2P121
A LC-DFT+vdW Study of the Diels-Alder Reactions and the Global Hardness
Response Analysis(University of Yamanashi, Japan) ○Raman K. Singh, Takao Tsuneda[Introduction] There have been considerable attentions drawn to the Diels-Alder reactions
especially in chemical reactivity calculations. The development of computational methods for the
exploration of reaction energetics, barrier heights, and frontier orbital energies are facilitated by
the benchmark results. Over the past two decades, density functional theory (DFT) has beenfrequently used to investigate Diels-Alder reactions and previous reports indicate that many
conventional DFTs show serious errors to give quantitative thermodynamic properties without
clarifying the underlying reasons. Besides this, these reactions have often been discussed on thefrontier orbital theory and the corresponding frontier orbital energies were used for explaining
their chemical reactivities and kinetics but it is difficult for most quantum chemistry methods toobtain correct orbital energies. In this study, we apply various types of long-range corrected (LC)and other major functionals to the Diels-Alder reactions (Figure 1) to ascertain the reasons forpoor enthalpies and then investigate the accuracy in the barrier height results. Furthermore, themaximum hardness rule on the reaction pathways was explored based on the orbital energies.1

Figure 1: Diels-Alder reactions involving ethylene, acetylene, maleic anhydride and maleimide
as dienophiles.
[Computational Details] We carried out calculations employing various types of DFT
functionals: LC, pure, hybrid and semiempirical functionals. The LC functionals include LCBOP, LCgau-BOP, LC-BLYP, CAM-B3LYP, LC-ωPBE and ωB97X. The LC-BOP and LCBLYP functionals were combined with local response dispersion (LRD) to evaluate thedispersion correlation effects on the Diels-Alder reactions. For comparison, pure BOP, hybrid
1

B3LYP, semiempirical dispersion-corrected B97-D, semiempirical hybrid meta BMK and M062x functionals were considered. The geometries have been optimized by each functional using
the cc-pVTZ basis set. All the optimized structures have positive and real frequency. The
Gaussian 09 suite of the program has been used to perform all the computations.
[Results and Discussion] Figure 2 clearly shows that the long-range correction significantly
improves the reaction enthalpies and the LRD correction has no effect on it. However, dispersion
correlation correction is crucial to give accurate barrier heights as can be seen in Fig. 3. Finally
we calculated the global hardness responses (GHRs), which are half of the HOMO-LUMO gaps,
along the intrinsic reaction coordinates (IRCs). Figure 4 depicts the calculated GHRs and thecorresponding total energies along the IRCs, where the GHRs and total energies are set to be zeroat the reactants. These figures show that LC-BOP GHR results first decrease slightly when thereaction proceeds from the reactants to the transition state and after that increase drasticallytoward the product, while B3LYP GHR curves increases monotonically right from the reactants
to the product via transition state. The former results suggest that the minimum GHR in thereaction pathway of such reactions is obtained either at the transition state or when the reacting
species are about to reach the transition state. We also get GHR curves similar to the B3LYP one
by the functionals examined here except for LC-BOP, LCgau-BOP and LC-BLYP. These
outcomes demonstrate that LC-DFT results satisfy the maximum hardness rule for overall
reaction paths while conventional functionals violate this rule on the reaction pathways.

Figure 2: Errors in the computed enthalpies (in kcal mol-1) with respect to CBS-QB3 results.

Figure 3: Errors in calculated reaction
Figure 4: GHRs, η and total energies E along thebarrier heights with the experimental
IRC.
results.
[1] Singh, R.K., Tsuneda, T. J. Comput. Chem. 2013, 34, 379–386.
2

2P122ᐦᗘỗ㛵ᩘἲ࡟ࡼࡿ Sc2C2@C82 ࡢ㟁Ꮚ≧ែィ⟬㸦ឡ፾኱Ꮫ㸧‫ۑ‬Ύ㔝཭┿ࠊ᪥▼Ꮥᏹࠊඵᮌ๰ࠊᐑᓮ㝯ᩥࠊ᪥㔝↷⣧The density functional theory calculations of Sc2C2@C82(Ehime Univ. ) ‫ۑ‬Y. Seino, T. Hinoishi, H. Yagi, T. Miyazaki, S. Hino࠙ᗎࠚ㔠ᒓෆໟࣇ࣮࡛ࣛࣞࣥࡣࠊ㔠ᒓཎᏊ࠿ࡽࣇ࣮ࣛࣞࣥࢣ࣮ࢪ࡬ࡢ
㟁Ꮚ⛣ືࡀ࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࡢ㟁Ꮚ⛣ືࢆไᚚࡍࡿࡇ࡜ࡀ

C2 ᅇ㌿㍈࡛ࡁࢀࡤࠊࣇ࣮ࣛࣞࣥ㢮ࡢศᏊ࣓࣮ࣔࣜࡸศᏊ㟁Ꮚࢹࣂ࢖ࢫ࡞࡝࡬ࡢ
ᛂ⏝ࡢྍ⬟ᛶࡀ㛤ࡅࡿࠋ㔠ᒓཎᏊ࠿ࡽࣇ࣮ࣛࣞࣥࢣ࣮ࢪ࡬ࡢ㟁Ꮚ⛣ືࢆ⌮ゎࡍࡿ࠺࠼࡛ࠊෆໟࣇ࣮ࣛࣞࣥࡢ㟁Ꮚ≧ែࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࡣ㔜せ࡛࠶ࡿࠋࡇࡢほⅬ࠿ࡽࠊᡃࠎࡣࣇ࣮ࣛࣞࣥ㢮ࡢ⣸እග㟁Ꮚࢫ࣌ࢡࢺࣝ㸦UPS㸧 ᐃ࡜⌮ㄽィ⟬ࢆ⾜ࡗ࡚ࡁࡓࠋࡇࢀࡲ࡛࡟ࠊ ᐃࡉࢀࡓUPS ࡜⌮ㄽィ⟬࡛ᚓࡽࢀࡓࢩ࣑࣮ࣗࣞࢩࣙࣥࢫ࣌ࢡࢺࣝ㸦SS㸧ࢆẚ

Fig. 1 Geometry of Lu2C2@C82㍑ࡍࡿࡇ࡜࡛ࠊࣇ࣮ࣛࣞࣥࡢᗄఱᏛⓗᵓ㐀ࡢỴᐃࡸࠊෆໟ✀࠿ࡽࣇ࣮ࣛࣞࣥࢣ࣮ࢪ࡬ࡢ㟁Ꮚ⛣ື㔞ࡢぢ✚ࡶࡾࡀ࡞ࡉࢀ࡚ࡁࡓࠋ
C2v ᑐ⛠ࡢ Lu2C2@C82 ࡢ UPS ࡣ⌮ㄽィ⟬࡟ࡼࡗ࡚ᚓࡽ
ࢀࡓ᭱㐺໬ᵓ㐀㸦Fig. 1㸧࡟ᇶ࡙࠸ࡓ SS ࡟ࡼࡗ࡚ࡼࡃ෌
⌧ࡉࢀࡿ㸦Fig. 2㸧ࡢ࡛ࠊLu2C2@C82 ࡣ Fig.1 ࡢᵓ㐀ࢆ࡜ࡿࡶࡢ࡜᥎ᐃࡉࢀࡓࠋࡲࡓࠊෆໟཎᏊᅋࢆྵࡴࢥࢫࢺࡢ
㧗࠸ィ⟬ࢆᐇ⾜ࡋ࡞ࡃ࡚ࡶࠊ✵ࡢࣇ࣮ࣛࣞࣥࣥࢣ࣮ࢪୖ
࡟㟁Ⲵࢆ௜ຍࡋ࡚ᚓࡽࢀࡓ SS ࡣᐇࡢ UPS ࢆ࠶ࡿ⛬ᗘ෌⌧ࡍࡿࡢ࡛ࠊෆໟཎᏊᅋ࠿ࡽࢣ࣮ࢪ࡬ࡢ㟁Ꮚ⛣ື㔞ࢆぢ✚ࡶࡿࡇ࡜ࡶ࡛ࡁࡿ㸦Fig.2㸧ࠋࡉࡽ࡟ࠊY2C2@C82 ࡜
Lu2C2@C82 ࡢ UPS ࡀఝ࡚࠸ࡿࡼ࠺࡟ࠊᵓ㐀ࡸ㟁Ꮚ⛣ື㔞ࡀྠࡌ࡛࠶ࢀࡤ㢮ఝࡢ UPS㸦㟁Ꮚ≧ែ㸧ࢆ୚࠼ࡿࡇ࡜ࡶ
᫂ࡽ࠿࡜࡞ࡗ࡚ࡁࡓࠋ
௒ᅇྲྀࡾୖࡆࡿ C2v-Sc2C2@C82 ࡢ㟁Ꮚ≧ែࡶࠊY2C2@C82
ࡸ Lu2C2@C82 ࡜ྠࡌ࡛࠶ࢁ࠺࡜ண᝿ࡉࢀࡓࡀࠊUPS ࡣᚤ

Fig. 2 The UPS and the SS of C2v-M2C2@C82(M=Sc, Y, Lu), C82-4, C82-6.

ጁ࡟␗࡞ࡗ࡚࠸ࡿ㸦Fig.2㸧
ࠋC3v-Sc2C2@C82 ࡢࢡࣛࢫࢱ࣮ࡣᅇ㌿ࡍࡿ࡜ࡢሗ࿌ࡶ࠶ࡿ[1]ࡢ࡛ࠊࡇࡢ㐪࠸ࡢ⌮⏤ࡢ୍ࡘ࡟ෆໟ Sc2C2 ཎᏊᅋࡢෆ㒊ᅇ㌿ࡀ⪃࠼ࡽࢀࡓࠋࡑࡇ࡛ࠊᮏሗ࿌࡛ࡣࠊC2v-Sc2C2@C82 ࡢ DFT ィ⟬ࢆ⾜࠸㺂UPS ࡜ࡢẚ㍑ࢆ㏻ࡋ࡚ࠊෆ㒊ᅇ㌿ࡢ᭷↓ࡸ Sc2C2 ࠿ࡽࢣ࣮ࢪ࡬ࡢ㟁Ꮚ⛣ື㔞࡟ࡘ࠸᳨࡚ウࡋࡓࡢ࡛ሗ࿌ࡍࡿࠋ

࠙ィ⟬᪉ἲࠚGaussian09 ࢆ⏝࠸ࠊB3LYP ࡟ᇶ࡙ࡃ DFT ィ⟬ࢆ⾜ࡗࡓࠋࡲࡎࠊࢡࣛࢫࢱ࣮Sc2C2 ࢆ
C2v-C82 ࢣ࣮ࢪ(No.9)࡟ෆໟࡉࡏࠊSc2C2@C82 ࡢᵓ㐀᭱㐺໬ࢆ⾜ࡗࡓࠋḟ࡟ᚓࡽࢀࡓ᭱㐺໬ᵓ㐀࡟ᑐࡋ࡚ࠊࢩࣥࢢ࣏ࣝ࢖ࣥࢺィ⟬ࢆ⾜࠺ࡇ࡜࡛ࠊKohn-Sham ㌶㐨࢚ࢿࣝࢠ࣮㸦KS㸧ࢆᚓࡓࠋࡑࡋ
࡚ Gaussian 㛵ᩘ࡟ࡼࡾ KS ࡟ᖜࢆࡶࡓࡏࠊSS ࢆồࡵࡓࠋᵓ㐀᭱㐺໬࠾ࡼࡧ⏕ᡂ࢚ࢿࣝࢠ࣮࡟࠾
࠸࡚ࡣᇶᗏ㛵ᩘ࡜ࡋ࡚ 6-31G(d)ࢆ⏝࠸ࠊ࢚ࢿࣝࢠ࣮ࢲ࢖࢔ࢢ࣒ࣛ࠾ࡼࡧ NPA ࡟㛵ࡋ࡚ࠊSc ཎᏊ࡟ࡣ TZPࠊC ཎᏊ࡟ࡣ DZP ࢆ⏝࠸ࡓ[2]ࠋ
࠙⤖ᯝ࡜⪃ᐹࠚDFT ィ⟬࡟ࡼࡗ࡚ᚓࡽࢀࡓ᭱㐺໬ᵓ㐀ࡣ 4 ✀㢮㸦Isomers 1-4㸧࡛࠶ࡗࡓ(Fig. 3)ࠋ
ࡇࢀࡽࡢᵓ㐀ࡢ࠺ࡕࠊIsomers 1-3 ࡣࢣ࣮ࢪ඲యࢆ C2v ᑐ⛠࡟ᣊ᮰ࡋᚓࡽࢀࡓࡶࡢ࡛࠶ࡾࠊIsomer
Isomer 1 ࢆᇶ‽࡜ࡋࡓ┦ᑐ࢚ࢿࣝࢠ࣮ࡣࠊ
Isomers
4 ࡣᑐ⛠ᛶ C2 ࡟ᣊ᮰ࡋ࡚ᚓࡽࢀࡓࡶࡢ࡛࠶ࡿࠋ
2-4 ࡢ㡰࡟+3.26kcal/molࠊ+12.6 kcal/molࠊ-3.37 kcal/mol ࡜࡞ࡗࡓࠋFig. 3 ࡟ࠊSc2C2@C82 ࡢ
UPS ࠾ࡼࡧࠊIsomers 1-4 ࡢ SS ࢆ♧ࡍࠋUPS ࢆࡶࡗ࡜ࡶࡼࡃ෌⌧ࡋ࡚࠸ࡿ SS ࡣ Isomer 1 ࡢࡶࡢ࡛ࡣ࠶ࡿࡀࠊࡑࢀ࡛ࡶࠊ௚ࡢෆໟࣇ࣮࡛ࣛࣞࣥࡢ⤖ᯝ࡜ẚ࡭ࡿ࡜ࠊ࠸ࡎࢀࡢ SS ࡶ UPS ࡢ෌⌧ᛶࡀᝏ࠸㸦Fig.3㸧ࠋࡑࡇ࡛ࠊෆໟࢡࣛࢫࢱ࣮ࡀࢣ࣮ࢪෆ࡛ᅇ㌿ࡋ࡚࠸ࡿྍ⬟ᛶࢆ⪃៖ࡋ࡚ࠊUPSࢆࡼࡃ෌⌧࡛ࡁࡿࡼ࠺࡟ࠊIsomers 1-4 ࡢ SS ࡟㔜⋡ࢆ➼౯࡛࠿ࡅ࡚㔜ࡡྜࢃࡏࡓ࡜ࡇࢁࠊUPSࢆࡼࡃ෌⌧ࡍࡿ SS ࡀᚓࡽࢀࡓ㸦Fig.4㸧
ࠋࡇࡢࡇ࡜ࡣࠊC2v-Sc2C2@C82 ࡛ࡶࠊෆໟ Sc2C2 ࡀᅇ㌿ࡋ࡚࠸ࡿྍ⬟ᛶࢆ♧၀ࡋ࡚࠸ࡿࠋࡋ࠿ࡋࠊIsomer 3 ࡢ⏕ᡂ࢚ࢿࣝࢠ࣮ࡣ㧗࠸ࡓࡵࠊ௚ࡢᵓ㐀࡜ྠࡌ㔜ࡳ࡛ྵࡲࢀ࡚࠸ࡿ࡜ࡣ⪃࠼࡟ࡃࡃࠊࡉࡽ࡟᳨ウࡍࡿᚲせࡀ࠶ࡿࠋࡲࡓࠊࡇࢀࡽ㸲ࡘࡢ Isomerࡢ NBO ゎᯒ࡜ศᏊ㌶㐨ࡢẚ㍑࠿ࡽࠊSc ࡣ+3 ౯࡛࠶ࡾ Sc2 ࠿ࡽ C2 ࡬ 2 㟁ᏊࠊSc2C2 ࠿ࡽ C82 ࢣ࣮
ࢪ࡬ 4 㟁Ꮚࡀ⛣ືࡋ࡚࠸ࡿ⤖ᯝ࡜࡞ࡗࡓࠋ
ࡉࡽ࡟ࡣࠊSc2C2 ࡀࢣ࣮ࢪෆ࡛ᅇ㌿ࡋ࡚࠸ࡿ࡜ࡍࡿ࡜ࠊSc2C2 ࡀࡑࢀࡒࢀࡢ Isomer ᵓ㐀࠿ࡽ௚ࡢᵓ㐀࡬࡜ኚ໬ࡍࡿ࢚ࢿࣝࢠ࣮㞀ቨࡢ኱ࡁࡉࡢぢ✚ࡶࡾࡀᚲせ࡜࡞ࡿࡀࠊࡇࡢⅬࡣ⌧ᅾ᳨ウ୰࡛࠶ࡿࠋ

Isomer 1㻌

Isomer 2㻌

Isomer 3㻌

Isomer 4㻌
Fig. 3 The UPS of Sc2C2@C82
and the SS of Isomers 1-4.㻌

Fig. 4 The UPS of Sc2C2@C82 and the SS
obtained from a linear combination of the
SS of Isomers 1-4.㻌

[1] Ramon Valencia et al. / J. Phys. Chem. A 2008, 112, 4550-4555[2] http://setani.sci.hokudai.ac.jp/sapporo/2P123㔞Ꮚ໬Ꮫ࡟ᇶ࡙ࡃࢩࣜࢭࣥࡢከᒙ㛫࡟࠾ࡅࡿ┦஫స⏝ࡢ◊✲㸦ᶓ὾ᅜ኱㝔࣭ᕤ㸧‫ۑ‬ὸ㔝ᝆ㸪బ⸨ᾈኴ
A quantum chemical study on interlayer interaction of silicene(Graduate school of Yokohama National University) ‫ۑ‬Asano Haruka, Sato Kota
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2.᪉ἲᮏ◊✲䛷䛿䚸ィ⟬䝥䝻䜾䝷䝮䛸䛧䛶Gaussian09䜢౑⏝䛧䚸㏆ఝἲ䛻䛿ศᏊ㛫ຊ䛾ᙳ㡪䜢⪃៖䛷䛝䜛ᐦᗘỗ㛵ᩘἲ䛾mPW1PW91ἲ[2]䚸ᇶᗏ㛵ᩘ䛻䛿6-31G(d)䜢⏝䛔䛶ィ⟬䜢⾜䛳䛯䚹䝅䝸䝉䞁䛾ᵓ㐀䝰䝕䝹䛸䛧䛶䚸ᖹ㠃ᵓ㐀䛸䝆䜾䝄䜾ᵓ㐀䛾Si䛾䝁䝻䝛䞁䝃䜲䝈(Si24H12)䜢⏝䛔䛯䚹䛣䛾ィ⟬䛷ᑟฟ䛥䜜䛯Ᏻᐃᵓ㐀䜢䝧䞊䝇䛸䛧䛶䚸2ᒙ䛾ィ⟬䜢⾜䛔䚸ᒙ㛫㊥㞳䛜2.0[䊅]䚸4.0[䊅]䚸
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1ᒙ䛻䛚䛡䜛䝅䝸䝉䞁䛾Ᏻᐃᵓ㐀䜢ᅗ1䛻♧䛧䛯䚹ึᮇᵓ㐀䛜ᖹ㠃ᵓ㐀䛰䛳䛯䝰䝕䝹䛿䚸᣺ືゎᯒ䛾⤖ᯝ䚸⹫䛾᣺ືᩘ䜢䜒䛴䛯䜑䛻Ᏻᐃᵓ㐀䛷䛿䛺䛔䛣䛸䛜ศ䛛䛳䛯䚹ึᮇᵓ㐀䛜䝆䜾䝄䜾ᵓ㐀䛰䛳䛯䝰䝕䝹䛿᣺ືゎᯒ䛾⤖ᯝ䚸ᐇᩘ䛾᣺ືᩘ䛾䜏䜢䜒䛴䛣䛸䛛䜙䚸Ᏻᐃᵓ㐀䛰䛸ุ᩿䛧䛯䚹Si䛿sp3ᛶ䛜ᙉ䛔䛯䜑䚸䛣䛾䜘䛖䛺䝆䜾䝄䜾䛺ᵓ㐀䛜Ᏻᐃᵓ㐀䛸䛺䛳䛯䛸⪃䛘䜙䜜䜛䚹Si-Si⤖ྜ㛗
䛿2.25[䊅]䚸⤖ྜゅ䛿117.2[㼻]䚸஧㠃ゅ䛿33.9[㼻]䚸HOMO-LUMOᕪ䛿2.11[eV]䛰䛳䛯䚹䛣䛾ᵓ㐀䜢䝧䞊䝇䛻2ᒙ䛾ィ⟬䜢⾜䛳䛯䚹
2ᒙ䛻䛚䛡䜛Ᏻᐃᵓ㐀䛾ィ⟬䛾⤖ᯝ䚸᭱䜒Ᏻᐃ䛷䛒䜛ᵓ㐀䛿䚸ᒙ䛜᏶඲䛻㔜䛺䛳䛶䛔䜛ึᮇᵓ㐀䛷䚸ᒙ㛫㊥㞳䛜4.0[䊅]䛷ィ⟬䜢䛧䛯䜒䛾䛷䛒䜚䚸ᅗ2䛻♧䛩䜘䛖䛺ᵓ㐀䛷཰᮰䛧䛯䚹࿘㎶㒊ศ䛿ᒙ㛫䛷⤖ྜ䜢䛧䛶䛔䜛䛜䚸୰ᚰ㒊ศ䛿ᒙ㛫㊥㞳䛜኱䛝䛟㛤䛔䛶䛧䜎䛳䛶䛔䛶ᒙ㛫䛷⤖ྜ䛧䛶䛔䛺䛔䚹୰ᚰ㒊ศ䛾Si-Si⤖ྜ㛗䛿2.26[䊅]䚸⤖ྜゅ䛿116.2[㼻]䚸஧㠃ゅ䛿38.3[㼻]䚸ᒙ㛫㊥㞳䛿
4.48[䊅]䛷䛒䜚䚸࿘㎶㒊ศ䛾Si-Si⤖ྜ㛗䛿2.38[䊅]䚸⤖ྜゅ䛿113.9[㼻]䚸஧㠃ゅ䛿0.0[㼻]䚸ᒙ㛫㊥㞳䛿2.39[䊅]䛰䛳䛯䚹ᅗ2䜢ጞ䜑䛸䛧䛶䚸䛹䛾䜘䛖䛺ᒙ㛫㊥㞳䛷ィ⟬䜢䛧䛶䜒䝅䝸䝉䞁䛿ᒙ㛫䛷⤖ྜ䜢䛧䛶䛧䜎䛳䛯䛯䜑䚸2ᒙ䛾≧ែ䜢ಖ䛳䛯䜎䜎Ᏻᐃ໬䛧䛯ᵓ㐀䛿1䛴䜒䛺䛛䛳䛯䚹ึᮇᒙ㛫㊥㞳
䛜2.0[䊅]䛷ᒙ䛜㔜䛺䛳䛶䛔䜛ᵓ㐀䛾ィ⟬⤖ᯝ䛿䚸ᒙ㛫䛷Si-Si䛜඲䛶⤖ྜ䛧䛶䛚䜚䚸sp3ᛶ䛜ᙉ䛔䛯䜑䚸HOMO-LUMOᕪ䛜ᑠ䛥䛟䛺䛳䛶䛔䜛䛸⪃䛘䜙䜜䜛䚹ᅗ1. 1ᒙ䛻䛚䛡䜛䝅䝸䝉䞁䛾Ᏻᐃᵓ㐀㻌㻌㻌㻌㻌㻌
㻌
ᅗ2. 2ᒙ䛻䛚䛡䜛䝅䝸䝉䞁䛾Ᏻᐃᵓ㐀㻌 ᅗ 3 䛸ᅗ 4 䛻ᒙ䛜᏶඲䛻㔜䛺䛳䛶䛔䛶ึᮇᒙ㛫㊥㞳䛜 4.0[䊅]䛛䜙ฟⓎ䛧䛯 2 ᒙ䛻䛚䛡䜛䝅䝸䝉䞁䛾Ᏻᐃᵓ㐀䛾 HOMO 䛸 LUMO 䜢♧䛩䚹HOMO-LUMO 䛿୰ኸ௜㏆䛻ᒁᅾ䛧䛶䛔䜛䛯䜑䚸
HOMO-LUMO ᕪ䛜኱䛝䛟䛺䛳䛶䛔䜛䛾䛰䛸⪃䛘䜙䜜䜛䚹ᅗ3. 2ᒙ䛻䛚䛡䜛䝅䝸䝉䞁䛾Ᏻᐃᵓ㐀䛾HOMO㻌 ᅗ4. 2ᒙ䛻䛚䛡䜛䝅䝸䝉䞁䛾Ᏻᐃᵓ㐀䛾LUMO
ẚ㍑ᑐ㇟䛾䜾䝷䝣䜵䞁䛾 2 ᒙ䛾ィ⟬⤖ᯝ䛿䚸ึᮇᵓ㐀䛾≧ែ䛻㛵ಀ䛺䛟䚸ᅗ 3 䛻♧䛩䜘䛖䛺ᵓ㐀䛷཰᮰䛧䛯䚹C-C ⤖ྜ㛗䛿 1.40[䊅]䚸
⤖ྜゅ䛿 120.0[㼻]䚸஧㠃ゅ䛿 0.0[㼻]䚸ᒙ㛫㊥㞳䛿 3.66[䊅]䛰䛳䛯䚹䜾䝷䝣䜵䞁䛿 sp2 ㌶㐨䛻䜘䜛⤖ྜ䛷䛒䜛䛯䜑䚸ᖹ㠃ᵓ㐀䛜Ᏻᐃ䛺ᵓ㐀䛸䛺䛳䛯䚹ᒙ㛫䛷⤖ྜ䛿䛧䛶䛚䜙䛪䚸䜶䝛䝹䜼䞊䛿ศᏊ㛫ຊ䛻䜘
䛳䛶䂴E=-0.019[eV]Ᏻᐃ໬䛧䛶䛚䜚䚸䜾䝷䝣䜵䞁䛾┦஫స⏝䛻䜘䜛Ᏻᐃ໬䛿䝅䝸䝉䞁䜘䜚䛿䜛䛛䛻ᑠ䛥䛔䚹
ᅗ 5. 2 ᒙ䛻䛚䛡䜛䜾䝷䝣䜵䞁䛾Ᏻᐃᵓ㐀
⾲1. ᒙ䛜᏶඲䛻㔜䛺䛳䛶䛔䜛ᵓ㐀䛛䜙䛾ᵓ㐀᭱㐺໬ᚋ䛾㻌㻌 㻌 HOMO-LUMOᕪ䛸䚸ᒙ㛫┦஫స⏝䛻䜘䜛Ᏻᐃ໬ึᮇᒙ㛫㊥㞳
Ᏻᐃ໬
HOMO-LUMOᕪ
[䊅]
[eV]
[eV]
2.0
-17.691.25
4.0-18.502.59
6.0-11.971.27
⾲2㻚㻌 ᒙ䛜䛪䜜䛶䛔䜛ᵓ㐀䛛䜙䛾ᵓ㐀᭱㐺໬ᚋ䛾㻌
HOMO-LUMOᕪ䛸䚸ᒙ㛫┦஫స⏝䛻䜘䜛Ᏻᐃ໬ึᮇᒙ㛫㊥㞳
Ᏻᐃ໬
HOMO-LUMOᕪ
[䊅]
[eV]
[eV]
2.0
-16.87
1.96
4.0-16.601.35
6.0-13.301.14䝅䝸䝉䞁䛜1ᒙ䛾䛸䛝䛿ᅗ1䛻♧䛩䜘䛖䛺䝆䜾䝄䜾䛺ᙧ䛜Ᏻᐃᵓ㐀䛸䛺䛳䛯䚹2012ᖺ䛾䝅䝸䝉䞁⏕ᡂ䛾ሗ࿌䛻䛚䛔䛶䜒䚸䝅䝸䝉䞁䛾ᵓ㐀䛿䝆䜾䝄䜾䛺ᙧ䛷䛒䛳䛯䛯䜑䚸䛣䛾⤖ᯝ䛿ಙ㢗䛷䛝䜛䜒䛾䛷
䛒䜛䚹2ᒙ䛻䛚䛡䜛䝅䝸䝉䞁䛾Ᏻᐃᵓ㐀䛿sp3㌶㐨䛻䜘䜛ᵓ㐀䜢ಖ䛸䛖䛸䛩䜛䛯䜑䚸pz㌶㐨䛻䜘䜛ᐤ୚䛜኱䛝䛟䚸ᒙ㛫䛷⤖ྜ䛧䛶䛧䜎䛳䛯䚹ᒙ䛜᏶඲䛻㔜䛺䛳䛶䛔䛶ึᮇᒙ㛫㊥㞳䛜4.0[䊅]䛛䜙ฟⓎ
䛧䛯2ᒙ䛻䛚䛡䜛䝅䝸䝉䞁䛾Ᏻᐃᵓ㐀䛾Mulliken population䜢ぢ䛯䛸䛣䜝䚸㞄䜚ྜ䛖Si-Si䛸ᒙ㛫䛷⤖ྜ䛧䛯Si-Si䛾population䛿䛸䜒䛻⣙0.27䛷䛒䜚䚸ᒙ㛫䛾⤖ྜ䛿ศᏊ㛫ຊ䛻䜘䜛ᙅ䛔⤖ྜ䛷䛿䛺䛟䚸ඹ᭷⤖ྜ䛷䛒䜛䛣䛸䛜ศ䛛䛳䛯䚹௨ୖ䛾⤖ᯝ䜘䜚䚸䝅䝸䝉䞁䛿1ᒙ䛷䛿Ꮡᅾ䛷䛝䜛䛜䚸2ᒙ䛾≧ែ䜢ಖ䛳䛯≧ែ䛷Ᏻᐃ໬䛩䜛䛣䛸䛿㞴䛧䛔䛸⪃䛘䜙䜜䜛䚹㻌
5䠊ཧ⪃ᩥ⊩㻌[1]Antoine Fleurence, et.al. Physical Review Letters 108, 245501,15 (2012).
[2]Carlo Adamo, et.al. J.Chem.Phys. 108(2),8, (1998).

2P124ᄙᚑಽ♽ಽሶ゠㆏ᴺߦࠃࠆᭂᕈಽሶ LiH ߳ߩ㓁㔚ሶ᧤❈ᯏ᭴ߩ⎇ⓥ
㧔ᮮᏒᄢ㒮࡮↢๮࠽ࡁ㧕 ٤ዊጊ↰㓉ⴕ, ┙Ꮉੳౖ
Multicomponent molecular orbital study on positron attachment to a polar molecule LiH(Yokohama City Univ.) ٤Takayuki Oyamada,

Masanori Tachikawa‫ޣ‬ᐨ‫ޤ‬㓁㔚ሶ e㧗ߪ㔚ሶߣ⾰㊂ߪหߓߛ߇‫ޔ‬㔚⩄߇㔚ሶߣㅒ╓ภߩᱜ㔚⩄ࠍᜬߟ෻☸ሶߢ޽ࠆ‫ޕ‬㔚ሶߣ㓁㔚ሶ߇ⴣ⓭ߔࠆߣ 2 ᧄ߆ࠄᢙᧄߩ J✢ࠍ᡼಴ߒߡኻᶖṌߔࠆ[1,2]‫ߩߎޕ‬ᕈ⾰ࠍ೑↪
ߒߚ㓁㔚ሶᶖṌಽశᴺߪ‫ޔ‬࿕૕ߩ᭴ㅧᰳ㒱࡮⴫㕙⸃ᨆ╬ߩ᧚ᢱ⹏ଔ߿‫ޔ‬㓁㔚ሶᢿጀ᠟ᓇᴺࠍ
ߪߓ߼ߣߔࠆක≮⸻ᢿߥߤ‫ޔ‬ᐢ޿ಽ㊁ߢታ↪ൻߐࠇߡ޿ࠆ‫ޕ‬㓁㔚ሶᶖṌಽశᴺߩၮ␆ߣߥࠆ
㔚ሶ-㓁㔚ሶኻᶖṌᯏ᭴߿㓁㔚ሶ᧤❈ᯏ᭴ߦߟ޿ߡℂ⸃ࠍჇߔߎߣߢ‫♖ࠅࠃޔ‬ᐲߩ㜞޿᧚ᢱ⸃ᨆ࡮⸻ᢿ߅ࠃ߮↹௝㜞⾰ൻ߇ታ⃻ߔࠆߣᦼᓙߐࠇࠆ‫ߒ߆ߒޕ‬㓁㔚ሶߩኼ๮߇⍴޿ߎߣ߆ࠄ‫ޔ‬ේሶ࡮ಽሶ߳ߩ㓁㔚ሶๆ⌕߿㓁㔚ሶ᧤❈ൻว‛ߩ‛ᕈ‫ޔ‬ኻᶖṌᯏ᭴╬ߩታ㛎⊛⸃ᨆߪ࿎㔍ߢ޽ࠅ‫ߚߒ߁ߎޔ‬ၮ␆⊛ᕈ⾰ߔࠄᱴߤ⸃᣿ߐࠇߡ޿ߥ޿ߩ߇⃻⁁ߢ޽ࠆ‫⎇ᧄޕ‬ⓥߩ⋡⊛ߪ㓁㔚
ሶ⑼ቇߩၮ␆ߣߥࠆ਄ㅀߩ‛ℂൻቇᯏ᭴ߦ߅ߌࠆ‫ޔ‬㔚ሶ-㔚ሶ⋧㑐߅ࠃ߮㔚ሶ-㓁㔚ሶ⋧㑐ߩᓎഀࠍ‫⎇ᧄޔ‬ⓥߢ㐿⊒ਛߩᄙᚑಽ♽ಽሶ゠㆏ᴺߦၮߠ߈ℂ⺰⊛ߦ⸃᣿ߔࠆߎߣߢ‫ޔ‬ක≮⸻ᢿᛛⴚ߿᧚ᢱ‛ᕈតᩏߩ᷹ቯ♖ᐲߩะ਄ߦ❬߇ࠆ᦭⋉ߥၮ⋚ᖱႎࠍឭଏߔࠆߎߣߢ޽ࠆ‫ޕ‬‫ ޤ⚦⹦ߩ▚⸘ޣ‬Ne ୘ߩ㔚ሶߣ‫ޔ‬1 ୘ߩ㓁㔚ሶ‫ޔ‬Nnuc ୘ߩ࿕ቯߐࠇߚේሶᩭ߆ࠄᚑࠆᄙᚑಽ♽ߦߟ޿ߡ‫ޔ‬㈩⟎㑆⋧੕૞↪(CI)ᴺߩోᵄേ㑐ᢙߪ‫ޔ‬ᰴᑼߩࠃ߁ߦዷ㐿ߢ߈ࠆ[3]‫ޕ‬
  

< tot

C 00 ) 0e

M 0p



¦'C

IJ

) Ie

M Jp

,

C IJ : CI ଥᢙ

IJߎߎߢ‫ ╙ޔ‬1 㗄ߪ Hartree-Fock (HF)ၮᐩ㈩⟎ࠍ⴫ߒ‫ߩઁޔ‬㗄ߪ m-㔚ሶബ⿠ߣ n-㓁㔚ሶബ⿠ߩ⚵วߖ߆ࠄᚑࠆബ⿠㈩⟎ࠍ⴫ߔ‫ޕ‬ฦ‫ߩޘ‬㔚ሶ-㓁㔚ሶ㈩⟎ߪ㔚ሶ Slater ⴕ೉ᑼ)I (e)ߣ‫ޔ‬㓁㔚ሶ
゠㆏MJ (p) ߩⓍߣߒߡ⴫ߐࠇࠆ‫ޕ‬น⢻ߥోߡߩ㔚ሶ࡮㓁㔚ሶബ⿠ߩ⚵วߖࠍ↪޿ࠆ Full-CI ᴺߪ‫ޔ‬‫ޟ‬㔚ሶ-㔚ሶ⋧㑐‫ޟߣޠ‬㔚ሶ-㓁㔚ሶ⋧㑐‫ߩޠ‬ਔലᨐࠍ฽ߺ‫ޔ‬ਈ߃ࠄࠇߚၮᐩ㑐ᢙߩ▸࿐ౝߢߪᦨ߽㜞♖ᐲߥ CI ߣ⸒߃ࠆ߇‫ޔ‬㈩⟎ᢙߩᜰᢙ㑐ᢙ⊛ߥჇᄢߩߚ߼‫ޔ‬Full-CI ᴺࠍታᣉߢ߈ࠆ♽ߪዋᢙ☸ሶ♽ߦ㒢ࠄࠇࠆ‫ޕ‬㔚ሶ⁁ᘒℂ⺰ߢ⦟ߊ⍮ࠄࠇߡ޿ࠆࠃ߁ߦ‫ޔ‬㔚ሶ-㔚ሶ⋧㑐ߩਥⷐㇱಽߪ‫ޟ‬2 㔚ሶബ⿠㈩⟎‫ߡߞࠃߦޠ‬ขࠅㄟ߹ࠇࠆ‫ޕ‬ห᭽ߩ⠨ኤ߆ࠄ‫ޔ‬㔚ሶ-㓁㔚ሶ⋧㑐ߩਥⷐㇱಽߪ‫ޟ‬1 㔚ሶ࡮1 㓁㔚ሶหᤨബ⿠㧔2 ☸ሶബ⿠㧕㈩⟎‫ࠅࠃߦޠ‬ขࠅㄟ߹ࠇࠆ[4]‫ޕ‬ᧄ⎇ⓥߢߪ‫ޔ‬ᭂᕈಽሶ LiH ߳ߩ㓁㔚ሶ᧤❈ᯏ᭴ߦ߅ߌࠆ‫ޟ‬㔚ሶ-㔚ሶ⋧㑐‫ޟߣޠ‬㔚ሶ-㓁㔚ሶ⋧㑐‫ߩޠ‬ᓎഀࠍ⺞ߴࠆߚ߼‫ޔ‬㓁㔚ሶⶄว૕ [LiH; e㧗]ߦߟ޿ߡ HF ᴺߣ‫ ⴫ޔ‬1 ߦ␜ߔฦ⒳ߩ
CI ᴺߢࠛࡀ࡞ࠡ࡯߅ࠃ߮㔚⩄ኒᐲߩ⸃ᨆࠍⴕߞߚ‫ޕ‬Ყセߩߚ߼‫ޔ‬Li㧙H ᩭ㑆〒㔌ߪ R=3.20 bohrߦ࿕ቯߒ‫ޔ‬H ᩭߩᐳᮡࠍේὐߣߒߚ‫ޕ‬㔚ሶၮᐩ㑐ᢙߦߪ 6-311G**ၮᐩࠍ↪޿ߡ‫ޔ‬㑐ᢙਛᔃߪLi ᩭߣ H ᩭ਄ߦ⸳⟎ߒߚ‫ޕ‬㓁㔚ሶၮᐩ㑐ᢙߦߪ [14s4p] ࠟ࠙ࠬဳ㑐ᢙࠍ↪޿ߡ‫ޔ‬ฦ‫゠ߩޘ‬㆏ᜰᢙߣ㑐ᢙਛᔃߪ HF ⸘▚ߢᄌಽ⊛ߦᦨㆡൻߒߚ୯ࠍ↪޿ߚ‫⎇ᧄޔߪߦ▚⸘ޕ‬ⓥࠣ࡞࡯ࡊߢ
⁛⥄ߦ㐿⊒ਛߩᄙᚑಽ♽ಽሶ゠㆏ᴺࡊࡠࠣ࡜ࡓࠍ↪޿ߚ‫ޕ‬⴫ 㧦[LiH; e㧗]ߦኻߒᧄ⎇ⓥߢታᣉߒߚ CI ⸘▚ߩಽ㘃ߣ⠨ᘦߐࠇߚ̌㊂ሶ☸ሶ㑆ߩ⋧㑐̍⸘▚ᣇᴺ(a) Full-CIe-p(b) CISDe-e(c) CISDTQ⠨ᘦߒߚബ⿠㈩⟎㔚ሶ-㔚ሶ⋧㑐㔚ሶ-㓁㔚ሶ⋧㑐ోߡߩ㔚ሶ࡮㓁㔚ሶബ⿠
1 㔚ሶബ⿠, 1 㓁㔚ሶബ⿠,
1 㔚ሶ࡮1 㓁㔚ሶหᤨബ⿠
1㨪4 㔚ሶബ⿠ߩߺ

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٤



‫⚿ޣ‬ᨐߣ⠨ኤ‫ ޤ‬࿑㧝(a)㨪(c)ߦฦ⒳ߩ CI ߣ HF ߩ㓁㔚ሶኒᐲߩᏅߣߒߡ᳞߼ߚ‫⋧ޟ‬㑐ߦࠃࠆ㓁㔚ሶᏅኒᐲಽᏓ‫ޠ‬Ucorr(r) = UCI(r)㧙UHF(r) ࠍ␜ߔ‫ޕ‬࿑ 1(a)ߦ␜ߔ Full-CI ߣ HF ߩ㓁㔚ሶᏅኒᐲಽᏓ߆ࠄ‫⋧ޔ‬㑐ߩᓇ㗀ߦࠃࠅ‫ޔ‬H ᩭ㆙ᣇߩ㓁㔚ሶኒᐲ㧔✛⦡ㇱಽ㧕߇ᷫዋߒ‫ޔ‬LiH ಽሶߩ㔚ሶኒᐲಽᏓࠍขࠅ࿐߻㗔ၞ㧔⿒⦡ㇱಽ㧕ߢ㓁㔚ሶኒᐲ߇Ⴧടߔࠆߎߣ߇ಽ߆ࠆ‫ޕ‬࿑ 1(b) ߩ‫ޟ‬㔚ሶ-㓁㔚ሶ⋧㑐‫ࠍߺߩޠ‬⠨ᘦߒߚ CI ߣ HF ߩᏅߣߒߡ᳞߼ߚ㓁㔚ሶᏅኒᐲಽᏓߪ‫ޔ‬CI ዷ㐿ߩ㈩⟎ᢙ
Mconfig ߇ߪࠆ߆ߦዋߥ޿ߦ߽㑐ࠊࠄߕ‫ޔ‬࿑ 1(a)ߩ⚿ᨐߣ߶߷ห᭽ߢ޽ࠆ‫ޕ‬ઁᣇ‫ޔ‬࿑ 1(c) ߩ‫ޟ‬㔚ሶ-㔚ሶ⋧㑐‫ߩޠ‬ߺࠍ⠨ᘦߒߚ CI ߣ HF ߩᏅߣߒߡ᳞߼
ߚ㓁㔚ሶᏅኒᐲಽᏓߪ‫ޔ‬࿑ 1(a), (b) ߣᲧߴ 2~3 ᩴዊߐ޿‫ޟߪࠇߎޕ‬㔚ሶ-㔚ሶ⋧㑐‫ߪޠ‬㓁㔚ሶኒᐲࠍ HF ߣᲧߴߡᱴߤ
ᄌൻߐߖߥ޿ߎߣࠍᗧ๧ߔࠆ‫ޕ‬ᓥߞߡ‫ޔ‬㊂ሶ☸ሶ㑆ߩ⋧㑐ߩౝ‫ޔ‬㓁㔚ሶኒᐲಽᏓ
ࠍᄌൻߐߖࠆߩߪ‫ޔ‬ਥߦ‫ޟ‬㔚ሶ-㓁㔚ሶ⋧㑐‫ޕࠆ߃⸒ߣࠆ޽ߢޠ‬߹ߚ‫⎇ᧄޔ‬ⓥߩࠛࡀ࡞ࠡ࡯⸃ᨆ߆ࠄ‫ޔ‬‫ޟ‬㔚ሶ-㓁㔚ሶ⋧㑐‫ࠆߔ⿠⺃߇ޠ‬㓁㔚ሶኒᐲಽᏓߩ෼❗ߦ઻߁‫ޔ‬㔚ሶ-㓁㔚ሶ㑆ᒁജߩૐਅ߇‫ޔ‬LiH ߳ߩ㓁㔚ሶ᧤❈ᯏ᭴
ߦ߅޿ߡ㊀ⷐߥᓎഀࠍᨐߚߔߎߣ߇⏕߆߼ࠄࠇߚ‫ޕ‬HF ᴺߢߪ㓁㔚ሶⷫ๺ജ߿
㔚ሶ-㓁㔚ሶኻᶖṌ₸ࠍㆊዊ⹏ଔߔࠆ௑
ะ߇޽ࠅ‫ޔ‬㓁㔚ሶ᧤❈ൻว‛ߩ⎇ⓥߢߪ‫ޔ‬‫ޟ‬㔚ሶ-㓁㔚ሶ⋧㑐‫ࠍޠ‬㜞♖ᐲቯ㊂⹏ଔߔࠆߎߣ߇㊀ⷐߢ޽ࠆ[5,6]‫ޕ‬࿑ 1㧦ฦ⒳ߩ CI ᴺߣ HF ᴺߩᏅߣߒߡ᳞߼ߚ
[LiH; e㧗]ߩ㓁㔚ሶᏅኒᐲಽᏓ‫ޕ‬ෳ⠨ߩߚ߼ߦ‫ޔ‬࿑ߦߪ HF ߢ᳞߼ߚ㔚ሶኒᐲ߽ὐ✢ߢ␜ߔ‫ޕ‬[1] 㓁㔚ሶ⸘᷹ߩ⑼ቇ, (ᣣᧄࠕࠗ࠰࠻࡯ࡊදળ, 1993). [2] M.Charlton and J.W.Humberston,
Positron Physics, (Cambridge University Press, Cambridge, 2001). [3] M.Tachikawa, Chem. Phys.
Lett. 350, 269, (2001). [4] M.Tachikawa,Y.Kita, and R.J.Buenker, Phys. Chem. Chem. Phys. 13,
2701, (2011). [5] Y. Kita et al., J. Chem. Phys. 131, 134310 (2009); J. Chem. Phys. 135, 054108(2011). [6] ┙Ꮉੳౖ, ർᐘᶏ, ᣣᧄ‛ℂቇળ⹹, 67, 33, (2012).

2 P125
多成分第一原理法による陽電子-ホルムアルデヒド複合体の理論的解析（横市大院・生命ナノ）○山田裕里佳，北幸海，立川仁典

Theoretical analysis of positronic formaldehyde by using multi-component first principle method(Yokohama City Univ.)○ Yurika Yamada, Yukiumi Kita, Masanori Tachikawa【序】
電子の反粒子である陽電子は、電子と衝突することにより対消滅を起こす。物質に入射された陽電子は、電子との対消滅へ至るまでの間に、原子や分子のイオン化および励起、ポジトロニウム（陽電子と電子の一時的な束縛状態）の形成、そして陽電子複合体（陽電子と原子や分子から成る一時的な束縛状態）の形成等が起こりうると示唆されているが、その基礎的性質は十分に理解されていない。
Crawford は、1.625 debye 以上の双極子モーメントをもつ極性分子はその双極子場に陽電子を一つ束縛可能であることを理論的に示唆している[1]。極性分子に対する陽電子の束縛の例として、
近年 Surko らが振動 Feshbach 共鳴スペクトルと IR スペクトルから間接的に、C=O 基をもつ様々な分子の陽電子親和力（PA, 陽電子束縛エネルギー）を報告している[2]。しかし、C=O 基をもつ
最も単純な分子であるホルムアルデヒド分子の PA 値は測定できておらず、この分子の陽電子吸着能の解明には第一原理計算等を用いた理論的解析が期待されている。
陽電子複合体の諸性質を精密に解析可能な手法として、explicitly correlated Gaussian (ECG)基底関数を用いた変分計算、および量子モンテカルロ(QMC)法が知られている。ECG 計算は[H‒;e+]のような小さな系に対して変分的に最も精密な結果を与える[3]が、その莫大な計算コストのために適用範囲は極めて小規模な系に限られている。一方、QMC 法は ECG 法と同程度の計算精度を有しながらも、その計算コストは ECG 計算と比較して小さいため、大規模な陽電子複合体へも適用可能である。そこで本研究では、ホルムアルデヒド分子の陽電子吸着能を精密に予測することを目的とし、QMC 法による陽電子親和力の理論的解析を行った。

【計算の詳細】ホルムアルデヒド分子の陽電子親和力は次式より算出した：PA(CH2O) = E(CH2O) – E(CH2O;e+)
ここで、E(CH2O) および E(CH2O;e+) はそれぞれホルムアルデヒド分子とその陽電子複合体の変分エネルギーである。本研究では、変分モンテカルロ(VMC)法および拡散モンテカルロ(DMC)法という二種類の QMC 法により、これら変分エネルギーの精密算定を行った。まず、ホルムアル
デヒド分子を CCSD/aug-cc-pVTZ レベルにて構造最適化し、この分子の平衡構造を決定した。また、ホルムアルデヒド分子への陽電子吸着による構造変化は非常に小さいと仮定し、陽電子複合体に対しても同一の平衡構造を用いた。QMC 計算では Slater-Jastrow 型試行波動関数を用い、Slaterpart の生成には Hartree-Fock (HF)法（電子基底: aug-cc-pVTZ、陽電子基底: 12s9p3d1f GTFs）を用いた。また、Jastrow 因子には二体項（電子-電子、電子-核、電子-陽電子、陽電子-核項）および三体項（電子-電子-核項）を導入し、それらの変分パラメータを分散最小化法により最適化した。
そして DMC 計算は、初期 walker 数を 9,600 とし、0.001 から 0.010 a.u.の虚時間 step を用い実行した。DMC 計算の虚時間 step 依存性を取り除くために、これらの結果から外挿により虚時間 stepが 0.000 a.u.の際の値を推定した。

【結果】
ホルムアルデヒド分子およびその陽電子複合体の変分エネルギー、そしてホルムアルデヒド分子の陽電子親和力を Table 1 に示した。HF 法による陽電子親和力は正の値となったものの、例えば Strasburger が報告している configuration interaction (CI)計算[4]と比べても非常に過小評価している。従って、陽電子親和力の算定に対しては、相関効果（特に、電子-陽電子相関）を取り込むことが重要である。VMC 計算は一般に CI 計算よりも良い変分エネルギーを与えるが、陽電子親和力の値は負に転じている。この HF 計算と定性的にも異なる結果は、VMC 計算で回収した陽電子複合体の相関エネルギーの割合(76.4%)が、親分子に対する割合(77.4%)よりも相対的に低いためであり、主に陽電子複合体の試行波動関数の精度に起因すると考えられる。一方、DMC 計算によって相関エネルギーを精密に取り込んだ結果、陽電子親和力は+25(3) meV となった。この DMC 法の陽電子親和力は CI 法による値よりも大きく、従って電子相関および電子-陽電子相関を精密に評価することにより陽電子親和力は増大することが分かる。
高精度 QMC 計算に基づいた本計算により、ホルムアルデヒド分子がその平衡構造において陽電子親和力+25(3) meV を持ち得ることが明らかになった。その他詳細はポスターにて発表を行う。
Table 1   
 (PA)

E(CH2O) [hartree]

E(CH2O;e+) [hartree]

PA(CH2O) [eV]HF

–113.91399–113.91401

0.00053

VMC–114.3494(17)–114.3446(18)–0.132(66)DMC–114.47684(8)–114.47781(7)0.0254(29)

CI a





0.0186

a: Ref. [4].

【参考文献】[1] O. H. Crawford, Proc. Phys. Soc. 91, 279 (1967). [2] J. R. Danielson, J. J. Gosselin, and C. M. Surko,
Phys. Rev. Lett. 104, 233201 (2010). [3] J. Mitroy, Phys. Rev. A, 73, 054502 (2006). [4] K. Strasburger,
Struct. Chem. 15, 415 (2004).

2P126
࢖ࣜࢪ࣒࢘ゐ፹ࢆ⏝࠸ࡿ 2-࢔ࣝ࢟ࣝࣆࣜࢪࣥࡢ఩⨨㑅ᢥⓗ C(sp3)-H ⤖ྜ࣍࢘⣲໬཯ᛂࡢᶵᵓゎᯒ㸦໭኱㝔⌮㸧○㧗 ᩄ㸪๓⏣ ⌮㸪Ṋḟ ᚭஓ㸪⃝ᮧ ṇஓ

Theoretical study on the mechanism of Ir catalyzed site-selective borylation of a C(sp3)-H bond in 2-alkylpyridines(Hokkaido University) ○Min Gao, Satoshi Maeda, Tetsuya Taketsugu, Masaya Sawamura

Introduction
The borylation reaction catalyzed by transition metal complex has attracted lots of interest because theorganoboron compounds act as useful intermediates and reagents in organic synthesis. Recently,
Sawamura and coworkers reported that a silica-supported monophosphine (Silica-SMAP)-Ir catalyst
showed high site-selectivity in the C(sp3)-H borylation of substituted pyridines [1]. In this reaction, theC(sp3)-H borylation occurred selectively at the position γ to the N atom in substituted pyridines as shownin Scheme 1. In this study, we examine the detailed mechanism of this reaction to clarify the reaction
pathways leading to the two different products and discuss the reason for the high site-selectivity.

͸ͲԨ

Scheme 1. Silica-SMAP-Ir catalyzed site-selective borylation of 2-ethylpyridine [1].
Computational Method
In the present study, all the reaction pathways were obtained by using the artificial force induced reaction(AFIR) method [2, 3] which use the gradient and Hessian calculated by Gaussian 09 programs. We carriedout calculations using the ONIOM (BP86:PM6) method for the initial search. Then, all obtained
geometries were reoptimized with the DFT method using the M06L functional. The effective corepotential ECP60MWB given by the Stuttgart/Bonn group was used in describing Ir atom where 5s2 5p6
5d7 6s2 are considered as the valence electrons with the VDZ basis set from the same group, whereas the
cc-pVDZ basis set was used for all the other atoms. Frequency calculations at the same level of theory
have also been performed to identify the stationary points as minima or transition states.
Results and Discussion
In Silica-SMAP, phosphine is supported by the Silica surface, and this allows generation of 1 : 1complexes between the phosphine and Ir. In other words, only one phosphine ligand can coordinate to theIr atom due to the silica support. This allows coordination of the N atom in substituted pyridines to Ir, andgives reasonable interpretation on the high site-selectivity [1]. Therefore, we started calculations from thecoordination step of 2-ethylpyridine to a four coordinated P-Ir(III)-(Bpin)3 complex giving six coordinatedcomplexes. It should be noted that the silica surface is not included in our calculation model, because it
does not have significant effects on the reaction center of given complexes. According to our calculation
results, the reaction occurs via the following steps: (1) coordination of the N atom in 2-ethylpyridine to theIr atom; (2) oxidative addition of a C-H bond to the Ir atom to form a seven coordinated intermediate; (3)dissociation of H-Bpin with small barrier; (4) reductive elimination of the borylated product; (5) oxidative
addition of (Bpin)2 to the Ir atom to get back the catalyst. This catalytic cycle is very similar to thatobtained in a previous work with two-point ligand coordination [4]. Details of the catalytic cycle will bereported in the poster session.
We studied the effect of N coordination in 2-ethylpyridine and compared energy barriers for the CH activation at the β and γ positions. The coordination of N atom plays an important role in the catalytic
cycle especially in the step (2). Barriers for the oxidative addition without N coordination were found to
be too high to occur, no matter in the case of the β or γ C-H bonds. The high selectivity is achieved at thetransition state in the step (2). The β position C-H and the γ position C-H can undergo the oxidative
addition through five- and six-membered-ring transition states, respectively. As seen in Fig. 1, the barrier
for the C-H activation at the β position through the five-membered-ring transition state is much higher inenergy than that for the γ position. This is due to the geometrical strain to form the five-membered-ringtransition state. The strain energy will be analyzed by using the energy decomposition analysis anddiscussed in the poster presentation.

Figure 1. Energy profile (in kJ/mol) for the C-H activation step calculated with M06L functional.
[1] S. Kawamorita, R. Murakami, T. Iwai and M. Sawamura, J. Am. Chem. Soc.135, 2947 (2013).
[2] S. Maeda and K. Morokuma, J. Chem. Phys. 132, 241102 (2010).
[3] S. Maeda, K. Ohno and K. Morokuma, Phys. Chem. Chem. Phys. 15, 3683 (2013).
[4] H. Tamura, H. Yamazaki, H. Sato and S. Sakaki, J. Am. Chem. Soc. 125, 16114 (2003).

2P127
GRRM/AFIR ἲ࡟ࡼࡿ࢟ࣛࣝࣇ࢙ࣟࢭࢽࣝ࣍ࢫࣇ࢕ࣥ-Au(I)㘒య࡟ࡼࡿ
࢖ࢯࢩ࢔ࣀ㓑㓟࢚ࢫࢸࣝ୙ᩧ࢔ࣝࢻ࣮ࣝ཯ᛂᶵᵓࡢ⌮ㄽゎ᫂(໭኱㝔•⥲ྜ໬Ꮫ 1ࠊ໭኱㝔•⌮ 2) ‫ۑ‬ᑠụ༓᫂ 1ࠊ๓⏣⌮ 2ࠊṊḟᚭஓ 2ࠊ⃝ᮧṇஓ 2

GRRM/AFIR study on the mechanism of asymmetric isocyanoacetate aldol
reaction catalyzed by a chiral ferrocenylphosphine-gold(I) complex(Hokkaido Univ.) Chiaki Koike, Satoshi Maeda, Tetsuya Taketsugu, and Masaya Sawamura࠙◊✲⫼ᬒࠚ ❧య㑅ᢥᛶไᚚࡣ཯ᛂ㛤Ⓨ࡟࠾ࡅࡿ᭱㔜せㄢ㢟ࡢ୍ࡘ࡛࠶ࡿࠋ㧗࠸㑅ᢥᛶࡣࠊᕦጁ࡞㓄఩Ꮚタィ࡟ࡼࡗ࡚ᐇ⌧ࡉࢀࡿࡓࡵࠊࡑࡢᣦ㔪ࢆᚓࡿࡓࡵ࡟ࠊ㑅ᢥᛶࡢ㉳※࡟㛵ࡍࡿ⌮ㄽ◊✲ࡢ㔜せᛶࡀ㧗ࡲࡗ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊ࢟ࣛࣝࣇ࢙ࣟࢭࢽࣝ࣍ࢫࣇ࢕ࣥ-Au(,)㘒యࡀゐ፹ࡍࡿ㧗❧య㑅ᢥⓗ࢔ࣝࢻ࣮ࣝ཯ᛂ࡟ࡘ࠸࡚㑅ᢥᛶ࡟㛵ࡍࡿ⌮ㄽ◊✲ࢆ⾜࠺ࠋᮏ཯ᛂ࡛ࡣࠊ㔠ゐ፹ࡢᏑᅾୗࠊ࢖ࢯࢩ࢔ࣀ࢔ࢭࢸ࣮ࢺ(CNCH2COOR) ࡜࢔ࣝࢹࣄࢻ(RCHO)㛫࡛࢔ࣝࢻ࣮ࣝ཯ᛂ࡟
⥆ࡃศᏊෆ⎔໬཯ᛂࡀ㐍⾜ࡍࡿࡇ࡜࡛ࠊ࢜࢟ࢧࢰࣜࣥ trans య(4S, 5R)ࡀ㧗཰⋡࡛ᚓࡽࢀࡿࠋ

Fig. 1 㧗❧య㑅ᢥⓗ࢔ࣝࢻ࣮ࣝ཯ᛂ[1]ᮏ཯ᛂࡢ㧗❧య㑅ᢥᛶࡣࠊC-C ⤖ྜ⏕ᡂࡢ㑄⛣≧ែ(TS)࡟࠾ࡅࡿ࢟ࣛࣝ࡞ࣇ࢙ࣟࢭࢽࣝ࣍ࢫ
ࣇ࢕ࣥ㦵᱁࡟ᑟධࡉࢀࡓഃ㙐࡜ᇶ㉁ࡢ㛫ࡢ┦஫స⏝࡟⏤᮶ࡍࡿ࡜᥎ᐃࡉࢀ࡚࠸ࡿࠋ
❧య㑅ᢥᛶࡣࠊ㛵㐃ࡍࡿ TS ࠾ࡼࡧ୰㛫యࡢ㓄ᗙࢆ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚⥙⨶᥈⣴ࡍࡿࡇ࡜࡟ࡼࡾゎᯒ࡛ࡁࡿࠋᮏ཯ᛂࡢሙྜࠊࣇ࢙ࣟࢭࣥ㦵᱁࡟ᑟධࡉࢀࡓഃ㙐ࡢᦂࡽࡂ࡟ࡼࡾഃ㙐ࡢྥࡁࡸ࢖ࢯࢩ࢔ࣀ࢔ࢭࢸ࣮ࢺࡢ㓄ྥ࡞࡝ࡀ␗࡞ࡿ㠀ᖖ࡟ከᩘࡢ㓄ᗙࡀᏑᅾࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ
ࡑࡢࡼ࠺࡞ሙྜࠊᚑ᮶ࡢᵓ㐀᭱㐺໬ἲ࡛ࡢゎᯒࡣᅔ㞴࡛࠶ࡿࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊᙜ◊✲ᐊࡢ๓⏣ࡽ࡟ࡼࡾ㛤Ⓨࡉࢀࡓ Artificial Force Induced Reaction (AFIR)ἲ[2]ࢆ⏝࠸ࡓ཯ᛂ⤒㊰ࢧࣥࣉࣜࣥࢢࢆᐇ⾜ࡋࠊᮏ཯ᛂࡢ㧗❧య㑅ᢥᛶࡢ㉳※ࢆ⌮ㄽゎ᫂ࡍࡿࠋ࠙ィ⟬ᡭἲࠚ
⏝࠸ࡿᇶ㉁࡜ゐ፹ࢆ B3LYP-D ἲ࡛ᵓ㐀᭱㐺໬ᚋࠊ࢖ࢯࢩ࢔ࣀ࢔ࢭࢸ࣮ࢺࡢ㔠ゐ፹࡬ࡢ㓄఩ᵓ㐀ࢆ᥈⣴ࡋࡓࠋ඲࡚ࡢ㓄఩ᵓ㐀࡟࠾࠸࡚ഃ㙐ࡢ࢔࣑ࣥ࡬ࡢࣉࣟࢺࣥ⛣ື⤒㊰ࢆồࡵࠊᚓࡽࢀࡓ࢚ࣀ࣮ࣛࢺ࡜࢔ࣝࢹࣄࢻศᏊࢆ AFIR ἲ࡟ࡼࡗ࡚཯ᛂࡉࡏࡓࠋ
཯ᛂᶵᵓࡢึᮇ᥈⣴ࡣ PM6

ἲ࡛⾜࠸ࠊᚓࡽࢀࡓ AFIR ⤒㊰ࢆ ONIOM(M06L:PM6)ἲ࡟ࡼࡾ෌᭱㐺໬ᚋࠊ⤒㊰࡟ἢࡗࡓ TSࢆᚓࡓࠋࡇࢀࡽࡢ TS ࡣ᭱⤊ⓗ࡟ M06L ἲ࡛෌᭱㐺໬ࡍࡿࠋ࠙⤖ᯝࠚゐ፹࡜࢚ࣀ࣮ࣛࢺࡢ㘒యᵓ㐀ࢆ᥈⣴ࡋࡓ⤖ᯝࠊ኱ูࡋ࡚୕✀㢮ࡢᏳᐃ㓄ᗙࡀᚓࡽࢀࡓࠋࡉ
ࡽ࡟ࠊࡇࢀࡽࡢᵓ㐀࡟ᑐࡋ࡚࢔ࣝࢹࣄࢻࢆ཯ᛂࡉࡏࡓ⤖ᯝࠊC-C ⤖ྜ⏕ᡂ࡟㛵ࡍࡿ TS ィ 36ಶࡀᚓࡽࢀࡓࠋࡇࢀࡽ 36 ಶࡣ஧✀㢮࡟኱ู࡛ࡁࡿ㸸ձC-C ⤖ྜ⏕ᡂ࡜⎔໬ࡀྠ᫬࡟㐍⾜ࡋࠊ༠ዌⓗ࡟ 5 ဨ⎔ᆺ୰㛫య(Fig. 2 ୖẁ)ࡀ⏕ᡂࡍࡿ⤒㊰ࠊղC-C ⤖ྜ⏕ᡂ࡜ྠ᫬࡟࢔ࣝࢹࣄࢻࡢ
㓟⣲ཎᏊࡀ࢔࣑ࣥୖࡢࣉࣟࢺࣥᘬࡁᢤࡃ Fig. 2 ୗẁࡢ୰㛫యࢆ⏕ᡂࡍࡿ⤒㊰ࠋ࡝ࡕࡽࡢ୰㛫
యࡶࠊᇶ㉁ྠኈࡢ཯ᛂ㠃ࡢ㐪࠸࡟ࡼࡗ࡚ Fig. 2 ࡟♧ࡍ 4 ✀㢮࡟ศ㢮࡛ࡁࡿ㸸trans య(4S, 5R),
trans య(4R, 5S), cis య(4S, 5S), cis య(4R, 5R)ࠋࡑࢀࡒࢀࡢࣃࢱ࣮ࣥࡢ୰࡛ࡶࠊ㓄఩Ꮚࡸᇶ㉁ࡢ
㓄ᗙࡀ␗࡞ࡿ⤒㊰ࡀከᩘᏑᅾࡍࡿࡓࡵࠊྜィ 36 ಶࡢ཯ᛂ⤒㊰ࡀᚓࡽࢀࡓࠋ

Fig. 2 AFIR ἲ࡛ᚓࡽࢀࡓ 8 ✀㢮ࡢ୰㛫య┤᥋ 5 ဨ⎔ࡀ⏕ᡂࡍࡿձࡢ⤒㊰࡛ࡣࠊ࢔ࣝࢹࣄࢻࡢ㓟⣲ཎᏊࡀ࢔࣑ࣥୖࡢࣉࣟࢺࣥ࡜┦஫స⏝ࡍࡿࡇ࡜࡟ࡼࡗ࡚ TS ࡀ 50 kJ/mol ⛬ᗘࡶᏳᐃ໬ࡍࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ୍᪉ࠊղࡢ⤒㊰࡛ࡣ༢࡟┦஫స⏝ࡍࡿࡔࡅ࡛࡞ࡃࠊ࢔࣑ࣥୖࡢࣉࣟࢺࣥࢆᘬࡁᢤ࠸࡚ࡋࡲ࠺ࠋࡇࡢ࡜ࡁࠊࣉࣟ
ࢺࣥᘬࡁᢤࡁࢆక࠺ղࡢ⤒㊰ࡢ᪉ࡀձࡼࡾࡶప࠸ TS ࢆ୚࠼ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡘࡲࡾࠊ࢚ࢿ
ࣝࢠ࣮ⓗ࡟ࡣࣉࣟࢺࣥᘬࡁᢤࡁࢆక࠺ղࡢ⤒㊰ࡢ᪉ࡀ᭷฼࡛࠶ࡿࠋձࡢ⤒㊰࡛ࡣࠊTS ࡟࠾࠸࡚࢚ࣀ࣮ࣛࢺࡢ CNC ゅࡀ‴᭤ࡋ࡚࠾ࡾࠊࡇࢀࡀ TS ࡢ୙Ᏻᐃ໬ࡢཎᅉ࡛࠶ࡿ࡜᥎ᐹࡉࢀࡿࠋ
୍᪉ղࡢሙྜࠊC-C ⤖ྜ⏕ᡂᚋ࡟⎔໬ࡢ཯ᛂࢫࢸࢵࣉࡀᏑᅾࡋࠊࡑࡢ཯ᛂ㞀ቨ࡟ࡘ࠸᳨࡚ウࢆ㐍ࡵ࡚࠸ࡿࠋࡲࡓࠊࡇࢀࡽ஧✀㢮ࡑࢀࡒࢀ࡟ࡘ࠸࡚ฟ᮶ᚓࡿ඲࡚ࡢ❧య␗ᛶయ࡬ࡢ⤒㊰ࡀᚓࡽࢀ࡚࠾ࡾࠊࡑࢀࡽࢆヲ⣽࡟᳨ウࡋࠊ❧య㑅ᢥᛶ࡟ࡘ࠸࡚㆟ㄽࡍࡿࠋ࠙ཧ⪃ᩥ⊩ࠚ
[1] Ito, Y.; Sawamura, M.; Hayashi. T. J. Am. Chem. Soc. 1986, 108, 6405-6406.
[2] Maeda, S.; Morokuma, K. J. Chem. Phys. 2010, 132, 241102 (4 pages).

2 P128
GRRM/AFIR Á!*- 2-BQO>R=T7=IPU0Òvinylogous Mannich-type x"»¹ø­: Ăü×©Ċ vs. Ëm×©Ċđ•ë|r 1s(s-đ•Ð 2) ¸µĈ 1lÓÐ 2½¼] 2

GRRM/AFIR study on the mechanism of vinylogous Mannich-type reaction
with 2-trimethylsiloxyfuran: kinetic control vs. thermodynamic control(Hokkaido Univ.) Ryohei Uematsu, Satoshi Maeda, and Tetsuya TaketsuguÛÞð®
γ-J@FP3CĚ·#º
'"°»|£rïÊÌ!}%.-°Ò±Ě·"pÏ×

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0Ä|-X£jĄèe

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86% isolated yieldanti/syn = 53:47
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Ph

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HRA2U:JT?9-"Ėĕ-3M

£.-¾Ē×»¹(b)+.±ÛÞ#ÛÞ"lÓ+!*,čÖ.x§åÁ- Artificial Force Induced Reaction (AFIR)Á 0ąÒ-x
[2]

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, Me  Ph !# PM6 0.`"x!ďZ-ĉj!# B3LYP/6-31G 0ć¦¼!DFT ùâ[M06-2X/6-31+G(d) & 6-31G(d)] locally update plane (LUP)Á[3]0õ
 + .  AFIR ç Ā 0 intrinsic reaction coordinate (IRC) ! ā     !  DFT ù â[M06-2X/6-311+G(2d,p) & 6-31G(d)]ĆÝÍ¢¹ă"¯ąr0õ¹ă5ER8V0
À

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çĀ0çÔÙ!Ãþ.-/cíÕ¡e#Ú"x[Ďeã[!ÑØ×Ì!y²-0÷i±èü#Ø×Ì`"cíÕ¡e)jøÌ0ãé×!§å-#'
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5ER8Vďg)ĆÝÍ¢¹ăá!ď#¬~-vîªÎ
[1] G. Landelle et al., Tetrahedron Lett. 53, 2414 (2012).
[2] S. Maeda et al., J. Chem. Phys. 132, 241102 (2010).
[3] C. Choi et al., J. Chem. Phys. 94, 751 (1991).

2P129Aun-mAgm ࢡࣛࢫࢱ࣮(n = 7-9) ࡟ࡼࡿ H-H ⤖ྜάᛶ໬㸸
GRRM ἲࢆ⏝࠸ࡓ⌮ㄽண(໭኱⌮㸯㸪໭኱㝔⌮㸰㸪ி኱ゐ፹㟁ụ㸱) ‫ۑ‬㧗ᮌ∾ே㸯㸪㧗ᩄ㸰㸪๓⏣⌮㸰,㸱㸪Ṋḟᚭஓ㸰,㸱

H-H bond activation by Aun-mAgm clusters (n = 7-9) :GRRM study on the reactivity(Hokkaido Univ.1, Kyoto Univ.2) ○Makito Takagi1, Min Gao1, Satoshi Maeda1,2, Tetsuya Taketsugu1,2࠙◊✲⫼ᬒࠚ㏆ᖺ㸪㔠ࢡࣛࢫࢱ࣮࡟௦⾲ࡉࢀࡿ㔠ᒓࢡࣛࢫࢱ࣮ࡢゐ፹άᛶࡀὀ┠ࡉࢀ࡚࠸ࡿ㸬ྜ㔠ࢡࣛࢫࢱ࣮ࡢ཯ᛂᛶࡣᵓᡂࡍࡿཎᏊࡢ⤌ᡂࡸࡑࡢᵓ㐀࡟౫Ꮡࡍࡿ㸬ࡑࡇ࡛㸪཯ᛂᛶࢆ⌮ㄽணࡍࡿ࡟ࡣ㸪ᵝࠎ࡞ᖹ⾮ᵓ㐀ࡢࢡࣛࢫࢱ࣮࡜཯ᛂ≀࡜ࡢ཯ᛂ⤒㊰ࢆ⥙⨶ⓗ࡟ồࡵࡿᚲせࡀ࠶ࡿ㸬ࡇࡢ࡜ࡁ㸪ࡇࢀࢆᐇ⾜ࡍࡿ࡟ࡣ㸰ࡘࡢၥ㢟ࡀ࠶ࡿ㸬㸯ࡘ┠ࡣ㔠ᒓࢡࣛࢫࢱ࣮ࡢᵓ㐀ࡀከᩘᏑᅾࡋ㸪ࡑࡢ࡝ࢀࡀゐ፹࡜ࡋ࡚᭷ຠ࡛࠶ࡿ࠿ࢃ࠿ࡽ࡞࠸ࡇ࡜࡛࠶ࡿ㸬ࡑࡢࡓࡵᵝࠎ࡞ᖹ⾮ᵓ㐀ࢆồࡵࡿᚲせࡀ࠶ࡿࡀ㸪ᚑ᮶ࡢ᪉ἲ࡛ࡣᖹ⾮ᵓ㐀ࢆ⥙⨶ⓗ࡟ồࡵࡿࡇ࡜ࡣ㞴ࡋ࠿ࡗࡓ㸬㸰ࡘ┠ࡣ㸪ᵝࠎ࡞ᵓ㐀ࡢ㔠ᒓࢡࣛࢫࢱ࣮࡜ศᏊ࡜ࡢ㛫ࡢ཯ᛂ⤒㊰᥈⣴ࡀ㞴ࡋ࠸ࡇ࡜࡛࠶
ࡿ㸬㑄⛣≧ែࡀồࡲࢀࡤࡑࡇ࡛ࡢ㈇ࡢ᭤⋡ࢆᣢࡘᅛ᭷࣋ࢡࢺࣝࡢ᪉ྥ࡬ୗࡿࡇ࡜࡟ࡼࡗ࡚ᖹ
⾮ᵓ㐀ࢆồࡵࡿࡇ࡜ࡣᐜ᫆࡟࡛ࡁࡿࡀ㸪཯ᛂ≀ࡢ㡿ᇦ࠿ࡽ࡝ࡢ᪉ྥ࡟㐍ࡵࡤ㑄⛣≧ែࡀ࠶ࡿ࠿ࢆุูࡍࡿ᪉ἲࡀ࡞࠿ࡗࡓࡓࡵ㸪཯ᛂ≀ࡢ㡿ᇦ࠿ࡽ㑄⛣≧ែࢆ⣔⤫ⓗ࡟ồࡵࡿࡇ࡜ࡣ࡛ࡁ
࡞࠿ࡗࡓ㸬ࡇࢀࡽ㸰ࡘࡢၥ㢟ࡣ㸪㏆ᖺ㛤Ⓨࡉࢀࡓ 2 ✀㢮ࡢ཯ᛂ⤒㊰⮬ື᥈⣴ἲ[1]࡟ࡼࡗ࡚ゎỴ࡛ࡁࡿ㸬
ADDF(㠀ㄪ࿴ୗ᪉ṍࡳ㏣㊧)ἲࡣ㸪Ᏻᐃᵓ㐀࠿ࡽูࡢᏳᐃᵓ㐀࡬ྥ࠿࠺⤒㊰࡛ࡣᐇ㝿ࡢ࣏ࢸࣥࢩࣕࣝࡀㄪ࿴࣏ࢸࣥࢩࣕࣝࡼࡾࡶపࡃ࡞ࡿ(㠀ㄪ࿴ୗ᪉ṍࡳ)ࡇ࡜࡟╔┠ࡋ㸪␗ᛶ໬࠾ࡼࡧศゎ⤒㊰ࢆ⮬ື᥈⣴ࡍࡿ᪉ἲ࡛࠶ࡿ㸬ࡇࡢ᪉ἲ࡟ࡼࡗ࡚㸯ࡘ┠ࡢၥ㢟ࢆゎỴ࡛ࡁࡿ㸬AFIR(ேᕤຊㄏ㉳཯ᛂ)ἲࡣ཯ᛂ≀ྠኈ࡟㊥㞳࡟ẚ౛ࡋࡓຊࢆ࠿ࡅࡿࡇ࡜࡛㸪⏕ᡂ≀࡬ࡢ㞀ቨࢆ࡞ࡃࡋ㸪཯ᛂ≀ࡢ㡿ᇦ࠿ࡽฟⓎࡋ࡚ຠ⋡ࡼࡃ⏕ᡂ≀࡜ࡑࡇ࡬ࡢ⤒㊰ࢆồࡵࡿ᪉ἲ࡛࠶ࡿ㸬ࡇࡢ᪉ἲ࡟ࡼ
ࡾ㸪㸰ࡘ┠ࡢၥ㢟ࢆゎỴ࡛ࡁࡿ㸬ᮏ◊✲࡛ࡣࡇࢀࡽ㸰ࡘࢆ⤌ࡳྜࢃࡏࡓ GRRM ᡓ␎ࢆ⏝࠸ࡿࡇ࡜࡛㸪Au-Ag ྜ㔠ࢡࣛࢫࢱ࣮
ࡢᵝࠎ࡞ᖹ⾮ᵓ㐀࡜Ỉ⣲ศᏊࡢ཯ᛂ⤒㊰ࢆ⣔⤫ⓗ࡟᥈⣴ࡋ㸪⤌ᡂࡸᵓ㐀ࡀࢡࣛࢫࢱ࣮ࡢάᛶ
࡟࡝ࡢࡼ࠺࡞ᙳ㡪ࢆ୚࠼ࡿ࠿᳨ウࡍࡿ㸬࠙ィ⟬ᡭἲࠚᮏ◊✲࡛ࡣ ADDF ἲࢆ⏝࠸࡚ Au-Ag ྜ㔠ࢡࣛࢫࢱ࣮ࡢྛ⤌ᡂࡢᖹ⾮ᵓ㐀Ỵᐃࢆ⾜࠸㸪ᚓࡽࢀࡓᖹ⾮ᵓ㐀(᭱Ᏻᐃᖹ⾮ᵓ㐀࠿ࡽ 20 kJ/mol ௨ෆࡢᵓ㐀)࡜Ỉ⣲ศᏊࡢ཯ᛂ⤒㊰᥈⣴ࢆ⾜ࡗࡓ㸬ࡲࡓ㸪㔜せ࡞⤒㊰࡟㛵ࡋ࡚ࡣศᏊ㌶㐨ࢆồࡵ࡚཯ᛂᛶࢆ᳨ウࡋࡓ㸬ᵓ㐀Ỵᐃࡸ཯ᛂ⤒㊰᥈⣴࡟ࡣ GRRM ࣉࣟࢢ࣒ࣛ㛤Ⓨ⪅∧ࢆ౑ࡗࡓ㸬࢚ࢿࣝࢠ࣮࡜࢚ࢿࣝࢠ
࣮໙㓄ࡣ PBE ỗ㛵ᩘ࡟ᇶ࡙ࡃᐦᗘỗ㛵ᩘἲ(DFT)࡟ࡼࡾィ⟬ࡋࡓ㸬ィ⟬ࣉࣟࢢ࣒ࣛࡣ SIESTAࢆ౑࠸㸪ᇶᗏ㛵ᩘࡣ DZP ࢆ⏝࠸ࡓ㸬ศᏊ㌶㐨ࡢィ⟬࡟ࡣ Gaussian09 ࢆ฼⏝ࡋࡓ㸬࠙⤖ᯝࠚᅗ 1 ࡟ n = 7 ࡢሙྜ࡟ࡘ࠸࡚ྛ⤌ᡂ࡛ࡢ᭱ࡶ㞀ቨࡢప࠸ H-H ⤖ྜゎ㞳ࡢ࢚ࢿࣝࢠ࣮
ࣉࣟࣇ࢓࢖ࣝࢆ♧ࡍ㸬ࡇࡢ࡜ࡁ㸪H-H ⤖ྜゎ㞳ࡢ⮬⏤࢚ࢿࣝࢠ࣮㞀ቨࡀప࠸⛬ࢡࣛࢫࢱ࣮ࡢ
H-H ⤖ྜάᛶ໬⬟ࡀ㧗࠸࡜ゝ࠼ࡿ㸬ࡇࢀࡽࡢ⤒㊰࡛ࡣࢡࣛࢫࢱ࣮࡟Ỉ⣲ศᏊࡀ྾╔ࡋࡓ≧ែ([Aun-mAgm]-H2)࠿ࡽ㑄⛣≧ែ(TS)ࢆ⤒࡚Ỉ⣲ศᏊࡀゎ㞳ࡋࡓ≧ែ
(H-[Aun-mAgm]-H)࡬࡜⮳ࡿ㸬ᅗ 1 ࡢ⦪㍈ࡣᅗ
2 ࡟♧ࡍྛ⤌ᡂ࡛ࡢࢡࣛࢫࢱ࣮ࡢ᭱Ᏻᐃᵓ
㐀࡜Ỉ⣲ศᏊࡀ↓㝈࡟㞳ࢀࡓ≧ែ࡛ࡢ⮬⏤࢚ࢿࣝࢠ࣮ࡢ࿴࡟ᑐࡍࡿ┦ᑐ࢚ࢿࣝࢠ
್࣮࡛࠶ࡿ㸬ࡲࡓ㸪ᅗ 1 ࡢ[Aun-mAgm]-H2 ࡢᵓ㐀ࢆᅗ 3 ࡟♧ࡍ㸬

ᅗ 1㸬n 㸻7 ࡢ H-H ⤖ྜάᛶ໬ࡢ཯ᛂ㞀ቨ

ᅗ 1 ࠿ࡽࢃ࠿ࡿࡼ࠺࡟ m = 0-2 ࡢࢡࣛࢫࢱ࣮ࡢ㞀ቨࡀపࡃ㸪m = 0,1 ࡛ࡣάᛶ໬⬟ࡀ࡯ࡰ➼ࡋ࠸㸬ࡲࡓ㸪ᅗ 2 ࡜ᅗ 3 ࡢẚ㍑࠿ࡽ㸪ࢡࣛࢫࢱ࣮ࡢ᭱Ᏻᐃᵓ㐀ࡀ᭱ࡶ㧗࠸άᛶ

Au7Ag0

Au6Ag1

Au5Ag2

Au4Ag3

Au3Ag4

Au2Ag5

Au1Ag6

Au0Ag7ࢆ♧ࡍ࡜ࡣ㝈ࡽ࡞࠸ࡇ࡜ࡀࢃ࠿ࡿ㸬ᅗ 3 ࠿ࡽάᛶ໬⬟ࡢ㧗࠸ࢡࣛࢫࢱ࣮ࡣᖹ㠃ᵓ㐀ࢆ࡜ࡗ࡚࠸ࡿ஦ࡀࢃ࠿ࡿ㸬ࡑࡢ௚࡟ࡘ࠸࡚
ࡣ඲࡚❧యᵓ㐀࡛࠶ࡾ㸪m = 7 ࡢ㞀ቨࡀ᭱ࡶ㧗࠸㸬m = 3-6 ࡢሙྜ࡛ࡣ㸪m ࡀወᩘࡢࢡ

ᅗ 2㸬
㸬n = 7 ࡢ᭱Ᏻᐃࢡ
ࢡࣛࢫࢱ࣮ᵓ㐀ࣛࢫࢱ࣮ࡢ᪉ࡀ㧗࠸άᛶ໬⬟ࢆᣢࡗ࡚࠸
ࡿ㸬ࡲࡓ㸪അᩘ࣭ወᩘࡑࢀࡒࢀࡢ୰࡛ࡣ㔠ࡢ๭ྜࡀከ࠸࡯࡝άᛶ໬⬟ࡀ㧗࠸㸬
ᅗ 3 ࡟♧ࡍࡼ࠺࡟㸪ྛ⤌ᡂࡢ᭱ࡶప࠸㞀[Au7Ag0]-H2[Au6Ag1]-H2[Au5Ag2]-H2[Au4Ag3]-H2[Au3Ag4]-H2[Au2Ag5]-H2[Au1Ag6]-H2[Au0Ag7]-H2

ቨ࡬⧅ࡀࡿ⤒㊰࡛ࡣ㸪Ỉ⣲ศᏊࡣ㔠ཎᏊ࡟྾╔ࡋ࡚࠸ࡿ㸬㟁Ẽ㝜ᛶᗘࡣ Au > Ag ࡛࠶
ࡿࡢ࡛ Au ࡀ㟁Ꮚ㇏ᐩ࡟࡞ࡗ࡚࠾ࡾ㸪ࡑࡇ࠿ࡽ㟁Ꮚࡢ౪୚ࢆཷࡅ࡚ H-H ⤖ྜࡀάᛶ໬ࡍࡿ⤒㊰ࡢ㞀ቨࡀ᭱ࡶప࠸ࡓࡵ࡜⪃࠼

ᅗ 3㸬
㸬ᅗ 1 ࡢ[Aun-mAgm]-H2 ࡢᵓ㐀ࡽࢀࡿ㸬ศᏊ㌶㐨ࢆぢࡿ࡜㸪ᅗ 4 ࡢࡼ࠺࡟ᖹ㠃ᙧࡢ[Aun-mAgm]-H2 ࡟ࡘ࠸࡚ࡣỈ⣲ศᏊࡢ LUMO ࡀࢡࣛࢫࢱ࣮ࡢ SOMO ࡜㔜࡞ࡿࡼ࠺࡟྾╔ࡋ࡚࠸ࡿ஦ࡀࢃ࠿
ࡗࡓ㸬ࡇࡢࡇ࡜࠿ࡽࡶࢡࣛࢫࢱ࣮࠿ࡽ㟁Ꮚ౪୚ࢆཷࡅ
࡚ H-H ⤖ྜࡀάᛶ໬ࡉࢀ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿ㸬n 㸻 8,9 ࡢࢡࣛࢫࢱ࣮࡟ࡘ࠸࡚ࡣᙜ᪥ሗ࿌ࡍࡿ㸬ᅗ 4㸬Au7Ag0 ࡜Ỉ⣲ศᏊࡢศᏊ㌶㐨

࠙ཧ⪃ᩥ⊩ࠚ
[1] S. Maeda, K. Ohno, and K. Morokuma, Phys. Chem. Chem. Phys., 15, 3683 (2013).

2P130
GRRM/AFIR ἲ࡜㑄⛣≧ែ⌮ㄽࢆ⤌ࡳྜࢃࡏࡓゐ፹ࢧ࢖ࢡࣝࡢ㏿ᗘゎᯒ―⤒㊰➇ྜࢆ⪃៖ࡋࡓ఩⨨࠾ࡼࡧ❧య㑅ᢥᛶ―(໭኱㝔⥲ྜ໬Ꮫ 1, ໭኱㝔⌮ 2) ‫ۑ‬ఫ㇂ 㝧㍜ 1, ๓⏣ ⌮ 2, Ṋḟ ᚭஓ 2

Kinetic analysis of catalytic cycles on the basis of path searching by GRRM/AFIR andmodeling by Transition State Theory—Regio- and stereo-selectivity with considering competition of multiple pathways—(Hokkaido Univ.) ࠐYosuke Sumiya, Satoshi Maeda, and Tetsuya Taketsugu[◊✲⫼ᬒ]
ࡇࢀࡲ࡛࡟ᵝࠎ࡞ゐ፹ࢧ࢖ࢡࣝࡢ඲ㇺࡀ㔞Ꮚ໬Ꮫィ⟬࡟ࡼࡗ࡚ゎ᫂ࡉࢀ࡚ࡁࡓࠋከࡃࡢ
ඛ⾜◊✲࡛ࡣࠊ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝୖࡢ᭱ࡶ㧗࠸㑄⛣≧ែ(TS)ࢆᚊ㏿ẁ㝵࡜௬ᐃࡋࠊࡑ
ࡢ TS ࢆゎᯒࡍࡿࡇ࡜࡛཯ᛂࡢ㐍⾜ࡋࡸࡍࡉࡸ㑅ᢥᛶࡀ㆟ㄽࡉࢀ࡚ࡁࡓࠋࡋ࠿ࡋࠊࢱ࣮ࣥ࢜
࣮ࣂ࣮㢖ᗘ(TOF)ࡸ఩⨨࠾ࡼࡧ❧య␗ᛶయࡢ⏕ᡂẚ࡞࡝ࠊᐇ㦂್࡜ẚ㍑ࡋᚓࡿ㔞ࢆ㆟ㄽࡍࡿ㝿࡟ࡣࠊ࢚ࢿࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࢆ㆟ㄽࡍࡿࡔࡅ࡛ࡣ୙༑ศ࡛࠶ࡿࠋ౛࠼ࡤḟᘧ࡛⾲ࡉࢀ
ࡿ TOF ࡛ࡣࠊ‫⾲ࡢݒ‬ᘧ࡟ࢧ࢖ࢡࣝ୰ࡢ඲࡚ࡢ୰㛫య࡜ TS ࡢ⮬⏤࢚ࢿࣝࢠ࣮࡜⃰ᗘࡀྵࡲࢀࠊ
ࡇࢀࡽ඲࡚ࡀ TOF ࡢィ⟬್࡟ຠ࠸࡚ࡃࡿࠋ
 ൌ

‫ݒ‬
ሺ‫ݒ‬ǣ  ࡢ⏕ᡂ㏿ᗘࠊሾ ሿǣゐ፹⃰ᗘሻሾ ሿ

ᐇ㝿࡟ࠊ᭱ࡶ㧗࠸ TS ࡢࡳࡀ TOF ࡢィ⟬್ࢆᨭ㓄ࡍࡿࢃࡅ࡛ࡣ࡞࠸ࡇ࡜ࡀ࠸ࡃࡘ࠿ࡢ⣔࡟࠾࠸࡚ሗ࿌ࡉࢀ࡚࠸ࡿ[1]ࠋࡉࡽ࡟ࠊ཯ᛂࡢᮏ➽࡜ࡣ㛵ಀ࡞࠸(ゐ፹ࢧ࢖ࢡࣝ୰࡟㟢ࢃ࡟⌧ࢀ࡞࠸)୰㛫యࡀࢧ࢖ࢡࣝຠ⋡ࢆⴠ࡜ࡍ஦౛ࡶሗ࿌ࡉࢀ࡚࠾ࡾ[2]ࠊὀពࡀᚲせ࡛࠶ࡿࠋ
TOF ࡸ␗ᛶయࡢ⏕ᡂẚ࡞࡝ࢆぢ✚ࡶࡿ࡟ࡣࠊձ㛵୚ࡋᚓࡿ඲࡚ࡢ୰㛫య࡜ TS ࢆ᥈⣴ࡋࠊղࡑࢀࡽࢆ⏝࠸ࡓ㏿ᗘゎᯒ࡟ࡼࡗ࡚཯ᛂ≀ࠊ඲࡚ࡢ୰㛫యࠊ⏕ᡂ≀ࠊ࠾ࡼࡧࠊ඲࡚ࡢ๪⏕ᡂ≀ࡢ⃰ᗘࡢ᫬㛫Ⓨᒎࢆࢩ࣑࣮ࣗࣞࢩࣙࣥࡍࡿᚲせࡀ࠶ࡿࠋࡇࢀࡲ࡛ࠊ」㞧࡞ゐ፹ࢧ࢖ࢡ࡛ࣝࡣձࢆ⣔⤫ⓗ࡟⾜࠺ࡇ࡜ࡀᅔ㞴࡛࠶ࡗࡓࡀࠊ㏆ᖺࠊᙜ◊✲ᐊࡢ๓⏣ࡽ࡟ࡼࡾ㛤Ⓨࡉࢀ
ࡓ GRRM ࣉࣟࢢ࣒ࣛ࡟ࡼࡾࡇࢀࡀྍ⬟࡜࡞ࡗࡓࠋࡑࡇ࡛ᮏ◊✲࡛ࡣࠊGRRM/AFIR ἲ[3]࡟
ࡼࡿ཯ᛂ⤒㊰⣔⤫᥈⣴࡛๪⏕ᡂ≀࡬ࡢ⤒㊰ࡸࢧ࢖ࢡࣝ࡟㟢ࢃ࡟⌧ࢀ࡞࠸୰㛫యࢆྵࡴゐ፹ࢧ࢖ࢡࣝࡢ඲ㇺࢆᵓ⠏ࡋࠊࡉࡽ࡟㑄⛣≧ែ⌮ㄽ࡟ᚑࡗࡓ㏿ᗘゎᯒ࡟ࡼࡗ࡚ TOF ࡸ఩⨨࠾ࡼࡧ❧య␗ᛶయ࡞࡝๪⏕ᡂ≀ࢆྵࡵࡓ඲⏕ᡂ≀ࡢ⏕ᡂẚࢆண ࡍࡿࣉࣟࢢ࣒ࣛࢆ㛤Ⓨࡋࡓࠋ[ィ⟬ᡭἲ]
༢⣧࠿ࡘศᒱࡀከ࠸ゐ፹ࢧ࢖ࢡࣝࡢ౛࡜ࡋ࡚ࠊᅗ 1 ࡢ࢜ࣞࣇ࢕࣓ࣥࢱࢭࢩࢫ཯ᛂࢆ㑅ࢇࡔࠋ࢜ࣞࣇ࢕ࣥ࡜ࡋ࡚ࣉࣟ࣌ࣥࢆࠊゐ፹࡜ࡋ࡚ CH2 ࢝ࣝ࣋ࣥࢆ᭷ࡍࡿᅗ 2 ࡢ Ru ゐ፹ࢆ⏝࠸ࡓࠋ୰㛫య࠾ࡼࡧ TS ࡣ GRRM/AFIR ἲ࡛᥈⣴ࡋࡓࠋࡲࡓࠊ཯ᛂ≀ࡀ㓄఩ࡲࡓࡣゎ㞳ࡍࡿ↓㞀ቨࡢ⤒㊰࡟ᑐࡋ࡚ࡣኚศᆺ㑄⛣≧ែ(VTS)ࢆồࡵࡓࠋᚓࡽࢀࡓ඲࡚ࡢ TS ࠾ࡼࡧ VTS ࡛࢝ࣀࢽ࢝ࣝ㏿ᗘᐃᩘࢆồࡵࠊ୍㐃ࡢ㏿ᗘᘧࢆ 4 ḟࡢ Runge-Kutta ἲ࡟ࡼࡾゎᯒࡋࡓࠋᅗ 1. ࢜ࣞࣇ࢕࣓ࣥࢱࢭࢩࢫࡢゐ፹ࢧ࢖ࢡࣝ

ᅗ 2. ゐ፹࡜ࡋ࡚⏝࠸ࡓ Ru 㘒యィ⟬౛][ィᅗ 3 ࡟ࣉࣟ࣌ࣥࡀ VTS ࢆ⤒࡚ゐ፹࡟㓄఩ࡋࠊTS ࢆ⤒࡚࣓ࢱࣛࢧ࢖ࢡࣝ࡜࿧ࡤࢀࡿ 4 ဨ⎔ᵓ㐀ࢆᙧᡂࡋࠊࡉࡽ࡟ TS ࢆ⤒࡚ࣉࣟ࣌ࣥࡲࡓࡣ࢚ࢳࣞࣥࢆ⏕ᡂࡍࡿ཯ᛂ⤒㊰࡟ἢࡗࡓ࢚ࢿ
ࣝࢠ࣮ࣉࣟࣇ࢓࢖ࣝࢆ♧ࡍࠋᅗ 3 ࡣࠊᅗ 1 ࡢゐ፹ࢧ࢖ࢡࣝࡢ༙࿘ศ࡟┦ᙜࡍࡿࠋ࢚ࢳࣞࣥ
ࡀゎ㞳ࡋࡓᚋࡢ㘒యࡣ C(H)CH3 ࢝ࣝ࣋ࣥࢆ᭷ࡋࠊࡉࡽ࡟ࣉࣟ࣌ࣥ࡜཯ᛂࡍࡿࡇ࡜࡟ࡼࡗ࡚
C(CH3)2 ࢝ࣝ࣋ࣥࢆᣢࡘ㘒య࡬࡜ኚ໬ࡋᚓࡿࠋࡲࡓࠊࣉࣟ࣌ࣥྠኈࡢ࣓ࢱࢭࢩࢫ࡛ࡣࠊ࢚ࢳ
ࣞࣥ࡜ࣈࢸࣥࡀ⏕ᡂࡋࠊࡉࡽ࡟ࠊࣈࢸࣥ࡜ࣉࣟ࣌ࣥࠊࣈࢸࣥ࡜ࣈࢸࣥ࡞࡝ࠊᵝࠎ࡞࣓ࢱࢭ
ࢩࢫ཯ᛂࡀ㐍⾜ࡋᚓࡿࠋᙜ᪥ࡣࠊ඲࡚ࡢ࣓ࢱࢭࢩࢫ཯ᛂ⤒㊰ࢆ⪃៖ࡋࡓ㏿ᗘゎᯒࢆ⾜࠸ࠊ
TOF ࠾ࡼࡧ⏕ᡂ≀࡜๪⏕ᡂ≀ࡢ⏕ᡂẚࢆ⟬ฟࡍࡿࠋࡉࡽ࡟ࠊTOF ࡸ⏕ᡂẚࡢண ࡔࡅ࡛࡞ࡃࠊࡇࢀࡽࢆᨭ㓄ࡍࡿ୰㛫యࡸ㑄⛣≧ែࢆᩘ್ⓗ࡟≉ᐃࡍࡿᶵ⬟ࡶᐇ⿦ࡍࡿࠋ

ᅗ 3. B3LYP ἲ࡟ࡼࡿ Ru ゐ፹(ᅗ 2)ࢆ⏝࠸ࡓࣉࣟ࣌ࣥࡢ࣓ࢱࢭࢩࢫ཯ᛂ⤒㊰[1] S. Kozuch and J. M. L. Martin, Chem. Phys. Chem. 12, 1413 (2011).
[2] A. Uhe, S. Kozuch and S. Shaik, J. Comput. Chem. 32, 978 (2010).
[3] S. Maeda, K. Ohno and K. Morokuma, Phys. Chem. Chem. Phys. 15, 3683 (2013).

2P131
GRRM ࡟ࡼࡿࣃࣛࢪ࣒࢘ྵ᭷ᅛᐃ໬࢖࢜ࣥᾮయゐ፹ࡢ࢝ࣝ࣎ࢽ࣮ࣞࢩࣙࣥ཯ᛂࡢᶵᵓゎ᫂㸦ᮾ኱㝔᪂㡿ᇦ㸨࣭Institute of Chemical Technology㸨㸨㸧‫ۑ‬బࠎᮌᓅᙪ㸨࣭Khedkar
Mayur V. 㸨㸨࣭B.M.Bhanage㸨㸨

GRRM study for mechanism of carbonylation reactions catalyzed by Pd
ion-containing immobilized ionic liquid catalyst
㸦University of Tokyo, Institute of Chemical Technology㸧Takehiko Sasaki㸨࣭Khedkar Mayur
V. 㸨㸨࣭B.M.Bhanage㸨㸨[ᗎ] ࢩࣜ࢝ᢸయࡢỈ㓟ᇶ࡟ࠊ1-࣓ࢳ࣮ࣝ3-ࢺ࣓ࣜࢺ࢟ࢩࣜࣝࣉࣟࣆࣝ࢖࣑ࢲࢰ࣒ࣜ࢘
ࢡࣟࣜࢻࢆ཯ᛂࡉࡏࡿࡇ࡜࡛ࠊᅛᐃ໬࢖࢜ࣥᾮయゐ፹ࢆㄪ〇ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
[PdCl4]2-࢔ࢽ࢜ࣥࢆᑟධࡋࡓሙྜ࡟ࠊࣚ࢘໬࢔ࣞࣥ࡜୍㓟໬Ⅳ⣲ࠊ࢔ࣝࢥ࣮ࣝ(ࡲࡓࡣࣇ࢙ࣀ࣮ࣝࠊ࢔࣑ࣥ)ࢆ཯ᛂ≀࡜ࡋࡓ࢝ࣝ࣎ࢽ࣮ࣞࢩࣙࣥ཯ᛂࡀ㧗ຠ⋡࡛㐍⾜ࡍࡿࡇ࡜ࡀぢฟࡉࢀࡓࠋᵝࠎ࡞ⰾ㤶᪘࢚ࢫࢸࣝ໬ྜ≀ࠊ࢔࣑ࢻ໬ྜ≀ࢆᑟࡃゐ፹཯ᛂ࡜ࡋ࡚
฼⏝ྍ⬟࡛࠶ࡿࠋࡇࡢ᭷ຠ࡞ゐ፹཯ᛂࡢᶵᵓࢆゎ᫂ࡍࡿࡓࡵ࡟ࠊGaussian09 ࡜
GRRM ࢆ⏝࠸࡚ィ⟬໬Ꮫⓗ᳨ウࢆ⾜ࡗࡓࠋ[ィ⟬᪉ἲ] ᵓ㐀᭱㐺໬࡜཯ᛂ⤒㊰᥈⣴࡟ࡣࠊGRRM1) ࡜ Gaussian09 ࢆ⏝࠸ࡓࠋPd࡜ I ࡢᇶᗏ㛵ᩘ࡜ࡋ࡚ࡣࠊLANL2DZࠊ H,C,N,O ࡟ࡘ࠸࡚ࡣࠊ6-311G ࢆ⏝࠸ࡓࠋࡲࡓࠊᐦᗘỗ㛵ᩘ࡜ࡋ࡚ࠊPBE1PBE ࢆ⏝࠸ࡓࠋ[⤖ᯝ࡜⪃ᐹ]ᐇ㦂⤖ᯝ࡜ࡋ࡚ぢฟࡉࢀ࡚࠸ࡿࡇ࡜ࢆࡣࡌࡵ࡟グ㏙ࡍࡿࠋᡃࠎࡣࠊ࢖࢜ࣥᾮయࡢᛶ㉁ࢆ฼⏝ࡋ࡚ᅛయゐ፹ࢆタィࡍࡿࠊ࡜࠸࠺ほⅬ࠿ࡽࠊ࢖࣑ࢲࢰ࣒ࣜ࢘࢝ࢳ࢜ࣥࢆྵࡴ
࢖࢜ࣥᾮయศᏊࢆᢸయ⾲㠃࡟ᅛᐃ໬ࡋࠊ࢝࢘ࣥࢱ࣮࢔ࢽ࢜ࣥ࡜ࡋ࡚ࠊ㔠ᒓሷ໬≀࢖࢜ࣥࢆᑟධࡋࠊ࢟ࣕࣛࢡࢱࣜࢮ࣮ࢩࣙࣥࠊ᭷ᶵྜᡂ཯ᛂゐ፹࡜ࡋ࡚ࡢᛂ⏝ࢆ⾜ࡗ࡚ࡁ࡚࠸ࡿ 2,3)ࠋ
ࢫ࣮࣒࢟㸯࡟ᅛᐃ໬ࡢᡭ㡰ࢆ♧ࡍࠋᵝࠎ࡞㑄⛣㔠ᒓ࢖࢜ࣥࡀᐜ᫆࡟ᑟධ࡛ࡁࠊ෌౑⏝ྍ⬟࡞ゐ፹⣔ࡀᚓࡽࢀNࡿࡇ࡜ࡀ฼Ⅼ࡛࠶ࡿࠋ௒
343 K
Cl
3 N
(MeO)3Si
3 Cl+(OMe)3SiN+
48 hᅇࡣࠊ[PdCl4]2-ࢆᑟධࡋNࡓゐ፹ ImmPd_IL ࢆ⏝(1)
1- Methylimidazole࠸࡚ࠊ࢝ࣝ࣎ࢽ࣮ࣞࢩࣙ
OH
Silica(Aerosil 300),
Toluene, reflux 48 hࣥ཯ᛂ࡬ࡢ㐺⏝ࢆ⾜ࡗOHࡓࠋ
ImmPd-ILࢫ࣮࣒࢟㸯࢖࢜ࣥᾮయᅛᐃ໬

PdCl2

ACN,
Reflux, 24h

SiO

O
O

Si

3 N

OMe

Imm-ILCl+

N࢔ࣝࢥ࣮ࣝࡀ཯ᛂ≀ࡢሙྜ࡟ࠊ࣮ࣚࢻ࣋ࣥࢮ

ࣥࠊ୍㓟໬Ⅳ⣲ࠊ࣓ࢱࣀ࣮ࣝࠊ㸦ࡲࡓࡣ࢚ࢱࣀ࣮ࣝ㸧ࡢሙྜࡢ཯ᛂࡣࠊ཰⋡ 94-95㸣
࡛ᑐᛂࡍࡿ⏕ᡂ≀ࡀᚓࡽࢀࡓࠋ᭦࡟ࠊ࣮ࣚࢻ࣋ࣥࢮࣥࡢㄏᑟయࡸ࢔ࣝࢥ࣮ࣝࡢᵓ㐀ࢆኚ࠼ࡓሙྜ࡟ࡶࠊ70%௨ୖࡢ཰⋡࡛⏕ᡂ≀ࡀᚓࡽࢀࡿࡇ࡜ࡀศ࠿ࡗࡓࠋྛ⏕ᡂ≀ࡢᵓ㐀ࡣࠊNMR ᐃ࡟ࡼࡾྠᐃࡋ࡚࠸ࡿࠋ
ゐ፹ࢆᅇ཰ࡋ
O
࡚ࠊ⧞ࡾ㏉ࡋ౑
HO-R1
OR1⏝ࡋࡓሙྜࡶࠊ
O
㸲ᅇ෌౑⏝ࡋ࡚
OH
R
R
I
2ࡶࠊ཰⋡ࡣࠊ89㸣
O
ImmPd-IL
R2
࡜㧗࠸್ࢆ♧ࡋࠊCOO
RR
ᮏゐ፹ࡀ㧗άᛶ
NHR3R4
NR3R4
ࢆ⥔ᣢࡋ࡚࠸ࡿ R = H, CH3, OCH3, NO2, Clࡇ࡜ࡀࢃ࠿ࡿࠋ R1 = CH3, C2H5, n-C4H5, benzyl
R
R = H, CH ,OCH3, Cl࢔ࣝࢥ࣮ࣝࡢ௦ R2, R = H, 3aryl, alkylࢫ࣮࣒࢟㸰 ࢝ࣝ࣎ࢽ࣮ࣞࢩࣙࣥ཯ᛂ
34ࢃࡾ࡟ࠊᵝࠎ࡞
ࣇ࢙ࣀ࣮ࣝㄏᑟయࢆ཯ᛂ≀࡜ࡋ࡚౑⏝ࡋࡓ
ሙྜࡶࠊ70%௨ୖࡢ཰⋡࡛ᑐᛂࡍࡿ⏕ᡂ≀ࡀᚓࡽࢀ࡚࠾ࡾࠊ཯ᛂᛶࡢ㧗ࡉࢆ♧ࡋ࡚࠸ࡿࠋ࢔࣑ࣥ㢮ࢆ཯ᛂ≀࡜ࡋࡓሙྜ࡟ࠊ㸯⣭࢔࣑ࣥࠊࡲࡓࡣ㸰⣭࢔࣑ࣥࢆ౑⏝ࡋࡓሙྜࠊ
཯ᛂࡀⰋዲ࡟㐍⾜ࡋࡓࠋⰾ㤶᪘࢔࣑ࣥࡔࡅ
࡛࡞ࡃࠊ⬡⫫᪘࢔࣑ࣥࡶ 80%௨ୖࡢ཰⋡࡛཯ᛂࡋ࡚࠸ࡿࠋ࡞࠾ࠊ࣮ࣚࢻ࢔ࣞࣥ࡟ࢽࢺ
ࣟᇶ࡞࡝ࡢ㟁Ꮚ྾ᘬᛶࡢ⨨᥮ᇶࡀ⤖ྜࡋࡓ ᅗ㸯 CO ࡜࣮ࣚࢻ࣋ࣥࢮࣥࡀ Cl ࡜⨨᥮ࡋሙྜ࡟ࡣ཰⋡ࡀୗࡀࡿഴྥࡀㄆࡵࡽࢀࡓࠋ ࡓ୰㛫య
XPS ᐃࢆ⾜ࡗࡓ࡜ࡇࢁࠊPd ✀ࡀࠊ཯ᛂ࡟ࡼࡗ࡚ࠊ㑏ඖࢆཷࡅ࡚ࠊ㸮౯ࡢ࣓ࢱࣜࢵ
ࢡ࡞ Pd ✀࡟ኚ໬ࡋ࡚࠸ࡿࡇ࡜ࡀぢฟࡉࢀࡓࠋ ཯ᛂᶵᵓࡢィ⟬࡟ᙜࡓࡗ࡚ࡣࠊࡲࡎࠊ[PdCl4]2-ࡢ྾╔࡟㛵ࡋ᳨࡚ウࢆ⾜ࡗࡓࠋX ⥺⤖ᬗゎᯒࡢ⤖ᯝ࠿ࡽࡶࠊࡇࡢ࢔ࢽ࢜ࣥࡣᖹ㠃㸲㓄఩ࢆࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗ࡚࠸ࡿࠋ
ࡇࡢ࢔ࢽ࢜ࣥࡢ≧ែ࡟㛵ࡋ࡚ࡣࠊCO ࡟ࡘ࠸࡚ࡶࠊ࢔࣑ࣥ࡟ࡘ࠸࡚ࡶ྾╔ࡀ࡛ࡁ࡞࠸
ࡇ࡜ࡀศ࠿ࡗࡓࠋᚑࡗ࡚ࠊ཯ᛂ㐣⛬࡜ࡋ࡚ࡣࡲࡎ Cl ࡀ࢝ࣝ࣎ࢽࣝ㓄఩Ꮚ࡟⨨᥮ࡉࢀࡿࡇ࡜ࠊ᭦࡟ࡶ࠺ࡦ࡜ࡘࡢ Cl ࡀ࣮ࣚࢻ࣋ࣥࢮࣥ࡟⨨᥮ࡉࢀࡿࡇ࡜ࢆ௬ᐃࡋ࡚ࡑࡢᵓ
㐀ࡢ᭱㐺໬ࢆ⾜ࡗࡓࠋࡇࡢᵓ㐀ࢆᅗ㸯࡟♧ࡍࠋࡇࡢ୰㛫యࡢ C̿I ⤖ྜࡀษ᩿ࡋ࡚ࠊ
Pd-I ⤖ྜࡣࡑࡢࡲࡲಖᏑࡉࢀ࡚ࠊ࢝ࣝ࣎ࢽࣝ㓄఩Ꮚ࡜ࣇ࢙ࢽࣝᇶࡢ⤖ྜࡀ⏕ᡂࡍࡿ୰㛫యࢆ⤒࡚ࠊ᭦࡟࢔ࣝࢥ࣮ࣝ࡜཯ᛂࡍࡿࡇ࡜࡛⏕ᡂ≀ࡀ⏕ᡂࡍࡿ࡜ྠ᫬࡟ Pd ࠿ࡽ⬺㞳ࡋࠊPd-H ⤖ྜࡀṧࡿࠊ࡜࠸࠺཯ᛂ⤒㊰࡟ࡘ࠸࡚ࠊ⌧ᅾ᳨ウࢆ⾜ࡗ࡚࠸ࡿࠋ
ᮏ◊✲ࡣࠊJSPS-DST ஧ᅜ㛫஺ὶ஦ᴗ㸦ඹྠ◊✲㸧࠿ࡽᨭ᥼ࢆཷࡅࡓࠋ
[ཧ⪃ᩥ⊩]
1) S. Maeda and K.Ohno, Chem. Phys. Lett. 404, 95 (2005).
2)T. Sasaki, C. Zhong, M. Tada, and Y. Iwasawa, Chem. Commun. 2506-2508 (2005).
3) T. Sasaki, M.Tada, C.Zhong, T. Kume, and Y. Iwasawa, J. Mol. Catal. A-Chemical, 279, 200-209
(2008).

࡟ࡊ࡝ࠞ੤឵ 0' ෸߮ $ELQLWLR ࡈ࡜ࠣࡔࡦ࠻ 02 ⸘▚ࠍ⸘▚ࠍ↪޿ߚ
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ੑ㊂૕ߩ᳓ਛߢߩ
᳓ਛߢߩ቟ቯ㈩ᐳត⚝ߢߩ቟ቯ㈩ᐳត⚝቟ቯ㈩ᐳត⚝
㧔⼾ᯅᛛⴚ⑼ቇᄢቇᄢቇ㒮 ‫⵾↰᧛ޔ‬૞ᚲ 㧕ጟᧄᤩẴ ‫ޔ‬⍫㊁◊ᔒ ‫ޔ‬㊁᧛๺຦ ‫ޔ‬ᯫ⽴ା৻ ‫ޔ‬ᩙ↰ౖਯ 

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ߩᴦ≮ᴺ෸߮ᴦ≮⮎ߩ㐿⊒ߪ✕ᕆߩ⎇ⓥ⺖㗴ߣߥߞߡ޿ࠆ‫ޔߪߦ∝⊒ߩߎޕ‬⣖ౝߢߩࠕࡒࡠࠗ࠼
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$ȕ $ȕ  ߇ṁᶧਛߢ቟ቯߥੑ㊂૕ࠍᒻᚑߔࠆߎߣ߇␜ߐࠇߚ߇‫ޔ‬ੑ㊂૕ߩࠃ߁ߥዊߐߥಝ㓸૕ߩᒻᚑߪಝ㓸ߩᣧ޿Ბ㓏ߢ⍍ᤨߦ⿠ߎࠆߚ߼‫ޔ‬ታ㛎ᚻᴺߩߺࠍ↪޿ߚ㜞ಽ⸃⢻ߩ᭴ㅧ᳿ቯߪ࿎㔍
ߢ޽ࠆ>@‫ޔ߼ߚߩߘޕ‬ฎౖಽሶേജቇ 0' ᴺࠍ↪޿ߚಽሶࠪࡒࡘ࡟࡯࡚ࠪࡦ߇‫ޔ‬᭽‫ ߥޘ‬$ȕ ಝ㓸૕ࡕ࠺࡞ߦኻߒߡታⴕߐࠇ‫ޔ‬ಝ㓸૕ߩ᭴ㅧߦ㑐ߔࠆ㊀ⷐߥᖱႎࠍᓧߡ޿ࠆ‫ޕ‬ᧄ⎇ⓥߢߪ‫ࠞ࡝ࡊ࡟ޔ‬੤឵ 0' 5(0' ᴺࠍ↪޿‫ޔ‬$ȕ  ੑ㊂૕ߩ᳓ਛߢߩ቟ቯ㈩ᐳࠍᐢ▸࿐ߦត⚝ߒ‫ޔ‬DELQLWLR ࡈ࡜ࠣࡔࡦ࠻ಽሶ゠㆏ )02 ⸘▚ࠍ↪޿‫ᦨޔ‬቟ቯ㈩ᐳࠍ᳿ቯߒߚ‫)ޔߦࠄߐޕ‬02⸘▚ߩ⚿ᨐࠍၮߦ‫ޔ‬$ȕ  ߦ฽߹ࠇࠆߤߩࠕࡒࡁ㉄߇ੑ㊂૕ߩᒻᚑߦ㊀ⷐߢ޽ࠆ߆ࠍ⸃᣿ߒߚ‫ޕ‬ߎߩ⚿ᨐߪ‫ޔ‬$ȕ ಝ㓸ᯏ᭴ߩೋᦼᲑ㓏ߩ⸃᣿ߦ‫ߥ↪᦭ޔ‬ᖱႎߦߥࠆߣ⠨߃ࠆ‫ޕ‬‫▚⸘ޣ‬ᚻᴺ‫ޤ‬ᧄ⎇ⓥߢߪ‫ޔ‬$ȕ  ੑ㊂૕ߩೋᦼ᭴ㅧߣߒߡ‫ޔ‬$ȕ  ✢⛽ߩታ㛎᭴ㅧ 3'%,'/01/02ࠍណ↪ߒߚ‫ߩࠄࠇߎޕ‬᭴ㅧࠍၮߦ‫ ߩ┵ᧃ &ޔ‬,OH ෸߮ $OD ࠍઃടߒߚ $ȕ  ੑ㊂૕᭴ㅧࠍ ୘૞ᚑߒ‫ޔ‬5(0' ෸߮ DELQLWLR)02 ⸘▚ࠍ↪޿‫ߩߘޔ‬ਛߢߩᦨ቟ቯ᭴ㅧࠍ᳿ቯߒߚ‫ᦨߩߘޕ‬቟ቯ᭴ㅧࠍၮߦ‫ޔ‬1 ᧃ┵ߩᱷၮࠍ⵬ቢߒߡ $ȕ  ੑ㊂૕᭴ㅧࠍ૞ᚑߒ‫ߩߘޔ‬᭴ㅧࠍ 5(0' ⸘▚ߩೋᦼ᭴ㅧߣߒߚ‫ޕ‬ᰴߦ‫ޔ‬਄⸥ߢ૞ᚑߒߚੑ㊂૕᭴ㅧߩ๟࿐ߦ  ୘ߩ᳓๺᳓ࠍઃടߒߡ᳓๺ߒ‫ࠞ࡝ࡊ࡟ߩߘޔ‬ࠍ ± . ߩ᷷ᐲ▸࿐ߢ  ୘૞ᚑߒ‫ ޔ‬QV ߩ 5(0' ⸘▚ࠍⴕߞߚ‫ࠄ߆▚⸘ߩߘޕ‬ᓧࠄࠇߚ ±. ߩ 0' ࠻࡜ࠫࠚࠢ࠻࡝߆ࠄ‫ᦨࠇߙࠇߘޔ‬ዊߩࡐ࠹ࡦࠪࡖ࡞ࠛࡀ࡞ࠡ࡯ࠍᜬߟ቟ቯ㈩ᐳࠍࠨࡦࡊ࡝ࡦࠣߒ‫ ޔ‬୘ߩઍ⴫᭴ㅧࠍᓧߚ‫ߩࠄࠇߎޕ‬ઍ⴫᭴ㅧࠍಽሶജቇ 00 ᴺߦࠃࠅᦨㆡൻߒ‫ޔ‬$ȕ  ੑ㊂૕ߩ᳓ਛߢߩ቟ቯ᭴ㅧࠍ᳿ቯߒߚ‫ޕ‬5(0' ෸߮ 00 ⸘▚ߢߪ‫ޔ‬ฎౖಽሶജ႐ ))6% ෸߮ 7,33(Z ᳓ಽሶࡕ࠺࡞ࠍ↪޿ߚ‫ᦨޕ‬ᓟߦ‫ᦨޔ‬ㆡൻߒߚ᳓๺᭴ㅧߦኻߒ‫ޔ‬03*ᴺࠍ↪޿ߚ DELQLWLR)02 ⸘▚ߦࠃࠅ‫⸃ࠍ࡯ࠡ࡞ࡀࠛޔ‬ᨆߒ‫ߩߘޔ‬୯ࠍၮߦ‫ᦨޔ‬቟ቯߥੑ㊂૕᭴ㅧࠍ᳿ቯߒߚ‫ߩߘޕ‬㓙‫ޔ‬$ȕ  ੑ㊂૕ߩ๟࿐  c ⒟ᐲߦሽ࿷ߔࠆ᳓๺᳓ࠍ㗼ߦ⠨ᘦߔࠆߎߣߦࠃ
ࠅ‫ޔ‬᳓๺᳓߇ੑ㊂૕ߩ቟ቯᕈߦਈ߃ࠆᓇ㗀ࠍ᣿ࠄ߆ߦߒߚ‫)ޔߦࠄߐޕ‬02 ⸘▚ߩ⚿ᨐ߆ࠄ‫ޔ‬$ȕ ߦ฽߹ࠇࠆߤߩࠕࡒࡁ㉄߇ੑ㊂૕ߩᒻᚑߦ㊀ⷐߢ޽ࠆ߆ࠍ᣿ࠄ߆ߦߒߚ‫ޕ‬‫⚿▚⸘ޣ‬ᨐߣ⠨ኤ‫ޤ‬±. ߩ 0' ࠻࡜ࠫࠚࠢ࠻࡝߆ࠄࠨࡦࡊ࡝ࡦࠣߒߚ  ୘ߩ $ȕ  ੑ㊂૕ߩઍ⴫᭴ㅧࠍ‫ޔ‬
00 ᴺࠍ↪޿ߡᦨㆡൻߒ‫ ߩࠄࠇߘޔ‬7RWDOHQHUJ\ ࠍ DELQLWLR)02 ᴺߦࠃࠅ⸘▚ߒߚ⚿ᨐࠍ 7DEOHߦ␜ߔ‫ޕ‬. ߩ 0' ࠻࡜ࠫࠚࠢ࠻࡝ߩઍ⴫᭴ㅧ )LJXUH ߇ᦨ቟ቯߣߥࠅ‫ߩઁߩߘޔ‬᭴ㅧࠃࠅ߽
ዋߥߊߣ߽  NFDOPRO ⒟ᐲ቟ቯߢ޽ࠆߎߣ߇ಽ߆ߞߚ‫ߩߎޕ‬᭴ㅧ߇ᦨ቟ቯߣߥࠆⷐ࿃ࠍ᣿ࠄ߆
ߦߔࠆߚ߼‫ޔ‬᳓๺ߒߚ $ȕ  ੑ㊂૕᭴ㅧࠍ‫ޔ‬ੑ㊂૕෸߮᳓๺᳓ߩߺߩ♽ߦಽߌ‫ޔ‬᳓๺᭴ㅧߣห
᭽ߦࠛࡀ࡞ࠡ࡯ࠍ᳞߼ߚ‫⚿ߩߘޕ‬ᨐ‫ޔ‬᳓๺ߒߚ $ȕ  ੑ㊂૕᭴ㅧߩ቟ቯᕈߪ‫ޔ‬$ȕ ੑ㊂૕⥄૕ߩ቟ቯᕈࠃࠅ߽‫ߩߘޔ‬๟࿐ߦሽ࿷ߔࠆ᳓๺᳓ห჻ߩಝ㓸ߦࠃࠆ቟ቯᕈߦ‫ࠅࠃޔ‬ᒝߊᓇ㗀ߐࠇࠆߎߣ
߇᣿ࠄ߆ߣߥߞߚ‫⚿ߩߎޕ‬ᨐߪ‫ޔ‬$ȕ  න㊂૕ߩ᳓๺᭴ㅧߦኻߔࠆ⸘▚⚿ᨐ>@ߣห᭽ߢ޽ࠆ‫ޕ‬)LJXUH  ߦ␜ߔࠃ߁ߦ‫ᦨޔ‬቟ቯ᭴ㅧߪන㊂૕㑆ߢ  ߟߩ ȕVKHHW ᭴ㅧࠍᒻᚑߒߡ޿ࠆ‫ߩࠄࠇߘޕ‬ȕVKHHW ᭴ㅧߪ‫ߩࠇߙࠇߘޔ‬න㊂૕ߩ /\V3KH ߩ㗔ၞ‫ޔ‬෸߮ 0RQRPHU ߩ ,OH0HW ߩ㗔ၞߣ
0RQRPHU ߩ ,OH0HW ߩ㗔ၞߢᒻᚑߐࠇߡ߅ࠅ‫ޔ‬ᓟ⠪ߩ ȕVKHHW ߪࠫ࠶ࡄ࡯᭽᭴ㅧࠍ᦭ߒߡ޿ࠆ‫ޕ‬߹ߚ‫ޔ‬0RQRPHU ߩಽሶౝߢߪ‫*ޔ‬OX$VQ ߩ㗔ၞߢ ȕ ࡋࠕࡇࡦ᭴ㅧࠍᒻᚑߒߡ޿ࠆ‫ޔߦࠄߐޕ‬ ୘ߩᦨㆡൻ᭴ㅧߩ  ᰴ᭴ㅧߩ․ᓽߣߒߡ‫ޔ‬9DO*O\ ߩ㗔ၞߦࡌࡦ࠼߿࠲࡯ࡦ᭴ㅧࠍ᦭ߒߡ޿
ࠆߎߣ߇᜼ߍࠄࠇࠆ‫ޕ‬ታ㛎>@ߢߪ‫ߩߎޔ‬㗔ၞߪࡌࡦ࠼ᚗ޿ߪ࠲࡯ࡦ᭴ㅧࠍᒻᚑߔࠆߎߣ߇␜ߐ
ࠇߡ߅ࠅ‫⎇ᧄޔ‬ⓥߩ⚿ᨐߪታ㛎ߣቯᕈ⊛ߦᲧセߢ߈ࠆߣ⠨߃ࠆ‫ޕ‬߹ߚ‫ޔ‬$ȕ  ߩੑ㊂૕᭴ㅧߩᒻᚑߦ㊀ⷐߥࠕࡒࡁ㉄ࠍ᣿ࠄ߆ߦߔࠆߚ߼‫ޔ‬$ȕ ߦ฽߹ࠇࠆࠕࡒ
ࡁ㉄ห჻ߩ⋧੕૞↪ࠛࡀ࡞ࠡ࡯ࠍ⸃ᨆߒߚ‫⚿ߩߘޕ‬ᨐߩ⹦⚦ߪ‫ޔ‬ᒰᣣߩࡐࠬ࠲࡯ߦߡ⊒⴫ߔࠆ‫ޕ‬

7DEOH7RWDOHQHUJLHV 7( IRUWKHVROYDWHG$ȕ   
GLPHUREWDLQHGE\DELQLWLR)02PHWKRG
0RQRPHU
7HPSHUDWXUH . 7( NFDOPRO ǻ7( 
0RQRPHU
1 
 
&
1

 
 
  
 
& 
 )LJXUH  0RVW VWDEOH VWUXFWXUH IRU WKH VROYDWHG
$ȕ   GLPHU VDPSOHG IURP WKH  . 
WUDMHFWRU\ VROYDWLQJ ZDWHU PROHFXOHV DUH QRW   VKRZQ0RQRPHULVEOXHZKLOH0RQRPHULVUHG ‫ޣ‬ෳ⠨ᢥ₂‫ޤ‬>@6RUHJKDQ%HWDO-%LRO&KHP  >@*DU]RQ5RGULJXH]:HWDO-%LRO
&KHP     >@ *DU]RQ5RGULJXH] : HW DO - %LRO &KHP   >@5LHN5HWDO(XU-%LRFKHP  >@=KDQJ6HWDO-6WUXFW%LRO  >@+RX/HWDO-$P&KHP6RF  >@2NDPRWR$
HW DO &KHP 3K\V /HWW     >@3HWNRYD $7HW DO 3URF 1DWO $FDG 6FL86$  >@3DUDYDVWX$.HWDO%LRSK\V-  

   ࠕࡒࡠࠗ࠼ ȕ ࠲ࡦࡄࠢ⾰
࠲ࡦࡄࠢ⾰ߩ C ᧃ┵ᱷၮ߇ᧃ┵ᱷၮ߇ੑ㊂૕ᒻᚑߦੑ㊂૕ᒻᚑߦਈ߃ࠆᓇ㗀
߃ࠆᓇ㗀㧦
ᓇ㗀㧦

ฎౖ MD ෸߮ Ab initio ࡈ࡜ࠣࡔࡦ࠻ MO ᴺࠍ↪޿ߚ⸃ᨆ޿ߚ⸃ᨆ    㧔⼾ᯅᛛⴚ⑼ቇᄢቇᄢቇ㒮 ‫⵾↰᧛ޔ‬૞ᚲ 㧕   ⍫㊁◊ᔒ ‫ޔ‬ጟᧄᤩẴ ‫ޔ‬㊁᧛๺຦ ‫ޔ‬ᯫ⽴ା৻ ‫ޔ‬ᩙ↰ౖਯ The effect of C-terminal residue of amyloid-ȕ on its dimer formation:
classical MD and ab initio fragment MO calculations  (Toyohashi University of Technology1, Murata Manufacturing Co., Ltd.2)
  A. Yano1, A. Okamoto1, K. Nomura1, S. Higai2 and N. Kurita1‫ޤߦ߼ߓߪޣ‬ࠕ࡞࠷ࡂࠗࡑ࡯∛㧔AD㧕ߪ‫⹺ޔ‬⍮∝ߩਛߢᦨ߽ᄙ޿∝⁁ߢ޽ࠅ‫࠼ࠗࡠࡒࠕޔߪߦ∝⊒ߩߘޔ‬β
࠲ࡦࡄࠢ⾰㧔Aβ㧕ߩಝ㓸߇ᷓߊ㑐ଥߒߡ޿ࠆ‫ޕ‬Aβߪ‫࠼ࠗࡠࡒࠕޔ‬೨㚟૕࠲ࡦࡄࠢ⾰߇‫ࠢࡄࡦ࠲ޔ‬⾰ಽ⸃㉂⚛ߢ޽ࠆβ ෸߮γ ࠮ࠢ࡟࠲࡯࠯ߦࠃߞߡಾᢿߐࠇࠆ੐ߦࠃࠅ↢ᚑߐࠇࠆ‫ޕ‬Aβߩಝ㓸ᕈߣᲥᕈߪ‫ޔ‬Aβߩ C ᧃ┵ߩࠕࡒࡁ㉄ᱷၮᢙߦࠃߞߡᄌൻߔࠆ੐߇⍮ࠄࠇߡ޿ࠆ‫ޔߢ߹ࠇߎޕ‬42 ୘ߩࠕࡒࡁ㉄߆ࠄᚑࠆ Aβ(1-42)߇‫ޔ‬ಝ㓸ᕈߣᲥᕈ߇㜞ߊ‫ޔ‬Aβಝ㓸૕ߩਥᚑಽߢ޽ࠆߣߐࠇߡ߈ߚ߇‫ޔ‬43୘ߩࠕࡒࡁ㉄߆ࠄᚑࠆ Aβ(1-43)߇‫ޔ‬Aβ(1-40)߿ Aβ(1-42)ߥߤߩઁߩ Aβࠃࠅᒝ޿ಝ㓸ᕈߣᲥᕈࠍ␜
ߔ੐߇‫ᦨޔ‬ㄭߩታ㛎ߢႎ๔ߐࠇߡ޿ࠆ[1,2]‫ ࠆߥ⇣߇࠭ࠗࠨߩࠄࠇߎޔߒ߆ߒޕ‬Aβߩಝ㓸ᯏ᭴ߩ⋧㆑‫ޔ‬෸߮ C ᧃ┵ߩ Thr43 ߇ಝ㓸ᕈߦߤߩࠃ߁ߥᓇ㗀ࠍ෸߷ߔ߆ߪᧂ⸃᣿ߢ޽ࠆ‫ޕ‬ᧄ⎇ⓥߢߪ‫ޔ‬Aβ(1-42)ߣ Aβ(1-43)ߩಝ㓸ᕈߩ⋧㆑ࠍ᣿ࠄ߆ߦߔࠆ⋡⊛ߢ‫ޔ‬Aβ(1-42)ੑ㊂૕‫ߩߎޔ‬ᣇߩ Aβ(1-42)ߩ C ᧃ┵ߦ 43 ⇟⋡ߩࠕࡒࡁ㉄ Thr43 ࠍઃടߒߚੑ㊂૕‫ޔ‬෸߮ਔᣇߩ Aβ(1-42)ߩ C
ᧃ┵ߦ Thr43 ࠍઃടߒߚ Aβ(1-43)ੑ㊂૕ߩ᭴ㅧࠍ૞ᚑߒ‫ࠞ࡝ࡊ࡟ޔ‬੤឵ಽሶേജቇ(REMD)ᴺࠍ↪
޿ߡ‫ޔ‬ฦੑ㊂૕᭴ㅧߩ᳓ਛߢߩ቟ቯ㈩ᐳࠍᐢ▸࿐ߦត⚝ߒߚ‫࠻ࡦࡔࠣ࡜ࡈޔߦࠄߐޕ‬ಽሶ゠㆏
㧔FMO㧕⸘▚ࠍ↪޿‫ޔ‬ฦ቟ቯ㈩ᐳߩࠛࡀ࡞ࠡ࡯ࠍ㜞♖ᐲߦ⸘▚ߒ‫ᦨޔ‬቟ቯߥ㈩ᐳࠍ᳿ቯߒߚ‫߹ޕ‬ߚ‫ޔ‬FMO ⸘▚ߩ⚿ᨐࠍၮߦ‫ޔ‬Aβන㊂૕㑆ߩ⋧੕૞↪ࠍ⸃ᨆߒ‫ޔ‬C ᧃ┵ߩࠕࡒࡁ㉄ Thr43 ߩઃട߇‫ޔ‬Aβੑ㊂૕ߩಝ㓸ᕈߦߤߩࠃ߁ߥᓇ㗀ࠍਈ߃ࠆ߆ࠍ᣿ࠄ߆ߦߒߚ‫⚿ߩߎޕ‬ᨐߪ‫ޔ‬᭽‫ߩ࠭ࠗࠨߥޘ‬Aβߦኻߔࠆಝ㓸ᯏ᭴ߩೋᦼᲑ㓏ߩ⸃᣿ߦ‫ߥ⋉᦭ޔ‬⍮⷗ࠍਈ߃ࠆ߽ߩߢ޽ࠆ‫ޕ‬‫▚⸘ޣ‬ᚻᴺ‫ޤ‬ᧄ⎇ⓥߢߪ‫ޔ‬ੑ㊂૕ߩೋᦼ᭴ㅧߣߒߡ‫ޔ‬Aȕ(9-40)✢⛽ߩታ㛎᭴ㅧ(PDB ID: 2LMN, 2LMO)ࠍណ↪
ߒߚ‫ߩࠄࠇߎޕ‬᭴ㅧߩ C ᧃ┵ߦ Ile41 ෸߮ Ala42 ࠍઃടߒ‫ޔ‬Aȕ(9-42)ੑ㊂૕᭴ㅧࠍ 16 ୘૞ᚑߒ‫ޔ‬᳓ਛߢߩ REMD ෸߮ ab initio FMO ⸘▚ࠍታⴕߒ‫ߩߘޔ‬ਛߩᦨ቟ቯߥ᭴ㅧࠍ᳿ቯߒߚ‫ᦨߩߘޕ‬቟ቯ᭴ㅧࠍၮߦ‫ޔ‬N ᧃ┵஥ߩ 1 ߆ࠄ 8 ⇟⋡ߩᱷၮࠍ⵬ቢߒ‫ޔ‬Aȕ(1-42)ੑ㊂૕ߩೋᦼ᭴ㅧࠍ૞ᚑߒߚ‫ޕ‬ᦝߦ‫ޔ‬Aβ(1-42)ੑ㊂૕᭴ㅧߦኻߒ‫ޔ‬Thr43 ࠍ ᣇߩ Aβߩ C ᧃ┵ߩߺߦઃടߒߚ᭴ㅧ‫ޔ‬෸߮ Thr43ࠍਔᣇߩ Aβߩ C ᧃ┵ߦઃടߒߚ Aβ(1-43)ੑ㊂૕ߩ᭴ㅧࠍ૞ᚑߒ‫ߩࠄࠇߘޔ‬᭴ㅧߩ⚂ 2 ୚ߩᄢ߈ߐߩࡏ࠶ࠢࠬࠍ⸳ቯߒ‫ࠬࠢ࠶ࡏߩߘޔ‬ౝߦ᳓๺᳓ࠍઃടߒ‫ޔ‬REMD ⸘▚ߩೋᦼ᭴ㅧߣߒߚ‫ޕ‬
REMD ⸘▚ߢߪ‫ޔ‬270.0 ߆ࠄ 363.8 K ߩ᷷ᐲ▸࿐ߢ 52 ୘ߩ࡟ࡊ࡝ࠞࠍ૞ᚑߒ‫ޔ‬10 ns ߩ REMD ⸘▚ࠍⴕߞߚ‫ࠄ߆▚⸘ߩߘޕ‬ᓧࠄࠇߚ 289.6 ߆ࠄ 310.7 K ߩ᷷ᐲߩ࡟ࡊ࡝ࠞߦኻߔࠆฦ MD ࠻࡜ࠫࠚࠢ࠻࡝߆ࠄ‫ᦨ߇࡯ࠡ࡞ࡀࠛ࡞ࡖࠪࡦ࠹ࡐޔ‬ૐߩ᭴ㅧࠍࠨࡦࡊ࡝ࡦࠣߒ‫ޔ‬13 ୘ߩઍ⴫᭴ㅧࠍᓧߚ‫ޕ‬ߎࠇࠄߩઍ⴫᭴ㅧࠍಽሶജቇ(MM)ᴺߦࠃࠅᦨㆡൻߒ‫ޔ‬ฦ᭴ㅧߩ᳓ਛߢߩ቟ቯ᭴ㅧࠍ᳿ቯߒߚ‫ޕ‬
REMD ෸߮ MM ⸘▚ߢߪ‫ޔ‬ฎౖಽሶജ႐ FF99SB ෸߮ TIP4P-Ew ᳓ಽሶࡕ࠺࡞ࠍ↪޿ߚ‫ᦨޕ‬ᓟߦ‫ޔ‬ᦨㆡൻߒߚ᳓๺᭴ㅧߦኻߒ‫ޔ‬MP2/6-31G ᴺࠍ↪޿ߚ ab initio FMO ⸘▚ߦࠃࠅ‫ࠍ࡯ࠡ࡞ࡀࠛޔ‬㜞♖ᐲߦ⸃ᨆߒ‫ߩߘޔ‬୯ࠍၮߦ‫ᦨޔ‬቟ቯߥੑ㊂૕᭴ㅧࠍ᳿ቯߒߚ‫ޔߡߒߘޕ‬FMO ⸘▚ߩ⚿ᨐ߆ࠄ‫ޔ‬Aȕ(1-42)‫ޔ‬Aȕ(1-43)ߦ฽߹ࠇࠆߤߩࠕࡒࡁ㉄߇ੑ㊂૕ߩᒻᚑߦ㊀ⷐߢ޽ࠆ߆‫ޔ‬Aȕ(1-42)ߩ C ᧃ┵߳ߩࠕࡒࡁ㉄ઃട߇ Aβߩಝ㓸ᕈߦߤߩࠃ߁ߥᓇ㗀ࠍਈ߃ࠆ߆ࠍ᣿ࠄ߆ߦߒߚ‫ޕ‬‫⚿▚⸘ޣ‬ᨐߣ⠨ኤ‫ޤ‬
289.6–310.7 K ߩ MD ࠻࡜ࠫࠚࠢ࠻࡝߆ࠄࠨࡦࡊ࡝ࡦࠣߒߚ 13 ୘ߩ Aȕ(1-43)ੑ㊂૕ߩઍ⴫᭴ㅧࠍ‫ޔ‬
MM ᴺࠍ↪޿ߡᦨㆡൻߒ‫ ߩࠄࠇߘޔ‬Total energy (ET)ࠍ ab initio FMO ᴺߦࠃࠅ⸘▚ߒߚ‫ޕ‬FMO ⸘▚ߦࠃࠅᓧߚฦ᭴ㅧߩ ET ࠍ೑↪ߒ‫ޔ‬න㊂૕㑆ߩ Binding energy (EB)▚಴ߒߚ‫ޕ‬Aβ(1-42)ੑ㊂૕෸߮
Aβ(1-43)ੑ㊂૕ߩฦᦨㆡൻ᭴ㅧߩਛߢ‫ޔ‬EB ߇ᦨᄢߢ޽ࠆ᭴ㅧߦኻߒ‫ޔ‬EB ߩ୯ࠍᲧセߒߚ⚿ᨐࠍ
Table 1 ߦ␜ߔ‫ޕ‬Aβ(1-43)ੑ㊂૕ߩᣇ߇ Aβ(1-42)ੑ㊂૕ࠃࠅ EB ߇ 164.8 kcal/mol ᄢ߈ߊߥࠆ‫ޕ‬ᓥߞߡ‫੹ޔ‬࿁ߩ FMO ⸘▚ߦࠃࠅ‫ޔ‬Aβ(1-43)ੑ㊂૕ߩᣇ߇ Aβ(1-42)ੑ㊂૕ࠃࠅ߽ Aβ㑆ߩ⚿ว߇ᒝߊߥ
ࠆߎߣࠍ␜ߔߎߣ߇ߢ߈ߚ‫⚿ߩߎޕ‬ᨐߪታ㛎[1, 2]ߣቯᕈ⊛ߦ৻⥌ߒߡ޿ࠆ‫ޕ‬߹ߚ‫ޔ‬C ᧃ┵߳ߩࠕࡒࡁ㉄ઃട߇ Aβ㑆ߩ⚿วߦਈ߃ࠆᓇ㗀ࠍ⺞ߴࠆߚ߼‫ޔ‬Aβ(1-42)ੑ㊂૕ߣ
Aβ(1-43)ੑ㊂૕ߦኻߒ‫ޔ‬Aβߩฦࠕࡒࡁ㉄㑆ߩ⋧੕૞↪ࠛࡀ࡞ࠡ࡯ࠍᲧセߒߚ‫ޕ‬Figure 1 ߦ␜ߔࠃ߁
ߦ‫ޔ‬Aβ(1-43)ੑ㊂૕ߦ߅޿ߡ‫ޔ‬Aβ(1-42)ੑ㊂૕ࠃࠅᒁജ⋧੕૞↪߇ᦨ߽ᒝߊߥߞߚㇱ૏ߪ‫⩄ޔ‬㔚ࠕࡒࡁ㉄ߩห჻ߩ Asp23 ߣ Lys28 㑆ߩ⋧੕૞↪ߢ޽ࠅ‫ޔ‬64.4 kcal/mol‫ޔ‬ᒁജ⋧੕૞↪߇ᒝߊߥࠆ‫߹ޕ‬ߚ‫ޔ‬C ᧃ┵ Thr43 ߽න㊂૕㑆ߩ⋧੕૞↪ߩᒝൻߦነਈߒߡ߅ࠅ‫ޔ‬Thr43 ߣ߽߁৻ᣇߩ Aβ(1-43)ߩ
Arg5 㑆ߦ‫ޔ‬36.9 kcal/mol ߩᒁജ⋧੕૞↪߇↢ߓࠆ‫ޕ‬C ᧃ┵߳ߩࠕࡒࡁ㉄ઃടߦࠃࠅ‫ࠕߩࠄࠇߎޔ‬ࡒࡁ㉄㑆ߩ⋧੕૞↪߇ᄌൻߒ‫ޔ‬Aβੑ㊂૕㑆ߩ⚿ว߇ᒝ߹ࠆߎߣ߇‫੹ޔ‬࿁ߩ⸘▚ߢ᣿ࠄ߆ߦߥߞߚ‫ޕ‬
Table 1 Total energies (ET) and binding energies (EB) for the solvatedAββ(1-42) dimer and Aββ(1-43) dimer obtained by ab initio FMO method

E T (kcal/mol)EB
㼺E B
Solvated Aβ Solvated Aβ
Solvated Aβ 1,151 water(kcal/mol)
molecule
dimer
monomer 1
monomer 2Aβ(1-42) dimer 䋭74792906.1 䋭64889743.8 䋭64889573.4 䋭54986728.1 317.0 䋭164.8
0.0 Aβ(1-43) dimer 䋭75245142.6 䋭65115961.2 䋭65115681.0 䋭54986981.4 481.8
StructureN
Asp23:Lys28

N terminal

㧙64.4 (kcal/mol)C
C terminal

Figure 1 Interaction energies (kcal/mol) between
Figure 2 Structure of Aββ(1-43) dimer withamino acid residues for Aββ(1-43) dimer compared
the largest binding energy
with those for Aββ(1-42) dimer‫ޣ‬ෳ⠨ᢥ₂ෳ⠨ᢥ₂‫ޤ‬‫[ޤ‬1]T. Saito et al., Nature,14 (2011)1023. [2]A. Sandebring et al., PloS one, 8.2(2013) e55847.

➨୍ཎ⌮ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡟ࡼࡿከᏍᛶ㔠ᒓ㘒యࡢ≉ᛶゎᯒ

2P134(㇏ᶫᢏ⾡⛉Ꮫ኱Ꮫ኱Ꮫ㝔 1 ࠊᮧ⏣〇సᡤ 2)‫ۑ‬ᮡᮏᣅஓ 1ࠊᒸᮏ᫭⃈ 1ࠊ▮㔝⠜ᚿ 1ࠊᷓ㈅ಙ୍ 2ࠊⱝᒸᣅ⏕ 2ࠊᰩ⏣඾அ 1

Ab initio molecular simulations for porous coordination polymers(Toyohashi University of Technology1, Murata Manufacturing Co., Ltd.2)
۵T. Sugimoto1, A. Okamoto1, A. Yano1, S. Higai2, T. Wakaoka2 and N. Kurita1
࠙ࡣࡌࡵ࡟ࠚ
㏆ᖺࠊ᪂つ࡞ከᏍ㉁ᮦᩱ࡜ࡋ࡚ࠊከᏍᛶ㔠ᒓ㘒య (porous coordination polymers: PCP) ࡀ኱࠸࡟ὀ┠ࡉࢀ࡚࠸ࡿ[1]ࠋࡑࡢ PCP ࡣࠊ㔠ᒓ࢖࢜ࣥ࡟᭷ᶵ㓄఩Ꮚࡀ⤖ྜࡋࡓ㘒యᵓ㐀ࢆᇶᮏ࡜ࡋࡓᕧ኱
࡞࿘ᮇᵓ㐀ࢆᙧᡂࡋ࡚࠾ࡾࠊ㔠ᒓ࢖࢜ࣥ࡜᭷ᶵ㓄఩Ꮚ࡜ࡢ⤌ࡳྜࢃࡏࢆኚ࠼ࡿࡇ࡜࡟ࡼࡾࠊᵝࠎ࡞ࢧ࢖ࢬࡢ⣽Ꮝࢆᣢࡘ PCP ࢆྜᡂࡍࡿࡇ࡜ࡀฟ᮶ࡿࠋ
ᮏ◊✲࡛ࡣࠊPCP ୰ࡢ㔠ᒓ࢖࢜ࣥ᭷ᶵ㓄఩Ꮚ㛫ࡢ⤖ྜ≧ែࡢไᚚࢆ┠ᣦࡋࠊAl ࢆྵࡴ PCP ࡛࠶ࡿ MIL-101-NH2 ࡟ࡘ࠸࡚ࠊࡇࢀࢆᵓᡂࡍࡿ᭱ᑠ༢఩ࡢࢡࣛࢫࢱ࣮ࡢᵓ㐀Ᏻᐃᛶࢆࠊᐦᗘỗ㛵ᩘ⌮ㄽ (density functional theory: DFT) ࡟ᇶ࡙ࡃ➨୍ཎ⌮ศᏊࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⏝࠸࡚ࠊヲ⣽࡟ゎᯒࡋࡓࠋ᭦࡟ࠊࣇࣛࢢ࣓ࣥࢺศᏊ㌶㐨 (fragment molecular orbital: FMO) ィ⟬࡟ࡼࡾࠊࢡࣛࢫࢱ࣮
ࡢᏳᐃ໬࡟ࠊ࡝ࡢࡼ࠺࡞┦஫స⏝ࡀ㔜せ࡛࠶ࡿ࠿ࢆㄪ࡭ࡓࠋ
࠙ィ⟬ᡭἲࠚ
 Al ࢆྵࡴ MIL-101-NH2 ࡣᐇ㦂࡛ྜᡂࡉࢀ࡚࠸ࡿࡀࠊࡑࢀࢆ ᵓᡂࡍࡿ᭷ᶵ㓄఩Ꮚ࡛࠶ࡿ
2-amino-1,4-benzenedicarboxylate (BDC-NH2) ୰ࡢ NH2 ᇶࡢ఩⨨ࡣ≉ᐃࡉࢀ࡚࠸࡞࠸ࠋࡑࡇ࡛ࠊࡲ
ࡎࠊNH2 ࢆྵࡲ࡞࠸ BDC ࠿ࡽᡂࡿࢡࣛࢫࢱ࣮ࡢᏳᐃᵓ㐀ࢆồࡵࠊBDC ୰ࡢᵝࠎ࡞఩⨨࡟ NH2 ࢆ⨨᥮ࡋࡓࠋࡑࡋ࡚ࠊࡇࢀࡽࡢࢡࣛࢫࢱ࣮ࡢᵓ㐀ࢆ᭱㐺໬ࡋࠊ඲࢚ࢿࣝࢠ࣮(Total energy: ET)ࢆẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊ᭱Ᏻᐃ࡞⨨᥮఩⨨ࢆỴᐃࡋࡓࠋࡉࡽ࡟ࠊNH2 ࡢ᭷↓࡟ࡼࡿ Al ࡜㓄఩Ꮚ㛫ࡢ┦஫స⏝ࡢኚ໬ࢆゎᯒࡋࡓࠋNH2 ࡢ⨨᥮఩⨨࡜ࡋ࡚ࠊ඲࡚ࡢ NH2 ࢆ୰ᚰࡢ Al ഃ࡟㓄⨨ࡋࡓᵓ㐀
(BDC-NH2-near)ࠊ୰ᚰ࠿ࡽ㞳ࢀࡓ఩⨨࡟㓄⨨ࡋࡓᵓ㐀 (BDC-NH2-far)ࠊ೫ࡾ࡞ࡃᆒ➼࡟㓄⨨ࡋࡓᵓ㐀 (BDC-NH2-even) ࡢ 3 ✀㢮ࢆ⪃៖ࡋࠊ⨨᥮఩⨨ࡢኚ໬࡟ࡼࡿ MIL-101-NH2 ࡢᵓ㐀ኚ໬ࢆㄪ࡭ࡓࠋ
ࡲࡓࠊࢡࣛࢫࢱ࣮࿘ᅖࡢࣉࣟࢺࣥ (H+) ⃰ᗘࡢኚ໬࡟ࡼࡿࠊࢡࣛࢫࢱ࣮ࡢᵓ㐀ኚ໬ࢆ᫂ࡽ࠿࡟ࡍ
ࡿࡓࡵࠊ᭷ᶵ㓄఩Ꮚࡢ Al ഃࡢ COO– 㒊఩࡟ H+ࢆ௜ຍࡋࠊDFT ィ⟬ࢆ⏝࠸Ᏻᐃᵓ㐀ࢆồࡵࡓࠋᵓ㐀᭱㐺໬ィ⟬ࡢ㝿ࠊࢡࣛࢫࢱ࣮ࡢ࿘ᅖࡢ⁐፹ࡢᙳ㡪ࡣࠊ㐃⥆⁐፹㏆ఝࢆ⏝࠸࡚⪃៖ࡋࡓࠋ⁐፹࡜ࡋ࡚ࠊࢪ࣓ࢳ࣒ࣝ࣍ࣝ࢔࣑ࢻ (DMF) ࡜Ỉࢆ⪃࠼ࠊAl ࢆྵࡴ MIL-101-NH2 ࡢᵓ㐀Ᏻᐃᛶ࡬ࡢ⁐፹ࡢຠᯝࢆ᳨ウࡋࡓࠋ ḟ࡟ࠊMIL-101-NH2 ࡢ NH2 ⨨᥮఩⨨ࠊཬࡧࣉࣟࢺࣥ௜ຍ࡟ࡼࡾࠊࢡࣛࢫࢱ࣮ࡢ┦ᑐⓗ࡞Ᏻᐃᛶࡀኚ໬ࡍࡿཎᅉࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊFMO ィ⟬ࢆ⏝࠸ࠊMIL-101-NH2 ୰ࡢྛᵓᡂศᏊ㛫ࡢ┦஫స⏝࢚ࢿࣝࢠ࣮ࢆồࡵࠊ࡝ࡢ㒊ศ㛫ࡢ┦஫స⏝ࡀࢡࣛࢫࢱ࣮ࡢᏳᐃ໬࡟㔜せ࡛࠶ࡿ࠿ࢆゎᯒࡋࡓࠋ࠙ィ⟬⤖ᯝ࡜⪃ᐹࠚ ┿✵୰࡛᭱㐺໬ࡋࡓ 3 ✀㢮ࡢࢡࣛࢫࢱ࣮ࡢᏳᐃᵓ㐀ࢆ Figure 1 ࡟ࠊ┿✵୰ཬࡧ㐃⥆⁐፹ࢆ⏝࠸࡚᭱㐺໬ࡋࡓྛᵓ㐀ࡢ ET ࢆ Table 1 ࡟♧ࡍࠋFigure 1 ࡢྛᵓ㐀ࢆẚ㍑ࡍࡿ࡜ࠊ࡝ࡢᵓ㐀࡟ࡶ኱ࡁ࡞
㐪࠸ࡣ࡞ࡃࠊMIL-101-NH2 ࡢᏳᐃᵓ㐀ࡣࠊNH2 ࡢ⨨᥮఩⨨࡟ࡣṤ࡝౫Ꮡࡋ࡞࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋ

ࡲࡓࠊTable 1 ࡟♧ࡍࡼ࠺࡟ࠊࣉࣟࢺࣥ௜ຍ๓ࡢࢡࣛࢫࢱ࣮࡛ࡣࠊ3 ✀㢮ࡢᵓ㐀ࡢ࢚ࢿࣝࢠ࣮ᕪࡀࠊ
᭱኱࡛ࡶ 2.5 kcal/mol ࡛࠶ࡾࠊNH2 ࡢ⨨᥮఩⨨ࢆኚ࠼࡚ࡶᏳᐃᛶࡣ኱ࡁࡃࡣኚ໬ࡋ࡞࠸ࠋణࡋࠊ┿✵୰࡜⁐፹୰࡛ࠊ3 ✀㢮ࡢᵓ㐀ࡢ┦ᑐⓗᏳᐃᛶࡣኚ໬ࡍࡿࠋ
ḟ࡟ࠊࢡࣛࢫࢱ࣮࿘ᅖࡢࣉࣟࢺࣥ⃰ᗘࡢቑຍ࡟ࡼࡾࠊ᭷ᶵ㓄఩Ꮚࡢ COO– 㒊఩࡟ H+ࡀ௜ຍࡋࡓᵓ㐀 (pro-BDC ཬࡧ pro-BDC-NH2)ࢆ DFT ィ⟬࡛᭱㐺໬ࡋࠊET ࢆィ⟬ࡋࡓ⤖ᯝࢆ Table 1 ࡟♧ࡍࠋࣉࣟࢺࣥ௜ຍ๓ࡢ BDC-NH2 ࡟ᑐࡍࡿ⤖ᯝ࡜ẚ㍑ࡍࡿ࡜ࠊྛᵓ㐀ࡢ ET ࡣ኱ࡁࡃ␗࡞ࡾࠊ୰ᚰ㒊ࡢAl ࠿ࡽ㞳ࢀࡓ఩⨨࡛ NH2 ⨨᥮ࢆ⾜࡞ࡗࡓᵓ㐀ࡀࠊ┿✵୰ࠊ⁐፹୰ࡢ࠸ࡎࢀ࡛ࡶࠊ᭱Ᏻᐃ࡜࡞ࡿࠋ
௨ୖࡢᵝ࡟ࠊ᭷ᶵ㓄఩Ꮚ࡬ࡢࣉࣟࢺࣥ௜ຍ࡟ࡼࡾࠊBDC-NH2 ࡢᏳᐃᵓ㐀ࡣ኱ࡁࡃᙳ㡪ࡉࢀࡿࡇ࡜
ࡀࠊึࡵ࡚᫂ࡽ࠿࡟࡞ࡗࡓࠋ

(b) BDC-NH2-even(a) BDC-NH2-near(c) BDC-NH2-far

Figure 1 Structures of clusters composed of BDC-NH2 and Al in vacuum optimized by DFT calculations

Table 1 Total energies (ET) for clusters in vacuum, water and DMF

Cluster
BDC
BDC-NH2-near
BDC-NH2-even
BDC-NH2-far
pro-BDC
pro-BDC-NH2-nearpro-BDC-NH2-even
pro-BDC-NH2-far

vacuumwater

DMF

E T(kcal/mol)

ΔE T

ET

ΔE T

ET

ΔE T

−2940099.8−3148675.5−3148673.3−3148673.1−2940754.6−3149361.4−3149381.6−3149405.8

䠉
0.0
2.2
2.3
䠉
44.4
24.2
0.0

−2940161.3−3148747.9−3148749.1−3148750.3−2941612.6−3150227.9−3150233.7−3150241.0

䠉
2.5
1.2
0.0
䠉
13.2
7.3
0.0

−2940159.7−3148746.2−3148747.2−3148748.4−2941592.8−3150207.7−3150214.6−3150222.3

䠉
2.2
1.1
0.0
䠉
14.6
7.7
0.0

࠙ཧ⪃ᩥ⊩ࠚ
[1] for example, Jeong Yong L. et al., Chem. Soc. Rev. 38, 1450 (2009).

2 P135"    
%*6  ,'&'7 .502



93$!8$:/+(;# 4;)-1

Theoretical Study on the Geometric and the Formation of s-d Hybridization of
Aluminum Cluster Doped Copper Atom
(Chiba Institute of Technology) Chiaki Ishibashi, Kaoru Onoe, Hidenori Matsuzawa
P_hß:E=>I$aJ_:E=>I"$Ê14!¯6»
z!

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−6?IB Aln :E=>I#X¦3 Cu 6?IB Aln−:EØâ{°#à[6²Ô¶"¥ÐQn$Û½ß

=>I"¬¸:E=>I#X¦Ø/â{°"3 Cu b{#ä6Ó):E=>I$ CuAln− (n=2-13)6Ü'41#X¦Ø6ªà«"02©-1"#¦Ø"

3Ý_°(partial density of states: PDOS)6Ì¢Khanna 1#²Ô¹¾"04%

CuAl13 $O" Al # 3s  3p _

1!3ÕÙ"Cu # 4s  3d ÕÙ

k+43 1)

E=>I#X¦Ø/â{°"3 Cu b{#ä6slY$*7−

ÔU$O" CuAln (n=11-13):E=>I# PDOS #Â£:!¡Ð

1#X¦Øâ{°"

3 Cu b{#ä6Þ¶"ÑZ#sl3Ï¿«CuAln− (n=11-13):E=>I#}¦Ø6 B3LYP «rà$ 6-311+G*´Às-d ­#ÒÁ!s63-"#¦Ø# PDOS Ì¢6ÆÏ¿BH;EC$ Gaussian 09 6PDOS Ï¿$ GaussSum 6´Â£d'ÄCuAln− (n=2-13)#44#µ
W6k-}¦Ø6©-n=8 +$Nb{#!¦Øn=9, 10 $ wheel-like ¦Ø6

n=11-13 $ icosahedral ¦Ør¡æ¤"!3oê" n=11-13 #}¦Ø(a)0'®}¦Ø(b)644»n=11 #}¦Ø
è1-11-aé$Al

N"|p3 icosahedral¦Ø#w\" Cu b{VÃ3+®}!

1-11-b $Cu 6k- wheel-like ¦Ø63
n=12 $}! 1-12-a AlN"VÃ

34 icosahedral ¦Ø!3J®}¦
Øè1-12-bé$Cu

N"VÃ¼n=13 $Cu

:E=>I#N"|p3

è1-13-aéo 1. CuAln− (n=11-13):E=>I#X¦ØAlç:E=>I#N"|p3è1-13-bé02.}"! ¨" wheel-like ¦Øè1-11-béAl 6N". icosahedral ¦Øè1-12-aéCu 6N".
é
icosahedral ¦Øè1-13-aé# PDOS _{ÕÙ#°6o 2 "»wheel-like ¦Øè1-11-bé$5.0-6.0eV "y!É#@I:Ùè2a"é$Cu # 3d ÕÙ43Ä

7

84.9%Al # s ÕÙ

9.09%Cu # 3d ÕÙ_"0

143+4.0eV R× 6.0eV TK"|p3@I:$ Al # s ÕÙ p ÕÙ­43!Ä|p3#N..y!@I:63_{Õ wheel-like ¦Ø$Cu # 3d ÕÙ Al #ÕÙ#­$*

1431-12-a "SÇ43 Al 6Nb{3 icosahedral q$4.8-5.9eV#AHI?!@I:#¦ÕÙ#&3 3a"ÕÙ$Cu # 3d ÕÙ
25.3%wheel-like q"1) Al # s ÕÙ_u3

s-d ­

70.4%Al # s ÕÙ43$ÎáJ6.2eV #<DIB!@I:è5a"ÕÙé$Cu # 3d ÕÙ$ 22.8%Al # s ÕÙ$ 47.2%s-d ­63#]j$1-11-a / 1-13-b .i§Al
3 icosahedral ¦Ø$L~^! s-d ­636m31-13-a #0b{3 icosahedral q$5.3eV  7.2eV "@I:3d ÕÙ_x# Al # sN"" Cu 6N_È341$4. Cu #0' p ÕÙ_6i"k,5.3eV #@I:63 13a ÕÙ$ Cu # 3d ÕÙ$ 29.0%Al # s ÕÙ$ 47.3%!+7.2eV #@I:63 5aÕÙ$ Cu # 3d ÕÙ$ 54.9%Al # s ÕÙ$ 29.3%TK~^! s-d ­63 oë#_{ÕÙ31-12-b .#]j$v51!

11-11-b #0`"_º! shell ¦Ø6k7 1D shell

5
Ê

" Cu



! wheel-like ¦Ø$Cu # 3d ÕÙ_ Al # s ÕÙ
!icosahedral ¦Ø63 Cu # 3d ÕÙ_

0' 2D shell 63

¤#w\"3th$3d ÕÙ_6
1-13-a #0

1#:E=>I$gÅ"!3

1-12-a #0! Cu+f2Ö-!-"L~^! shell 63J

æ¤#N"!3¦Ø$N Cu # 3d ÕÙæ¤ Al # s ÕÙÂhÕÙ63 1D shell 6eÂhÕÙ63 2D shell 63Å"!2~^! s-d ­

³3s-d ­##à[

!

1

æ

5

TK

g

1:E=>I#X¦Ø#Ú

o 2 wheel-like qAl b{N# icosahedral qCu b{N# icosahedral q"cÄ±1) S. N. Khanna et al., J. Chem. Phys. 114, 9792 (2001)

3 PDOS2 P136      



ĜuñđRĝðĎ µvĞÞĀ z_ÔĞÛÅ uºĞ½Ð àp
Theoretical Study of Hydrogen Absorption on LiAln- (n=1-7) clusters(Chiba Institute of Technology)

Fumihiro Kusama, Yukari Isogai, Chiaki Ishibashi,
Hidenori Matsuzawa¢¯l}Č:N?AS#Ğ"è¯+=4@2oª/ÄôĖÒ®2^.

k/-Ğ·÷ú+Æî­EHå"¬ÖÂü0/

"X*Ğ3P8OČ3PJF5K:N?AS#Ğ"Õ¯¸Î*Ýâ0.ĞÃą+ĕÒ®!ď/Ě,$ÔÿÜá´0/¦Üá*0& Li-Al + Na-Al :N?AS"ÃąĕÒ®"ďb!ÏØĞÔÿ×!Üá2

Y# LiAln(n=1-7):N?AS!ÏØĞËæò}Č"nÖ2øċ!g0Ğ:N?AS!Ëæx2Úē"ÃąĕÒ®"t!
ÖĞ¤Íď´Ôÿ2þç!Âü"/ ûä¸Î 0&"Üá-©-0æx2|î

Đ.ZrĞ00"/ LiAln(n=1-7):N?AS"»Ãą!ĞË

óÃą2Ì)Ğ­2²sù¾ýa&Ğ©-0»Ãą-ĞËæÚ!,/t7GP9S2Ì)ûä# B3LYP ÎĞ£ď´ 6-311++G**2Ö

ĞIQ;NK# Mac Pro V Gaussian 09M 2`Ö é¿y$íLiAln(n=1-7):N?AS" H xÚ#Ğn=1-4 ö-0/Ú!,/Ãą+ĕÒ®"tn=5-7 *jÓ0/LiAln(n=1-4):N?AS! H x»Đ!
ÚÒ®2

ğ!ßn=1 "ĞH x#ġd& Al !ZrAlH4.

Li+"Ď Li-(H)-Al "ÀÅ2Ġ8°§¯/& HOMO "ĕ#ĞÀÅĈlh]!lSOMO "ĕ# Li "e!¡/Ąć!{0/"H x"Út
7GP9SĜEHĝ# 70.2 kcal/mol ĢdØ" H x#Ćqĕ"¡Ąćõw0/"Ò®*EH # 69.2 kcal/mol /°!Ún=2 #Ğ:N?ASÃą2cÒ® H x#ģd&Zr/"ĞAl-Al é}ë±0
HOMO # Al-Al "é}­Ąć!

/*!ģd" H xh]!¡/LUMO # Li V!l/Ğn=1 " SOMO !Ê%*"EH #»*67.5 kcal/mol 

Td H xZr/ĞH x# Al-Al Ď!\ìĞAl-Al "ĂĔ# 3.17 Å.é}m0/"é¿ĞHOMO  Li V"¡/,!

.Ğ2nd HOMO [W"Ąć!* Al-Al "é}­Ąć#ö-0

H3Al-(H)-AlH3 "MFBDÃą2^."ÈĒ:N?ASÃą0í//n=3 #:N?AS"Ãą2c&&H x# 11 d&Ú/" 11 dØ" H x#n=1 "~Ä! Li "e!ÚHOMO # Li
V"¡l/2nd
3rd HOMO # Al-(H)-Al,$-

LiAlH5,$ Al-(H)-Li "HOMOÀÅĈlh]2'Al-Al Ď! H xĉì*Al-Al é}#m¶0

HxģdÚ"t7GP
LiAl2H69SĜ66 kcal/molĝ»*

-

HOMO

0#>6PLCP" 1D shell čÉ!
/<S?

.:N?AS"­ā¥-0/ H x´í11 d":N?ASÃą0/­#

-/Ĝ60 kcal/molĝn=4 

LiAl3H11

2nd HOMO

3rd HOMO

1st SOMO

2nd SOMO#12 d& H xÚ»Ã
ą#UĊĘÒ®"ĠM

FBD" H3Al-(H)-AlH3  Li !ĉ\/

-LiAl4H12n=1 - 4 &#¼×!:N?ASï
ă"ěÁ2c-H xZręÒ®[V!

/ Al-Al é}m0—ğLiAln (n=1-4):N?AS! H x»Đ!ÚÒ®

:N?AS0/H x2»Đ!
Út7GP9S#¤#/f!

.&:N?ASěÁ0//

 n=5 [V#H x"Ú´/!

:N?ASěÁ-Çã!

ěÁÃą2t &:N?AS"­ā2c/n=5 #ģd" Hx2ÚÈĒ:N?AS"ěÁt/H x´ 11~12 d:N?AS"Ãą017 dZr1ĠMFBD" H3Al-(H)-AlH3  Li !ĉ\n=6 #iĖ]ěÁ"

:N?AS! H xZr/H xĤdZr1ĤĖ]ěÁ0/ĜėÑ! Li xĉì0/ĝ"¨#H x/!0

Li x2X«! H3Al-(H)-AlH3 "MFBDĉì0/0# n=7 "}*~ÄH x
ĤdZr1:N?AS"ěÁt"¨# H3Al-(H)-AlH3 "Ãą2^/[V-Ú/ H x"ê´# n "r*!/:N?AS"ěÁ2cÒ®" H x"Ú´#(1 n=1-4 "¸n=5-7 ,.*&Li"'!Ù³ H xZr/"#Rydberg Ąć/}!Đ-0/¹-

2 P137!$ )" "* #(&'C5H4 
C5H3 % (eèĉO) äÎ ü, °À Ù_

Theoretical Study on the Reaction of Metastable Diacetylene
with Ground State Propyne in Titan's Atmosphere- Formation Reactions of C5H4 and C5H3 (Graduate School of Technology, Chiba Institute of Technology)○Nawata Daisuke, Matsuzawa Hidenori
?7?N%y«$£­$ê«{ìdmÆ4p5f86M>K$ (haze).®·ē]

/ 200~300km {Â#¶"®·z%¾Ò"Zdj#Ì¢21Haze 4µ¢1]$T-Ç#;6=@

LN(C4H2)%Þã4qk1

j$ēb÷È"1,polymer$`đX½Ô211996 Frost / 1)%¿RĄĐÈN(C4H2*)

FMDN(CH3CCH) j1



;6=@L

C7H4, C6H2, C5H4, C5H3

Ì¢1

Ēá²4}r
C4H2* + CH3CCH  C7H4 + 2H, H2
 C6H2 + CH3 + H, CH4(2)

 C5H4 + C2H2

(3)

 C5H3 + C2H2 + H(4)

Frost /%Ēá².02/$]$Ì¢j
³

(1)

(1)~(4)

$j·µ4¦

$óß%ª/ #""¯ÖÛ%kÊ

·µ$îċ"(3)

QÐēj(4)#ÄÂ4ĎàĒÓ]ùā¼#.0 C5H4Ì¢j$jI9A<H4ª/¹Ë(180K, 0,001atm)##n¬#ÅaÓ"å-é?7?N1j$ñÜ©¼µÿ­ĂdjÆ

C5H3

4´ò$}r1Ì¢ÆTĈX(Int)ăÚÈ(TS)$ëµÿ4»,jàø4 IRC ñÜ×ô*ČÂ¤c4å¡8BK:PYaÓCJIP?P%¤cð±#.»,ëµÿ$Ü\ÅIRC ñÜ%B3LYP/cc-pVDZ LGK¤cð±% CCSD/cc-pVDZ LGKé
C5H3 $U"Ì¢àø4x 1 #ØjÆ$¿Rá².&åC5H4ĄĐÈ

C4H2*%­$ 3Bu È

4ÍÕ8BK:P% C4H2*3Bu CH3CCH$8BK:P4|¿#Ü\C5H4#é#ýjć1$C5H3 $Ì¢àø%C4H2*
#Ñ"1©o

CH3CCH/ý~m%

C7H4

C6H2 Ì¢àø$TĈX4¢1Int1 $¢#âºÝúÚvúÑd÷ĆËusË4¢1 Int5 $usË

ą

vú1

 Int6"1$ Int6 #cis-trans Ñd% C5H4 + C2H2 Ì¢àø(x 1 $öØàø)'ºÝúÚ
C2H3 Ì¢àø(x 1 $čØàø)']1
T#8BK:PĊ


Āé1

#-

( 5!Ã,jÆØt21Q©Ì¢Æ1 C5H4

Ì¢àø$"#÷w1 å$jàø÷~m% C5H3 +*jàøþ

C5H3 $8BK:P"®#W$gw%C5H3/21C5H4 Ì¢j%x 1 #ØàøVz1""3jàø$÷~m-8BK:P$+4^Íj3/Frost /$Ē% C5H3 $kÊ

#-

]

ćíÁÝ

C5H3 Ì¢j%Q$àøÌ¢Æ$kÊ#ď4i)

?7?N¹Ë(180K, 0.001atm)#

1C5H4ï¥21

.& C5H3 Ì¢j$8N?KDPd(ΔH)%22-27.3kcal/mol, -25.9kcal/mol 0Sàø[#ÒÅj
*:E<$çÏ8BK:Pd(ΔG)%22-27.2kcal/mol,-27.0kcal/mol 0Sàø[#çÒÓ#jĀé1Øt21

áõÃ.&ΔG $Y.0jàø#"8BK:PĊΔHÒÅj çÒÓ#jĀé1

& C5H3 $Ì¢%læ

/21*jàø§$¸ûå-®^"j

Øt21

x 1. C4H2*

CH3CCH/?7?N¹T#

 C5H4/C5H4 % C5H3 .0/$ C5H4 + C2H2 *% C5H3 + C2H3 $Ì¢àøhå¨É
1) Rex K. Frost et al. , J. Am. Chem. Soc. ,118, pp4451-4461 (1996).

2P138ᅛయ୰࡛ບ㉳ࡋࡓศᏊࡢᵓ㐀⦆࿴࡟㛵ࡍࡿ⌮ㄽⓗ◊✲(ி኱㝔ᕤ 1, ி㒔኱Ꮫゐ፹㺃㟁ụඖ⣲ᡓ␎ࣘࢽࢵࢺ 2, ஑⏘኱ᕤ 3)○ᡂ⏣┿ᘯ 1, బ⸨ၨᩥ 1,2, ୰ᑿ჆⚽ 3

Theoretical Study of Dynamics of Molecules on the Excited Statein Solid States(Dept. Molecular Engineering, Graduate School of Engineering, Kyoto University 1,
ESICB, Kyoto University 2,
Dept. Applied Chemistry and Biochemistry, Faculty of Engineering, Kyushu Sangyo University 3)○Masahiro Narita1, Hirofumi Sato1,2, Yoshihide Nakao3࠙ᗎࠚ᪂ࡋ࠸ π ඹᙺศᏊࡢ◊✲㛤Ⓨࡣ᭷ᶵ㟁Ꮚᮦᩱ࡬ࡢᛂ⏝ࡀᮇᚅࡉࢀࠊᐇ㦂࡜⌮ㄽィ⟬ࡢ༠ຊ࡟ࡼࡿศᏊタィ࣭ྜᡂ࣭ホ౯ࡀ⾜ࢃࢀ࡚࠸ࡿࠋ⌧ᅾ㔞Ꮚ໬Ꮫ⌮ㄽ࡟ᇶ࡙ࡃィ⟬ࡣ୍⯡࡟༢ศᏊ࣭Ꮩ❧⣔ࢆ௬ᐃࡋ࡚⾜ࢃࢀ࡚࠸ࡿࡀࠊᅛయᮦᩱࡢᶵ⬟ࡸᛶ㉁࡟ࡣจ㞟ࡋࡓศᏊࡢ㓄ྥࡸ❧య㓄ᗙࡀ኱ࡁࡃᙳ㡪ࡍࡿ

Scheme 1ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡲࡓࠊගᶵ⬟ᛶศᏊ࡛ࡣ྾཰࣭Ⓨග࢚ࢿࣝࢠ࣮࡜ゝࡗࡓගᏛⓗᛶ㉁࡟ຍ࠼
࡚ࠊບ㉳≧ែ࡟࠾ࡅࡿᵓ㐀⦆࿴ࡸ⇕᣺ື࡜ゝࡗࡓືⓗ࡞ᛶ㉁ࡶ㔜せ࡜࡞ࡿࠋࡇࢀࡲ࡛ࡢ◊✲࠿ࡽࠊ
Scheme 1 ࡟♧ࡋࡓศᏊ[1]ࡢᅛయ୰࡟࠾ࡅࡿᏳᐃᵓ㐀ࡣᏙ❧⣔࡜ྠࡌࡃࠊᇶᗏ≧ែ࡛࣋ࣥࢮࣀ࢖ࢻ
ᵓ㐀ࠊບ㉳≧ែ࡛࢟ࣀ࢖ࢻᵓ㐀ࢆ࡜ࡾࠊᅛయ୰ࡢ྾཰࢚ࢿࣝࢠ࣮ࡣ⁐ᾮ୰࡜኱ࡁࡃኚࢃࡽ࡞࠸ࡇ
࡜ࡀ♧၀ࡉࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊScheme 1 ࡢศᏊ࡟ࡘ࠸࡚ Car-Parrinello Molecular Dynamics(CPMD)ィ⟬[2]ࢆ⾜࠸ࠊᇶᗏ≧ែཬࡧບ㉳≧ែ࡟࠾ࡅࡿ⇕᣺ືࡢㄪᰝࢆ⾜ࡗࡓࠋࡲࡓࠊᇶᗏ≧ែ࡟࠾ࡅࡿᵓ㐀࡜㏿ᗘࢆࢧࣥࣉࣜࣥࢢࡋ࡚ບ㉳≧ែ࡛ࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜࠸ࠊᆶ┤ບ㉳ࡋࡓศᏊࡀᵓ㐀⦆࿴ࡍࡿ㐣⛬࡟ࡘ࠸࡚ഃ㙐ࡸ࿘ᅖࡢศᏊࡀ୚࠼ࡿᙳ㡪ࡢ᳨ウࢆ⾜ࡗࡓࠋ࠙ィ⟬᪉ἲࠚ
CPMD ィ⟬࡟ࡘ࠸࡚ࠊᖹ㠃Ἴᇶᗏࠊᨃ࣏ࢸࣥࢩࣕࣝࠊ࿘ᮇⓗቃ⏺᮲௳ࢆ⏝࠸࡚ࠊBLYP ἲ࡛⾜ࡗࡓࠋࣘࢽࢵࢺࢭࣝ࡟ࡣ X ⥺ᵓ㐀ゎᯒ࡟ࡼࡗ࡚ᚓࡽࢀ࡚࠸ࡿ 2 ศᏊࢆྵࢇࡔ୕ᩳᬗࢆ⏝࠸ࠊ ᗘࡣ
300±2K ࡛ࢫࢣ࣮ࣜࣥࢢࢆ⾜ࡗࡓࠋ௬᝿㟁Ꮚ㉁㔞ࡣ 400 a.u.ࠊ᫬㛫้ࡳᖜࡣ 4 a.u.(=0.0968 fs)࡜ࡋࡓࠋ
ᇶᗏ≧ែཬࡧບ㉳≧ែ࡟࠾ࡅࡿ⇕᣺ືࡢ 9.68 ps ᖹ⾮໬ࡋࡓᚋ࡟ 9.68 ps ศࡢࢺࣛࢪ࢙ࢡࢺࣜ࠿ࡽ
ゎᯒࢆ⾜ࡗࡓࠋບ㉳≧ែ࡛ᵓ㐀⦆࿴ࡍࡿ㐣⛬ࡣࠊᇶᗏ≧ែࡢᵓ㐀ཬࡧึᮇ㏿ᗘࢆࢧࣥࣉࣜࣥࢢࡋࠊ
ບ㉳≧ែ࡛ࢩ࣑࣮ࣗࣞࢩࣙࣥࢆᐇ⾜ࡋࠊ0.29 ps ศࡢࢺࣛࢪ࢙ࢡࢺࣜ 100 ᮏ࠿ࡽゎᯒࢆ⾜ࡗࡓࠋ࠙⤖ᯝ࡜⪃ᐹࠚ
⇕᣺ືࡢࢺࣛࢪ࢙ࢡࢺࣜ࡟ᑐࡋ࡚ࠊ⣔ෆࡢศᏊ᣺ືࢆㄪᰝࡍࡿࡓࡵ࡟ᘧ(1)࡛⾲ࡉࢀࡿ⣔ෆࡢ඲ཎᏊࡢ㏿ᗘ⮬ᕫ┦㛵㛵ᩘ VACF(t)ࢆồࡵࠊࣇ࣮࢚ࣜኚ᥮ࢆ⾜࠺ࡇ࡜࡛⣔ࡢࣃ࣮࣡ࢫ࣌ࢡࢺࣝࢆᚓࡓࠋ
() =

1






< ( )( + ) >… (1)< ()( ) >1.0
R = H ࡜ࡋࡓࣔࢹࣝศᏊ࡜ᐇᅾࡍࡿ R = Pr ࡢศᏊ࡟ࡘ࠸࡚ࠊFig. 1 ࡟㏿ᗘ⮬ᕫ┦㛵㛵ᩘࢆ♧ࡋࡓࠋᐇᅾศᏊ࡛ࡣࠊࣔࢹࣝศᏊ࡟ẚ࡭࡚ῶ⾶ࡀ᪩ࡃࠊ
0.5 ps ⛬ᗘ࡛┦㛵ࡀ࡯ࡰኻࢃࢀࡿࡇ࡜ࡀศ࠿ࡿࠋ
୍᪉ࣔࢹࣝศᏊ࡛ࡣࠊ1 ps ࠿ࡽ 2 ps ୍࡛ᗘ㈇ࡢ್

ࣔࢹࣝศᏊ_ᇶᗏ≧ែ

0.8

ᐇᅾศᏊ_ᇶᗏ≧ែ

0.6
0.4
0.2

ࢆ࡜ࡗࡓᚋ࡟෌ࡧቑຍࡋࠊ4 ps ࢆ㉸࠼ࡿ㛗࠸࿘ᮇ

0.0ࡢ᣺ືࡀぢࡽࢀࡓࠋ

-0.2

0.0

Fig. 2 ࡟ࡣࣃ࣮࣡ࢫ࣌ࢡࢺࣝࢆ♧ࡋࡓࠋࣔࢹࣝศ -0.4

0.5

1.0

1.5

2.0

2.5
(ps)

Fig. 1 ㏿ᗘ⮬ᕫ┦㛵㛵ᩘ

Ꮚ࡛ࡣ 900 cm-1 ཬࡧ 2062 cm-1 ࡟኱ࡁ࡞ࣆ࣮ࢡࡀ
⌧ࢀ࡚࠸ࡿࠋᏙ❧ศᏊ࡟࠾ࡅࡿᇶ‽᣺ືゎᯒ࡜ࡢࣔࢹࣝศᏊ_ᇶᗏ≧ែẚ㍑࠿ࡽࠊࡇࢀࡽࡢࣆ࣮ࢡࡣࡑࢀࡒࢀ π ඹᙺᖹ㠃

ᐇᅾศᏊ_ᇶᗏ≧ែࡢ㠃እṍࡳཬࡧࢣ࢖⣲࡜ഃ㙐ࡢఙ⦰᣺ື࡟┦ᙜࡍࡿ࡜⪃࠼ࡽࢀࡿࠋྠᵝ࡟ࠊᐇᅾศᏊࡢ 1430 cm-1
࡜ 2790 cm-1 ࡢࣆ࣮ࢡࡣࡑࢀࡒࢀ π ඹᙺ⣔ࡢ㠃ෆఙ⦰ཬࡧഃ㙐ࡢᦂࢀ᣺ື࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓ
ࣔࢹࣝศᏊ࡛ࡢࡳࠊ኱ࡁ࡞ࣆ࣮ࢡࡀ 50 cm-1 ௨ୗࡢ㡿ᇦ࡟Ꮡᅾࡍࡿࡀࠊୖ㏙ࡋࡓࣔࢹࣝศᏊࡢ㏿ᗘ┦

0

1000

2000

3000

4000 -1(cm )Fig. 2 ࣃ࣮࣡ࢫ࣌ࢡࢺࣝ

㛵㛵ᩘ࡟࠾ࡅࡿ㛗࿘ᮇ᣺ື࡟ᑐᛂࡍࡿ࡜⪃࠼ࡽࢀࡿࠋᏙ❧ศᏊࡢᇶ‽᣺ືゎᯒ࡜ࡢẚ㍑࠿ࡽࠊࡇࢀࡣ π ඹᙺᖹ㠃ࡢ㠃እṍࡳ࡟┦ᙜࡍࡿࠋᚑࡗ࡚ࠊ
ᐇᅾศᏊ࡛ࡣഃ㙐࡟ࡼࡗ࡚ π ඹᙺ⣔ࡢᖹ㠃ᛶࡀಖࡓࢀ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ
ᆶ┤ບ㉳ࡋࡓ┤ᚋࡢᵓ㐀⦆࿴㐣⛬࡟ࡘ࠸࡚ࡶྠ

1.0

ᵝ࡟㏿ᗘ⮬ᕫ┦㛵㛵ᩘࢆィ⟬ࡋࡓ㸦Fig. 3㸧ࠋྠ㛵

0.8ᩘࡣࠊࣔࢹࣝศᏊ࣭Ꮩ❧⣔ᐇᅾศᏊ࣭ᅛయ୰ᐇᅾ

0.6

ศᏊ࡛࡯ࡰኚࢃࡽ࡞࠿ࡗࡓࠋࡇࢀࡣ୺࡞ኚ఩ࡀศ

0.4

Ꮚࡢ㦵᱁㒊ศ࡟⏤᮶ࡋ࡚࠾ࡾࠊഃ㙐ࡸ࿘ᅖศᏊࡢ

0.2

ᐤ୚ࡀᑡ࡞࠸ࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋࡲࡓࠊᏙ❧⣔࠾ࡼࡧᅛయ୰ࡢᐇᅾศᏊ࡟ࡘ࠸࡚ࠊບ㉳≧ែࡢᐃᖖ≧ែ࡟࠾ࡅࡿ┦㛵㛵ᩘࡣ⦆࿴㐣⛬ࡢ┦㛵㛵ᩘ࡜㢮ఝࡋ࡚࠾ࡾࠊ୧⪅ࢆᵓᡂࡍࡿ᣺ືࡀᮏ㉁ⓗ࡟ྠࡌ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿࠋᏙ❧ศᏊࡢᇶ‽᣺ືᅛయ୰ศᏊ_⦆࿴㐣⛬

0.0-0.2 0

0.1

0.2

0.3

(ps)

-0.4
Fig. 3 ⦆࿴㐣⛬ࡢ㏿ᗘ⮬ᕫ┦㛵㛵ᩘゎᯒ࡜ࡢẚ㍑࠿ࡽࠊࡇࢀࡣ π ඹᙺᖹ㠃ࡢ㠃ෆఙ⦰࣮ࣔࢻ࡟┦ᙜࡋࠊບ㉳࡟కࡗ࡚࣋ࣥࢮࣀ࢖ࢻᵓ
㐀࠿ࡽ࢟ࣀ࢖ࢻᵓ㐀࡬࡜Ᏻᐃᵓ㐀ࡀኚ໬ࡍࡿࡇ࡜࡟୍⮴ࡍࡿࠋ࠙ᩥ⊩ࠚ[1] H. Yamada, C. Xu, A. Fukazawa, A. Wakamiya, S. Yamaguchi, Macromol. Chem. Phys., 210, 904(2009).
[2] R. Car and M. Parrinello, Phys. Rev. Lett., 55, 2471 (1985).

2P139AlPO4(110) Rh dimer âPoGÇqÛ PoG°O7F8H ãO Z 1 Àp 1, 2
1

2

A DFT study of Rh dimer adsorption on AlPO4(110) surface(ESICB, Kyoto Univ.1, FIFC, Kyoto Univ.2) Masafuyu Matsui1, Shigeyoshi Sakaki1, 2
~Ë Rh ¶r-tridymite iCFÓ0D?![G- Rh/AlPO4 #¾_ÎIXÇqà¤/¯½©ÖÇq£«-,"à¤"af# Rh" sintering â¶r"TÃÝJ"×ã"\!,% sintering "\/(*"# Rh-O-P ¹b!),Ö{-T¬NU¨,,")
¨

!Çq"¤

u!ÔÄ

^/Ö{¶rTÃÝØ"¬NU

"Ê¸!#§ËGvß"MÝ!

Rh  AlPO4 ÃÝØ"¬NU¨
/*

")

Hinokuma *!)+kd1-Ìn®³#("+")!tu`/(*,!,'Rh dimer " AlPO4(110) ÃÝ$"c­tu"ÉWc­¬N

U¨"Ûr¦!jÆ/6B=A9D DFT Èµ/¨Â
ÃÝA9Dc­51:"ÃÝÓ·
PO ! H

AlPO4(110)ÃÝ"A9D"ä²Þ/»P !ÒS`sÕËÃÝ (Type I (g 1 (a))).

: (1) Y

(2) Type I ÃÝ" Al ! OHÒSeÃÝ (Type II (g 2 (b)))Rh dimer c­51:Type I # P ÒSÓ·51: (PO@Type I) Type II # P ÒSÓ·51: (PO@Type II)  Al ÒS
Ó·51: (AlO@Type II) !y,c­2;D3H/'51:"tu"ÙType II 51:$"c­#ª! H2 ½Ú/R

/ÉW) Type I, Type II $"c­2;D3H/-

        uº,
Èµ¡ AlPO4 7 | (15 atomic layer)*,6B=A9D/¨Y"c­Ï´å|Q¥/ bulk Ï!hu´ 2 |%/ÏÑ`>E4B@# VASP /V}Ý¢jPAW potential, PBE functional /¨6<F[/»Èµ/Â¹»x c­2;D3H/ Table I !¯PO@Type I
AlO@TypeII $"c­tu`#z.

tuc­51:+"c­2;D3H#H2 "½Ú2

;D3HâH2 elimination energy: Eelim[H2]. Type II "&ãc­Ï$"Ïm`!R

dimer

ÃÝ"Ktu`2;D3H (deformation energy: Edeform)Ktu` dimer ÃÝØ"tu`2;D3H![Æ,,u`¬NU¨2;D3H (interaction energy; Eint)

 

 

 



 

PO@Type II 

 Eint         g!Ãä, Edeform[AlPO4]            

 

   ![Æ,-/¯"

AlO@Type II "c­tu`"Ð!wL,.

,% Bader population analysis "g 1¹/Ãå!¯Y"lbá ; P, Í ; O, ¿; Hã

 Rh

AlPO 4(110) "  Ï. Type I (a), Type II (b). âÜ; Al,* AlPO4 $"ÛÁ±_Å*-,

PO@Type II  AlO@Type II #]¼"ÛÁ±_o-

M¼"

Eint "Ð!wL,(".-,

ad sitePO@Type I

PO@Type II

AlO@Type IIad sitespin

Eadsinglet-3.39

triplet-3.59

quintet-3.65

singlet-1.80

triplet-1.96

quintet-1.79

singlet-0.57

triplet-0.47

quintet-0.32

Eelim[H2]

Edeform[AlPO4]

Edeform[Rh2]Eint

PO@Type I(none)

+1.86

+0.05

-5.96

PO@Type II

+6.37

+0.23

+0.01

-8.76

AlO@Type II

+6.52

+0.88

+0.00

-7.93

Bader population of Rh dimer

PO@Type I

17.95 (-0.05)

PO@Type II

16.08 (-1.92)

AlO@Type II

17.28 (-0.72)

1Ad siteS. Hinokuma et al. / Catalysis Today 175 (2011) 593–597