2002 Fiscal Year Annual Research Report

量子的化学原理の深化と実現

Research Project

Project/Area Number	14GS0217
Research Institution	Kyoto University
Principal Investigator	中辻博京都大学, 工学研究科, 教授 (90026211)
Co-Investigator(Kenkyū-buntansha)	波田雅彦東京都立大学, 理学研究科, 教授 (20228480) 榊茂好京都大学, 工学研究科, 教授 (20094013) 加藤重樹京都大学, 理学研究科, 教授 (20113425) 長谷川淳也京都大学, 工学研究科, 助手 (30322168) 森田明弘京都大学, 理学研究科, 助手 (70252418) 江原正博京都大学, 工学研究科, 助教授 (80260149)
Keywords	化学原理 / シュレーディンガー方程式の厳密解 / 理論精密分光学 / 生命量子論 / 巨大分子系 / 凝縮系 / 相対論的量子化学 / 遷移金属錯体
Research Abstract	1.量子化学基礎理論の精密化と再構築:シュレーディンガー方程式の解である正確な波動関数の構造について研究を行った。励起状態の正確な波動関数を求める方法として、ICI-CI法およびECC-CI法を定式化し、多くの励起状態を一挙に計算できる方法を開発した。逆(inverse)ハミルトニアンを用いて定義される逆シュレーディンガー方程式が、シュレーディンガー方程式と等価であり、変分原理を満たすことを示した。逆ハミルトニアンを用いてICI法を一般化し、正確な解を与える解法を提案した。 2.ファインなスペクトロスコピーと反応の量子ダイナミクス:ポテンシャル曲線の不連続を解消する方法を開発し、励起状態やイオン化状態の分光定数の理論計算に応用した。多電子過程を精密に記述するSAC・CI general-R法を用いて、価電子イオン化状態や内殻励起・イオン化状態を高い精度で計算し、精密な帰属を与えた。Dirac-Fock法や擬相対論に基づく電子相関理論を、多体摂動法や結合クラスター法で実現した。X^-,XO_4^-(X=F,Cl,Br,I)のX核磁気遮蔽定数やSe,Te,Sn,Pb等の重原子核の磁気遮蔽定数の理論研究を行い、相対論と電子相関の効果を同時に考慮することの重要性を示した。精密な量子動力学法によって、H_3の2S状態の前期解離過程を研究した。また、H_2COの全自由度のポテンシャルを決定し、解離反応の速度定数や反応のモード選択性を解明した。 3.巨大系に共通する電子状態理論:QM/MM法を用いて、光合成反応中心の電子移動とプロトン移動のカップリングのメカニズムについて、反応に伴う構造緩和と蛋白が色素の電子状態に及ぼす影響について研究した。 4.生体反応系の電子論とダイナミクスの解明:人工光合成系や分子素子への応用が期待される2種類のポルフィリン二量体について、SAC-CI法により励起状態を研究した。複雑な吸収スペクトルの帰属に成功し、二量化による電子構造の変化を明らかにした。緑色蛍光蛋白色素(GFPC)とそのミュータントの吸収スペクトル、蛍光スペクトルを帰属し、実在する分子を特定した。Fe(III)ポルフィリンシアン化物の電子状態をSAC-CI法で研究した。励起状態も含めて、常磁性化学シフトの挙動がスピン伝達機構により合理的に説明できることを示した。 5.凝縮系における反応の電子論とダイナミクス:極性媒質の反応場下におけるダイナミクスを取り扱う新しい理論的方法を開発し、水分子やN-メチルアセトアミド分子のIRやRamanスペクトルに応用した。 6.遷移金属錯体の構造と触媒反応のメカニズム:二酸化炭素水素化反応およびアルケンのヒドロシリル化反応の反応機構と中心金属の電子状態との関連を明らかにした。また、金属フタロシアニンの構造と物性の関連性を電子配置から明らかにした。

Research Products
(37 results)

All Other

All Publications (37 results)

[Publications] H.Nakatsuji: "Structure of the wave function. IV. Excited states from exponential ansatz and comparative calculations by the iterative configuration interaction and extended coupled cluster theories"J. Chem. Phys.. 116. 1811-1824 (2002)
[Publications] H.Nakatsuji, M.Ehara: "Structure of the exact wave function. V. Iterative configuration interaction method for molecular systems within finite basis"J. Chem. Phys.. 117. 9-12 (2002)
[Publications] H.Nakatsuji: "Inverse Schrodinger equation and the exact wave function"Phys. Rev. A. 65. 052122-1-052122-15 (2002)
[Publications] Y.Honda, M.Hada, M.Ehara, H.Nakatsuji, J.Downing, J.Michl: "Relativistic effects on magnetic circular dichroism studied by GUHF/SECI method"Chem. Phys. Lett.. 355. 219-225 (2002)
[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Quasirelativistic theory for the magnetic shielding constant. I. Formulation of Douglass-Kroll-Hess transformation for the magnetic field and its application to atomic systems"J. Chem. Phys.. 118. 1015-1026 (2002)
[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Quasirelativistic theory for the magnetic shielding constant. II. Gauge-including atomic orbitals and applicaitons to molecules"J. Chem. Phys.. 118. 1027-1035 (2002)
[Publications] M.Nakata, M.Ehara, H.Nakatsuji: "Density matrix varitional theory : Application to the potential energy surfaces and strongly correlated systems"J. Chem. Phys.. 116. 5432-5439 (2002)
[Publications] M.Ishida, M.Ehara, H.Nakatsuji: "Outer-and inner-valance ionization spectra of NH_3, PH_3, and AsH_3 Symmetry-adapted cluster configuration interaction general-R study"J. Chem. Phys.. 116. 1934-1943 (2002)
[Publications] P.Tomasello, M.Ehara, H.Nakatsuji: "Electronic excitation spectra of Cl_2O, ClOOCl, and F_2O : A SAC-CI study"J. Chem. Phys.. 116. 2425-2432 (2002)
[Publications] Z.Hu, R.J.Boyd, H.Nakatsuji: "Molecular Structure and Excited States of CpM(CO)_2 (Cp=5-C_5H_5 ; M=Rh,Ir) and [CI_2Rh(CO)_2]-. Theoretical Evidence for a Competitive Charge Transfer Mechanism"J. Am. Chem. Soc.. 124. 2664-2671 (2002)
[Publications] Y.Honda, M.Hada, M.Ehara, H.Nakatsuii: "Excited and ionized states of aniline : Symmetry adapted cluster configuration interaction theoretical study"J. Chem. Phys.. 117. 2045-2052 (2002)
[Publications] M.Ehara, M.Ishida, H.Nakatsuji: "Fine theoretical spectroscopy using symmetry adapted cluster-configuration interaction general-R method : Outer-and inner-valance ionization spectra of CS_2 and OCS"J. Chem. Phys.. 117. 3248-3255 (2002)
[Publications] K.Toyota, M.Ehara, H.Nakatsuji: "Elimination of singularities in molecular orbital derivatives : minimum orbital-deformation (MOD) method"Chem. Phys. Lett.. 356. 1-6 (2002)
[Publications] K.Ishimura, M.Hada, H.Nakatsuji: "Ionized and excited states of ferrocene : Symmetry adapted cluster-configuration-interaction study"J. Chem. Phys.. 117. 6533-6537 (2002)
[Publications] M.Ehara, S.Yasuda, H.Nakatsuji: "Outer-and inner-valence ionization spectra of N_2O and HN_3 : SAC-CI study"Z. Phys. Chem.. 217. 161-176 (2003)
[Publications] A.K.Das, M.Ehara, H.Nakatsuji: "Excited states of Na and Al iso-lelctronic ions : Symmetry adapted cluster-configuration interaction study"Int. J. Quantum Chem.. 87. 81-88 (2002)
[Publications] Y.Honda, M.Hada, M.Ehara, H.Nakatsuji: "Excited and Ionized States of p-Benzoquinone and its Anion Radical : SAC-CI Theoretical Study"J. Phys. Chem. A. 106. 3838-3849 (2002)
[Publications] K.Toyota, M.Ishida, M.Ehara, M.J.Frisch, H.Nakatsuji: "Singularity-free analytical energy gradients for the SAC/SAC-CI method : coupled perturbed minimum orbital-deformation(CPMOD) approach"Chem. Phys. Lett.. 367. 730-736 (2002)
[Publications] E.S.Kryachko, H.Nakatsuji: "Ab Initio Study of Lower Energy Phenol-Waterln4 Complexes : Interpretation of Two Distinct Infrred Patterns in Spectra of Phenol-Water Tetramer"J. Phys. Chem. A.. 106. 731-742 (2002)
[Publications] W.Nowak, Y.Ohtsuka, J.Hasegawa, H.Nakatsuji: "Density Functional Study on Geometry and Electronic Structure of Nitrile Hydratase Ative Site Model"Intern. J. Qunatum Chem.. 90. 1174-1187 (2002)
[Publications] J.Hasegawa, M.Ishida, H.Nakatsuji: "Energetics of the Electron Transfer from Bacteriopheophytin to Ubiquinone in the Photosynthetic Reaction Center of Rhodoqseudomonas Viridis : Theoretical Study"J. Phys. Chem. B.. 107. 838-847 (2002)
[Publications] T.Miyahara, H.Nakatsuji, J.Hasegawa, A.Osuka, N.Aratani, A.Tsuda: "Ground and excited states of linked and fused zinc porphyrin dimers : symmetry adapted cluster (SAC-CI)-configuration interaction (CI) study"J. Chem. Phys.. 117. 6533-6537 (2002)
[Publications] T.Yonehara, S.Kato: "Role of isomerization channel in unimolecular dissociation reaction H2CO->H2+CO : ab initio global potential energy surface and classical trajectory analysis"J. Chem. Phys.. 117. 11131-11138 (2002)
[Publications] M.Tashiro, S.Kato: "Quantum dynamics study on predissociation of H3 Rydberg states : Importance of indirect mechanism"J. Chem. Phys.. 117. 2053-2062 (2002)
[Publications] H.Sakurai, S.Kato: "Theoretical Study of the Metal Oxidation Reaction Ti+O_<2->>TiO+O : Ab Intio Calculation of the Potential Energy Surface and Classical Trajectory Analysis"J. Phys. Chem. A.. 106. 4350-4357 (2002)
[Publications] A.Morita, S.Kato: "The Charge Response Kernel with Modified Electrostatic Potential Charge Model"J. Phys. Chem. A.. 90. 3909-3916 (2002)
[Publications] M.Tashiro, S.Kato: "Predissociation of H_3 2s Rydberg state : quantum dynamics study"Chem. Phys. Lett.. 354. 14-19 (2002)
[Publications] S.Iuchi, A.Morita, S.Kato: "Molecular Dynamics Simulation with the Charge Response Kernel : Vibrational Spectra of Liquid Water and N-Methylacetamide in Aqueous Solution"J. Phys. Chem. B. 106. 3466-3476 (2002)
[Publications] Y.Goto, N.Nakashima, M.Takafuji, S.Sakaki, H.Ihara: "Selectivity Enhancement for Diastereomer Separation in RPLC Using Crystalline-Organic Phase-Bounded Silica Instead of Simply-Hydrophobized Silica Chromatographia"Chromatographia. 56. 19-23 (2002)
[Publications] Y.Musashi, S.Sakaki: "Theoretical Study of Rhodium(III)-Catalyzed Hydrogenation of Carbon Dioxide into Formic Acid. Significant Differences in Reactivity among Rhodium(III). Rhodium(I), and Ruthenium(II) Complexes"J. Am. Chem. Soc.. 124. 7588-7603 (2002)
[Publications] S.Sakaki, M.Sumimoto, M.Fukuhara, M.Sugimoto, H.Fujimoto, S.Matsuzaki: "Why Does the Rhodium-Catalyzed Hydrosilylation of Alkenes Take Place Through a Modified Chalk-Harrod Mechanism? A Theoretical Study"Organometallics. 21. 3788-3802 (2002)
[Publications] T.Tomita, T.Takahama, M.Sugimoto, S.Sakaki: "Why is the Nickel(II) diphenyldiimine Complex the Best Catalyst for polymerization of Ethylene in Three Kinds of Cationic Nickel(II) Complexes, [Ni(CH_3)L]^+ (L=Diphenyldiimine, 2,2'-Bipyridine, or 1,2-Diphosphinoethane)? A Theoretical Study"Organometallics. 21. 3788-3802 (2002)
[Publications] M.Sumimoto, S.Sakaki, S.Matsuzaki, H.Fujimoto: "Significant differences in electronic structure among X-, α-and β-forms of lithium phthalocyanine"Dalton Trans.. 31-33 (2002)
[Publications] T.Hamada, S.Tanaka, H.Koga, Y.Sakai, S.Sakaki: "Kinetic study of the photo-induced electron transfer reaction between ruthenium(II) complexes of 2,2'-bipyridine derivatives and methyl viologen. Effects of bulky substituents introduced onto 2,2'-bipyridine"Dalton Trans.. 692-698 (2002)
[Publications] H.Koga, T.Hamada, S.Sakaki: "Synthesis of methylviologen-pendent iron porphyrins as functional model of reduction enzeime and its application to six electron reduction of nitrobenzene to aniline"Dalton Trans.. 1153-1160 (2003)
[Publications] M.Ehara, M.Ishida, K.Toyota, H.Nakatsuii: "Reviews in Modern Chemistiy"Ed. by K. D. Sen, World Scientific, Singapore. 27 (2002)
[Publications] Shigeyoshi Sakaki: "Catalysis by Metal Complexes vol.25 ; Computational Modelling of Homogeneous Catalysis"Ed. by Feliu Maseras and Agusti Lledos, Kluwer. 28 (2002)

2002 Fiscal Year Annual Research Report

量子的化学原理の深化と実現

Principal Investigator

中辻 博 京都大学, 工学研究科, 教授 (90026211)

Research Products

[Publications] H.Nakatsuji: "Structure of the wave function. IV. Excited states from exponential ansatz and comparative calculations by the iterative configuration interaction and extended coupled cluster theories"J. Chem. Phys.. 116. 1811-1824 (2002)

[Publications] H.Nakatsuji, M.Ehara: "Structure of the exact wave function. V. Iterative configuration interaction method for molecular systems within finite basis"J. Chem. Phys.. 117. 9-12 (2002)

[Publications] H.Nakatsuji: "Inverse Schrodinger equation and the exact wave function"Phys. Rev. A. 65. 052122-1-052122-15 (2002)

[Publications] Y.Honda, M.Hada, M.Ehara, H.Nakatsuji, J.Downing, J.Michl: "Relativistic effects on magnetic circular dichroism studied by GUHF/SECI method"Chem. Phys. Lett.. 355. 219-225 (2002)

[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Quasirelativistic theory for the magnetic shielding constant. I. Formulation of Douglass-Kroll-Hess transformation for the magnetic field and its application to atomic systems"J. Chem. Phys.. 118. 1015-1026 (2002)

[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Quasirelativistic theory for the magnetic shielding constant. II. Gauge-including atomic orbitals and applicaitons to molecules"J. Chem. Phys.. 118. 1027-1035 (2002)

[Publications] M.Nakata, M.Ehara, H.Nakatsuji: "Density matrix varitional theory : Application to the potential energy surfaces and strongly correlated systems"J. Chem. Phys.. 116. 5432-5439 (2002)

[Publications] M.Ishida, M.Ehara, H.Nakatsuji: "Outer-and inner-valance ionization spectra of NH_3, PH_3, and AsH_3 Symmetry-adapted cluster configuration interaction general-R study"J. Chem. Phys.. 116. 1934-1943 (2002)

[Publications] P.Tomasello, M.Ehara, H.Nakatsuji: "Electronic excitation spectra of Cl_2O, ClOOCl, and F_2O : A SAC-CI study"J. Chem. Phys.. 116. 2425-2432 (2002)

[Publications] Z.Hu, R.J.Boyd, H.Nakatsuji: "Molecular Structure and Excited States of CpM(CO)_2 (Cp=5-C_5H_5 ; M=Rh,Ir) and [CI_2Rh(CO)_2]-. Theoretical Evidence for a Competitive Charge Transfer Mechanism"J. Am. Chem. Soc.. 124. 2664-2671 (2002)

[Publications] Y.Honda, M.Hada, M.Ehara, H.Nakatsuii: "Excited and ionized states of aniline : Symmetry adapted cluster configuration interaction theoretical study"J. Chem. Phys.. 117. 2045-2052 (2002)

[Publications] M.Ehara, M.Ishida, H.Nakatsuji: "Fine theoretical spectroscopy using symmetry adapted cluster-configuration interaction general-R method : Outer-and inner-valance ionization spectra of CS_2 and OCS"J. Chem. Phys.. 117. 3248-3255 (2002)

[Publications] K.Toyota, M.Ehara, H.Nakatsuji: "Elimination of singularities in molecular orbital derivatives : minimum orbital-deformation (MOD) method"Chem. Phys. Lett.. 356. 1-6 (2002)

[Publications] K.Ishimura, M.Hada, H.Nakatsuji: "Ionized and excited states of ferrocene : Symmetry adapted cluster-configuration-interaction study"J. Chem. Phys.. 117. 6533-6537 (2002)

[Publications] M.Ehara, S.Yasuda, H.Nakatsuji: "Outer-and inner-valence ionization spectra of N_2O and HN_3 : SAC-CI study"Z. Phys. Chem.. 217. 161-176 (2003)

[Publications] A.K.Das, M.Ehara, H.Nakatsuji: "Excited states of Na and Al iso-lelctronic ions : Symmetry adapted cluster-configuration interaction study"Int. J. Quantum Chem.. 87. 81-88 (2002)

[Publications] Y.Honda, M.Hada, M.Ehara, H.Nakatsuji: "Excited and Ionized States of p-Benzoquinone and its Anion Radical : SAC-CI Theoretical Study"J. Phys. Chem. A. 106. 3838-3849 (2002)

[Publications] K.Toyota, M.Ishida, M.Ehara, M.J.Frisch, H.Nakatsuji: "Singularity-free analytical energy gradients for the SAC/SAC-CI method : coupled perturbed minimum orbital-deformation(CPMOD) approach"Chem. Phys. Lett.. 367. 730-736 (2002)

[Publications] E.S.Kryachko, H.Nakatsuji: "Ab Initio Study of Lower Energy Phenol-Waterln4 Complexes : Interpretation of Two Distinct Infrred Patterns in Spectra of Phenol-Water Tetramer"J. Phys. Chem. A.. 106. 731-742 (2002)

[Publications] W.Nowak, Y.Ohtsuka, J.Hasegawa, H.Nakatsuji: "Density Functional Study on Geometry and Electronic Structure of Nitrile Hydratase Ative Site Model"Intern. J. Qunatum Chem.. 90. 1174-1187 (2002)

[Publications] J.Hasegawa, M.Ishida, H.Nakatsuji: "Energetics of the Electron Transfer from Bacteriopheophytin to Ubiquinone in the Photosynthetic Reaction Center of Rhodoqseudomonas Viridis : Theoretical Study"J. Phys. Chem. B.. 107. 838-847 (2002)

[Publications] T.Miyahara, H.Nakatsuji, J.Hasegawa, A.Osuka, N.Aratani, A.Tsuda: "Ground and excited states of linked and fused zinc porphyrin dimers : symmetry adapted cluster (SAC-CI)-configuration interaction (CI) study"J. Chem. Phys.. 117. 6533-6537 (2002)

[Publications] T.Yonehara, S.Kato: "Role of isomerization channel in unimolecular dissociation reaction H2CO->H2+CO : ab initio global potential energy surface and classical trajectory analysis"J. Chem. Phys.. 117. 11131-11138 (2002)

[Publications] M.Tashiro, S.Kato: "Quantum dynamics study on predissociation of H3 Rydberg states : Importance of indirect mechanism"J. Chem. Phys.. 117. 2053-2062 (2002)

[Publications] H.Sakurai, S.Kato: "Theoretical Study of the Metal Oxidation Reaction Ti+O_<2->>TiO+O : Ab Intio Calculation of the Potential Energy Surface and Classical Trajectory Analysis"J. Phys. Chem. A.. 106. 4350-4357 (2002)

[Publications] A.Morita, S.Kato: "The Charge Response Kernel with Modified Electrostatic Potential Charge Model"J. Phys. Chem. A.. 90. 3909-3916 (2002)

[Publications] M.Tashiro, S.Kato: "Predissociation of H_3 2s Rydberg state : quantum dynamics study"Chem. Phys. Lett.. 354. 14-19 (2002)

[Publications] S.Iuchi, A.Morita, S.Kato: "Molecular Dynamics Simulation with the Charge Response Kernel : Vibrational Spectra of Liquid Water and N-Methylacetamide in Aqueous Solution"J. Phys. Chem. B. 106. 3466-3476 (2002)

[Publications] Y.Goto, N.Nakashima, M.Takafuji, S.Sakaki, H.Ihara: "Selectivity Enhancement for Diastereomer Separation in RPLC Using Crystalline-Organic Phase-Bounded Silica Instead of Simply-Hydrophobized Silica Chromatographia"Chromatographia. 56. 19-23 (2002)

[Publications] Y.Musashi, S.Sakaki: "Theoretical Study of Rhodium(III)-Catalyzed Hydrogenation of Carbon Dioxide into Formic Acid. Significant Differences in Reactivity among Rhodium(III). Rhodium(I), and Ruthenium(II) Complexes"J. Am. Chem. Soc.. 124. 7588-7603 (2002)

[Publications] S.Sakaki, M.Sumimoto, M.Fukuhara, M.Sugimoto, H.Fujimoto, S.Matsuzaki: "Why Does the Rhodium-Catalyzed Hydrosilylation of Alkenes Take Place Through a Modified Chalk-Harrod Mechanism? A Theoretical Study"Organometallics. 21. 3788-3802 (2002)

[Publications] M.Sumimoto, S.Sakaki, S.Matsuzaki, H.Fujimoto: "Significant differences in electronic structure among X-, α-and β-forms of lithium phthalocyanine"Dalton Trans.. 31-33 (2002)

[Publications] H.Koga, T.Hamada, S.Sakaki: "Synthesis of methylviologen-pendent iron porphyrins as functional model of reduction enzeime and its application to six electron reduction of nitrobenzene to aniline"Dalton Trans.. 1153-1160 (2003)

[Publications] M.Ehara, M.Ishida, K.Toyota, H.Nakatsuii: "Reviews in Modern Chemistiy"Ed. by K. D. Sen, World Scientific, Singapore. 27 (2002)

[Publications] Shigeyoshi Sakaki: "Catalysis by Metal Complexes vol.25 ; Computational Modelling of Homogeneous Catalysis"Ed. by Feliu Maseras and Agusti Lledos, Kluwer. 28 (2002)

中辻博京都大学, 工学研究科, 教授 (90026211)