2003 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) 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展開した。原子、分子のシュレーディンガー方程式を解くために問題であった特異点を回避する方法として、Scaledシュレーディンガー方程式を提案し、正確な解を安定に求めることができる方法を開発した。この方程式に基づくFree ICI法を、原子や分子系に応用することにより、方法の有用性を示した。とくに、水素分子では世界記録の厳密なエネルギーを求めることに成功した。 2.理論精密分光学と反応の量子ダイナミクス:SAC-CIエネルギー勾配法のプログラムを改良し、ポルフィリン化合物の励起状態の構造最適化を可能とした。現時点で世界最大の計算である。これにより、free-base porphinの1重項、3重項励起状態の安定構造を決定した。多電子過程を精密に記述するSAC-CI gene ral-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。相対論的分子軌道法を用いて、チタン、タングステン等遷移金属核のNMR化学シフトの理論研究を行い、遷移金属のNMR化学シフトのメカニズムが、d電子の状態を敏感に反映することを明らかにした。4成分Dirac法への電子相関の導入やNMR計算を進めるための基底関数系の開発を進めた。自由度を制限した小成分の基底関数系を使う際には、atomic-balanceを使うことによって良好な結果を得ることを示した。精密な量子動力学法によって、NOCl分子の全自由度ポテンシャル上における高振動励起状態のダイナミクスを解明した。 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:SAC-CIプログラムを改良し、大規模な計算を可能にした。これによりタンパク質を含めた生体分子色素の計算が可能となった。フィトクロムの励起状態に応用し、その色素の構造を励起スペクトルから初めて理論的に同定した。励起スペクトルの変化から、光異性化機構を解明した。種々のFe(III)-cyanide-porphyrin錯体のC-13NMR化学シフトと分子構造及び励起電子状態との関連を纏めた。 5.凝縮系における反応の電子論とダイナミクス:極性媒質における励起状態を取り扱う理論的方法を、アセトニトリル中におけるナフトール誘導体のプロトン移動型励起状態に応用した。 6.遷移金属錯体の構造と触媒反応のメカニズム:理論的にも実験化学的にも興味深い錯体触媒反応を取り上げ、理論的研究から、反応機構の解明と反応予測を行った。イリジウム錯体を触媒としたベンゼンのジボロンによる直接ボリル化触媒反応ではこれまでにない特異な酸化状態の中間体を経る反応機構を明らかにした。

Research Products
(22 results)

All Other

All Publications (22 results)

[Publications] M.Ishida, K.Toyota, M.Ehara, M.J.Frisch, H.Nakatsuji: "Analytical Energy Gradient of the Symmetry-Adapted-Cluster Configuration-Interaction General-R method for singlet to Septet Ground and Excited States"J.Chem.Phys.. 120. 2593-2605 (2004)
[Publications] H.Yamashita, S.Takada, M.Hada, H.Nakatsuji, M.Anpo: "Experimental Study and Ab Initio Molecular Orbital Calculation on the Photolysis of n-butyrophenone Included within the Alkali Metal Cation-exchanged ZSM-5 Zeolite"J.Photochem.Photobio.A. 160. 37-42 (2003)
[Publications] A.K.Das, J.Hasegawa, T.Miyahara, M.Ehara, H.Nakatsuji: "Electronic Excitations of the Green Fluorescent Protein Chromophone in its Protoonation States : SAC/SAC-CI Study"J.Comp.Chem.. 24. 1421-1431 (2003)
[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Generalized-UHF Theory for Magnetic Properties with Quasi-Relativistic Hamiltonian"Rec.Adv.Comp.Chem.6. (in press).
[Publications] P.Tomasello, M.Ehara, H.Nakatuji: "Theoretical Investigation on the Valance Ionization Spectra of Cl20, ClOOCl, and F20 by Correlation-Based Configuration Interaction Methods"J.Chem.Phys.. 118. 5811-5820 (2003)
[Publications] M.Ehara, S.Yasuda, H.Nakatsuji: "Fine Theoretical Spectroscopy Using SAC-CI General-R Method : Outer-and Inner-Valence Ionization Spectra of N2O and HN3"Z.Phys.Chem.. 217. 161-176 (2003)
[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 (2003)
[Publications] J.Hasegawa, M.Ishida, H.Nakatsuji: "Energetics of the Electron Transfer from Bacteriophephytin to Ubiquinone in the Photosynthetic Reaction Center of Rhosopseudomonas Viridis : Theoretical Study"J.Phys.Chem.B. 107. 838-847 (2003)
[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Quasirelativistic Theory for the Magnetic Shielding Constant. II. Gauge-Including Atomic Orbitals and Applications to Molecules"J.Chem.Phys.. 118. 1027-1035 (2003)
[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Quasirelativistic Theory for the Magnetic Shielding Constant. I. Formulation of Douglass-Kroll-Hess Transformation for the Magnetic Filed and Its Application to Atomic Systems"J.Chem.Phys.. 118. 1015-1026 (2003)
[Publications] Masahiko Hada: "Quantum-Chemical Calculations for Paramagnetic 13C NMR Chemical Shifts of Iron-Bound Cyanide Ions of Iron Porphyrins in Ground and Low-Lying Excited States Containing Ferric (dxy)2(dxz,yz)3 and (dxy)1(dxz,yz)4 Configurations"J.Am.Chem.Soc.. 126. 486-487 (2004)
[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] H.Koga, T.Arai, T.Hamada, S.Sakaki: "Application of metalloporphyrins and methylviologen-pendant iron porphyrin to reduction of diphenylsulfoxide"J.Mol.Cat.(A). 200. 223-228 (2004)
[Publications] S.Sakaki: "Theoretical Study of C-H-Bond Activation and Related Reaction"Bull.Korean Chem.Soc.. 24. 829 (2003)
[Publications] H.Tamura, H Yamazaki, H.Sato, S.Sakaki: "Iridium-Catalyzed Borylation of Benzene with Diboron. Theoretical Elucidation of Catalytic Cycle Including Unusual Iridium(V) Intermediates"J.Am.Chem.Soc.. 125. 16114-16126 (2003)
[Publications] S.Sakaki, T.Takayama, M.Sumimoto, M.Sugimoto: "Theoretical Study of Cp_2Zr-Catalyzed Hydrosilylation of Ethylene. Reaction Mechanism Including New σ-Bond Activation"J.Am.Chem.Soc.. (in press).
[Publications] H.Sato, F.Hirata, S.Sakaki: "Distortion of Electronic Structure in Solvated Molecules : Tautomeric Equilibrium of 2-Pyridone and 2-Hydroxypridine in Water Studied by the RISM-SCF/MCSCF Method"J.Phys.Chem.A. (in press).
[Publications] H.Sato, S.Sakaki: "A Comparison of Electronic Structure Theories for Solvated Molecule : RISM-SCF versus PCM"J.Phys.Chem.A. (in press).
[Publications] S.Yamazaki, S.Kato: "Excited-state proton transfer of 1-[(dimethylamino)methyl]-2-naphthol in acetonitrile solvent : RISM-SCF and MRMP approach"Chem.Phys.Lett.. 386. 414-418 (2004)
[Publications] T.Ishida, S.Kato: "Theoretical Perspectives on the Reaction Mechanism of Serine Proteases : The Reaction Free Energy Profiles of the Acylation Process."J.Am.Chem.Soc.. 125. 12035-12048 (2003)
[Publications] T.Yamashita, S.Kato: "Regularity in highly excited vibrational dynamics of NOCl (X 1A') : Quantum mechanical calculations on a new potential energy surface"J.Chem.Phys.. 119. 4251-4261 (2003)
[Publications] K.Ohmiya, S.Kato: "Solution reaction path Hamiltonian based on reference interaction site model self-consistent field method : Application to Menshutkin-type reactions"J.Chem.Phys.. 119. 1601-1610 (2003)

2003 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] M.Ishida, K.Toyota, M.Ehara, M.J.Frisch, H.Nakatsuji: "Analytical Energy Gradient of the Symmetry-Adapted-Cluster Configuration-Interaction General-R method for singlet to Septet Ground and Excited States"J.Chem.Phys.. 120. 2593-2605 (2004)

[Publications] H.Yamashita, S.Takada, M.Hada, H.Nakatsuji, M.Anpo: "Experimental Study and Ab Initio Molecular Orbital Calculation on the Photolysis of n-butyrophenone Included within the Alkali Metal Cation-exchanged ZSM-5 Zeolite"J.Photochem.Photobio.A. 160. 37-42 (2003)

[Publications] A.K.Das, J.Hasegawa, T.Miyahara, M.Ehara, H.Nakatsuji: "Electronic Excitations of the Green Fluorescent Protein Chromophone in its Protoonation States : SAC/SAC-CI Study"J.Comp.Chem.. 24. 1421-1431 (2003)

[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Generalized-UHF Theory for Magnetic Properties with Quasi-Relativistic Hamiltonian"Rec.Adv.Comp.Chem.6. (in press).

[Publications] P.Tomasello, M.Ehara, H.Nakatuji: "Theoretical Investigation on the Valance Ionization Spectra of Cl20, ClOOCl, and F20 by Correlation-Based Configuration Interaction Methods"J.Chem.Phys.. 118. 5811-5820 (2003)

[Publications] M.Ehara, S.Yasuda, H.Nakatsuji: "Fine Theoretical Spectroscopy Using SAC-CI General-R Method : Outer-and Inner-Valence Ionization Spectra of N2O and HN3"Z.Phys.Chem.. 217. 161-176 (2003)

[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 (2003)

[Publications] J.Hasegawa, M.Ishida, H.Nakatsuji: "Energetics of the Electron Transfer from Bacteriophephytin to Ubiquinone in the Photosynthetic Reaction Center of Rhosopseudomonas Viridis : Theoretical Study"J.Phys.Chem.B. 107. 838-847 (2003)

[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Quasirelativistic Theory for the Magnetic Shielding Constant. II. Gauge-Including Atomic Orbitals and Applications to Molecules"J.Chem.Phys.. 118. 1027-1035 (2003)

[Publications] R.Fukuda, M.Hada, H.Nakatsuji: "Quasirelativistic Theory for the Magnetic Shielding Constant. I. Formulation of Douglass-Kroll-Hess Transformation for the Magnetic Filed and Its Application to Atomic Systems"J.Chem.Phys.. 118. 1015-1026 (2003)

[Publications] Masahiko Hada: "Quantum-Chemical Calculations for Paramagnetic 13C NMR Chemical Shifts of Iron-Bound Cyanide Ions of Iron Porphyrins in Ground and Low-Lying Excited States Containing Ferric (dxy)2(dxz,yz)3 and (dxy)1(dxz,yz)4 Configurations"J.Am.Chem.Soc.. 126. 486-487 (2004)

[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] H.Koga, T.Arai, T.Hamada, S.Sakaki: "Application of metalloporphyrins and methylviologen-pendant iron porphyrin to reduction of diphenylsulfoxide"J.Mol.Cat.(A). 200. 223-228 (2004)

[Publications] S.Sakaki: "Theoretical Study of C-H-Bond Activation and Related Reaction"Bull.Korean Chem.Soc.. 24. 829 (2003)

[Publications] H.Tamura, H Yamazaki, H.Sato, S.Sakaki: "Iridium-Catalyzed Borylation of Benzene with Diboron. Theoretical Elucidation of Catalytic Cycle Including Unusual Iridium(V) Intermediates"J.Am.Chem.Soc.. 125. 16114-16126 (2003)

[Publications] S.Sakaki, T.Takayama, M.Sumimoto, M.Sugimoto: "Theoretical Study of Cp_2Zr-Catalyzed Hydrosilylation of Ethylene. Reaction Mechanism Including New σ-Bond Activation"J.Am.Chem.Soc.. (in press).

[Publications] H.Sato, F.Hirata, S.Sakaki: "Distortion of Electronic Structure in Solvated Molecules : Tautomeric Equilibrium of 2-Pyridone and 2-Hydroxypridine in Water Studied by the RISM-SCF/MCSCF Method"J.Phys.Chem.A. (in press).

[Publications] H.Sato, S.Sakaki: "A Comparison of Electronic Structure Theories for Solvated Molecule : RISM-SCF versus PCM"J.Phys.Chem.A. (in press).

[Publications] S.Yamazaki, S.Kato: "Excited-state proton transfer of 1-[(dimethylamino)methyl]-2-naphthol in acetonitrile solvent : RISM-SCF and MRMP approach"Chem.Phys.Lett.. 386. 414-418 (2004)

[Publications] T.Ishida, S.Kato: "Theoretical Perspectives on the Reaction Mechanism of Serine Proteases : The Reaction Free Energy Profiles of the Acylation Process."J.Am.Chem.Soc.. 125. 12035-12048 (2003)

[Publications] T.Yamashita, S.Kato: "Regularity in highly excited vibrational dynamics of NOCl (X 1A') : Quantum mechanical calculations on a new potential energy surface"J.Chem.Phys.. 119. 4251-4261 (2003)

[Publications] K.Ohmiya, S.Kato: "Solution reaction path Hamiltonian based on reference interaction site model self-consistent field method : Application to Menshutkin-type reactions"J.Chem.Phys.. 119. 1601-1610 (2003)

中辻博京都大学, 工学研究科, 教授 (90026211)