1P103FMO ࢫ࣮࣒࢟࡟ᇶ࡙࠸ࡓບ㉳≧ែゎᯒἲࡢ᪂つᐇ⿦‫ཱྀ⏣ۑ‬ᑦ㈗ 1㸪ᮃ᭶♸ᚿ 1,2㸪୰㔝㐩ஓ 2,3㸪ᒣୗ຾⨾ 4㸪⏣୰ᡂ඾ 2,5(1. ❧ᩍ኱ࠊ2. JST-CREST, 3. ᅜ❧⾨⏕◊ࠊ4. NEC ࢯࣇࢺࠊ5. ⚄ᡞ኱)‫ ڦ‬㟁Ꮚ㑄⛣࢚ࢿࣝࢠ࣮ࡢᑐ⿵ṇ㏆ᖺࠊ኱つᶍศᏊ⣔ࡢ㟁Ꮚ≧ែࡢᐇ⏝ⓗ࡞ィ⟬᪉ἲ࡜ࡋ࡚ࠊࣇࣛࢢ࣓ࣥࢺศᏊ㌶㐨ἲ (Fragment
Molecular Orbital; FMO ἲ)ࡀὀ┠ࢆ㞟ࡵ࡚࠸ࡿ[1-3]ࠋFMO ィ⟬࡟ࡼࡗ࡚▱ࡿ஦ࡢฟ᮶ࡿ≀⌮㔞ࡣ
ᵝࠎ࡛࠶ࡿࡀࠊගᛂ⟅ࢱࣥࣃࢡ㉁࡞࡝࡟㛵ࡍࡿບ㉳≧ែࡢ࢚ࢿࣝࢠ࣮ࡣ CIS (Configuration
Interaction Singles), ࡞ࡽࡧ࡟㟁Ꮚ┦㛵ࢆྵࡵࡓ CIS(D) (CIS with perturbed doubles)⣔ࡢ᪉ἲ࡛ྍ⬟࡛࠶ࡿ[4,5]ࠋFMO ࢫ࣮࣒࢟࡟ᇶ࡙ࡃບ㉳≧ែࡢィ⟬ࡣࠊศᏊ඲య(Layer 1)ࢆ Hartree Fock ࡛ࣞ࣋ࣝࡲࡎゎࡁࠊḟ࡟ගᛂ⟅ࢆᢸ࠺㒊ศ࡜࿘㎶㒊ศ࠿ࡽ࡞ࡿάᛶ㡿ᇦ(Layer 2)࡟ᑐࡋ࡚ࠊCIS(D)࡞࡝
ࡢບ㉳≧ែィ⟬ࢆ㐺⏝ࡍࡿከᒙᆺ(Multilayer FMO; MFMO)࡛⾜ࢃࢀࡿ[6]ࠋࡋ࠿ࡋ࡞ࡀࡽࠊFMO- HFẁ㝵ࡢ dimer-SCF ࡢィ⟬ࢥࢫࢺࡣ඲య࡟ᑐࡋ࡚ᨭ㓄ⓗ࡛࠶ࡾࠊ⯆࿡㡿ᇦࡢࡳࡢゎᯒ࡛ࠊ࠿ࡘࠊ」ᩘࡢᵓ㐀࡟ᑐࡍࡿゎᯒࢆ⾜࠺㝿࡟ࡣ㞀ᐖ࡜࡞ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ2005 ᖺ࡟ᖹ⏣ࡽࡀᥦ᱌ࡋࡓ㟁Ꮚ㑄⛣࢚ࢿࣝࢠ࣮࡟ᑐࡍࡿᑐ⿵ṇ[7]ࢆ┤ᡖ࡟ᑟධࡍࡿࡇ࡜࡛ࠊィ⟬᫬㛫ࡢ▷⦰࡜ඹ࡟࢚ࢿࣝࢠ࣮࡟ᑐࡍࡿከయຠᯝࡢᑟධࢆヨࡳࡓ(1, 2 ᘧ; w ࡣບ㉳࢚ࢿࣝࢠ࣮ࠊC ࡣ୰ᚰ㡿ᇦࡢࣇࣛࢢ࣓ࣥࢺࢆ⾲ࢃࡍ)ࠋ࡞࠾ࠊᐇ⿦ࡣ⚾ࡓࡕࡀ⮬୺㛤Ⓨࡋ࡚࠸ࡿ ABINIT-MPX ࡟ᑐࡋ࡚⾜ࡗࡓࠋͳǦ   ‫ ׷‬ɘ ൌ ɘ ሺͳሻ‫ ڦ‬CIS(D)ἲ࠿ࡽࡢᨵⰋ

ʹǦ   ‫ ׷‬ɘ ൌ ɘ ൅ ෍ሺɘ െ ɘ ሻሺʹሻ്୍᪉ࠊ⚾㐩ࡣ୍㟁Ꮚບ㉳㓄⨨㛫┦஫స⏝ࢆᇶᮏ࡜ࡋ࡚㧗ḟ┦㛵ࢆᑟධࡍࡿບ㉳≧ែ⌮ㄽࡢᥦ᱌ࢆ⾜ࡗ࡚ࡁࡓࠋCIS(D)࡟ࡼࡿ CIS ࡢ㟁Ꮚ㑄⛣࢚ࢿࣝࢠ࣮࡟ᑐࡍࡿ⿵ṇ್wCIS(D)ࡣࠊᇶᗏ≧ែࡢ MP2ࡢᕪศ┦㛵࢚ࢿࣝࢠ࣮㡯(T2U1 㡯)࡜㌶㐨⦆࿴㡯(U2 㡯)ࡢ࿴࡛᭩ࡅࡿࡀࠊT2U1 㡯ࡢ MP2 ᣺ᖜ࡟ᑐࡋ࡚෌つ᱁໬ࢆ⾜ࡗࡓ PR-CIS(D) [8] ࡸࠊ᭦࡟ U2 㡯ࡢᦤື⾲ᘧࡢ࢚ࢿࣝࢠ࣮ศẕ୰࡟࠶ࡿ༨᭷㌶㐨࢚ ࢿ ࣝ ࢠ ࣮ ࡟ ᑐ ࡋ ࡚ Green 㛵 ᩘ ࡟ ࡼ ࡿ ஧ ḟ ࡢ ⮬ ᕫ ࢚ ࢿ ࣝ ࢠ ࣮ ࡢ ⧞ ࡾ ㎸ ࡳ ⿵ ṇ ࢆ ⾜ ࡗ ࡓPR-CIS(D)ss(2) (-ss(2); 2nd order Self energy Shift, [9])࡞࡝ࡢ㏆ఝᡭἲ࡟ࡘ࠸࡚ࡣ᪤࡟ሗ࿌῭ࡳ࡛࠶ࡿࠋ᭱㏆ࠊࡇࡢ⮬ᕫ࢚ࢿࣝࢠ࣮ࢩࣇࢺ್ࡢ⧞ࡾ㎸ࡳࢆ T2U1 㡯࡟ࡶᣑᙇࡋࡓࡀ[10]ࠊᮏ◊✲࡛ࡣࡇࢀࢆ
FMO ࡢᩥ⬦࡟ἢ࠺ᵝ࡟ ABINIT-MPX ࡟ᐇ⿦ࡋࡓࠋ‫ࣥࢩࢺࢩ ڦ‬Ỉ࿴จ㞟⣔ ࡣࡌࡵ࡟ࢸࢫࢺィ⟬࡜ࡋ࡚ࠊFMO-MD (ab initio Molecular Dynamics based on FMO) ࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡗ࡚ᚓࡽࢀࡓࢩࢺࢩࣥỈ࿴จ㞟⣔ࡢᵓ㐀(Figure 1)࡟ᑐࡋࠊບ㉳࢚ࢿࣝࢠ࣮ࡢᑐ⿵ṇゎᯒࢆࡋ࡚ࠊ࢚ࢿࣝࢠ್࣮ࡸィ⟬ࢥࢫࢺࡢホ౯ࢆࡋࡓ[11,12]ࠋ࡞࠾ࠊMD ィ⟬ࡣࠊ࢚ࢿࣝࢠ࣮ᚤศ
㔞࡟㛵ࡋ࡚ࡣ FMO-HF/6-31G ࡛ࣞ࣋ࣝ ABINIT-MPX ࡟ࡼࡗ࡚⟬ฟࡋࠊศᏊືຊᏛィ⟬ࣉࣟࢢ࣒ࣛPEACH ࡜㐃ᦠࡉࡏᐇ⾜ࡋࡓࠋFigure 2 ࡣ࠶ࡿࢧࣥࣉࣜࣥࢢⅬ࡟࠾ࡅࡿࠊFMO2-PR-CIS(Ds)/6-31G*
ィ⟬(PR-CIS(Ds); CIS(D)ࡢ࢚ࢿࣝࢠ࣮⿵ṇᘧ୰࡟ MP2 ࡢవ๫⦆࿴࢚ࢿࣝࢠ࣮㡯(T1U1 㡯)ࢆ᥇⏝ࡋࠊࡇࡢ㒊ศ࡜ T2U1 㡯ࡢ MP2 ᣺ᖜ࡟ᑐࡋ࡚෌つ᱁໬ࡋࡓᡭἲ)ࢆ⾜ࡗࡓ㝿ࡢwCI-wC ࡢᐤ୚ࢆ⾲ࡋ࡚࠸ࡿࠋ୰ᚰࣇࣛࢢ࣓ࣥࢺࡣࢩࢺࢩࣥศᏊࡢࡳ࡛ࠊࢢࣛࣇࡢᶓ㍈ࡣྛࣇࣛࢢ࣓ࣥࢺ࡟ᒓࡍࡿ᭱▷ཎᏊ㛫㊥㞳࡛࠶ࡿࠋࡇࢀ࡟ࡼࡿ࡜ࠊ7.5ύ⛬ᗘ(ỈศᏊࡢಶᩘࡣ 30 ⛬ᗘ)࡛཰᮰ഴྥ࡜࡞ࡗ࡚࠾ࡾࠊ཰᮰
ࡋࡓບ㉳࢚ࢿࣝࢠ್࣮࡜ MFMO ࡟ࡼࡿィ⟬್࡜ࡢ㛫ࡢㄗᕪࡣ໬Ꮫⓗ⢭ᗘࡢ⠊ᅖෆ࡟࠾ࡉࡲࡗࡓࠋ

wCI - wC

(eV)
0.04
0.02

(ύ)
0.00
3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

-0.02
-0.04
-0.06
-0.08

Figure 1 Ỉ࿴ࢩࢺࢩࣥศᏊ

Figure 2 wCI-wC ࡢᐤ୚‫ ڦ‬㉥Ⰽ⺯ගࢱࣥࣃࢡ㉁ ̿ DsRed ⥆࠸࡚ࠊ⌈⍚⏤᮶ࡢ㉥Ⰽ⺯ගࢱࣥࣃࢡ㉁࡛࠶ࡿ DsRed࡟ᑐࡋ࡚ࡶ㟁Ꮚ㑄⛣࢚ࢿࣝࢠ࣮ࡢᑐ⿵ṇࢆ⾜ࡗࡓ(Figure 3)ࠋࡇࡢ⣔ࡣ࢔࣑ࣀ㓟 225 ṧᇶ࠿ࡽᵓᡂࡉࢀࠊbᶡᵓ㐀࡟ໟࡲࢀࡓⰍ⣲㒊ศࡣ Gln66-Tyr67-Gly68 ࡢ 3 ṧᇶ ࠿ ࡽ ᡂ ࡗ ࡚ ࠾ ࡾ ࠊ ࡍ ࡛ ࡟ MFMO ࡟ ᇶ ࡙ ࠸ ࡓ
FMO-HF:PR-CIS(Ds)/6-31G*࡛ࣞ࣋ࣝࡣホ౯῭ࡳ࡛࠶ࡿ
[13,14]ࠋᑐ⿵ṇ࡟ᇶ࡙࠸ࡓ FMO2-PR-CIS(Ds)/6-31G*ィ⟬࡟ࡼࡾບ㉳࢚ࢿࣝࢠ࣮ࢆぢ✚ࡶࡗࡓ⤖ᯝࠊᐇ㦂್ࡸከᒙ
FMO ࡟ࡼࡿ⤖ᯝ࡜ࡼࡃᑐᛂࡋࡓࡢ࡜ྠ᫬࡟ࠊ₇⟬᫬㛫ࡢ▷⦰࡟ᡂຌࡋࡓࠋ

Figure 3 DsRed ࡢbᶡᵓ㐀‫ࡵ࡜ࡲ ڦ‬
௨ୖࢆ㋃ࡲ࠼ᑐ⿵ṇ࡟㛵ࡋ࡚ࡣ PR-CIS(D)ss(2)ィ⟬ࡸ୕య⿵ṇࡢᑟධࠊࡑࡋ࡚୰ᚰࣇࣛࢢ࣓ࣥࢺࡢᣑ኱࡞࡝ࢆ᥇⏝ࡍࡿࡇ࡜࡛ࠊLayer 2 㡿ᇦࡢ㟢ࢃ࡞ᣑ኱࡞ࡋ࡟ᐇ㦂್࡜ࡢᑐᛂࡸィ⟬᫬㛫ࡢ኱ᖜ࡞▷⦰ࡀྍ⬟࡟࡞ࡿ࡜⪃࠼ࡽࢀࡿࡢ࡛ࠊ⌧ᅾヲ⣽࡞ゎᯒࢆ㐍ࡵ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ‫ ڦ‬ㅰ㎡ᮏ◊✲ࡣ JST-CRESTࠕࣇࣛࢢ࣓ࣥࢺศᏊ㌶㐨ἲ࡟ࡼࡿ⏕యศᏊィ⟬ࢩࢫࢸ࣒ࡢ㛤Ⓨࠖ࡜⛉◊㈝࣭
≉ᐃ㡿ᇦࠕᐇᅾ⣔ࡢศᏊ⌮ㄽࠖࠊࡑࡋ࡚❧ᩍ኱Ꮫࠕᮍ᮶ศᏊ◊✲ࠖࡢࣉࣟࢪ࢙ࢡࢺࠊཬࡧࠕ❧ᩍSFRࠖ࠿ࡽࡢᨭ᥼ࢆཷࡅ࡚࠸ࡿࠋ‫ ڦ‬ཧ⪃ᩥ⊩[1] K. Kitaura et al., Chem. Phys. Lett., 313 (1999) 701. [2] D. G. Fedorov et al., J. Phys. Chem. A, 111(2007) 6904. [3] “The Fragment Molecular Orbital Method”, CRC press (2009). [4] M. Head-Gordon et al.,Chem. Phys. Lett., 219 (1994) 21. [5] Y. Mochizuki et al., Theor. Chem. Acc., 117 (2007) 541. [6] D. G.
Fedorov et al., J. Phys. Chem. A, 109 (2005) 2638. [7] S. Hirata et al., Mole. Phys., 103 (2005) 2255. [8] Y.
Mochizuki and K. Tanaka, Chem. Phys. Lett., 443 (2007) 389. [9] Y. Mochizuki, Chem. Phys. Lett., 453(2008) 109. [10] Y. Mochizuki, Chem. Phys. Lett., 472 (2009) 143. [11] Y. Komeiji et al., Chem. Phys. Lett.,
372 (2003) 342. [12] Y. Komeiji et al., J. Mole. Struct., 898 (2009) 2. [13] Y. Mochizuki et al., Chem. Phys.
Lett., 433 (2007) 360. [14] N. Taguchi et al., J. Phys. Chem. B, 113 (2009) 1153.