣᣦ᦬ࡉࢀ࡚࠸ࡿࠋࡇࡢၥ㢟ࢆゎỴࡍࡿࡓࡵ࡟ࠊ㔞Ꮚຠᯝࢆྲྀࡾᢅ࠼ࡿ➨୍ཎ⌮⤒㊰✚ศࢩ࣑࣮ࣗࣞࢩࣙࣥࡶే⏝ࡋ࡚⾜࠼ࡿࢩ࣑࣮ࣗࣞࢱࡢ㛤Ⓨࢆ⾜ࡗࡓࠋ㔞Ꮚຠᯝࢆྲྀࡾᢅ࠺ࡓࡵ࡟ࡣ  ಶࡢࣞࣉࣜ࢝ࢆ୪ิࡋ࡚ࢩ࣑࣮ࣗࣞࢺࡍࡿᚲせࡀ࠶ࡿࡓࡵࠊ㉸୪ิᶵ௨እ࡛ࡣᐇ⾜ࡀ㞴ࡋ࠸ࠋ㓟໬≀㟁ᴟࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟࠾࠸࡚ࡣࠊ㓟໬≀≉᭷ࡢᵓ㐀ࡢከᵝᛶࡢࡓࡵࠊᵓ㐀ࢧࣥࣉࣜࣥࢢࡀᚲせ࡜࡞ࡿࠋࡇࡢࢧࣥࣉࣜࣥࢢࢆຠ⋡ⓗ࡟⾜࠺ࡓࡵࡢ➨୍ཎ⌮ࣔࣥࢸ࢝ࣝࣟィ⟬ࣉࣟࢢ࣒ࣛࢆస
ᡂࡋࡓࠋ➨୍ཎ⌮⤒㊰✚ศἲࢆ⏝࠸ࡓࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾࠊⓑ㔠⾲㠃ୖࡢỈ⣲྾╔࡟ᑐࡍࡿ㔞Ꮚຠᯝࢆྲྀࡾධ
ࢀࠊ㟁Ꮚ࢚ࢿࣝࢠ࣮ᦆኻศග ((/6 ࢆ⏝࠸ࡓศගᏛⓗᐇ㦂࡜ᩚྜᛶࡢ࠶ࡿィ⟬⤖ᯝࢆึࡵ࡚ᚓࡿࡇ࡜ࡀ࡛ࡁ
ࡓࠋࡇࡢࡇ࡜࡟ࡼࡾࠊᐇ㦂࡜ィ⟬ࡢ୧㠃࠿ࡽ㟁ᴟࡢᚤどⓗ࡞ᵓ㐀ࢆ᥈ࡾᐃ㔞ⓗ࡞㆟ㄽࡀ࡛ࡁࡿࡼ࠺࡟࡞ࡗࡓࠋ
㓟໬≀㟁ᴟ࡟ࡘ࠸࡚ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡘ࠸࡚ࡶࠊᵝࠎ࡞ࢻ࣮ࣃࣥࢺࢆྵࡴከᩘࡢィ⟬ࢆ⾜࠸ࠊࡑࢀ࡟ᇶ
࡙ࡃࢹ࣮ࢱゎᯒࢆ⾜࠺᪉ἲࢆ⪃᱌ࡋࡓࠋࡇࢀࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾ㓟໬≀ࡢࡼ࠺࡞ከᵝᛶࢆᣢࡘ≀㉁࠿ࡽ࡞ࡿ
㟁ᴟࡢ≀㉁タィࡀྍ⬟࡟࡞ࡾࠊᐇ㝿㓟໬ࢪࣝࢥࢽ࣒࢘࠾ࡼࡧ㓟໬ࢳࢱࣥ࡟࡝ࡢࡼ࠺࡞ࢻ࣮ࣆࣥࢢࢆࡍࢀࡤά
ᛶࡀୖࡀࡿࡢ࠿࡟ࡘ࠸࡚⌮ㄽணࢆࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋࡇࡢ▱ぢ࡟ᇶ࡙ࡃᐇ㦂ࡀ㐍⾜ࡋ࡚࠸ࡿࠋࡇࢀࡶ኱ᆺ

ࡢィ⟬ᶵࢆ⏝࠸࡚ึࡵ࡚ᚓࡽࢀࡿᡂᯝ࡛࠶ࡿ ᅗ  ࠋᅗ  㟁ᴟ⾲㠃ୖࡢ཯ᛂ୰㛫య(OH, OOH)ࡢ྾╔࢚ࢿࣝࢠ࣮ࠋࢪࣝࢥࢽ࢔⾲㠃ୖࡢ㓟⣲✵Ꮝࢧ࢖ࢺ࡛ࡣ⌮᝿㟁ᴟ᮲௳㸦‫ۼ‬㸧ࢆ㏻ࡿ⥺ୖ࡟྾╔࢚ࢿࣝࢠ࣮ࡀ఩⨨ࡍࡿࡓࡵࠊࢻ࣮ࣃࣥࢺࢆኚ࠼ࡿ
ࡇ࡜࡟ࡼࡾ㧗άᛶࡀⓎ⌧࡛ࡁࡿ࡜ண᝿ࡉࢀࡿࠋࡇࢀࡣⓑ㔠➼࡛ࡣ‶ࡓࡍࡇ࡜ࡀ࡛ࡁ࡞࠸ࠋ

- 441 -

 ➨୍ཎ⌮ศᏊືຊᏛ࡟ࡼࡿ஧ḟ㟁ụ㟁ᴟ࣭㟁ゎᾮᶵᵓࢩ࣑࣮ࣗࣞࢩࣙࣥ
ከ㔜୪ิ໬࡟ࡼࡿ㧗ຠ⋡໬Ꮫ཯ᛂ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬ࢆ┠ⓗ࡜ࡍࡿᇶ┙࢔ࣉࣜ VWDW&30' ࡟ࡘ࠸࡚ࡣࠊࡍ
࡛࡟㟁Ꮚ≧ែィ⟬ࡢ㧗㏿໬ࠊ࣓ࣔࣜ᭷ຠ฼⏝࠾ࡼࡧ ,2 ୪ิ໬ࢆᐇ⿦ࡍࡿࡇ࡜࡟ࡼࡾࠊ┠ᶆ್࡛࠶ࡿ  ཎᏊ௨ୖࡢ⣔࡟ᑐࡍࡿ➨୍ཎ⌮ࢧࣥࣉࣜࣥࢢィ⟬ࡢᐇ᪋࡟ᡂຌࡋࡓࠋ௧࿴ඖᖺᗘࡣࠊࡉࡽ࡞ࡿ୪ิຠ⋡ྥୖࢆ┠ᣦࡋ࣮ࣟࢻ࢖ࣥࣂࣛࣥࢫࡢㄪᰝ࡜ᑐ⟇ࢆ⾜ࡗࡓࠋࣉࣟࣇ࢓࢖ࣝ࡟ࡼࡿㄪᰝ⤖ᯝ࡛ࡣࠊㄪᰝ࡟౪ࡋࡓධຊࢹ
࣮ࢱ࡛኱ࡁ࡞࢖ࣥࣂࣛࣥࢫࡣⓎ⏕ࡋ࡞࠿ࡗࡓࡀࠊ௒ᚋࡢᑐ⟇࡜ࡋ࡚ࠊࣜࢫࢱ࣮ࢺ᫬ࡢ㈇Ⲵࣂࣛࣥࢫᨵၿ⟇ࢆᐇ⿦ࡋࠊࡑࡢືసࢆ☜ㄆࡋࡓࠋࡇࢀ࡟ࡼࡾ኱つᶍィ⟬ᐇ⾜᫬ࡢᅔ㞴ࡉࡀ㍍ῶ࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿࠋࡉࡽ࡟ VWDW
&30' ࡢබ㛤࡟ྥࡅ࡚ࠊࣜࢡ࢚ࢫࢺ࡟ᛂࡌࡓࣃࢵࢳ㓄ᕸࡢ :(% ࢩࢫࢸ࣒ࢆᵓ⠏ࡋ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ

⌧ᅾࠊ኱ᆺ⵳㟁ụࡢ㛤Ⓨ࡟ྥࡅࡓᇶ♏ᇶ┙ᢏ⾡ࡢ㛤Ⓨࡀ┒ࢇ࡟⾜ࢃࢀ࡚࠸ࡿࡀࠊᐇ⏝໬࡟ࡣࡉࡽ࡞ࡿ㧗ᛶ⬟໬ࠊᏳ඲ᛶྥୖࡀᚲせ࡜࡞ࡿࠋࡋ࠿ࡋࠊᐇ㦂ほᐹࡢᅔ㞴ࡉࡶ┦ࡲࡗ࡚ࡑࡢཎᏊ࣭ศᏊ࡛ࣞ࣋ࣝࡢᐇែࡣࡲ
ࡔࢃ࠿ࡗ࡚࠸࡞࠸ࠋ⚾ࡓࡕࡣ㺀ி㺁ࢥࣥࣆ࣮ࣗࢱ࡞࡝ࡢ኱つᶍࢫࣃࢥࣥࢆ㧗ຠ⋡฼⏝ྍ⬟࡞➨୍ཎ⌮ィ⟬ࣉࣟࢢ࣒ࣛ VWDW&30' ࡞࡝ ࡢᨵⰋ࣭㛤Ⓨࢆ⾜࠺ࡇ࡜࡛ࠊ㟁ụࡢືస⎔ቃ࡟࠾ࡅࡿཎᏊ࣭ศᏊࡢ」㞧࡞ࢲ࢖ࢼ࣑ࢡ
ࢫ࣭໬Ꮫ཯ᛂࢆ⢭ᗘࡼࡃ࠿ࡘຠ⋡ⓗ࡟ィ⟬࡛ࡁࡿࡼ࠺࡟ࡋࡓࠋ

௧࿴ඖᖺᗘࡢᡂᯝ࡜ࡋ࡚ࡣࠊ㟁ゎᾮ⣔࡟㛵ࡍࡿᚤどⓗ≀ᛶ࡟㛵ࡍࡿࣁ࢖ࢻ࣮ࣞࢺ࣓ࣝࢺ୰ࡢỈศᏊࡢᣲື
࡟ࡘ࠸࡚ࡶ⌮ゎࢆ㐍ࡵࡓࠋຍ࠼࡚ࠊ࣊ࢸࣟᅛᅛ⏺㠃ࡢ㧗ຠ⋡ᵓ㐀ࢧࣥࣉࣜࣥࢢࢆྍ⬟࡜ࡍࡿ᪂ᡭἲ ࣊ࢸࣟᅛᅛ⏺㠃 &$/<362 ἲ ࢆ㛤Ⓨࡋ㸦ᅗ 㸧ࠊࡑࢀࢆඖ࡟඲ᅛయ㟁ụࡢ㓟໬≀ṇᴟ̿◲໬≀㟁ゎ㉁⏺㠃࡟࠾ࡅࡿ࢖࢜
ࣥ㍺㏦ࡢᚤどⓗ࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡉࡽ࡟㈇ᴟ̿ᅛయ㟁ゎ㉁⏺㠃࡟ࡘ࠸࡚ࡶ◊✲ࡋࠊ㈇ᴟ6(, ⭷⏺
㠃࡟࠾ࡅࡿ /L ࢖࢜ࣥ㍺㏦ࡢ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡟ࡼࡾࠊࡑࡢᚤどⓗ࣓࢝ࢽࢬ࣒ࢆᐇドࡋࡓࠋࡲࡓ⾲㠃཯ᛂ㏿ᗘㄽࠊ㟁ゎᾮ࣭㟁ゎ㉁ᶵᲔᏛ⩦ゎᯒ࡞࡝࡟㛵ࡍࡿᡭἲ㛤Ⓨࡶ㐍ᒎࡉࡏࡓࠋ

ᅗ 2.͆࣊ࢸࣟᅛᅛ⏺㠃 CALYPSO ἲ͇ࡢィ⟬ࡢὶࢀࠋࢱ࣮ࢤࢵࢺ࡜࡞ࡿ࣊ࢸࣟᅛᅛ⏺㠃㸦⏺㠃᪉఩ࡲ࡛㸧ࢆ୚࠼ࡿ࡜ࠊࡲࡎ᱁Ꮚ୙ᩚྜࢆ᭱㐺໬ࡋࡓィ⟬ࢭࣝࡀỴᐃࡉࢀࡿࠋḟ࡟⏺㠃㡿ᇦ࡜࿧ࡤࢀࡿ✵㛫ࢆ㸰ࡘࡢᮦᩱࡢ㛫࡟సᡂࡋ㸦㯤Ⰽ࡜⥳Ⰽࡢ㛫ࡢ㡿ᇦ㸧ࠊࡑࡇ࡟ᵝࠎ࡞ཎᏊࢆຍ࠼ࡘࡘ㸦ᅗ୰ࡢ୸ࠊᅄゅࠊ୕ゅ㸧ࠊ࣊ࢸࣟᅛᅛ⏺㠃ࡢ㞟ᅋᵓ㐀⦆࿴ࠊᒁᡤᵓ㐀⦆࿴ࢆ CALYPSO ἲࡢ࢔ࣝࢦࣜࢬ࣒ࢆ⏝࠸࡚⾜࠺ࠋࡑࢀࡽࡢ᥈⣴ࡢ୰࡛඲࢚ࢿࣝࢠ࣮ࡢప࠸ࠊᐇ⌧ᛶࡢ㧗࠸࣊ࢸࣟᅛᅛ⏺㠃ᵓ㐀⩌ࢆᢳฟࡋࠊࡑࢀࡽࡢᵓ㐀࡟࠾ࡅࡿ㟁Ꮚ࣭࢖࢜ࣥ≧ែࡢゎᯒࢆ⾜࠺ࠋ- 442 -

ΰྜ0&0'཯ᛂἲ࡟ࡼࡿ6(,⭷ᙧᡂࢩ࣑࣮ࣗࣞࢩࣙࣥ
MDࢯࣝࣂ࡟㛵ࡋ࡚ࡣࠊ኱つᶍ⣔࡛ࡢᏳᐃ࠿ࡘຠ⋡ⓗ࡞ィ⟬ࢆᐇ⌧ࡉࡏࡿࡓࡵ࡟ࠊLAMMPSࣉࣟࢢ࣒ࣛࢆ
᥇⏝ࡋࠊᣑᙇ⣔ࡢ᪉ἲࢆ⏝࠸࡚㟁ᴟ㟁఩୍ᐃ᮲௳ࢆ‶ࡓࡍ㟁Ꮚศᴟຠᯝࡢྲྀᢅ࠸ࢆᐇ⌧ࡋࡓࠋࡲࡓࠊMD ࢯࣝࣂ࡜ࡣู࡟ࠊRedMoonࡢ໬Ꮫ཯ᛂࡢ᥇ᢥ࣭Რ༷ࢆᢅ࠺࣮ࣝࢳࣥࢆᨵⰋࡋࡓࠋࡇࢀ࡟ࡼࡗ࡚ࠊ኱つᶍ⣔࡟࠾ࡅࡿ⿕⭷ᙧᡂࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ྍ⬟࡟ࡍࡿ࡜ඹ࡟ࠊQM/MM ィ⟬࡛ᚓࡽࢀࡓ⏕ᡂ≀ẚ࡜ྠ➼࡞⤖ᯝࢆྂ඾ຊሙィ⟬ࡢࡳ࠿ࡽࡶᚓࡽࢀࡿࡇ࡜ࢆ☜ㄆࡋࠊRedMoonࡢᛂ⏝⠊ᅖࢆᣑᙇࡋࡓࠋ

ࣜࢳ࣒࢘࢖࢜ࣥ஧ḟ㟁ụ࡟࠾࠸࡚㟁ᴟ㟁఩࡟కࡗ࡚⏕ࡌࡿ㟁ᴟ⾲㠃ࡢ㟁Ꮚศᴟຠᯝࢆ⪃៖ࡍࡿ࡜ࠊ⁐፹࡜ࡋ࡚ࡢ࢚ࢳ࣮ࣞࣥ࢝࣎ࢿ࣮ࢺ㸦EC㸧ࡢ㟁ᴟ⾲㠃➨୍ᒙ࡛ࡢ㓄ྥࡀ㟁ᴟ㟁఩࡟ᙉࡃ౫Ꮡࡋ࡚⏕ࡌࡿࡇ࡜ࡀศ࠿
ࡗࡓࠋࡇࡢ஦ᐇ࠿ࡽࠊ⿕⭷ᙧᡂࡀECࡢ㑏ඖ࠿ࡽጞࡲࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡲࡓࠊ⿕⭷ᙧᡂࢩ࣑࣮ࣗࣞࢩࣙࣥ
ࡢ⤖ᯝ࠿ࡽࠊࡇࢀࡲ࡛ࡢ㟁ᴟศᴟࡀ↓࠸ሙྜ࡟ẚ࡭࡚ࠊ⿕⭷ᵓᡂせ⣲ࡢ୍ࡘ࡛࠶ࡿⅣ㓟࢖࢜ࣥࡀ㟁ᴟ⾲㠃࡟ᙉࡃ྾╔ࡋ⥆ࡅࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡇࢀࡣࠊ⿕⭷-㟁ᴟ⏺㠃ࡢᵓ㐀࡟㛵ࡍࡿ᭷⏝࡞▱ぢ࡛࠶ࡾࠊ㟁ᴟ࡬ࡢࣜࢳ࣒࢘࢖࢜ࣥᤄධࡢ࣓࢝ࢽࢬ࣒࡟ᙉࡃᙳ㡪ࡍࡿࠋࡉࡽ࡟㟁ụసື⎔ቃୗ࡛ணࡉࢀࡿ⿕⭷ᵓ㐀ኚ໬ࡢศᏊᶵᵓࢆㄪᰝࡋࡓࠋࡑࡢ⤖ᯝࠊ(1)⿕⭷ࡣ⇕㐠ື࡛ࡣᐜ᫆࡟ᔂቯࡏࡎ࡟㏫࡟จ㞟ࡍࡿࡇ࡜ࠊ(2)㟁ᴟ⾲㠃ࡢ㟼㟁⎔ቃࡢኚ໬࡟ᑐࡋ࡚⿕⭷ᵓ㐀ࡣ㕌ឤ࡛࠶ࡿࡇ࡜ࠊ(3)⿕⭷ࡢᵓᡂせ⣲࡜ࡋ࡚Ꮡᅾࡍࡿࣜࢳ࣒࢘࢖࢜ࣥࡢᣑᩓࡀࠊ
㟁ゎᾮ࡟᥋ࡋࡓ⿕⭷ᵓ㐀ࢆቯࡍࡇ࡜ࠊࢆ᫂ࡽ࠿࡟ࡋࡓࠋࡇࢀࡽࡢ⤖ᯝࡀഅ↛࡛࡞࠸ࡇ࡜ࢆ♧ࡍࡓࡵ࡟ࠊ⊂❧ࡋࡓึᮇ᮲௳࡛సᡂࡋࡓ」ᩘ㸦᭱ప10ಶ㸧ࡢ⭷ᵓ㐀ࢆㄪᰝࡍ࡭ࡁࡇ࡜ࠊࡑࡋ࡚㠀ᖖ࡟㐜࠸⿕⭷ᵓ㐀ኚ໬ࢆ㏣࠺ࡓࡵ࡟ྜィ࡛᭷ຠⓗ࡟ᩘȣs ௨ୖࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࡀᚲせ࡛࠶ࡿࡇ࡜࠿ࡽࠊ኱ᆺ୪ิィ⟬ᶵࡢ౑⏝ࡀ㠀ᖖ࡟㔜せ࡛࠶ࡿ࡜ゝ࠼ࡿࠋ

3.4 ศᏊືຊᏛ࡟ࡼࡿ㟁ゎ㉁⭷ࢩ࣑࣮ࣗࣞࢩࣙࣥ
MODYLAS ࡢィ⟬ࡣ኱ࡁࡃศࡅ࡚ FMM ィ⟬㒊ࡢ₇⟬࡜㏻ಙࠊ
ᑐ┦஫స⏝ィ⟬㒊ࡢ₇⟬࡜㏻ಙ࡜࠿ࡽ࡞ࡿࠋ
ࡇࡢ୰࡛ࠊ᫖ᖺᗘࡲ࡛࡟FMM₇⟬࡟ᑐࡋ࡚ᇶᗏ㛵ᩘࡢsolid harmonics࡬ࡢ⨨᥮ࠊ₞໬ᘧࠊከᴟᏊࡢᑐ⛠ᛶࡢ฼⏝ࠊᴟᗙᶆ㍈ࡢᅇ㌿࡟ࡼࡿ༢⣧໬࡞࡝᪂つ࢔ࣝࢦࣜࢬ࣒ࡢᐇ⿦ࢆ⾜࠸ࠊ┦஫స⏝┤᥋ィ⟬࡟࠾࠸࡚₇⟬᫬㛫ࢆ⣙40%๐ῶࡋࠊFMM₇⟬ࡢ₇⟬㔞ࢆ⣙1/6࡟ࡲ࡛๐ῶࡋࠊ₇⟬᫬㛫ࡶ1/4࡟๐ῶࡍࡿࡇ࡜࡟ᡂຌࡋ࡚ࡁ
ࡓࠋ௒ᖺᗘࡣࠊ᪂つ࡞㏻ಙ࢔ࣝࢦࣜࢬ࣒MTDἲࢆ㛤ⓎࡋࠊࡇࢀࢆMODYLAS࡟ᐇ⿦ࡋࠊࢳ࣮ࣗࢽࣥࢢࡋࡓࠋ
୍᪉࡛ࠊSIMD ᭱㐺໬ࠊᅽຊࢸࣥࢯࣝホ౯⏝FMM ィ⟬࡞࡝ࢯࣇࢺ඲యࡢ᭱㐺໬ࢆ⾜ࡗࡓࠋࡇࢀࡽ࡟ࡼࡾࠊ
ࠕிࠖࢥࣥࣆ࣮ࣗࢱࢆ⏝࠸ࡓ࣋ࣥࢳ࣐࣮ࢡ࡟࠾࠸࡚ࡣ⌧බ㛤∧MODYLAS࡜ẚ㍑ࡋ࡚2.4ಸࡢィ⟬㏿ᗘᛶ⬟ࢆᐇ⌧ࡋࡓ㸦ᅗ3㸧ࠋࡲࡓࠊhydronium࢖࢜ࣥ࡟ࡼࡿ༢⣧࡞㍺㏦࡟ຍ࠼࡚ࠊ໬Ꮫ཯ᛂࡢ⤌ࡳ᥮࠼࡟ࡼࡿࣉࣟࢺࣥ⛣ື཯ᛂࠊࡉࡽ࡟
ࡣGrotthussᶵᵓࢆࡶྵࡴࣉࣟࢺࣥ㍺㏦ࢆグ㏙࡛ࡁࡿEVBࣔࢹࣝࢆMODYLAS࡟ᐇ⿦ࡋࠊ୪ิ໬ࢆ⾜ࡗࡓࠋ⮬⏤࢚ࢿࣝࢠ࣮ィ⟬࡟㛵ࡋ࡚ࡶࠊMODYLAS࡟࠾࠸࡚⇕ຊᏛ✚ศἲࢆᚲせ࡟ᛂࡌࡓᙧᘧ࡛ỗ⏝ⓗ࡟฼⏝࡛ࡁࡿࡼ࠺ࠊ┦஫స⏝㛵ᩘ୰࡬ࡢᦤືࣃ࣓࣮ࣛࢱȢࡢᑟධࡸFMMィ⟬࡟࠾ࡅࡿbackground chargeࡢྲྀࡾᢅ࠸ࡢ
ᩚഛࢆ⾜࠸ࠊ࠸ࡎࢀࡶMODYLAS࡟ᐇ⿦ࡋࠊ᳨ドࢆ⾜ࡗࡓࠋ- 443 -

ᅗ 3. ࠕிࠖࢆ⏝࠸ࡓ MODYLAS ࡢ࣋ࣥࢳ࣐࣮ࢡࠋ
୙ᆒ୍⣔࡟࠾࠸࡚ࡣศᏊࡢᣑᩓಀᩘࡣ఩⨨࡟౫Ꮡࡍࡿࠋࡇࡢ఩⨨࡟౫ᏑࡋࡓศᏊࡢᣑᩓಀᩘࢆຠ⋡ⓗ࡟ホ
౯ࡍࡿ᪂つィ⟬᪉ἲࢆ㛤Ⓨࡋࡓࠋࡇࢀࡣࠊὀ┠ࡋ࡚࠸ࡿศᏊࢆ✵㛫ⓗ࡟ flat-bottomed potential ࢆ⏝࠸࡚✵㛫ⓗ࡟ᣊ᮰ࡍࡿࡇ࡜࡟ࡼࡾࠊ఩⨨ᣊ᮰ࢆ࠿ࡅ࡞ࡀࡽࡶືຊᏛ࡟ᙳ㡪ࢆ୚࠼࡞࠸᪉ἲ࡟ᇶ࡙࠸࡚ᣑᩓಀᩘࢆホ౯ࡍࡿࡶࡢ࡛࠶ࡿࠋࡇࡢ఩⨨࡟౫Ꮡࡋࡓᣑᩓಀᩘࡘࡲࡾ⛣ືᗘ࡜ࠊ఩⨨࡟౫Ꮡࡋࡓ⮬⏤࢚ࢿࣝࢠ࣮࡜ྜࢃࡏ࡚
ືⓗࣔࣥࢸ࢝ࣝࣟィ⟬ࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊ⁐㉁ࡢ኱ᇦⓗ࡞ᾐ㏱ಀᩘࢆ㏱㐣⤒㊰࡜ඹ࡟ホ౯ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
ᮏᖺᗘࡣࠊ⡆༢࡞␯Ỉᛶࣔࢹࣝ⏺㠃࡟࠾ࡅࡿศᏊࡢᣑᩓಀᩘࡢ఩⨨౫Ꮡᛶࡢ㆟ㄽࢆ㏻ࡋ࡚ࡇࡢ᪉ἲࡢ᳨ドࢆ⾜ࡗࡓࠋࡇࢀ࡟ࡼࡾࠊ⇞ᩱ㟁ụ㟁ᴟ୕┦⏺㠃ࡸ㟁ゎ㉁⭷ࣂࣝࢡ୰ࡢ㓟⣲ࠊỈ⣲ࠊࣉࣟࢺࣥ࡞࡝≀㉁㍺㏦ࢆศ
Ꮚᵓ㐀࡜㛵㐃ࡉࡏ࡞ࡀࡽᐃ㔞ⓗ࡟㆟ㄽࡍࡿࡇ࡜ࡀྍ⬟࡜࡞ࡾࠊ㟁ᴟࠊ࢔࢖࢜ࣀ࣐࣮ᮦᩱࡢ㛤Ⓨࠊ⏺㠃ᵓ㐀ࡢ᭱㐺໬࡟኱ࡁࡃ㈉⊩࡛ࡁࡿࠋ

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㸦᪩✄⏣኱㸧

1◊✲┠ⓗࠊෆᐜ
໬Ꮫ࢚ࢿࣝࢠ࣮๰ᡂ࠿ࡽᾘ㈝࡟⮳ࡿ㐣⛬࡟࠾࠸࡚ࠊ࣓ࢱࣥࡸ CO2 ࡢศ㞳࣭ᅇ཰ࠊ㈓ⶶࠊゐ፹཯ᛂ࡟ࡼࡿ࢚

ࢿࣝࢠ࣮࣭㈨※ࡢ᭷ຠ฼⏝࡟㛵ࢃࡿᇶ┙ᢏ⾡ࢆ㛤Ⓨࡋࠊ㧗ຠ⋡࡞ศ㞳࣭ᅇ཰ࠊ㈓ⶶࠊ┦஫ኚ᥮ἲࡢᐇ⏝࡬ࡢᶫΏࡋ࡜ࡍࡿࡓࡵࡢᣦ㔪ࢆᥦ౪ࡍࡿࠋࡑࡢࡓࡵ࡟ࠊ㟁Ꮚ≧ែ⌮ㄽ࡜ศᏊືຊᏛἲࢆᇶ┙࡜ࡋࡓ⤫ྜࢩ࣑ࣗࣞ
࣮ࢩࣙࣥᢏ⾡ࢆᵓ⠏ࡋࠊᐇ⏝ⓗ࡞≀㉁タィ࡟ྥࡅศᏊࣞ࣋ࣝ࠿ࡽࡢᣦ㔪ࢆᥦ౪ࡍࡿࠋࣁ࢖ࢻ࣮ࣞࢺศゎ࡟ࡼ
ࡿ࣓ࢱࣥ㈨※ࡢ᥇ྲྀ᪉ἲࡢຠ⋡໬ࠊ⇞ᩱ㟁ụ㠀ⓑ㔠⣔ゐ፹ࡢ㛤Ⓨࠊ࢔࣑ࣥࢆࡣࡌࡵ㧗ຠ⋡ᮦᩱࢆ⏝࠸ࡓ CO2
ࡢศ㞳࣭ᅇ཰ᢏ⾡ࡢⓎᒎ࡟㈉⊩ࡍࡿࡇ࡜࡟ࡼࡾࠊ࢚ࢿࣝࢠ࣮ከᾘ㈝ᆺᕤᴗࣉࣟࢭࢫࢆ㠉᪂ࡍࡿࠋ໬Ꮫ࢚ࢿࣝࢠ࣮ࢆᑐ㇟࡜ࡍࡿᮏࢧࣈㄢ㢟ࡣࠊࣁ࢖ࢻ࣮ࣞࢺࠊゐ፹ࠊCO2 ศ㞳࣭ᅇ཰࠿ࡽᵓᡂࡉࢀࡿࠋ࢚ࢿࣝ
ࢠ࣮㈨※࡜ࡋ࡚኱㔞࡟Ꮡᅾࡍࡿ࣓ࢱࣥࣁ࢖ࢻ࣮ࣞࢺࡢຠ⋡ⓗ᥇ྲྀἲࡢ㛤Ⓨࢆ┠ᣦࡋ࡚ࠊ኱つᶍ㛗᫬㛫 MD ࢩ࣑࣮ࣗࣞࢩࣙࣥ(MODYLASࠊGROMACS ฼⏝㸧ࢆᐇ᪋ࡋ࡚ࠊ࣓ࢯࢫࢣ࣮࡛ࣝࡢゎ㞳ࡢᶵᵓゎ᫂ࠊゎ㞳ࡢᚊ㏿㐣⛬ࡢ᥈⣴ࢆ⾜࡞࠸ࠊຠ⋡ⓗ࡞⼥ゎἲ࡬ࡢᣦ㔪ࢆᚓࡿࠋࡲࡓࠊ኱つᶍ࡞ᵓ㐀᥈⣴࠿ࡽࠊ⵳෭ᮦ࡜ࡋ࡚ࡢࢭ࣑
ࢡࣛࢫ࣮ࣞࢺࡢᛶ⬟ࡢྥୖࡢࡓࡵࡢໟᣓⓗ࡞ホ౯ࢆ⾜࠺ࠋゐ፹࡛ࡣࠊ཯ᛂ⤒㊰⮬ື᥈⣴ἲ㸦GRRM㸧ࢆ㉸୪ิ㟁Ꮚ≧ែィ⟬ࢯࣇࢺ࢙࢘࢔࡜㐃⤖ࡍࡿࡇ࡜࡟ࡼࡾᮍ▱ࡢゐ፹㛤Ⓨ࡟᭷⏝࡞ィ⟬໬Ꮫᡭἲࡢ㛤Ⓨࢆ┠ᣦࡍ࡜࡜ࡶ࡟ࠊ⇞ᩱ㟁ụ㠀ⓑ㔠⣔ゐ፹࡟↔Ⅼࢆᙜ࡚ࡓ◊✲ࢆ⾜࠺ࠋCO2 ศ㞳࣭ᅇ཰࡛ࡣࠊศ๭⤫἞ἲࢆ୰ᚰ࡜ࡋࡓ࢔ࣉࣜ(DC-DFTB-K)ࡢ㧗ᗘ໬ࢆ⾜࠸ࠊᾘ㈝࢚ࢿࣝࢠ࣮ࢥࢫࢺࢆ๐ῶࡍࡿ᪂つ࢔࣑ࣥࡢᥦ᱌࣭᭱㐺࡞࢔࣑ࣥΰྜẚࡢணࢆ⾜࠺ࠋ᭦࡟ࠊ⁐ᾮ⣔ࡔࡅ࡛࡞ࡃ㔠ᒓ᭷ᶵᵓ㐀య㸦MOF㸧ࡸࢮ࢜ࣛ࢖ࢺࡢࡼ࠺࡞ከᏍ㉁ᮦᩱࢆ⏝࠸ࡓᡭἲ࡟㛵ࡍࡿᢏ⾡ࢆ☜❧ࡍࡿࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ(1) ࣁ࢖ࢻ࣮ࣞࢺ࡟࠾࠸࡚ࡣࠊ⣙ 12,000 ࡢỈศᏊ࠿ࡽ࡞ࡿ⣔ࡢศᏊືຊᏛィ⟬࡟ࡼࡗ࡚࣮࢝࣎ࣥࢼࣀࢳࣗ
࣮ࣈࢆෆໟࡍࡿໟ᥋Ỉ࿴≀ࡢ⏕ᡂᶵᵓࢆ◊✲ࡋࡓࠋࡲࡓࠊ2 ✀㢮ࡢ⁐㉁࡟ࡘ࠸࡚ 100 ࢆ㉸࠼ࡿ⇕ຊᏛࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚Ỉࡢᐦᗘᦂࡽࡂ࡜┦ศ㞳ࢆ◊✲ࡋࡓࠋศᏊືຊᏛィ⟬࡟ࡣ GROMACS ࢆ⏝࠸ࡓࠋ(2) ゐ፹࡟࠾࠸࡚ࡣࠊSIESTA ࢆ⏝࠸ࡓ GGA-PBE/DZP ࣞ࣋ࣝࡢィ⟬࡟ࡼࡾࠊfcc(111)ཬࡧ(100)⾲㠃ࢫࣛࣈࣔࢹࣝ㸦┿✵ᒙ 15 Å㸧࡜⾲㠃࡟ᵝࠎ࡞㓄ྥࢆࡋࡓ྾╔Ꮚࡀ྾╔ࡋࡓ≧ែࢆᵓ㐀᭱㐺໬ࡋࠊᗄఱ࣭㟁Ꮚᵓ㐀ࢆࢹ࣮ࢱ࣮࣋ࢫ໬㸦Ⓩ㘓ᩘ 3 ୓௳௨ୖ㸧ࠋ

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(3) CO2 ࡢศ㞳࣭྾཰࡟࠾ࡅࡿ฼⏝࢔ࣉࣜࢣ࣮ࢩࣙࣥࡣࠊࣞࣉࣜ࢝஺᥮ἲࢆ⏝࠸ࡓィ⟬࡛ࡣࠊ⣙ 1500 ཎᏊ࠿ࡽ࡞ࡿỈ⁐ᾮ୰ࡢࢪ࢔ࣛࢽࣥศᏊࡢᵓ㐀ࢧࣥࣉࣜࣥࢢࢆྲྀࡾᢅࡗࡓࠋ࣓ࣔࣜ౑⏝㔞๐ῶ࢔ࣝࢦࣜࢬ࣒ࡢືస᳨ド࡛ࡣࠊ᭱኱ 23,437,500 ཎᏊࡢ⣧Ỉ⣔ࢆ⏝࠸ࡓࠋ࢔࣑ࣥ-CO2 ⁐ᾮ⣔ࡢ⇕ຊᏛ㔞⮬ື໬ィ⟬࡛ࡣࠊ⣙ 270 ✀ࡢ࢔࣑ࣥศᏊࡘ࠸࡚ィ⟬ࢆᐇ⾜ࡋࡓࠋMOF ࡟ࡼࡿ CO2 ᅛᐃ໬཯ᛂ࡛ࡣࠊMOFࠊCO2ࠊ࠾ࡼࡧ཯
ᛂᶵᵓゎᯒࡢᑐ㇟࡜ࡋࡓࢫࢳࣞࣥ࢜࢟ࢩࢻ࠿ࡽ࡞ࡿࣔࢹࣝ࡟ᑐࡋࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࠊࡉࡽ࡟⁐፹ࢆྵࡴ⣔࡟ࡘ࠸࡚ࡶ᳨ウࢆ⾜ࡗࡓࠋ࠸ࡎࢀࡢィ⟬࡟࠾࠸࡚ࡶࠊDC-DFTB-K ࡲࡓࡣศᏊືຊᏛィ⟬ᶵ⬟ࢆᙉ໬ࡋࡓ DCDFTBMD ࢆ⏝࠸ࡓࠋ

3

◊✲ᡂᯝ

3.1 ࣓ࢱࣥࣁ࢖ࢻ࣮ࣞࢺ
࣓ࢱࣥࣁ࢖ࢻ࣮ࣞࢺࡢ㈨※໬ࡸᾏᗏ࡬ࡢ CO2 ᗫᲠࡢᐇ⌧࡟ࡣࠊࡑࡢ⇕ຊᏛⓗᏳᐃᛶࡢホ౯ࡀ୙ྍḞ࡛࠶ࡿࠋࡑࡢࡓࡵ࡟ࠊᡃࠎࡣ

ᗘ(T)ࠊᅽຊ(P)ࠊࡑࡋ࡚ࢤࢫࢺࡢࣔࣝศ⋡(xg)ࢆ⊂❧ኚᩘ࡜ࡋ࡚ࣁ࢖ࢻ࣮ࣞࢺ⏕ᡂ᮲௳ࢆồࡵࡿᇶ♏ཎ⌮ࢆぢฟࡋࠊࡑࢀ࡟ᇶ࡙࠸ࡓࢯࣇࢺ㛤Ⓨࢆ࣓ࢱࣥ௨እࡢኳ↛࢞ࢫࡸᕼ࢞ࢫ࡟ᣑᙇࡋࡓࠋ
⤖ᬗࡢ⌮ㄽ◊✲ࡢࡓࡵ࡟ࡣࠊࡲࡎࡑࡢᵓ㐀ࢆ⏕ᡂࡍࡿᚲせࡀ࠶ࡿࠋໟ᥋Ỉ࿴≀ࡸඹᏑࡍࡿịࡢ࡯࡜ࢇ࡝ࡣ
ࣉࣟࢺࣥ↓⛛ᗎ⤖ᬗ࡛࠶ࡾࠊࡲࡓ⣔඲యࢆ↓ศᴟ࡜ࡍࡿᚲせࡀ࠶ࡾࠊࡑࡢᵓ㐀ࡢ⏕ᡂࡣᐜ࡛᫆ࡣ࡞࠸ࠋᡃࠎ
ࡣࠊᵝࠎ࡞ໟ᥋Ỉ࿴≀ࡸịࡢᵓ㐀ࢆ⏕ᡂ࡛ࡁࡿ᪂ࡋ࠸࢔ࣉࣜࠊGenIce ࢆ㛤Ⓨࡋࠊࡇࢀࢆ㡰ḟᨵⰋࡋ࡚⏕ᡂ࡛ࡁࡿị✀ࢆቑຍࡉࡏࡓࠋ
⤖ᬗࡢ᰾⏕ᡂࡣᐦᗘᦂࡽࡂ࡟ࡼࡗ࡚ಁ㐍ࡉࢀࡿࠋ㏻ᖖࡢᾮయ࡜␗࡞ࡾࠊỈࡢሙྜࡣ஧ࡘࡢᾮ┦ࡢᏑᅾࡀ኱
ࡁ࡞ᐦᗘᦂࡽࡂ࡜㛵ಀࡋ࡚࠸ࡿࠋᡃࠎࡣ NaCl ࡜ Ne ࡜࠸࠺඲ࡃ␗࡞ࡿ⁐㉁ࡀỈࡢᾮ-ᾮ┦㌿⛣࡟ཬࡰࡍຠᯝ
ࢆศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ゎᯒࡋࡓ㸦ᅗ 1㸧ࠋໟ᥋Ỉ࿴≀ࡢほⅬ࡛ࡣࠊᑠࡉ࡞␯Ỉ≀㉁࡛࠶ࡿ Ne
ࡀࡼࡾ㔜せ࡛࠶ࡿࠋᡃࠎࡢゎᯒ࡟ࡼࡾࠊ࡝ࡕࡽࡢ⁐㉁ࡶ┦ศ㞳ࡢᗘࢆୖ᪼ࡉࡏࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ

୍᪉ࠊᅽຊ࡟ࡘ࠸࡚ࡣࠊNaCl ࡣῶᑡࠊNe ࡣቑຍࡉࡏࡿຠᯝࡀ࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢ⤖ᯝࡣ␯Ỉⓗ࡞≀㉁ࡀ⁐ࡅࡓỈࡢᦂࡽࡂࡀ㧗ᅽ࡛኱ࡁࡃ࡞ࡾࡸࡍ࠸࡜࠸࠺ࡇ࡜ࢆ♧ࡋ࡚࠾ࡾࠊࡇࡢ⌧㇟ࡀໟ᥋Ỉ࿴≀ࡢ᰾⏕ᡂࡢ㥑ືຊ࡜ఱࡽ࠿ࡢ㛵ಀࡀ࠶ࡿྍ⬟ᛶࡀ࠶ࡿࠋ

ᅗ 1. ᑠࡉ࡞␯Ỉ⢏Ꮚ(㉥㸧࡟ࡼࡗ࡚ಁ㐍ࡉࢀࡿỈࡢᾮ-ᾮ┦ศ㞳ໟ᥋Ỉ࿴≀ࢆᵓᡂࡍࡿࢤࢫࢺศᏊࡢ኱ࡁࡉ࡟ࡣୖ㝈ࡀ࠶ࡿࠋ㏻ᖖࡢໟ᥋Ỉ࿴≀࡛ࡣ࢝ࢦᵓ㐀ࡢ୰࡟ࢤࢫࢺ
ࢆෆໟࡍࡿࠋ௚ࡢᙧ≧ࠊ౛࠼ࡤᰕ≧ࡢ✵㛫ࢆ⪃࠼ࡿ࡞ࡽࡤࠊࡼࡾ኱ࡁ࡞ࢤࢫࢺࢆෆໟࡋࡓỈ࿴≀ࢆసࢀࡿࡢ
࡛ࡣ࡞࠸࠿ࠋࡇࡢ࢔࢖ࢹ࢔ࢆࡶ࡜࡟ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊࡑࡢ⤖ᯝࠊᐇ㝿࡟࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ
ࢆ୍ᐃ㛫㝸࡛୪࡭ࡓࢼࣀࣈࣛࢩࡢ࿘ࡾ࡟ࡇࢀࡲ࡛࡟ぢࡘ࠿ࡗ࡚࠸࡞࠸᪂ࡋ࠸⤖ᬗᵓ㐀ࡀ⮬Ⓨⓗ࡟ᙧᡂࡍࡿࡇ࡜ࢆぢฟࡋࡓ㸦ᅗ2㸧ࠋࡲࡓࠊࡇࢀࡲ࡛࡟㛤Ⓨࡋࡓ⤫ィຊᏛⓗ࡞⌮ㄽࢆᛂ⏝ࡍࡿࡇ࡜࡛ࠊࡇࡢ᪂ᵓ㐀ࡢ⇕ຊᏛⓗ࡞Ᏻᐃᛶࡸయ✚ࢆぢ✚ࡶࡿࡇ࡜࡟ᡂຌࡋࡓࠋ

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ᅗ 2. ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡢෆໟࡍࡿ᪂ࡋ࠸ໟ᥋Ỉ࿴≀ࡢ㦵᱁ᵓ㐀

3.2 ゐ፹
཯ᛂ⤒㊰⮬ື᥈⣴ࣉࣟࢢ࣒ࣛ㸦GRRM㸧ࡢ㉸୪ิ໬㟁Ꮚ≧ែィ⟬ࢯࣇࢺ࢙࢘࢔࡜ࡢ㐃⤖ࢆྵࡴ㧗ᗘ໬࡜ࠊᛂ⏝ㄢ㢟࡜ࡋ࡚⌮ㄽ-ᐇ㦂㐃ᦠ࡟ࡼࡿᮍ▱ࡢゐ፹཯ᛂᶵᵓゎ᫂࠾ࡼࡧ᪂つゐ፹ࡢ㛤Ⓨࢆ┠ᣦࡋࡓ◊✲ࢆ㐍ࡵ࡚࠸ࡿࠋ࢔ࣉࣜ㛤Ⓨ࡟ࡘ࠸࡚ࡣࠊゐ፹཯ᛂ࡛㔜せ࡜࡞ࡿᢸᣢຠᯝࢆ⪃៖ࡋࡓィ⟬ࢆᐇ⌧ࡍࡿࡓࡵࠊ௵ពࡢ MPI
୪ิ㟁Ꮚ≧ែィ⟬ࢯࣇࢺ࢙࢘࢔㸦≉࡟ VASP, SIESTA ࢆࢆ⏝࠸ࡓ࿘ᮇቃ⏺⣔ࡢ㔞Ꮚ໬Ꮫィ⟬㸧ࢆ⏝࠸ࡓ GRRM
㉸୪ิィ⟬ࢆྍ⬟࡟ࡍࡿ mpi_comm_spawn ࢆ⏝࠸ࡓ୪ิᶵ⬟ࡢᐇ⿦ࢆ㐍ࡵࡓࠋࡲࡓࠊி࠾ࡼࡧ࣏ࢫࢺி࡛ᚓ
ࡽࢀࡿ GRRM ฟຊࣇ࢓࢖ࣝࡼࡾศᏊᵓ㐀ࡸ࢚ࢿࣝࢠ࣮➼ࡢ᝟ሗࢆㄞࡳྲྀࡾศ㢮ࡋ࡚ࠊGRRM ィ⟬ࡢ⤖ᯝ࠿ࡽᐜ᫆࡟཯ᛂ⤒㊰ᆅᅗࢆసᡂࡍࡿࢯࣇࢺ࢙࢘࢔ SAFIRE(Simple AFIR connection Extractor)ࢆ㛤Ⓨࡋࡓ㸦ᅗ 3㸧ࠋࣉࣟࢢ࣒ࣛࡣබ㛤‽ഛ୰࡛࠶ࡿࠋ

ᅗ 3. GRRM ࡢฟຊࣇ࢓࢖ࣝࡼࡾ EQ㸦ᖹ⾮ᵓ㐀㸧ཬࡧ TS㸦㑄⛣≧ែᵓ㐀㸧ࡢ┦஫ࢆ⤖ྜࡍࡿ connectionࡢ᝟ሗࢆㄞࡳྲྀࡾศ㢮ࡋ࡚཯ᛂ⤒㊰ᆅᅗࢆసᡂࡍࡿࢯࣇࢺ࢙࢘࢔ SAFIRE
㸦Simple AFIR-calculationresults Extractor)ࢆ⏝࠸࡚ྍど໬ࡋࡓࢢࣜࢩࣥࡢ཯ᛂ⤒㊰ᆅᅗ୙ᆒ୍ゐ፹ࡢゐ፹άᛶࡣࠊ୺ゐ፹ඖ⣲✀ࡔࡅ࡛࡞ࡃࠊ⾲㠃ᵓ㐀ࡸࢻ࣮ࣆࣥࢢࠊḞ㝗࡞࡝ࡢゐ፹⮬㌟ࡢ≧ែࠊࡉࡽ࡟ࡣᢸయࡸຓゐ፹ࠊ

ᗘࠊゐ፹ㄪᩚἲ࡜࠸ࡗࡓ㠀ᖖ࡟ከࡃࡢࣇ࢓ࢡࢱ࣮࡟ࡼࡗ࡚ኚ໬ࡍࡿࠋࡇࢀࡽࡢᙳ

㡪ࡢ୍ࡘࡦ࡜ࡘ࡟ᑐࡋ࡚ࡣࠊ㔞Ꮚ໬Ꮫィ⟬➼ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ࡑࡢ࣓࢝ࢽࢬ࣒ࢆゎ᫂ࡍࡿࡇ࡜ࡀ

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ྍ⬟࠿ࡶࡋࢀ࡞࠸ࡀࠊࡇࢀࡽࡢᙳ㡪ࢆࡍ࡭࡚ྲྀࡾ㎸ࢇ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࡇ࡜࡟ࡼࡾゐ፹ᛶ⬟ࢆ⥲ྜⓗ࡟⟬ᐃࡍࡿࠊ࡜࠸࠺ࡢࡣࠕᐩᓅࠖࢆ⏝࠸ࡓ࡜ࡋ࡚ࡶ㞴ࡋ࠸ࠋࡑࡇ࡛Ⓨ᝿ࢆ㌿᥮ࡋࠊࣁ࢖ࢫ࣮ࣝࣉࢵࢺィ⟬࡟ࡼࡾ⌮᝿ⓗ࡟ࣔࢹࣝ໬ࡋࡓ㔠ᒓ⾲㠃࡟ᑐࡍࡿ཯ᛂ≀࣭୰㛫యࡢ྾╔ᵓ㐀࣭྾╔㟁Ꮚ≧ែࢆࢹ࣮ࢱ࣮࣋ࢫ໬
ࡋࠊᶵᲔᏛ⩦࡜⤌ࡳྜࢃࡏࡿࡇ࡜࡟ࡼࡗ࡚཯ᛂゎᯒࡸゐ፹᥈⣴࡟฼⏝࡛ࡁࡿࢩࢫࢸ࣒ࡢᵓ⠏ࢆ⾜ࡗࡓࠋලయ
ⓗ࡞฼⏝౛࡜ࡋ࡚ࠊ㔠ᒓゐ፹࡟ࡼࡿ࣓ࢱࣥỈ⵨Ẽᨵ㉁㸦MSR㸧཯ᛂࡢ࣓ࢱࣥ㌿໬⋡ࢆ༢୍ࡢㄽᩥ࠿ࡽྲྀᚓࡋ
࡚┠ⓗኚᩘ࡜ࡋࠊᮏࢹ࣮ࢱ࣮࣋ࢫ࠿ࡽグ㏙Ꮚࢆᵓ⠏ࡋ࡚ᅇᖐࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊMSR ཯ᛂ࡟ࡣ┤᥋㛵୚ࡋ
࡞࠸ C2 ࡢ྾╔࢚ࢿࣝࢠ࣮ࡀ㈇࡟┦㛵ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸦ᅗ 4㸧
ࠋࡇࢀࡣⅣ⣲ᯒฟ࡟ࡼࡿゐ፹ࡢ୙ά໬࡜
㛵㐃ࡋ࡚࠸ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀࡿࠋ
D    60 E 

Predicted conversion rate [%]

60

Ag
Au

40

40

20

0

60

Ni

Predicted conversion rate [%]

60

Pd

Cu

Pt

Ir

Rh

40

20

0

0

20

40

60

80

0
0

20

40

20

40

Ni

Au

Pd

Cu

Pt

Ir

Rh

20

40

20

0

60

80

0
0

60

Ag

20

40

60

Experimental conversion rate [%]Experimental conversion rate [%]ᅗ 4. ༢୍ㄽᩥ࠿ࡽᚓࡓ࣓ࢱࣥ㌿໬⋡㸦ᶓ㍈㸧࡜ᶵᲔᏛ⩦࡟ࡼࡾணࡉࢀࡓ್㸦⦪㍈㸧ࡢ┦㛵ࠋ(a)LASSOࠊ(b)MC+ἲ࡟ࡼࡿ⤖ᯝࠋ
3.3 CO2 ࡢศ㞳࣭ᅇ཰
DC-DFTB-K ࡛ࡣࠊ㉸୪ิ㟁Ꮚ≧ែィ⟬ἲ࡜ࣞࣉࣜ࢝஺᥮ἲࢆ⤌ࡳྜࢃࡏࡓศᏊືຊᏛ࣭࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ
ィ⟬ᡭἲࡢᐇ⿦ࢆ⾜ࡗࡓࠋᅗ 5(a)ࡣࠊỈ⁐ᾮ୰ࡢࢪ࢔ࣛࢽࣥศᏊࡢᵓ㐀ࢧࣥࣉࣜࣥࢢ㏿ᗘࢆᖹᆒ஧஌೫ᕪ࡟
ᇶ࡙ࡃࢡࣛࢫࢱࣜࣥࢢゎᯒ࡟ࡼࡗ࡚ẚ㍑ࡋࡓࡶࡢ࡛࠶ࡿࠋࣞࣉࣜ࢝஺᥮ἲࡢ㐺⏝࡟ࡼࡾࠊᵓ㐀ࢧࣥࣉࣜࣥࢢ
ຠ⋡ࡢྥୖࡀ♧ࡉࢀࡓࠋᅗ 5(b)ࡣࠊᮎ➃㛫㊥㞳ࢆ཯ᛂᗙᶆ࡜ࡍࡿ࣓ࢱࢲ࢖ࢼ࣑ࢡࢫࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ

ᅗ 5. ㉸୪ิ㟁Ꮚ≧ែィ⟬ἲ࡟ᇶ࡙ࡃศᏊືຊᏛ(MD)࣭࣓ࢱࢲ࢖ࢼ࣑ࢡࢫ(MTD)ィ⟬࡟࠾ࡅࡿỈ⁐ᾮ୰ࡢࢪ࢔ࣛࢽࣥศᏊࡢᵓ㐀ࢧࣥࣉࣜࣥࢢࡢࣞࣉࣜ࢝஺᥮(RE)ἲࡢ᭷↓࡟ࡼࡿẚ㍑ࠋ(a)ᖹᆒ஧஌೫ᕪ࡟ᇶ࡙ࡃ㠀㢮ఝᵓ㐀ࡢ᥈⣴ᩘࡢ⤒᫬ኚ໬ࠊ(b) MTD ィ⟬࠿ࡽᚓࡽࢀࡓᮎ➃㛫㊥㞳࡟ᑐࡍࡿ⮬⏤࢚ࢿࣝࢠ࣮᭤⥺ࡢ᫬㛫Ⓨᒎࠋ

- 449 -

࡚ᚓࡽࢀࡓ⮬⏤࢚ࢿࣝࢠ࣮᭤⥺ࡢ᫬㛫Ⓨᒎࢆ♧ࡍࠋᚑ᮶ࡢィ⟬࡛ࡣࠊ཯ᛂᗙᶆ௨እࡢ㐜࠸㐠ືࡢᙳ㡪࡟ࡼࡾࠊ⮬⏤࢚ࢿࣝࢠ࣮᭤⥺ࡣ᫬㛫࡟ᑐࡋ࡚኱ࡁࡃኚ໬ࡋࡓࠋࡇࡢၥ㢟ࡣ㧗㡿ᇦ࡬ࡢ㑄⛣ࢆྍ⬟࡜ࡍࡿࣞࣉࣜ࢝஺

᥮ἲࢆ㐺⏝ࡍࡿ࡜⦆࿴ࡉࢀࠊ⮬⏤࢚ࢿࣝࢠ࣮᭤⥺ࡢ཰᮰ᛶࡀ኱ࡁࡃᨵၿࡋࡓࠋࡇࢀࡽࡢ⤖ᯝ࡟ࡼࡾࠊ㛤Ⓨ࣭ᐇ⿦ࡋࡓᡭἲࡢ᭷ຠᛶࡀ♧၀ࡉࢀࡓࠋ

ᖹᡂ 30 ᖺᗘࡲ࡛࡟㛤Ⓨࡋࡓ࣓ࣔࣜ౑⏝㔞๐ῶ࢔ࣝࢦࣜࢬ࣒࡟ࡘ࠸࡚ࠊ୪ิィ⟬ࡢ᪉ἲ࡜ຠᯝ㸦ᛶ⬟㸧࡛㏙
࡭ࡓᕧ኱㓄ิࡢࢧ࢖ࢬ⦰ᑠ࡟ຍ࠼࡚ࠊ࣓ࣔࣜ࡟☜ಖࡍࡿࢹ࣮ࢱᵓ㐀ࡢぢ┤ࡋ࡜୰㛫ࢹ࣮ࢱࡢศᩓಖᏑ࡟㛵ࡍࡿ㧗ᗘ໬ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊᅗ 6 ࡟♧ࡍࡼ࠺࡟㧗ᗘ໬๓ࡼࡾ᭱኱ 1.7 ಸࡢཎᏊᩘࢆྵࡴ⣧Ỉ⣔ࡢ㉸୪ิ㟁Ꮚ≧ែィ⟬ࡀྍ⬟࡜࡞ࡗࡓࠋ1000 ୓ཎᏊ௨ୖࡢ⣔࡟ᑐࡍࡿ኱つᶍ࣋ࣥࢳ࣐࣮ࢡィ⟬ࡣࠊࠕிࠖࢆ฼⏝ࡋ࡚ࡇࡑฟࡏࡓᡂᯝ࡛࠶ࡿࠋᅗ 6㸬ࠕிࠖ࡟࠾࠸࡚㉸୪ิ㟁Ꮚ≧ែィ⟬࡟ᇶ࡙ࡃ MD 1 ࢫࢸࢵࣉࡢィ⟬ࢆᐇ⾜ྍ⬟࡞⣧Ỉ⣔࡟ྵࡲࢀࡿཎᏊᩘࡢࢥ࢔ᩘ౫Ꮡᛶࠋin-core/direct ࡣ࣓ࣔࣜ౑⏝㔞๐ῶ࢔ࣝࢦࣜࢬ࣒ࡢ㐺⏝↓/᭷ࢆ⾲ࡍࠋᩘᏐࡣ 128,000 ࢥ࢔࡛ィ⟬ࡀᐇ⾜ྍ⬟࡞᭱኱ࢧ࢖ࢬࢆ♧ࡍࠋ
࢔࣑ࣥ-CO2 ⁐ᾮ⣔࡛㉳ࡇࡿ཯ᛂࡢ⇕ຊᏛ㔞ࡢከ✀ࡢ࢔࣑ࣥ࡟ᑐࡍࡿண

ࢆྍ⬟࡜ࡍࡿࡓࡵࠊᅗ 7 ࡟♧ࡍ⇕ຊᏛ㔞ࡢ⮬ືィ⟬ᡭ㡰ࢆᵓ⠏ࡋࡓࠋ࢔࣑ࣥࡢゎ㞳཯ᛂ࡟ࡘ࠸࡚ࡣ⣙ 270 ✀࡟ᑐࡋ࡚ィ⟬ࢆᐇ⾜ࡋࠊ࠺ࡕ 68 ✀࡟ࡘ࠸࡚㓟ゎ㞳ᐃᩘ(pKa)࡟ኚ᥮ࡋࡓ್ࢆᐇ㦂್࡜ẚ㍑ࡋࡓࠋࡑࡢ⤖ᯝࠊᖹᆒ⤯ᑐㄗᕪ 0.37 pKa ༢఩ࡢ⢭ᗘ࡛

ᅗ 7. ໬Ꮫ཯ᛂࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ᇶ࡙ࡃ࢔࣑ࣥ-CO2 ⁐ᾮ⣔཯ᛂ࡟ᑐࡍࡿ⇕ຊᏛ㔞⮬ືィ⟬ࣇ࣮ࣟࠋ- 450 -

ィ⟬࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ඾ᆺⓗ࡞ 5 ✀ࡢ࢔࣑ࣥ࡟ࡘ࠸࡚࢝ࣝࣂ࣓࣮ࢺ⏕ᡂ཯ᛂ࡟㛵ࡍࡿ⇕ຊᏛ㔞ࢆぢ✚ࡶࡗࡓ࡜ࡇࢁࠊᐇ㦂್࡜ࡢㄗᕪࡣ 3.5 kJ/mol ⛬ᗘ࡜࡞ࡗࡓࠋ

MOF ࢆ⏝࠸ࡓ CO2 ᅛᐃ໬཯ᛂࡢ୍ࡘ࡜ࡋ࡚▱ࡽࢀࡿࢫࢳࣞࣥ࢜࢟ࢩࢻࡢ㛤⎔཯ᛂࢆ⤒⏤ࡋࡓࢫࢳࣞࣥ࢝
࣮࣎ࢿ࣮ࢺ⏕ᡂ཯ᛂࡢ཯ᛂᶵᵓࢆ໬Ꮫ཯ᛂࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡾゎᯒࡋࡓࠋࢫࢳࣞࣥ࢜࢟ࢩࢻࡢ㛤⎔཯ᛂ࡜ࡑࡢḟ࡟㉳ࡇࡿ CO2 ࡢᤄධ཯ᛂࡢ཯ᛂ࢚ࢿࣝࢠ࣮ኚ໬ࡣඛ⾜◊✲ࡢ⤖ᯝ࡜ᐃᛶⓗ࡟୍⮴ࡋࡓࠋ཯ᛂࢧ࢖ࢡ
ࣝࡢ᭱⤊ẁ㝵࡟࠾࠸࡚ࠊඛ⾜◊✲࡛♧၀ࡉࢀࡓ┤᥋஬ဨ⎔ࢆᙧᡂࡍࡿ㛢⎔཯ᛂࡼࡾࡶࠊ୐ဨ⎔ᙧᡂ࡟ࡼࡿ୰
㛫యࢆ⤒⏤ࡋࡓᚋ஬ဨ⎔࡬࡜⦰ᑠࡍࡿከẁ㝵཯ᛂࡢ᪉ࡀప࠸཯ᛂ㞀ቨ࡜࡞ࡿࡇ࡜ࢆぢฟࡋࡓࠋ㟁Ⲵゎᯒ࡟ࡼࡾࠊⓎぢࡋࡓ཯ᛂ⤒㊰ࡣồ᰾ᛶࡢ㧗࠸㒊఩ࡀᨷᧁࡉࢀ࡚㐍⾜ࡍࡿጇᙜ࡞⤒㊰࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ

4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
★[1] ▮ࢣᓮ⌶☻, ศᏊືຊᏛࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿࢡࣛࢫ࣮ࣞࢺࣁ࢖ࢻ࣮ࣞࢺࡢ⏕ᡂ࣭ศゎ࡜㜼ᐖ๣ࡢ◊✲, ➨ 55 ᅇ GH ◊✲఍. ᣍᚅㅮ₇★[2] ▮ࢣᓮ⌶☻, Ỉ࡜ịࡢ‽Ᏻᐃ≧ែࡢ┦ᅗ, ࢩ࣏ࣥࢪ࣒࢘ࠕịࡢศᏊ⛉Ꮫ IIࠖ㸦ᇸ⋢኱Ꮫ㸧. ᣍᚅㅮ₇★[3] ⏣୰⚽ᶞ, Ỉ㸪ị㸪ࢡࣛࢫ࣮ࣞࢺࣁ࢖ࢻ࣮ࣞࢺࡢᇶ♏⛉Ꮫ࡜ࡑࡢᕤᏛⓗྍ⬟ᛶ, ➨ 65 ᅇ⇕࢚ࢿࣝࢠ࣮
᭷ຠ฼⏝◊✲఍. ᣍᚅㅮ₇★[4] ⏣୰⚽ᶞ, Ỉ㸪ị㸪ໟ᥋Ỉ࿴≀ࡢᏳᐃᛶ࡜⇕≀ᛶ, ࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ࣮࣡ࢡࢩࣙࢵࣉ 2019. ᣍᚅㅮ
₇★[5] ᯇᮏṇ࿴, ᅛయ⾲㠃࡛⏕ࡌࡿ⇕࠸ị, PCoMS ࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍. ᣍᚅㅮ₇★[6] Tetsuya Taketsugu, Takuro Tsutsumi, and Yuriko Ono, A new strategy for reaction path concept and dynamics
effects, The 23rd International Annual Symposium on Computational Science and Engineering (ANSCSE23). ᣍ
ᚅㅮ₇★[7] T. Taketsugu, Reaction pathways and dynamics of the excited-state branching reaction of stilbene derivatives ,International Symposium on Ultrafast Molecular Dynamics (UMD2019) (Sendai). ᣍᚅㅮ₇★[8] Tetsuya Taketsugu, Takuro Tsutsumi, Shuichi Ebisawa, and Yuriko Ono, Reaction path concept: Intrinsic Reaction
Coordinate, Anharmonic Downward Distortion Following, and Ab Initio MD, The 9th Asia-Pacific Association ofTheoretical and Computational Chemists (APATCC-9). ᣍᚅㅮ₇★[9] Masato Kobayashi, Haruka Onoda, Tetsuya Taketsugu, Surface model calculation database for predicting catalytic
activity: An application to methane steam reforming, The 9th Asia-Pacific Association of Theoretical andComputational Chemists (APATCC-9). ᣍᚅㅮ₇★[10] T. Taketsugu, Excited-state branching reaction of stilbene derivatives, Theoretical and High Performance
Computational Chemistry 2019 (ICT-HPCC19) (Guiyang, China). ᣍᚅㅮ₇★[11] T. Taketsugu, Theoretical elucidation of photo-reaction mechanism: applications to stilbene derivatives, The 15th
Nanjing University-Hokkaido University-NIMS Joint Symposium (Nanjing, China). ᣍᚅㅮ₇★[12] ୰ ஭ ᾈ ᕭ , Theoretical Analyses of Condensed-Phase Chemical Reactions Based on Divide-and-Conquer
Density-Functional Tight-Binding Molecular Dynamics (DC-DFTB-MD) Simulations, ➨㸱㸳ᅇ໬Ꮫ཯ᛂウㄽ఍.
ᣍᚅㅮ₇- 451 -

★[13] J. Seino, R. Kageyama, M. Fujinami, Y. Ikabata, H. Nakai, Orbital-free density functional theory calculation
combined with semi-local machine-learned kinetic energy density functional, 2nd Global Forum on Advanced
Materials and Technologies for Sustainable Development (GFMAT-2). ᣍᚅㅮ₇★[14] Aditya Wibawa Sakti, Chien-Pin Chou, Hiromi Nakai, Density-Functional Tight-Binding Metadynamics Studyof Oxy-Carbon Diffusion on (100)-γ-Al2O3 Surface, The Ninth Conference of the Asia-Pacific Association ofTheoretical and Computational Chemists (APATCC 2019). ᣍᚅㅮ₇★[15] Junichi Ono, Chika Okada, Yoshifumi Nishimura, Hiromi Nakai, Large-scale quantum-mechanical molecular
dynamics simulations for the long-distance proton transfer in bacteriorhodopsin, The Ninth Conference of the AsiaPacific Association of Theoretical and Computational Chemists (APATCC 2019). ᣍᚅㅮ₇5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
★[1] M. Matsumoto, T. Yagasaki, H. Tanaka, A Bayesian approach for identification of ice Ih, ice Ic, high density, andlow density liquid water with a torsional order parameter, J. Chem. Phys. 150, 214504, 1-6 (2019).
★[2] T. Yagasaki, M. Matsumoto, H. Tanaka, Liquid-liquid separation of aqueous solutions: A molecular dynamics
study, J. Chem. Phys. 150, 214506, 1-8 (2019).
★[3] T. Yagasaki, M. Matsumoto, H. Tanaka, Formation of hot ice caused by carbon nanobrushes, J. Chem. Phys. 151,
064702, 1-8(2019).
★[4] H. Tanaka, T. Yagasaki, M. Matsumoto, On the role of intermolecular vibrational motions for ice polymorphs I:
Volumetric properties of crystalline and amorphous ices, J. Chem. Phys. 151, 114501 1-14 (2019).
★[5] H. Tanaka, T. Yagasaki, M. Matsumoto, On the role of intermolecular vibrational motions for ice polymorphs II:
Atomic vibrational amplitudes and localization of phonons in ordered and disordered ices, J. Chem. Phys. 152,
074501 (14pages) (2020).
★[6] M. Kobayashi, H. Onoda, Y. Kuroda, and T. Taketsugu, Surface adsorption model calculation database and its
application to activity prediction of heterogeneous catalysts, J. Comput. Chem. Jap., in press.
★[7] R. Miyazaki, N. Nakatani, S. V. Levchenko, T. Yokoya, K. Nakajima, K. Hara, A. Fukuoka, and J. Hasegawa, DFT
Mechanistic Study on the Complete Oxidation of Ethylene by the Silica-Supported Pt Catalyst: C═C Activation via
the Ethylene Dioxide Intermediate, J. Phys. Chem. C, 123, 12706-12715 (2019).
★[8] D. P. De Chavez, M. Gao, H. Kobayashi, A. Fukuoka, J. Hasegawa, Adsorption Mediated Tandem Acid Catalyzed
Cellulose Hydrolysis by Ortho-substituted Benzoic Acids, Mol. Catal., 475, 110459 (2019).
★[9] Y. Harabuchi, R. Tani, N. DeSilva, B. Njegic, M. S. Gordon, and T. Taketsugu, Anharmonic Vibrational
Computations with a Quartic Force Field for Curvilinear Coordinates , J. Chem. Phys., 151, 064104 (2019).
★[10] H. Uratani, C-P. Chou, H. Nakai, Quantum mechanical molecular dynamics simulations of polaron formation inmethylammonium lead iodide perovskite, Phys. Chem. Chem. Phys., 22, 97-106 (2020).

- 452 -┦㌿⛣࡜ὶື
Phase Transitions and Flows‫ۑ‬ᕝ຾ ᖺὒ㸦ᮾ໭኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧ࠊᮧᓥ 㝯ᾈ㸦ᮾ໭኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧ࠊ᳃஭ ὒᖹ㸦ᮾ໭኱Ꮫ኱Ꮫ㝔⌮Ꮫ◊✲⛉㸧ࠊ㔝ཱྀ ༤ྖ㸦ᮾி኱Ꮫ≀ᛶ◊✲ᡤ㸧ࠊΏ㎶ ᐂᚿ㸦៞ᛂ⩏ሿ኱Ꮫ⌮ᕤᏛ㒊㸧ࠊὸ㔝 ඃኴ㸦ᮾி኱Ꮫ≀ᛶ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡣࠊ㧗ὶ㏿ࡢᾮయ୰ࡢᒁᡤⓗ࡞ᅽຊኚ໬࡟ࡼࡗ࡚⏕ࡌࡿࠊẼἻࡢ⏕ᡂ࣭ᡂ㛗࣭ᾘ⁛ࢆక࠺ὶື⌧㇟࡛࠶ࡿࠋ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡀⓎ⏕ࡍࡿ࡜ࠊࢱ࣮ࣅࣥ࡞࡝ࡢὶయᶵᲔ࡟ᑐࡋ࡚ࠊᛶ⬟పୗࠊ㦁㡢ࡸ᣺ືࠊ࢚࣮ࣟࢪࣙࣥ࡞࡝ࠊᵝࠎ࡞ᙳ㡪ࢆ୚࠼ࡿࡓࡵࠊࡑࡢ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࡣᕤᏛⓗ࡟㠀ᖖ࡟㔜せ࡛࠶ࡿࠋ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢⓎ⏕࣓࢝ࢽࢬ࣒࡟ࡘ࠸࡚ࡣࠊᾮయ୰࡟ẼἻ᰾ࡀᏑᅾࡋࠊࡑࢀࡀ㣬࿴⵨Ẽᅽ௨ୗࡢ㡿ᇦ࡟ᡂ㛗࡟༑ศ࡞᫬㛫⁫ᅾࡍࡿࡇ࡜࡛Ⓨ⏕ࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ࣐ࢡࣟ࡞ὶືሙ୰࡛ࡢ࣑ࢡࣟ
࡞ẼἻ᰾ࡢࢲ࢖ࢼ࣑ࢡࢫࢆ㆟ㄽࡍࡿࡇ࡜ࡣᴟࡵ࡚ᅔ㞴࡞ࡓࡵࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢⓎ⏕࣓࢝ࢽࢬ࣒ࡣᮍࡔ༑
ศ࡞⌮ゎࡀ࡞ࡉࢀ࡚࠸࡞࠸ࠋ≉࡟ࠊἜᅽᶵᲔ࡞࡝࡛Ⓨ⏕ࡍࡿ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢࡼ࠺࡟ࠊẼἻ᰾ࡢᏑᅾࢆ௬
ᐃࡍࡿࡇ࡜ࡀᅔ㞴࡞ሙྜࠊὶືሙ୰ࡢ┦㌿⛣⌧㇟ࢆ┤᥋ⓗ࡟㆟ㄽࡋ࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࡓࡵࠊゎᯒࡣࡉࡽ࡟ᅔ
㞴࡟࡞ࡿࠋ
ࡇࡢࡼ࠺࡞┦㌿⛣ࢆక࠺ὶື⌧㇟ࡣࠊᖜᗈ࠸ࢫࢣ࣮ࣝࡢࢻ࣓࢖ࣥࡀඹᏑࡍࡿ」㞧࡞ᵓ㐀࡜ὶື≉ᛶࢆ♧ࡍ≉␗࡞⌧㇟࡛࠶ࡾࠊ࣑ࢡࣟࢫࢣ࣮ࣝࡢᙳ㡪ࡀ࣐ࢡࣟࢫࢣ࣮ࣝࡢὶື࡟ࢩ࣮࣒ࣞࢫ࡟ᙳ㡪ࢆ୚࠼ࡿ」㞧࡞ὶື࡛࠶ࡿࠋࡑࡇ࡛ࠊᮏㄢ㢟࡛ࡣࠊࡑࡢࡼ࠺࡞」㞧࡞ὶືࢆゎᯒࡍࡿࡓࡵ࡟ࠊ࣑ࢡࣟ≧ែ࡜࣐ࢡࣟ≧ែࢆྠ᫬࡟
ゎࡁྜ࠺࣐ࣝࢳࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲࢆ㛤Ⓨࡋ࡚࠸ࡿࠋࡇ࠺࠸ࡗࡓ࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩࣙࣥᡭἲࡢ
᭷ຠᛶࢆ☜ㄆࡍࡿࡓࡵ࡟ࡣࠊᐇ㦂஦ᐇ࡜ࡢẚ㍑ࠊ᳨ウࡶ໚ㄽ࡛࠶ࡿࡀࠊ࣑ࢡࣟࢫࢣ࣮ࣝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ
࡜ࡢẚ㍑ࠊ᳨ウࡶᚲせ࡛࠶ࡿࠋࡑࡢࡓࡵࠊ኱つᶍ࡞ศᏊືຊᏛ㸦MD㸧ィ⟬࡟ࡼࡗ࡚┦㌿⛣ࢆక࠺ὶࢀࡢゎᯒࢆ⾜࠸ࠊศᏊㄽ࡟❧⬮ࡋ࡚┦㌿⛣ࡢὶືሙ࡬ࡢᙳ㡪ࢆㄪ࡭ࡿࡇ࡜ࡣᮏ㉁ⓗ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋMD ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡓ⤖ᯝࢆ཯ᫎࡋࡓ࣐ࣝࢳࢫࢣ࣮ࣝࣔࢹࣝࢆᵓ⠏ࡍࡿࡇ࡜࡛ࠊࡼࡾ㧗⢭ᗘ࡟」㞧ὶືࡢゎᯒࡀྍ⬟࡟࡞ࡿࠋᮏ◊✲࡛ࡣࠊ0' ィ⟬࡟ࡼࡗ࡚ࠊ࿘ᮇⓗ࡟୪ࢇࡔ෇ᰕ࿘ࡾࡢ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢゎᯒࢆ⾜࠸ࠊẼἻࡢ⏕ᡂ࣭ᡂ㛗㐣⛬ࠊཬࡧࡑࢀࡽࡀ࿘ᅖࡢὶࢀ࡟୚࠼ࡿᙳ㡪ࢆ 0' ィ⟬࡟ࡼࡗ࡚ㄪ࡭ࡓࠋ

2◊✲᪉ἲࠊィ⟬᪉ἲ
3 ḟඖࡢ MD ィ⟬࡟ࡼࡗ࡚ࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥ࡟ࡼࡿẼᾮ஧┦ὶࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠺ࠋ⢏Ꮚ㛫ࡢ┦஫స⏝ࡣࠊḟᘧ࡛୚࠼ࡽࢀࡿ Lennard-Jones㸦LJ㸧࣏ࢸࣥࢩࣕࣝ ࡜ࡍࡿ㸸
( )=

( )−

( )−( − )0( )=4( ) ( ≤ )( > 0)(1)−ࡇࡇ࡛ࠊ ࡣ⢏Ꮚ㛫㊥㞳࡛࠶ࡾࠊ ࡜ ࡣࠊࡑࢀࡒࢀࠊ࢚ࢿࣝࢠ࣮࡜㛗ࡉࡢࢫࢣ࣮࡛ࣝ࠶ࡿࠋ ࡣ࣏ࢸࣥࢩࣕ
ࣝࡢษ᩿㊥㞳࡛࠶ࡾࠊࡇࡇ࡛ࡣ = 2.5 ࡜ࡋࡓࠋࣉࣛ࢖࣒ࡣ ࡟㛵ࡍࡿᚤศࢆ⾲ࡍࠋ௨ୗ࡛ࡣࠊ඲࡚ࡢ≀⌮㔞- 453 -

ࢆࠊ࢚ࢿࣝࢠ࣮ࢆ ࠊ㛗ࡉࢆ ࠊ᫬㛫ࢆ =ィ⟬ࢭࣝࡢ኱ࡁࡉࡣ

××/ ࡢ༢఩࡛ࡑࢀࡒࢀࡿࠋ ࡣ⢏Ꮚࡢ㉁㔞࡛࠶ࡿࠋ= 3600 × 1000 × 100ࡢ┤᪉య࡜ࡋࠊ඲᪉ྥ࡟࿘ᮇቃ⏺᮲௳ࢆㄢࡋࡓࠋ෇

ᰕࡣࡑࡢ⾲㠃ୖ࡟ LJ ⢏Ꮚࢆᅛᐃࡍࡿࡇ࡜࡛⾲⌧ࡋࡓࠋ2 ࡘࡢ෇ᰕࢆὶࢀ࡟ᆶ┤᪉ྥ࡟㓄⨨ࡍࡿࡇ࡜࡛ࠊ↓㝈࡟୪ࢇࡔ෇ᰕิࢆ⾲⌧ࡋࡓࠋࡇࢀ࡟ࡼࡾࠊୖୗࡢ࣐࢝ࣝࣥิࡀᖸ΅࡟ࡼࡗ࡚㠀ᑐ⛠࡞ᵓ㐀ࢆྲྀࡾᚓࡿࠋ෇

ᰕࡢୗὶഃ࡟ Langevin ⇕ᾎ࡟ࡼࡿᗘ࡜ὶ㏿ࡢไᚚࢆ⾜࠺㡿ᇦࢆタࡅࡓࠋὶධὶ㏿ࡣ = 1࡜ࡋࡓࠋὶධὶ

యࡢᐦᗘࡣ = 0.4࡜ࡋࠊ

≤ 2ࡢ⠊ᅖ࡛ኚ໬ࡉࡏࡓࠋ㉸⮫⏺㡿ᇦ࡛⮫⏺Ⅼ㸦

㏆ഐ࡟㝆

ᗘࡣ1 ≤

= 0.32,= 0.94㸧ࡋ࡚࠸ࡃࡇ࡜࡛࢟ࣕࣅࢸ࣮ࢩࣙࣥࢆⓎ⏕ࡉࡏࡓࠋ┦㌿⛣࡟ࡼࡿᙳ㡪ࢆ㆟ㄽࡍࡿࡓࡵ࡟ࠊ(1)ᘧ࡟࠾

࠸࡚ = 2 ࡜ࡋࡓ┦㌿⛣ࡀ㉳ࡇࡽ࡞࠸༢┦ὶࡢゎᯒࡶ⾜ࡗࡓࠋ㐠ື᪉⛬ᘧࡢᩘ್✚ศ࡟ࡣ LAMMPS ࢆ⏝࠸
ࡓࠋ

3

◊✲ᡂᯝ
ᅗ㸯ࡣᐦᗘሙ㸦ᕥ㸧࡜ᗘሙ㸦ྑ㸧ࡢࢫࢼࢵࣉࢩࣙࢵࢺ࡛࠶ࡿࠋࡲࡎࠊ㧗 㸦

ᗘ = 2㸧࡛ࡣẼἻࡢⓎ⏕ࡣㄆࡵࡽࢀࡎࠊ㠀࢟ࣕࣅࢸ࣮ࢩࣙࣥὶࢀࡀᚓࡽࢀࡓࠋ෇ᰕࡢᚋ᪉࡟㏫఩┦ྠᮇࡋࡓ࣐࢝ࣝࣥ
ࡇࡢྠᮇ࡟ࡼࡗ࡚ࠊ෇ᰕ࡟ാࡃ᣺ືࡀቑᖜࡉࢀࡿࡇ࡜ࡶศ࠿ࡗࡓࠋ

ิࡀⓎ⏕ࡋࡓࠋ

ࡢ୰ᚰ㒊ࡸ෇ᰕ㏆ഐࡣ௚ࡢ㒊ศ࡟ẚ࡭࡚ᐦᗘࡀపࡃ࡞ࡗ࡚࠸ࡿࡇ࡜࠿ࡽࠊࡇࢀࡽࡢ㡿ᇦࡣᅽຊࡀపࡃ࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋࡋࡓࡀࡗ࡚ࠊ

ᗘࢆୗࡆ࡚࠸ࡃ࡜ࠊࡇࢀࡽࡢ㡿ᇦ࡛࢟ࣕࣅࢸ࣮ࢩࣙࣥࡀⓎ⏕ࡍࡿࡇ࡜ࡀᮇᚅࡉࢀࡿࠋ
㝆ࡋ࡚࠸ࡃ࡜ࠊ = 1.3࡛ẼἻࡀⓎ⏕ࡋࡓࠋࡇࡢ

⏕ࡋࡓࠋࡲࡓࠊୖୗࡢ࣐࢝ࣝࣥ

ᗘ࡛ࡣ࣐࢝ࣝࣥ

ࡢᨺฟࢧ࢖ࢡࣝ࡟㐃ືࡋ࡚ẼἻࡀⓎิࡣ㠀࢟ࣕࣅࢸ࣮ࢩࣙࣥὶࢀ࡜ྠᵝ࡟㏫఩┦ྠᮇࡋࡓࡲࡲ࡛࠶ࡿࠋᒁᡤᖹ

⾮ࢆ௬ᐃࡍࡿ࡜ࠊ෇ᰕ㏆ഐࡢపᐦᗘ㡿ᇦࡣẼ┦࡛࠶ࡗࡓࡀࠊ෇ᰕᚋ᪉ࡢ

ࡢ୰ᚰ㒊ࡣపᐦᗘὶయ࡛࠶ࡿࡇ࡜

ࡀࢃ࠿ࡗࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡇࡢࡼ࠺࡞㠀ᖹ⾮≧ែ࡟࠾࠸࡚ࠊẼయ࡜ᾮయࢆ㆑ูࡍࡿࡇ࡜ࡣᅔ㞴࡛࠶ࡾࠊࡇ
ࡇ࡛ࡣᐦᗘࡀప࠸㒊ศࢆẼయ࡜⪃࠼ࡿࡢࡀጇᙜ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ = 1.25࡟࡞ࡿ࡜ࠊ෇ᰕ⫼ᚋ࡟Ẽ┦㡿ᇦࡀᙧᡂࡉࢀࠊ࣐࢝ࣝࣥ

ࡀᙧᡂࡉࢀࡿࡲ࡛ࡢ㊥㞳ࡀቑຍࡋࡓࠋࡲࡓࠊഹ࠿࡛ࡣ࠶ࡿࡀࠊୖୗࡢ࣐࢝ࣝࣥ

ࡢ఩┦࡟஘ࢀࡀ⏕ࡌࡓࠋࡉࡽ࡟
࣐࢝ࣝࣥᗘࢆୗࡆࠊ = 1.2࡟࡞ࡿ࡜ࠊ෇ᰕ⫼ᚋࡢẼ┦㡿ᇦࡀࡉࡽ࡟ᣑ኱ࡋࠊୖୗࡢ

ࡀ㠀ᑐ⛠࡞ᵓ㐀࡟࡞ࡗࡓࠋࡇࡢ㠀ᑐ⛠ᵓ㐀ࡣ㛗࿘ᮇ࡛ධࢀ᭰ࢃࡿࡇ࡜ࡶࢃ࠿ࡗࡓࠋ┦㌿⛣ࡀ㉳ࡇࡽ࡞࠸༢┦ὶࡢሙྜ࡛ࡣࠊ

ᗘኚ໬࡟ࡼࡗ࡚ࡇࡢࡼ࠺࡞ኚ໬ࡣ㉳ࡇࡽ࡞࠸ࠋࡋࡓࡀࡗ࡚ࠊẼἻⓎ⏕࡟ࡼࡿᐦᗘᦂࡽࡂࡀὶືሙ࡟኱ࡁ࡞ᙳ㡪ࢆ୚࠼ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ
ࡇࡢࡼ࠺࡞ᵓ㐀ࡢኚ໬࡟ࡼࡗ࡚ࠊ

࡟ࡼࡾບ㉳ࡉࢀࡿ᣺ືࡢ≉ᛶࡶኚ໬ࡍࡿࠋ༢┦ὶࡢሙྜࡣࠊ

ኚ໬࡟ࡼࡗ࡚⢓ᛶࡀኚ໬ࡍࡿࡔࡅ࠶ࡾࠊᥭຊ᣺ᖜ࡜

ᗘࡢᙧᡂ㛗ࡉࡣ༢ㄪ࡞᣺ࡿ⯙࠸ࢆ♧ࡍࡇ࡜ࡀࢃ࠿ࡗࡓࠋ࡜

ࡇࢁࡀࠊ/- ὶయࡢሙྜࡣࠊ ᗘࡢኚ໬࡟ࡼࡾ┦㌿⛣ࡀ⏕ࡌࡿࡓࡵࠊ⢓ᛶࡢኚ໬࡜┦㌿⛣ࡢᙳ㡪ࡢ➇ྜ࡟ࡼࡗ࡚㠀༢ㄪ࡞ኚ໬ࢆ♧ࡍࡇ࡜ࡀࢃ࠿ࡗࡓࠋ/- ὶయࡢሙྜࡣ1.25 ≤≤ 1.3ࡢ⠊ᅖ࡛ࠊ㝆࡜ඹ࡟ᥭຊ᣺ᖜࡣῶᑡ

ࡋࠊ᭱⤊ⓗ࡟ᾘኻࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ

ᙧᡂ㛗ࡉࡣࠊᥭຊ᣺ᖜࡢᾘኻ࡜ྠ᫬࡟๻ⓗ࡟ቑຍࡍࡿࡇ࡜

ࡶࢃ࠿ࡗࡓࠋࡋࡓࡀࡗ࡚ࠊᥭຊ᣺ᖜࡢᾘኻࡣࠊ

ᙧᡂ㛗ࡉࡢቑຍ࡟ࡼࡿࡶࡢ࡛ࡣ࡞ࡃࠊ෇ᰕ㏆ഐ࡛Ⓨ⏕ࡋࡓẼἻࡀࡢᨺฟ࡟క࠺᣺ືࡢఏ᧛ࢆ㜼ᐖࡋࡓࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ

௨ୖࡢࡼ࠺࡟ࠊ0' ィ⟬࡟ࡼࡗ࡚෇ᰕࢆ㏻㐣ࡍࡿ㝿࡟Ⓨ⏕ࡋࡓẼἻࡀᥭຊࡸὶືሙࡢ≉ᛶࢆ኱ࡁࡃኚ࠼ࡿࡇ
࡜ࢆศᏊࢫࢣ࣮ࣝ࠿ࡽ᫂ࡽ࠿࡟ࡋࡓࠋὶయゎᯒࡢᡭἲ࡜ẚ㍑ࡍࡿ࡜ࠊ0' ィ⟬࡛ࡣᵓᡂ᪉⛬ᘧࡸ≧ែ᪉⛬ᘧ࡜࠸ࡗࡓ⌧㇟ㄽⓗ࡞ࣔࢹࣝࡀ୙せ࡛࠶ࡾࠊศᏊㄽ࠿ࡽ⌧㇟ࢆ㆟ㄽ࡛ࡁࡿⅬࡀᙉࡳ࡛࠶ࡿࠋࡋࡓࡀࡗ࡚ࠊィ⟬ࢥࢫࢺࡢၥ㢟ࢆ㝖ࡅࡤࠊ୙⣧≀ࢆྵࡴ」㞧ὶయ୰ࡢẼᾮ஧┦ὶ࡞࡝ࡢゎᯒ࡟ࡶ 0' ィ⟬ࡣ᭷ຠ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋᐇ㝿ⓗ࡟ࡣࠊࡇࡇ࡛ᚓࡽࢀࡓ⤖ᯝࡢࡼࡾヲ⣽࡞ゎᯒࢆ⾜࠸ࠊẼἻࡢ⏕ᡂࠊᡂ㛗ࡢ࣓࢝ࢽࢬ࣒ࢆ཯ᫎࡋࡓ
࣐ࣝࢳࢫࢣ࣮ࣝࣔࢹࣝࡢᵓ⠏ࡀ௒ᚋࡢㄢ㢟࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

- 454 -



ᅗ 1
 LJ ὶయࡢᐦᗘሙ㸦ᕥ㸧࡜ᗘሙ㸦ྑ㸧ࡢࢫࢼࢵࣉࢩࣙࢵࢺࠋᅗ୰ࡢ㯮୸ࡣ෇ᰕ࡛࠶ࡿࠋ



4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪࣐͆࢝ࣝࣥ࡟ᑐࡍࡿ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢᙳ㡪͇㸪≀ᛶ◊✲ᡤࢫࣃࢥࣥ

ඹྠ฼⏝࣭CCMS ྜྠ◊✲఍ࠕィ⟬≀㉁⛉Ꮫࡢ᪂ᒎ㛤ࠖ
ࠊ2019 ᖺ 4 ᭶㸬‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪࣐͆࢝ࣝࣥ

࡟ᑐࡍࡿ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢᙳ㡪͇㸪ࡘࡃࡤࢯࣇࢺ࣐ࢱ

࣮◊✲఍ 2019㸪2019 ᖺ 8 ᭶㸬࡟ᑐࡍࡿ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢᙳ㡪 II͇㸪᪥ᮏ≀⌮Ꮫ఍ 2019‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪࣐͆࢝ࣝࣥᖺ⛅Ꮨ኱఍㸪2019 ᖺ 9 ᭶㸬㔝ཱྀ ༤ྖ㸪
͆ࢼࣅ࢚࣭ࢫࢺ࣮ࢡࢫ᪉⛬ᘧࡢ㞳ᩓ໬᫬ࡢゅ㐠ື㔞ಖᏑࡢ႙ኻ࡟ࡘ࠸࡚͇
㸪᪥ᮏ≀⌮Ꮫ఍ 2019ᖺ⛅Ꮨ኱఍㸪2019 ᖺ 9 ᭶㸬Ώ㎶ ᐂᚿ㸪᳃⏣ ᝅྐ㸪⸨ᇽ ┾἞㸪ᕝᓥ ┤㍤㸪͆ࣛࣥࢲ࣒ࣅࢵࢺิࢆ㧗㏿࡟⏕ᡂࡍࡿ࢔ࣝࢦࣜࢬ࣒ࡢ㛤Ⓨ͇㸪᪥ᮏ≀⌮Ꮫ఍ 2019 ᖺ⛅Ꮨ኱఍㸪2019 ᖺ 9 ᭶㸬‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪࣐͆࢝ࣝࣥ

࡟ᑐࡍࡿ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢᙳ㡪͇㸪ィ⟬≀㉁⛉Ꮫேᮦ⫱ᡂࢥࣥࢯ࣮ࢩ࢔࣒㸦PCoMS㸧ࢩ࣏ࣥࢪ࣒࢘ 㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱ஦ᴗሗ࿌఍ 2019㸪 2019ᖺ 10 ᭶㸬- 455 -

࡟ᑐࡍࡿ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡢᙳ 㡪͇㸪➨ 33 ᅇศᏊࢩ࣑‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪࣐࣮͆࢝ࣝࣥࣗࣞࢩࣙࣥウㄽ఍㸪2019 ᖺ 12 ᭶㸬‫ ۻ‬㔝ཱྀ༤ྖࠊὸ㔝ඃኴࠊΏ㎶ᐂᚿ㸪͆ศᏊືຊᏛィ⟬࡟ࡼࡿ࡜ẼἻ⏕ᡂࠊ㧗ศᏊࣞ࢜ࣟࢪ࣮ࡢ࢝ࢵࣉࣜࣥ

ࢢᶵᵓࡢゎᯒ͇
㸪➨ 9 ᅇᮦᩱ⣔࣮࣡ࢡࢩࣙࢵࣉ㸪2020 ᖺ 2 ᭶㸬‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ᐂᚿ㸪㔝ཱྀ༤ྖ㸪͆෇ᰕิ࿘ࡾࡢ࣐࢝ࣝࣥ

࢟ࣕࣅࢸ࣮ࢩ͇ࣙࣥ
㸪᪥ᮏ≀⌮Ꮫ఍➨ 75 ᅇᖺḟ኱఍㸪2020 ᖺ 3 ᭶㸬Ώ㎶ᐂᚿ㸪᳃⏣ᝅྐ㸪ᮏᒣ⿱୍㸪ᕝᓥ┤㍤㸪
࣏͆ࢵࢶᶍᆺ࡟࠾ࡅࡿ Binder ẚࡢ㠀༢ㄪ࡞᣺ࡿ⯙࠸࡟ࡘ࠸࡚

͆㸪᪥ᮏ≀⌮Ꮫ఍➨ 75 ᅇᖺḟ኱఍㸪2020 ᖺ 3 ᭶㸬ᮧᓥ㝯ᾈ, ᳃஭ὒᖹ, ᕝ຾ᖺὒ, ͇࣐ࣝࢳࢫࢣ࣮ࣝὶືࢩ࣑࣮ࣗࣞࢩࣙࣥ⏝ࣉࣛࢵࢺࣇ࢛࣮࣒ࡢ㛤Ⓨ͇,
PCoMS ࢩ࣏ࣥࢪ࣒࢘㸤ィ⟬≀㉁⛉Ꮫࢫ࣮ࣃ࣮ࢥࣥࣆ࣮ࣗࢱඹ⏝஦ᴗሗ࿌఍, 2019 ᖺ 10 ᭶.
ᕝ຾ᖺὒ, ࣐͆ࣝࢳࢫࢣ࣮ࣝὶືࢩ࣑ࣗࣞ㸫ࢩࣙࣥ⏝ࣉࣛࢵࢺࣇ࢛࣮࣒㸦MSSP㸧ࡢ㛤Ⓨࠊ࠾ࡼࡧࠊ」㞧ὶືࡢࢩ࣑࣮ࣗࣞࢩ͇ࣙࣥ, ➨ 9 ᅇᮦᩱ⣔࣮࣡ࢡࢩࣙࢵࣉ ~ࠕᐩᓅ࡛ࠖ㣕㌍࡬㸟ィ⟬ࢹ࣮ࢱࡢ౯್~, ⛅ⴥཎࢥࣥ࣋ࣥࢩ࣮ࣙࣥ࣍ࣝ, 2020 ᖺ 2 ᭶.
᳃஭ὒᖹ, ᕝ຾ᖺὒ, ͆」㞧ὶືࡢ࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩ͇ࣙࣥ, ࢭ࣑ࢼ࣮ࢩ࣮ࣜࢬ ࠕࢫࣃࢥࣥࣉ
ࣟࣇ࢙ࢵࢩࣙࢼࣝ No.24ࠖ, ᮾ໭኱Ꮫ㔠ᒓᮦᩱ◊✲ᡤ, 2019 ᖺ 10 ᭶.
᳃஭ὒᖹ, ᕝ຾ᖺὒ, ͆㧗ศᏊࢆྵࡴ」㞧ὶືࡢ࣐ࣝࢳࢫࢣ࣮ࣝࢩ࣑࣮ࣗࣞࢩ͇ࣙࣥ, ➨ 68 ᅇ㧗ศᏊウㄽ఍, ⚟஭኱Ꮫ ᩥி࢟ࣕࣥࣃࢫ, 2019 ᖺ 9 ᭶.
᳃஭ὒᖹ, ᮧᓥ㝯ᾈ, ᕝ຾ᖺὒ, Ⱚ㞙ே, ᑎ⏣ᘺ⏕, ㇂ཱྀ㈗ᚿ, ᒣᮏ㔞୍, ᅧᔱ㞝୍, ᯇ⏣ᬒ࿃, ኱す㡿, ὸ㔝ඃኴ, Ώ㎶ᐂᚿ, 㔝ཱྀ༤ྖ, ᑠᒇཱྀ๛༤, ఀ⸨ఙὈ, ᮏ⏣㝯, ͆ΰ┦ὶࡢ࣐ࣝࢳࢫࢣ࣮ࣝゎᯒ࡟㛵ࡍࡿࢧࣈㄢ
㢟 B ࡛ࡢ㐃ᦠ◊✲͇, ➨ 3 ᅇ࣏ࢫࢺࠕிࠖⴌⱆⓗㄢ㢟ࠕᇶ♏⛉Ꮫࡢᣮᡓ࣭ࠖ
ࠕᴟ㝈࣐ࢸࣜ࢔ࣝࠖྜྠබ㛤ࢩ࣏ࣥࢪ࣒࢘, ᮾ໭኱Ꮫ㔠ᒓᮦᩱ◊✲ᡤ, 2018 ᖺ 8 ᭶.
Y. Morii, T. Kawakatsu, "Multiscale Simulation Methods in Complex Fluids", 10th International Conference of the
Asian Consortium on Computational Materials Science (ACCMS-10), City University of Hong Kong, 2019 ᖺ 7 ᭶.

5ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
Y. Asano, H. Watanabe, H. Noguchi, "Finite-Size Effects on Kármán Vortex in Molecular Dynamics Simulation", J.

Phys. Soc. Jpn. 88, 075003 (2019).
‫ ۻ‬Y. Asano, H. Watanabe, H. Noguchi, "Effects of cavitation on Kármán vortex behind circular-cylinder arrays: A
molecular dynamics study", J. Chem. Phys. 152, 034501 (2020).
‫ ۻ‬ὸ㔝 ඃኴ㸪Ώ㎶ ᐂᚿ㸪㔝ཱྀ ༤ྖ㸪͆ศᏊືຊᏛィ⟬࡟ࡼࡿ」㞧ὶయ୰ࡢ࣐࢝ࣝࣥ

ࡢゎᯒ͇㸪ศᏊࢩ࣑

࣮ࣗࣞࢩࣙࣥᏛ఍ㄅ ࢔ࣥࢧࣥࣈࣝ 22㸪157 (2020)㸬
T. Murashima, S. Urata, S. Li, “Coupling Finite Element Method with Large Scale Atomic/Molecular Massively Parallel
Simulator (LAMMPS) for Hierarchical Multiscale Simulations”, European Physical Journal B, 92, 211 (2019).
ᮧᓥ㝯ᾈ, ࣑͆ࢡࣟࢫࢣ࣮ࣝ࡜࣐ࢡࣟࢫࢣ࣮ࣝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥ㐃ᡂ࡟ࡼࡿ㧗ศᏊᮦᩱ⣔ࡢ࣐ࣝࢳࢫࢣ࣮
ࣝࢩ࣑࣮ࣗࣞࢩ͇ࣙࣥ, ᪥ᮏ໬Ꮫ఍᝟ሗ໬Ꮫ㒊఍ㄅ, 37, 87 (2019).
S. Li, S. Urata, T. Murashima, “Multiscale Modeling of Plasticity in Amorphous & Polymeric Materials”, IACM
Expressions, 46, 10 (2020).

- 456 -኱つᶍ㟁Ꮚ≧ែィ⟬࡟ࡼࡿ᭷ᶵᮦᩱ⣔ࡢග㟁Ꮚ≀ᛶࡢゎᯒ
Optoelectronic Properties of Organic Materials by Large-Scale
Electronic Structure Calculations‫ ⏣⸨ۑ‬㈗ᩄ 㸦ศᏊ⛉Ꮫ◊✲ᡤ㸧1◊✲┠ⓗࠊෆᐜ
Internet-of-Thing ᫬௦ࡢࣇࣞ࢟ࢩࣈࣝࢹࣂ࢖ࢫ࡜ࡋ࡚ࠊ᭷ᶵ༙ᑟయᮦᩱࡀὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋ᭷ᶵ༙ᑟయᮦ

ᩱࡣ஘ࢀࡓศᏊ㞟ྜయ࡛࠶ࡾࠊࡑࡢග㟁Ꮚ≀ᛶࡣ᭷ᶵศᏊࡢᛶ㉁࣭ศᏊ㛫ࡢࣃࢵ࢟ࣥࢢᵓ㐀࣭ᵓ㐀஘ࢀ࡞࡝ࡢᵝࠎ࡞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ᯒࡋࠊ⏺㠃ຠᯝࡢࢹࣂ࢖ࢫᛶ⬟࡬ࡢᙳ㡪ࢆゎ᫂ࡍࡿࠋࡉࡽ࡟ࠊࡇࢀࡲ࡛㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓࣇࣛࢢ࣓ࣥࢺศᏊ㌶㐨(FMO)ἲࡢᶵ⬟ᣑᙇࢆࡉࡽ࡟㐍ࡵࡿࡇ࡜࡟ࡼࡾࠊ
࢟ࣕࣜ࢔ࡢ࢚ࢿࣝࢠ࣮‽఩ࡸ㟁Ꮚບ㉳≧ែࢆ㧗⢭ᗘ࡛ィ⟬࡛ࡁࡿᡭἲࢆᥦ᱌ࡍࡿࠋᛂ⏝ᑐ⛠࡜ࡋ࡚ࡣࠊ(A)࣌ࣥࢱࢭࣥ/ࣇ࣮ࣛࣞࣥ⏺㠃⣔ࡢ㟁Ⲵ⛣ື≧ែ࡜㟁Ⲵศ㞳࣭㟁Ⲵ෌⤖ྜࡢゎᯒࠊ(B)⤯⦕ᒙ-࣌ࣥࢱࢭࣥ⏺㠃⣔࡛ࡢ㟁Ꮚ≧ែ࡜࢟ࣕࣜ࢔㍺㏦≉ᛶࠊ(C)㧗ຠ⋡ኴ㝧㟁ụ⣔ࡢ㟁Ⲵ⛣ື≧ែࡢ㠀ᒁᅾ໬ຠᯝ࡜㟁Ⲵศ㞳࣭෌⤖ྜࡢゎᯒࠊ࡞࡝ࡢ◊✲㡯┠ࢆィ⏬ࡋࡓࠋ

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
FMO ἲࡢᯟ⤌ࡳ࡛ࡢ GW ἲࠊGW+BSE ἲࡢᐇ⿦ࢆ⾜ࡗࡓࠋ኱つᶍ GW ἲࡢᐇ⿦ࡢࡓࡵ࡟ࠊ(a)඲⣔ࡢศᴟ㛵ᩘ࡟ᑐࡍࡿࣇࣛࢢ࣓ࣥࢺศ๭㏆ఝ࡜ࠊࣇࣛࢢ࣓ࣥࢺෆ┦㛵ࢆ GW ࡛ࣞ࣋ࣝࠊ࿘ᅖࡢࣇࣛࢢ࣓ࣥࢺࡢㄏ㉳ศ
ᴟࢆ Coulomb-hole plus screened exchange (COHSEX)࡛ࣞ࣋ࣝᢅ࠺ࡉࡽ࡟ǼCOHSEX ㏆ఝࢆᥦ᱌ࡋࡓࠋࡇࢀࡽ
ࡢ㏆ఝἲࡢጇᙜᛶࢆ᳨ドࡋࡓ࡜ࡇࢁࠊศᴟ㛵ᩘࢆṇ☜࡟ィ⟬ࡋࡓሙྜࡢ‽⢏Ꮚ࢚ࢿࣝࢠ࣮ࢆᩘ༑ meV ௨ୗࡢ⢭ᗘ࡛෌⌧࡛ࡁࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓࠊࡇࢀࡽࡢ㏆ఝ࡟ᇶ࡙࠸ࡓ FMO-GW ἲࡢᐇ⿦࡟ࡼࡾᩘ༓ཎᏊ௨ୖࡢ
⣔ࡢ GW ィ⟬ࡀྍ⬟࡟࡞ࡾࠊࢡࣛࢫࢱ࣮࡟࠾ࡅࡿศᏊ⎔ቃ࡟౫Ꮡࡋࡓ HOMO-LUMO gap renormalization ࡸࠊศᏊ⎔ቃ࡟ࡼࡾບ㉳Ꮚ᮰⦡࢚ࢿࣝࢠ࣮ࡢ㐽ⶸຠᯝࡀྲྀࡾᢅ࠼ࡿࡼ࠺࡟࡞ࡗࡓࠋ
ࡉࡽ࡟ࠊGW+BSE ἲ࡜ exciton model ࢆ⤌ࡳྜࢃࡏࡓ㠀ᒁᡤⓗ࡞ບ㉳≧ែࡢィ⟬ᡭἲࡢᩚഛࡶ㐍ࡵ࡚࠸ࡿࠋ
ලయⓗ࡟ࡣࠊศᏊෆບ㉳≧ែࡸศᏊ㛫㟁Ⲵ⛣ືບ㉳≧ែࢆ⾲ࡍࣇࣛࢢ࣓ࣥࢺ CSF ࢆᇶᗏ࡜ࡋ࡚ࠊ඲ᙧࡢບ㉳≧ែࣁ࣑ࣝࢺࢽ࢔ࣥࢆᵓ⠏ࡍࡿࡇ࡜࡟ࡼࡾࠊศᏊ㞟ྜయࡢ㠀ᒁᡤⓗ࡞ບ㉳≧ែ㸦ࣇࣞࣥࢣࣝບ㉳Ꮚࠊ࣡ࢽ࢚ࣔࢵࢺບ㉳Ꮚ≧ែ࡞࡝㸧ࡢィ⟬ࡀྍ⬟࡜࡞ࡿࠋ᭷ᶵศᏊࢡࣛࢫࢱ࣮ࢆ⏝࠸ࡓ࣋ࣥࢳ࣐࣮ࢡィ⟬ࢆ㐍ࡵ࡚࠾ࡾࠊ
ࣇࣛࢢ࣓ࣥࢺศ๭࡞ࡋࡢ GW+BSE ࡢ⤖ᯝࢆᩘ༑ meV ⛬ᗘ࡛෌⌧࡛ࡁࡿࡇ࡜ࢆ☜ㄆࡋࡓࠋ㛤Ⓨࡋࡓᡭἲࡣࠊ

- 457 -኱つᶍ⣔ࡢບ㉳≧ែࢆ(LC-)TDDFT ௨ୖࡢ⢭ᗘ࡛ࡁࡿᩘᑡ࡞࠸ィ⟬ἲ࡛࠶ࡿࠋ
㛤Ⓨࡋࡓ FMO-GW ἲࢆ࣌ࣥࢱࢭࣥ/C60 ⏺㠃ࡢ㟁Ⲵ⛣ື≧ែࡢゎᯒ࡟ᛂ⏝ࡋࡓࠋࢻࢼ࣮/࢔ࢡࢭࣉࢱ࣮⏺㠃࡛ᙧᡂࡉࢀࡿ㟁Ⲵ⛣ື≧ែࡣࠊ㟁Ⲵศ㞳࣭㟁Ⲵ෌⤖ྜࡢ୰㛫≧ែ࡛࠶ࡾࠊࡉࡽ࡟ࡑࡢບ㉳࢚ࢿࣝࢠ࣮ࡀ㛤ᨺ㟁ᅽ್࡜ࡶ┦㛵ࡍࡿࡇ࡜࠿ࡽࠊ࢚ࢿࣝࢠ࣮ኚ᥮㐣⛬࡟࠾࠸࡚᰿ᖿࡢᙺ๭ࢆᢸ࠺ࠋᮏ◊✲࡛ࡣࠊedge-on 㓄ྥ࡜face-on 㓄ྥࡢ࣌ࣥࢱࢭࣥ/C60 ⏺㠃ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊ⏺㠃㟁Ⲵ⛣ື≧ែࡀ⏺㠃㓄ྥ࡟࡝ࡢࡼ࠺࡟౫Ꮡࡍ
ࡿ࠿ࢆㄪ࡭ࡓࠋ≉࡟ศᴟຠᯝ࡜㟁Ⲵࡢ㠀ᒁᅾ໬ຠᯝ࡜࠸࠺ほⅬ࠿ࡽࠊ㟁Ꮚ≧ែࡢẚ㍑ࢆ⾜ࡗࡓࠋ4Ⓨ⾲ᐇ⦼ࡲࡓࡣணᐃ
⸨⏣ ㈗ᩄ, ͇ࣇࣛࢢ࣓ࣥࢺศᏊ㌶㐨ἲࡢ㛤Ⓨ࡜᭷ᶵ༙ᑟయᮦᩱ࡬ࡢᛂ⏝͇,≀ᛶ◊✲ᡤࢫࣃࢥࣥඹྠ฼⏝࣭CCMS ྜྠ◊✲఍ࠕィ⟬≀㉁⛉Ꮫࡢ᪂ᒎ㛤ࠖ, ᮾி, 2019 ᖺ 4 ᭶ 3 ᪥
Takatoshi Fujita, “Theoretical Investigation on Effects of Polarization and Delocalization on Excited States in
Organic Semiconductors”, CEMS Topical Meeting Photoelectrons, Saitama, July 26, 2019⸨⏣ ㈗ᩄࠊ͇኱つᶍ➨୍ཎ⌮ィ⟬࡟ࡼࡿ᭷ᶵ༙ᑟయᮦᩱࡢ㟁Ꮚ≀ᛶ◊✲͇, ELSES ◊✲఍, ᮾி, 2019 ᖺ 9
᭶ 14 ᪥.
Takatoshi Fujita, “Charge Transfer States at the Organic Donor-Acceptor Interface from the Many-Body Green's
Function Method”, IMS-IAMS Joint Meeting, Okazaki, September 21, 2019
Takatoshi Fujita, “Development of the Large-Scale GW+Bethe-Salpeter Equation Method Based on Fragment
Molecular Orbital Method for Applications to Organic Materials”, APATCC 2019, Sydney, October 2, 20195ฟ∧ᐇ⦼ࡲࡓࡣணᐃ
Takatoshi Fujita, Yoshifumi Noguchi, Takeo Hoshi, “Charge-Transfer Excited States in the Donor/Acceptor Interface

from Large-Scale GW Calculations”, The Journal of Chemical Physics, The Journal of Chemical Physics, vol. 151, p.
114109. (2019).
Takeo Hoshi, Kuwata Akiyoshi, Kakuda Kohsuke, Takatoshi Fujita, Hiroyuki Matsui, “Numerical aspect oflarge-scale electronic state calculation for flexible device material”, Japan Journal of Industrial and Applied
Mathematics, vol. 36, pp.685-698. (2019).

- 458 -

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2»Ù!Ë BWaNä1. BAR GU4_@_K8Ú  ÛË{-Ä( c*Ë2BWaN±` ³Æ ±«ªÞ. Pacsin1 "/.* ®» ËÉ s\P[ µÕ2»

2 #

Pacsin1 ÊÚdâË ,.Â pyVE[ÁÓxVE[ëMartini VE[ì2l<SW\a<X_2ÏpyVE[!Pacsin1 A4RaíÊÚdâË <SW\a<X_2 GROMACS ÏÁÓxVE[!Pacsin1 A4RaïÊÚdâË ÂËb . Pacsin1 A4Ra i|ß¿<SW\a<X_2 GROMACS Ï,Òuºi| Pacsin1 è|j+.¶jË ¥²×
<SW\a<X_buckle Ëb . Pacsin1¥²?_<_9<SW\a<X_*Ï3 
500 nspy<SW\a<X_2Ï0Pacsin1 A4Ra ªÞx Ñ,/&-Pacsin1

A4Ra ¶jËÅ|.çÅ¤ªÞ+-*MYCFªÞ2.ªÞ M\7<LZD3
Ñ,/ Å©2*Martini VE[  Pacsin1 hw.JCF^a8 KYUa@2­)Pacsin1 A4RaïÊÚdâË <SW\a<X_2ÏÅ©né¼ek·.
i|« . s ëíì- 459 -

 i|«Òuºi| Pacsin1 è|j2VEZ_9x Ü¡} Ëã ~§¹
QC8=+-¾Ö/Ì¸¥ .ËëîìbáÇ<SW\a<X_2Ï0çË ¥²2×. s  £ Ë ¥²2Ø%.êºÔ¯/.BWa
N ¥²2àsºr´,f!Pacsin1 A4Ra ¥ Ëb +.ÎØ%.)buckle Ë2· b Pacsin1 A4Ra2áÇ<SW\a<X_2Ï.Pacsin1¥²?_<_9 « s 4 "!
 M. I. Mahmood, H. Noguchi and K. Okazaki#  "   " ! $ À  ¢¨¶°°µii  ¦ 5

!

 M. I. Mahmood, H. Noguchi and K. Okazaki (2019) “Curvature induction and sensing of the F-BAR protein Pacsin1
on lipid membranes via molecular dynamics simulations”, Sci. Rep., 9, 14557 (11 pages)- 460 -

⏕య㛵㐃ศᏊࡢ㉸ከẁ㝵↓㍽ᑕኻά࡜㔠ᒓ࢖࢜ࣥ஺᥮ࢮ࢜ࣛ࢖ࢺゐ፹ࢆ⏝࠸ࡓ࣓ࢱࣥάᛶ໬཯ᛂࡢ཯ᛂ⤒㊰᥈⣴
Exploring reaction pathways of the nonadiabatic cascade of
biomolecules and methane activation
by metal-ion-exchanged zeolite catalystsżࢃ࡜ ֞ʤ౨๼୉ָʥɼࠦ౽ ֺ࣒ʤ౨‫ۂ޽ښ‬୉ָʥ‫ڂݜ‬໪దɼ಼༲ຌ೧ౕͺҐԾ͹  ͯ͹՟ୌΝ஦ৼͶɾྖࢢԿָ‫ͳࢋܯ‬ൕԢಊྙָ‫ࢋܯ‬Νۨ࢘͢ͱखΕૌΞͫʁ ࣎ؔғଚືౕ൜‫਼ؖ‬๑Ν༽͏ͪ‫ܣ‬ൿ࢐ϟοϩ͹ଡஊ֌ໃ᫖ࣻࣨ‫ܨ׈‬࿑͹ಋఈ >࿨ช  ౵@ ; તࣙ༟ుࢢϪʖδʖϏϩηΝ༽͏ͪޭԿָൕԢ΢ϟʖζϱήཀྵ࿨͹֋൅>࿨ช  ౵@ ϟνϱΩρϕϨϱή༽ۜ଒΢Ψϱި‫׷‬κΨϧ΢φৰഖ͹ൕԢ஦ৼ͹ߑଆ݀ఈ>൅න @ຌߚͲͺɾࢶ໚͹౐߻৏ɾ  Ͷߞͮͱ֕ઈͤΖɿ ళષΪηΏεΥʖϩΪη͹क੔෾Ͳ͍ΖϟνϱΝ୺ોࣁ‫ͤ༽׈ͱ͢ͳݱ‬Ζ͞ͳ΃͹‫߶͗ৼؖ‬ΉΖͶͯΗɾϟνϱΝ෉ՅՃ஍͹߶͏Կ߻෼΃௜ંร‫ͤ׷‬Ζৰഖϕϫιη͹֋൅͗੟ΞͶ‫ݗ‬౾͠Ηͱ͏Ζɿ٤ᖔΔͺϟνϱ͖ΔϟνόʖϩΝਫ਼੔ͤΖൕԢ͹‫׈‬੓झͳ͢ͱ࢐Կ෼ΩοΨϱͳ͢ͱ΢Ψϱި‫׷‬γ΢φͶ಍೘͠Ηͪ 1LΩοΨϱझΝ఑Ҍ͢ͱ͏Ζ>@ɿͨ͞Ͳɾ͞͹Γ͑͵ 1L ΩοΨϱझ͗ϟνϱΩρϕϨϱήൕԢͶ΍༙ްͲ͍Ζ͖ʹ͖͑ɾືౕ൜‫਼ؖ‬๑Ν༽͏ͪ೦Կָ‫ࢋܯ‬Ͷ‫ͱ͏Ͱخ‬඲Ճͪ͢ɿ

‫ڂݜ‬๏๑ɼ‫ࢋܯ‬๏๑
Ήͥɾ/RER Δ͗఑Ҍͪ͢ &X ȝ2 >$O@&+$ κΨϧ΢φ͹ߑଆ>@Ν‫خ‬Ͷɾ&+$ ‫ܗ‬κΨϧ΢φʤ6L$O ʥΝϗʖηͶɾ1L ෵֫झ͖Δ͵Ζ>1L ȝ2 @>$O@&+$ ϠAlυϩৰഖߑଆΝߑ஛ͪ͢ɿ۫ରదͶͺɾ)LJ  ͶࣖͤΓ͑Ͷ &+$ κΨϧ΢φ͹  ҽ‫؂‬͹  ͯ͹ 7 γ΢φΝࢋͪ͢ɿ>1L ȝ2 @৏Ͷ͕͜Ζϟνϱ‫׈‬੓ԿͳͨΗͶ

Al

Ni

B

$O Ͳ ಋ ‫ ܗ‬஖ ‫ ͢ ׷‬ɾ ͨ Η Δ Ν ‫ ڮ‬΋ ࠐ ֪ 2 ‫ ࢢ ݬ‬Ͷ
>1L ȝ2 @ΝՏ‫ߑڰ‬ଆͲ಍೘ͪۜ͢଒΢Ψϱި‫׷‬Ν‫ܯ‬

Ni2+ Ni2+[Ni2(μ-O)]2+

ਦ ɿຌ‫>ͪ͏༽Ͳڂݜ‬1L ȝ2 @>$O@&+$ Ϡυϩৰഖߑଆͳͨ͹‫׈‬੓஦ৼ͹঴ྲྀන‫ى‬ɿ

- 461 -

Ӏ͘କ͏ͱً͞ΖΦνϱਫ਼੔‫ܨ‬࿑৏͹஦ؔରΝɾ٤ᖔΔ  ͹‫ع‬ๅͳΆ·ಋ౵͹ 83%(8 1LʶH9 '%-
3$: &XWRII H9ɾ ī ఼ Ϫϗϩ͹ືౕ൜‫਼ؖ‬๑ͲߑଆΝ࠹నԿͪ͢ɿ‫ࢋܯ‬Ͷͺ 9$63  ͳ $6( ΝૌΊ߻Κͦͱཤ༽ͪ͢ɿ    ‫ڂݜ‬੔Վ
118

1L ȝ2 >$O@&+$ ϠυϩৰഖͶ͕͜Ζ &+ ΩρϕϨϱήൕԢ͹ϛτϱεϡϩΦϋϩάʖϕϫϓΟ΢ϩͳ
1L±1L ݃߻ௗ͹ 5 1L±1L ͹รԿΝ )LJ  Ͷࣖͤɿ
>1L ȝ2 @‫׈‬੓Կ஦ৼͶ͕͏ͱͺɾ ͯ໪͹ &+ մ཯

Potential energy / kJ mol-1ຌ‫ڂݜ‬Ͷ͕͜Ζ೦Կָ‫ࢋܯ‬ͶΓΕ‫ٽ‬Όͪ
0

9

CH4

C2H6
ٔH2O

CH4
−118

‫ٷ‬஥ͳ &+ ୦཯ཱི͗ର্֒ͶΓΕͨΗͩΗ  N-
PRO ͕Γ; N-PRO ΍͹࢕ࣆΝචགྷͳͤΖ‫ٷ‬೦ൕ
ԢͲ͍ΖͪΌɾ&+ ΩρϕϨϱήൕԢͺඉ৙Ͷ਒ߨ͢Ͷ͚͏͞ͳ͗໎Δ͖Ͷ͵ͮͪɿ͠ΔͶ٤ᖔΔ͹
>1L ȝ2 @>$O@0), ৰഖϠυϩͶ͕͜Ζ‫ࢋܯ‬ͶΓΖͳɾ

Ni2(μ-O)-[Al]CHA

Dissociative
addition 1

Dissociative
addition 2

Ni2-[Al]CHA

R (Ni-Ni) = 3.18 Å

2.70 Å

2.81 Å

2.58 Å

Reaction coordinatesਦ ɿ>1L ȝ2 @>$O@&+$ ϠυϩৰഖͶ͕͜ΖϟνϱΩρϕϨϱήൕԢ͹ΦϋϩάʖϕϫϓΟ΢ϩ>1L ȝ2 @‫׈‬੓஦ৼͶΓΖϟνόʖϩਫ਼੔΍ N-PRO ΍͹‫ٷ‬೦ൕԢͲ͍Ζ>@ɿ͞͹ͪΌɾϟνόʖϩਫ਼੔΍ඉ৙Ͷً͞ΕͶ͚͚ɾϟνόʖϩ఺‫׷‬ൕԢͶΓΖ & ਫ਼੔͹Ն೵੓΍ఁ͏ͳߡ͓ΔΗΖɿ ٤ᖔΔ͹ 1L ‫>༙؜‬$O@0), ϠυϩৰഖΝ༽͏ͪ‫ࢋܯ‬ͶΓΖͳɾ>1L2@>1L ȝ2 @>1L ȝ2 @ͶΓͮͱϟνϱ͗‫׈‬੓Կ͠Ηͪ৖߻ɾ൅೦ൕԢͲଐౕ࿨దͶ΍ଐΏ͖Ͷϟνόʖϩ΃ͳ෨෾࢐Կ͠ΗΖ>@ɿҲ๏ɾຌ‫ڂݜ‬Ͷ͕͜Ζ 1L>$O@&+$ Ν༽͏ͪൕԢࣰ‫Ͳݩ‬ͺϟνόʖϩ͹ਫ਼੔ͺ֮೟͠Η͵͖ͮͪɿ͠ΔͶɾ6L 0$6
105 ηϘέφϩͶΓΖߑଆմੵ͹݃ՎΓΕɾ1L ͺ 1LXQLWFHOOʤୱҒ๖  ͯ͵͏͢  ͯͶ  ‫ݺ‬ఖౕʥͳ‫ݡ‬੷΍ΔΗͪɿҐ৏ΓΕɾ1L>$O@&+$ Ͷ͕͜Ζϟνϱ఺‫׷‬ൕԢ͹‫׈‬੓஦ৼͺɾ٤ᖔΔ͗ϟνϱ͖Δϟνόʖϩ΃͹࢐ԿͶ͕͏ͱ఑Ҍͪ͢Γ͑͵ 2 ‫ࢢݬ‬ͶΓΕՏ‫ߑͪ͢ڰ‬ଆΝ࣍ͯ෵֫ 1L ͹࢐Կ෼ΩοΨϱझͲͺ͵͚ɾࠐ֪ 2 ‫ ͳࢢݬ‬1L ͳ͗ు՛Νึ͏߻ͮͪୱ֫ 1L झ͗ࠐ֪ $O ‫ۛࢢݬ‬๥Ͷଚࡑ͢ͱ͏Ζߑଆͫͳߡ͓ΔΗΖɿ ൅නࣰ੹Ήͪͺ༩ఈ>@ ★. <DPD]DNL ³7KHRUHWLFDO WLPHUHVROYHG [UD\ VSHFWURVFRSLHV IRU ,5 LQGXFHG VWUXFWXUDO G\QDPLFV RI
QDQRPDWHULDOV´0LQL6\PSRVLXPRQXOWUDIDVWPROHFXODUG\QDPLFV ౨๼୉ָଡ‫ݫ‬෼࣯Ռָ‫ॶڂݜ‬ɾ‫ٸ‬৕‫ݟ‬ઍୈࢤʤডଶߪԍʥ ೧  ݆  ೖɿ>@★)2WD'6HELOOHDX11DNDWDQL.<DPD]DNL.8HGD.+DWDGD³3KRWRHOHFWURQ$QJXODU'LVWULEXWLRQVRIJDV
SKDVHPROHFXOHLQWHUPVRI0XOWLSOH6FDWWHULQJWKHRU\´ ୊  յԿָൕԢ౾࿨ճʤ3ʥɾ౨߁ౣܵढ़ชԿϙʖϩ ͚ΔΔɾ߁ౣ‫ݟ‬౨߁ౣࢤ ϛηνʖ൅න  ɾ ೧  ݆  ೖ>@★.<DPD]DNL$0DUFLQLDN60DHGD05HGX]]L9'HVSUp0+HUYp00H]LDQH71LHKDXV9/RULRW$.XOHII % 6FKLQGOHU , &RPSDJQRQ * 6DQVRQH ) /pSLQH ³)HPWRVHFRQG QRQDGLDEDWLF FDVFDGH DQG VXEVHTXHQWSKRWRIUDJPHQWDWLRQRI;89H[FLWHGFDIIHLQHPROHFXOH´ ,&3($&ɾ'HDXYLOOHɾϓϧϱη ϛηνʖ൅න  ೧  ݆  ೖ- 462 -

>@ ★. <DPD]DNL ³;)(/LQGXFHG &RXORPE H[SORVLRQ RI QDQRPROHFXOH DQG LWV DSSDULWLRQ WR PROHFXODU PRYLH´
+H..6D*2Q:*3UH&RQIHUHQFH'LVFXVVLRQ0HHWLQJ³'\QDPLF,PDJLQJIRU3K\VLFDO&KHPLFDODQG%LRORJLFDO,QWHUHVWV´ɾύ΢υϩϗϩή୉ָɾύ΢υϩϗϩήɾχ΢ςʤডଶߪԍʥ ೧  ݆  ೖɿ>@ ໨Ծ ਇ೯ղʀଞন ‫ޝ‬ʀҬ޳ Մ࠺ʀ߶޳ ദࢦʀപ஋ઔ ‫࢛ي‬ʀߒ‫ ݬ‬ਜ਼ദʀࢃ࡜ ֞ʀ‫ݬ‬ᔻ ༠ʀ઴ీ ཀྵʀߒാ ޻೯ʰ࣎ؔ෾մࢷ֐෾ޭ๑ͳԿָൕԢ‫ܨ‬࿑ࣙಊ୵ࡩ๑ͶΓΖ‫ܣ‬ൿ࢐Φητϩ͹ WUDQVĺFLV ޭҡ੓Կ‫ܨ‬࿑͹մ໎ʱԿָൕԢ‫ܨ‬࿑୵ࡩ͹ωϣʖϓϫϱτΡΠ ɾ໌‫ݻ‬Բ୉ָ ໼ғ‫ى‬೨ָढ़ިླྀ‫ؙ‬ɾѬஎ‫໌ݟ‬‫ݻ‬Բࢤʤ޳ಆ൅නʥɾ ೧  ݆  ೖ>@★ࢃࢃ࡜ ֞ʀཚ߻ ޼ฑʀ=-XUHNʀ56DQWUDʀ1%HUUDKʀ৏ీ݁ʀՑ໼ ༡ඛ ʰ; તࣙ༟ుࢢϪʖδʖͶΓͮͱӀً͘͞͠ΗΖ & ଡՃΩοΨϱ͹෾ࢢϓϧήϟϱφਫ਼੔ಊྙָʱԿָൕԢ‫ܨ‬࿑୵ࡩ͹ωϣʖϓϫϱτΡΠ ɾ ೧  ݆  ೖɾ໌‫ݻ‬Բ୉ָ ໼ғ‫ى‬೨ָढ़ިླྀ‫ؙ‬ɾѬஎ‫ݻ໌ݟ‬Բࢤɿ>@ ໨Ծ ਇ೯ղʀଞন ‫ޝ‬ʀҬ޳ Մ࠺ʀ߶޳ ദࢦʀപ஋ઔ ‫࢛ي‬ʀߒ‫ ݬ‬ਜ਼ദʀࢃࢃ࡜ ֞ʀ‫ݬ‬ᔻ ༠ʀ઴ీ ཀྵʀߒാ ޻೯ʰ௔ԽଐζΥρφϪʖδʖ෾ޭͳԿָൕԢ‫ܨ‬࿑ࣙಊ୵ࡩ๑ͶΓΖ‫ܣ‬ൿ࢐Φητϩ͹ WUDQV ĺ FLVޭҡ੓Կ‫ܨ‬࿑͹մ໎ʱ୊  յ෾ࢢՌָ౾࿨ճ ʤ$ʥɾ୊  յ෾ࢢՌָ౾࿨ճɾ໌‫ݻ‬Բ୉ָ ౨ࢃΫϡϱϏηɾѬஎ‫ݻ໌ݟ‬Բࢤʤ޳ಆ൅නʥ
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 Facile NO-CO elimination over zirconia-coated Cu(110) surfaces: Further evidence from DFT+U calculations
Hiroaki Koga, Akihide Hayashi, Yoshinori Ato, Saburo Hosokawa, Tsunehiro Tanaka, Mitsutaka Okumura
Applied Surface Science 508 (2020) 145252 (11pp.)
DOI: 10.1016/j.cattod.2018.07.023$[1] H. Koga, A. Hayashi, Y. Ato, K. Tada, S. Hosokawa, T. Tanaka, M. Okumura, Catal. Today, 332 (2019) 236.

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255."Comparison of Effective Exchange Integrals of H-H and H-He-H Chains vs. Single Molecules:
A Theoretical Study"
Kohei Tada, Takashi Kawakami, Yasutaka Kitagawa, Mitsutaka Okumura, Kizashi Yamaguchi
and Shingo Tanaka
Chem. Lett., 49(2), 137-140 (2020)
256."Theoretical Study on Magnetic Interaction in Pyrazole-Bridged Dinuclear Metal Complex:
Possibility of Intramolecular Ferromagnetic Interaction by Orbital Counter-Complementarity"
Takuya Fujii, Yasutaka Kitagawa, Kazuki Ikenaga, Hayato Tada, Iori Era and Masayoshi
NakanoMagnetochemistry, 6(1), 10 (2020)
257.%ULGJHဨ/HQJWKဨ'HSHQGHQW,QWUDPROHFXODU&KDUJH7UDQVIHULQ%LV GLDQLV\ODPLQR ဨ7HUPLQDWHG
Oligo(pဨSKHQ\OHQH V
Masashi Uebe, Kensuke Kaneda, Shinya Fukuzaki and Akihiro Ito
Chem. Eur. J., 25(68), 15455-15462 (2019)258."Electronic and Photoph\VLFDO3URSHUWLHVRIဨ$QWKU\OHQHဨ%ULGJHG%ဨʌဨ1'RQRUဨ$FFHSWRU
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Masashi Uebe, Daisuke Sakamaki and Akihiro Ito
ChemPlusChem, 84(9), 1305-1313 (2019)259.6\QWKHVLVRI1LWURJHQဨ&RQWDLQLQJ3RO\DURPDWLFVE\$]Dဨ$QQXODWLYHʌဨ([WHQVLRQRI
Unfunctionalized Aromatics"
Kou P. Kawahara, Wataru Matsuoka, Hideto Ito and Kenichiro Itami
Angew. Chem. Int. Ed., 59(16), 6383-6388 (2020)
260."Step-*URZWK$QQXODWLYHʌ-Extension Polymerization for Synthesis of Cove-Type Graphene
Nanoribbons"- 499 -

Yuuta Yano, Feijiu Wang, Nobuhiko Mitoma, Yuhei Miyauchi, Hideto Ito and Kenichiro Itami
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261."Inverse Hamiltonian method assisted by the complex scaling technique for solving the DiracCoulomb equation: Helium isoelectronic atoms"
Hiroyuki Nakashima and Hiroshi Nakatsuji
Chemical Physics Letters, 749, 137447 (2020)
262."Computed Atomic Force Microscopy Images of Chromosomes by Calculating Forces with
Oscillating Probes"
Takashi Sumikama, Adam. S. Foster and Takeshi Fukuma
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263."A Bayesian approach for identification of ice Ih, ice Ic, high density, and low density liquidwater with a torsional order parameter"
Masakazu Matsumoto, Takuma Yagasaki and Hideki Tanaka
J. Chem. Phys., 150(21), 214504 (2019)264."Liquid-liquid separation of aqueous solutions: A molecular dynamics study"
Takuma Yagasaki, Masakazu Matsumoto and Hideki Tanaka
J. Chem. Phys., 150(21), 214506 (2019)265."Formation of hot ice caused by carbon nanobrushes"
Takuma Yagasaki, Masaru Yamasaki, Masakazu Matsumoto and Hideki Tanaka
J. Chem. Phys., 151(6), 064702 (2019)266."On the role of intermolecular vibrational motions for ice polymorphs I: Volumetric propertiesof crystalline and amorphous ices"
Hideki Tanaka, Takuma Yagasaki and Masakazu Matsumoto
J. Chem. Phys., 151(11), 114501 (2019)267."On the role of intermolecular vibrational motions for ice polymorphs. II. Atomic vibrational
amplitudes and localization of phonons in ordered and disordered ices"
Hideki Tanaka, Takuma Yagasaki and Masakazu Matsumoto
J. Chem. Phys., 152(7), 074501 (2020)
268."Adsorption mediated tandem acid catalyzed cellulose hydrolysis by ortho-substituted benzoic
acids"
Danjo P. De Chavez, Min Gao, Hirokazu Kobayashi, Atsushi Fukuoka and Jun-ya Hasegawa
Molecular Catalysis, 475, 110459 (2019)269."Anharmonic vibrational computations with a quartic force field for curvilinear coordinates"
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Taketsugu
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270."Quantum mechanical molecular dynamics simulations of polaron formation inmethylammonium lead iodide perovskite"
Hiroki Uratani, Chien-Pin Chou and Hiromi Nakai
Phys. Chem. Chem. Phys., 22(1), 97-106 (2019)271."Intra-dimer row and inter-dimer row coupling of the vibrational modes of chemisorbed CO on
Si(001)-c(4×2) observed by angle-dependent transmission infrared spectroscopy"
Shinya Ohno, Shotaro Shimizu, Kazuma Tanaka, Shinya Yoshimoto and Jun Yoshinobu
J. Chem. Phys., 151(7), 074702 (2019)272."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Masaaki
Fujii
ChemPhysChem, 21(8), 712-724 (2020)
273."Electrode polarization effects on interfacial kinetics of ionic liquid at graphite surface: An
H[WHQGHGODJUDQJLDQဨEDVHGFRQVWDQWSRWHQWLDOPROHFXODUG\QDPLFVVLPXODWLRQVWXG\Taichi Inagaki and Masataka Nagaoka
J Comput Chem, 40(24), 2131-2145 (2019)274."Molecular Behavior of Linear Alkylbenzene Sulfonate in Hydrated Crystal, Tilted Gel, andLiquid Crystal Phases Studied by Molecular Dynamics Simulation"
Kosuke Takeda, Yoshimichi Andoh, Wataru Shinoda and Susumu Okazaki
Langmuir, 35(33), 10877-10884 (2019)275."Hydrogen Permeation in Hydrated Perfluorosulfonic Acid Polymer Membranes: Effect ofPolymer Crystallinity and Equivalent Weight"
Kotono Takeuchi, An-Tsung Kuo, Takeshi Hirai, Tatsuya Miyajima, Shingo Urata, Shinji
Terazono, Susumu Okazaki and Wataru Shinoda
J. Phys. Chem. C, 123(33), 20628-20638 (2019)276."Molecular dynamics study of solubilization of cyclohexane, benzene, and phenol into mixed
micelles composed of sodium dodecyl sulfate and octaethylene glycol monododecyl ether"
Kosuke Takeda, Kazushi Fujimoto, Noriyuki Yoshii and Susumu Okazaki
J Comput Chem, 40(31), 2722-2729 (2019)277."Large-scale molecular dynamics simulation of perfluorosulfonic acid membranes: Remappingcoarse-grained to all-atomistic simulations"
An-Tsung Kuo, Yusuke Miyazaki, Changwoon Jang, Tatsuya Miyajima, Shingo Urata, Steven
O. Nielsen, Susumu Okazaki and Wataru Shinoda
Polymer, 181, 121766 (2019)- 501 -

278.)DVWPXOWLSROHPHWKRGIRUWKUHHဨGLPHQVLRQDOV\VWHPVZLWKSHULRGLFERXQGDU\FRQGLWLRQLQ two
directions"
Noriyuki Yoshii, Yoshimichi Andoh and Susumu Okazaki
J Comput Chem, 41(9), 940-948 (2020)
279."Dependence of Absorption and Emission Spectra on Polymorphs of Gold(I) Isocyanide
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J. Phys. Chem. C, 123(8), 4773-4794 (2019)280."Catalysis of Cu Cluster for NO Reduction by CO: Theoretical Insight into the Reaction
Mechanism"
Nozomi Takagi, Kazuya Ishimura, Hiroki Miura, Tetsuya Shishido, Ryoichi Fukuda, Masahiro
Ehara and Shigeyoshi Sakaki
ACS Omega, 4(2), 2596-2609 (2019)281.7KHRUHWLFDOSUHGLFWLRQRI1L , ဨFDWDO\VWIRUK\GURVLO\ODWLRQRIS\ULGLQHDQGTXLQROLQH
Vijay Singh, Shigeyoshi Sakaki and Milind M. Deshmukh
J Comput Chem, 40(24), 2119-2130 (2019)282."Electronic processes in NO dimerization on Ag and Cu clusters: DFT and MRMP2 studies"
Nozomi Takagi, Masayuki Nakagaki, Kazuya Ishimura, Ryoichi Fukuda, Masahiro Ehara andShigeyoshi Sakaki
J Comput Chem, 40(1), 181-190 (2019)283."Reaction Behavior of the NO Molecule on the Surface of an Mn Particle (M = Ru, Rh, Pd, andAg; n = 13 and 55): Theoretical Study of Its Dependence on Transition-Metal Element"
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J. Phys. Chem. A, 123(32), 7021-7033 (2019)284."Characterization of Rh–Al Bond in Rh(PAlP) (PAlP = Pincer-type Diphosphino-Aluminyl
Ligand) in Comparison with Rh(L)(PMe3)2 (L = AlMe2, Al(NMe2)2, BR2, SiR3, CH3, Cl, orOCH3): Theoretical Insight"
Nishamol Kuriakose, Jia-Jia Zheng, Teruhiko Saito, Naofumi Hara, Yoshiaki Nakao andShigeyoshi Sakaki
Inorg. Chem., 58(8), 4894-4906 (2019)285."sp3 C–H Borylation Catalyzed by Iridium(III) Triboryl Complex: Comprehensive Theoretical
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J. Am. Chem. Soc., 141(25), 9854-9866 (2019)286."A new design strategy for redox-active molecular assemblies with crystalline porous structures
for lithium-ion batteries"- 502 -

K. Nakashima, T. Shimizu, Y. Kamakura, A. Hinokimoto, Y. Kitagawa, H. Yoshikawa and * D.
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with Primary Amines"
A. Hinokimoto, M. Tashiro, Y. Kitagawa and D. Tanaka*
Chem. Lett., 47(8), 1006-1009 (2018)288."Theoretical Study on Adjacent Agostic Interaction in Ruthenium Complexes"
Sahoko OHASHI, Satomi YAMANAKA and Keiko Takano
J. Comput. Chem. Jpn., 18(3), 162-163 (2019)289."Synthesis and Systematic StUXFWXUDO$QDO\VLVRI&DWLRQLF+DOIဨ6DQGZLFK5XWKHQLXPChalcogenocarbonyl Complexes"$\XPL6X]XNL<XLFKLUR0XWRK1RULNR7VXFKLGD&KLဨ:DL)XQJ6KRNR.LNNDZD,VDR
Azumaya and Shinichi Saito
Chem. Eur. J., 26(17), 3795-3802 (2020)
290."Systematic Interaction $QDO\VLVRI$QWLဨ+XPDQ,PPXQRGHILFLHQF\9LUXV7\SHဨ1HXWUDOL]LQJ
Antibodies with High Mannose Glycans Using Fragment Molecular Orbital and Molecular
Dynamics Methods"
0L\X.XVXPRWR.DRUL8HQRဨ1RWRDQG.HLNR7DNDQRJ Comput Chem, 41(1), 31-42 (2020)
291."Ruthenium Vinylidene Complexes Generated by Selective 1,2-Migration of P- and SSubstituents: Synthesis, Structures, and Dichromism Arising from an Intramolecular CH···O
Hydrogen Bond"
Takuya Kuwabara, Yutaka Aoki, Kousuke Sakajiri, Kazuki Deguchi, Shuhei Takamori, Ai
Hamano, Keiko Takano, Hirohiko Houjou and Youichi Ishii
Organometallics, 39(5), 711-718 (2020)
292."Theoretical Study of Formation of Methanol under Hydrothermal Conditions"
Satoshi Inaba
J. Phys. Chem. A, 124(22), 4496-4505 (2020)
293."Mechanochromism, Twisted/Folded Structure Determination, and Derivatization of (NဨPhenylfluorenylidene)acridane"
Yutaka Matsuo, Ya Wang, Hiroshi Ueno, Takafumi Nakagawa and Hiroshi Okada
Angew. Chem. Int. Ed., 58(26), 8762-8767 (2019)294."Reduced Knoevenagel Reaction of Acetetracenylene-1,2-dione with Acceptor Units for
Luminescent Tetracene Derivatives"
Yutaka Matsuo, Chu-Guo Yu, Takafumi Nakagawa, Hiroshi Okada, Hiroshi Ueno, Tian-Ge Sun- 503 -

and Yu-Wu Zhong
J. Org. Chem., 84(4), 2339-2345 (2019)295."Star-shaped magnesium tetraethynylporphyrin bearing four peripheral electron-accepting
diketopyrrolopyrrole functionalities for organic solar cells"
Huan Wang, Qihui Yue, Takafumi Nakagawa, Anna Zieleniewska, Hiroshi Okada, Keisuke
Ogumi, Hiroshi Ueno, Dirk M. Guldi, Xiaozhang Zhu and Yutaka Matsuo
J. Mater. Chem. A, 7(8), 4072-4083 (2019)296."Highly soluble C2v-symmetrical fullerene derivatives: efficient synthesis, characterization, andelectrochemical study"
Yue Ma, Kouya Uchiyama, Hiroshi Ueno, Hiroshi Okada, Hiroshi Moriyama and Yutaka
MatsuoOrg. Chem. Front., 6(9), 1372-1377 (2019)297."Synthesis of Benzothieno[60]fullerenes through Fullerenyl Cation Intermediates"
Yutaka Matsuo, Yun Yu, Xiao-Yu Yang, Hiroshi Ueno, Hiroshi Okada, Hiromasa Shibuya,
Yeong Suk Choi and Yong Wan Jin
J. Org. Chem., 84(10), 6270-6277 (2019)298."Improved solubility of asymmetric tetraethynylporphyrin derivatives for solution-processedorganic solar cells"
Keisuke Ogumi, Takafumi Nakagawa, Hiroshi Okada and Yutaka Matsuo
Organic Electronics, 71, 50-57 (2019)299."Penning ionization electron spectroscopy of anisole, thioanisole, and selenoanisole by collision
with He*(23S): Conjugation effects and conformational stability"
Yuki Ishiguro, Yoshihiro Yamakita and Naoto Hayashi
Chemical Physics Letters, 754, 137653 (2020)
300."Classical trajectory calculations for state-resolved Penning ionisation reactions of polycyclicaromatic hydrocarbon C10H8 in collision with He*(23S)"
Yoshihiro Yamakita and Naoki Kai
Molecular Physics, 117(21), 3184-3193 (2019)301."Synthesis and Photovoltaic 3URSHUWLHVRI%RURQȕဨ.HWRLPLQDWH'\HV)RUPLQJD/LQHDU'RQRUဨʌဨ$FFHSWRU6WUXFWXUH
Yuki Sakura, Fumina Yumioka, Takashi Funaki and Katsuhiko Ono
Chem. Asian J., 15(13), 1982-1989 (2020)
302."Effect of Step Edges on Adsorption Behavior for GaN(0001) Surfaces during Metalorganic
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Takumi Ohka, Toru Akiyama, Abdul Muizz Pradipto, Kohji Nakamura and Tomonori Ito
Crystal Growth & Design, 20(7), 4358-4365 (2020)- 504 -

303."Roles of growth kinetics on GaN non-planar facets under metalorganic vapor phase epitaxy
condition"
Yuki Seta, Toru Akiyama, Abdul Muizz Pradipto, Kohji Nakamura and Tomonori Ito
Appl. Phys. Express, 13(6), 065505 (2020)304."Ab initio calculations for the effect of wet oxidation condition on the reaction mechanism at
4H–SiC/SiO2 interface"
Tsunashi Shimizu, Toru Akiyama, Abdul-Muizz Pradipto, Kohji Nakamura, Tomonori Ito,
Hiroyuki Kageshima, Masashi Uematsu and Kenji Shiraishi
Jpn. J. Appl. Phys., 59(SM), SMMD01 (2020)305."Equilibrium Morphologies of Faceted GaN under the MetDORUJDQLF9DSRUဨ3KDVH(SLWD[\Condition: Wulff Construction Using Absolute Surface Energies"
Yuki Seta, Abdul-Muizz Pradipto, Toru Akiyama, Kohji Nakamura and Tomonori Ito
Phys. Status Solidi B, 257(4), 1900523 (2020)
306."Enantioselective Synthesis of Triple Helicenes by Cross-Cyclotrimerization of a Helicenyl
Aryne and Alkynes via Dynamic Kinetic Resolution"
Ayaka Yubuta, Tomoka Hosokawa, Masayuki Gon, Kazuo Tanaka, Yoshiki Chujo, Akihiro
Tsurusaki and Ken Kamikawa
J. Am. Chem. Soc., 142(22), 10025-10033 (2020)307.$QQXODWLYHʌ-Extension (APEX) Reactions for Precise Synthesis of Polycyclic Aromatic
Compounds"
Hideto Ito, Wataru Matsuoka, Yuuta Yano, Mari Shibata and Kenichiro Itami
J. Synth. Org. Chem. Jpn., 78(7), 671-682 (2020)
308."Machine-learning approach for constructing control landscape maps for three-dimensionalalignment of asymmetric-top molecules"
T. Namba, M. Yoshida and Y. Ohtsuki
J. Chem. Phys., 153(2), 024120 (2020)
309."A dinuclear Mo2H8 complex supported by bulky C5H2tBu3 ligands"
Yasuhiro Ohki, Kodai Ishihara, Moeko Yaoi, Mizuki Tada, W. M. C. Sameera and Roger E.
CramerChem. Commun., 56(58), 8035-8038 (2020)
310."Docking and Molecular Dynamics Study of the Carbohydrate Binding Module fromTrichoderma reesei Cel7A on the Surfaces of the Cellulose IIII Crystal"
Toshifumi Yui and Takuya Uto
J. Renew. Mater., 8(8), 863-878 (2020)
311."Photodissociation processes of a water–oxygen complex cation studied by an ion imaging
technique"- 505 -

Yuji Nakashima, Yuri Ito, Kenichi Okutsu, Motoyoshi Nakano and Fuminori Misaizu
Phys. Chem. Chem. Phys., 22(29), 16926-16933 (2020)
312."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)
313."Theoretical Study of Non-Markov Effects on Singlet Fission Dynamics of Model Pentacene
Dimers Using the Second-Order Time-Convolutionless Quantum Master Equation Method"
Wataru Yoshida, Kenji Okada, Hajime Miyamoto, Takayoshi Tonami, Takanori Nagami and
Masayoshi Nakano
J. Phys. Chem. C, 124(23), 12220-12229 (2020)
314."A slight bluish-white fluorescence from E,E-2,6-bis(4-cyanostyryl)pyridine pristine crystals"
Hiroyuki Mochizuki and Hitoshi Kusama
RSC Adv., 10(5), 2727-2733 (2020)- 506 -

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- 508 -

ㄽᩥᩘ


ㄽᩥ␒ྕ
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

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







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
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

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
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

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ࢥ࣮ࢻ
HK
HK
HN
HN
HP
HP
HP
HS
HS
HT
HT
HT
HT
HV
HW
HX
HY
HZ
H[
H[
H\
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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
IK

௦⾲⪅ྡ
኱㔝බ୍
࿴బ⏣ࠉ⿱᫛
㮚㔝ࠉᬒᏊ
ᮏከࠉ୍ᙪ
㫽ᒃࠉ⫕
Ᏻ⸨ࠉ㤶⧊
⡿⏣ࠉⱱ㝯
୰஭ࠉᾈᕭ
ᕝෆࠉ㐍
ᯇᮏࠉ୍Ⴙ
୰㔝ࠉᖾྖ
ᕝཱྀࠉ୍᭸
✄ⴥࠉ▱ኈ
᳃ࠉ⪷἞
ఀ⸨ࠉᙲᾈ
ᑠ㔝ࠉඞᙪ
ᕤ⸨ࠉ⪽
Ἴ⏣㞞ᙪ
ⓑ▼㈼஧
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໭ᑿࠉᙲᮁ
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኱ୗࠉ៞ḟ㑻
ࣜࣥࢺࢗࣝ࢜ࢺࠉṇ⨾
ෆ⏣ࠉᖾ᫂
୰㔝ࠉ⩏᫂
㔠ࠉ㗰
ᒣᓮࠉ⚈ᖹ
ᮃ᭶ࠉᘓ∞
Ᏹ⏣ᕝࠉኴ㑻
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⏣୰ࠉ኱㍜
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▼ᒣࠉ㐩ஓ
ᮧᒸࠉᱻ
బ⸨ࠉᚭ
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⏣୰ࠉ⸅
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࣓ࣥࣂ࣮ᩘ
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- 509 -

ㄽᩥᩘ


ㄽᩥ␒ྕ






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


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

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
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


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
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




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


ࢥ࣮ࢻ
IL
IL
IL
IL
IM
IM
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IN
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IO
IO
IO
IO
IP
IP
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IQ
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IQ
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IR
IR
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IS
IS
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IT
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IU
IU
IU
IU
IU
IU
IU

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⏣୰ࠉ⿱ஓ
ὸᏊࠉኊ⨾
ᖹ㔝ࠉᜏኵ
ᇛ㔝ࠉுኴ
ὸᕝࠉ኱ᶞ
ᯇ஭ࠉ஽
ゅᒣࠉᐶつ
➉ෆࠉ῕
ྜྷ⏣ࠉ⣖⏕
๓⏣ࠉ኱ග
ᾆࠉᗣஅ
⚟ᓥࠉၨᝅ
᪂ᇼࠉె⣖
ⓑ஭ࠉఙᐂ
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すෆࠉᬛᙪ
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஭ཱྀࠉెဢ
⚄㇂ࠉᫀᏹ
᝴Ⰻ⏣ࠉ▱ᶞ
㔝ཱྀࠉᕦ
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⚟⏣ࠉⰋ୍
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⊁㔝ࠉ┤࿴
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๓⏣ࠉ⌮
ఀໃᕝ⨾✑
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࣓ࣥࣂ࣮ᩘ






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- 510 -

ㄽᩥᩘ


ㄽᩥ␒ྕ
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

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⁪⏣ࠉⰋ
బ⸨❳㤿
ᐑ⏣኱㍜
ᑠỮࠉె♸
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ᒣᓮࠉ⚈Ꮚ
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- 511 -

ㄽᩥᩘ



ㄽᩥ␒ྕ
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௦⾲⪅ྡ
ዟᒣࠉඞᙪ
୰すࠉຬ௓
5XPSD3DO
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ஂୡࠉಙᙪ
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Ⅳ❤ࠉாྖ
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㤋ᒣࠉెᑦ
⸨⏣ࠉ㈗ᩄ
ᒣᓮࠉ㤾
㛗ᒸṇ㝯
Ⱚࠉ㞙ே
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୰஭ࠉᾈᕭ
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࣓ࣥࣂ࣮ᩘ

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- 512 -

ㄽᩥᩘ

ㄽᩥ␒ྕ




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




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
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

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
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ࢭࣥࢱ࣮࣏࣮ࣞࢺ 20
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