1993 年度実績報告書

分子系の多電子理論

研究課題

研究課題/領域番号	04243102
研究機関	京都大学
研究代表者	中辻博京都大学, 工学部, 教授 (90026211)
研究分担者	長村吉洋立教大学, 理学部, 教授 (50160841) 榊茂好熊本大学, 工学部, 教授 (20094013) 田中皓電気通信大学, 電気通信学部, 助教授 (00000860) 平尾公彦東京大学, 工学部, 教授 (70093169) 岩田末廣慶応義塾大学, 理工学部・分子科学研究所, 教授 (20087505)
キーワード	多電子理論 / SAC-CI法 / 励起状態 / 電子相関 / ポテンシャルエネルギー面 / 摂動論 / 触媒作用
研究概要	中辻は、励起分子の化学反応のポテンシャルを計算するために提案してきたSAC/SAC-CI法及びEG-CI法を、より多くの分子に対してその方法を適用できるように高スピン状態(四〜七重項)に拡張した。これらの方法は、完全解(Full-CI)を非常に精度良く再現することを確かめた。また、SAC-CI法を用いて金属錯体及び表面-分子系の励起状態の計算を行い、スペクトルの帰属や表面光化学反応のメカニズム解析を行った。岩田は、金属と水分子のクラスターM(H_2O)_n,M(H_2O)_n^+(M=Mg,Al,B)に対して、非経験的分子軌道法によって安定構造と水和エネルギーを計算し、金属原子を取り囲む水分子の構造の類似点と相違点を明らかにした。Mg(H_2O)_n^+に対しては、水素脱離反応の配位数依存性を明らかにした。その他、2成分原子クラスターや[(CO_2)_2H_2O]^-の安定構造も理論的に予測した。フルオロトルエンの内部回転ポテンシャル曲線の計算から、実験値と良く一致したエネルギー障壁を得た。また、Ar_n^+の光解離における非断熱過程の理論的記述とそのメカニズム解明にも成功した。平尾は、比較的簡便にポテンシャルエネルギー面を精度良く記述できるMultireference Moeller-Plesset(MRMP)法を開発し、O_3分子やF_2分子のポテンシャル面の計算に適用し、理論の精度と有用性を確かめた。また、非断熱遷移を起こすポテンシャル面間で交差線上での最安定点を決める新しい方法を開発した。田中は、化学反応のポテンシャル面を高精度に計算する多電子理論を発展させる目的で、多参照結合電子対近似(MRCPA)法を発展させてきた。本年度は、このMRCPA法を銅酸化物超伝導物質YBa_2Cu_3O_7の励起状態の電子構造、及びホルムアルデヒドの自動電離状態の計算に応用した。榊は、遷移金属錯体がWoodward-Hoffmann則禁制な2+2カップリング反応を許容にする作用、及び遷移金属錯体によるCO_2の触媒的固定化反応において重要な金属-ヒドリド結合へのCO_2挿入反応について定量的な検討を行った。これらの研究では、遷移状態や中間体の構造を理論的に予測し、電子相関を含めたより定量的な計算方法で活性化エネルギー、反応熱を与えた。長村は、ポテンシャルエネルギー面の解析的微分法を、ピナコール転位反応の機構や芳香族求電子置換反応などに適用することによって、これまで通説となってきた反応機構の妥当性を理論的立場から検証した。

研究成果

(42件)

すべてその他

すべて文献書誌 (42件)

[文献書誌] H.Nakatsuji,M.Ehara: "SAC-CI Method Applied to High-Spin Multiplicity" J.Chem.Phys.98. 7179-7184 (1993)
[文献書誌] K.Yasuda,H.Nakatsuji: "Theoretical Study of the Visible and Ultraviolet Spectra of Chromyl Chloride CrO_2Cl_2" J.Chem.Phys.99. 1945-1951 (1993)
[文献書誌] H.Nakatsuji,M.Ehara: "EGCI Method Applied to High-Spin Multiplicity" J.Chem.Phys.99. 1952-1961 (1993)
[文献書誌] Y.Fukunishi,H.Nakatsuji: "Cluster Model Study on GaAs Epitaxial Crystal Growth by As_2 Molecular Beam. I.As_2 Adsorption on GaAs Surface" Surf.Sci.291. 271-280 (1993)
[文献書誌] Y.Fukunishi,H.Nakatsuji: "Cluster Model Study on GaAs Epitaxial Crystal Growth by As_2 Molecular Beam. II.Mechanism Involving GaAs_2 Intermediate" Surf.Sci.291. 281-290 (1993)
[文献書誌] M.Hada,H.Nakatsuji,J.Ushio,M.Izawa,H.Yokono: "Highly Coordinate Germanium and Tin Complexes in the Allylation Reactions of Aldehydes" Organometal.12. 3398-3404 (1993)
[文献書誌] H.Nakatsuji,T.Higashioji,M.Sugimoto: "Theoretical Study of Metal NMR Chemical Shifts.Selenium Compounds" Bull.Chem.Soc.Jap.66. 3235-3240 (1993)
[文献書誌] K.Endo,C.Inoue,N.Kobayashi,T.Higashioji,H.Nakatsuji: "Spectra Analysis of the XPS Core and Valence Energy Levels of Polyvinyl Alcohol by an ab initio MO Method Using the 1,3,5-Hexanetriol Molecule" Bull.Chem.Soc.Jap.66. 3241-3244 (1993)
[文献書誌] H.Nakatsuji,T.Nakao: "Theoretical Study on Metal NMR Chemical Shifts.Germanium Compounds" Intern.J.Quantum Chem.(in press).
[文献書誌] H.Nakatsuji,M.Ehara,T.Momose: "Hyperfine Splitting Constants Studied by the SAC-CI Method" J.Chem.Phys.(in press).
[文献書誌] H.Nakatsuji: "Electronic Mechanisms of Metal Chemical Shifts from Ab Initio Theory" NATO ASI Series C386. 263-278 (1993)
[文献書誌] T.Sakai,K.Tanaka: "A CSF based multi reference coupled pair approximation II-as a size consistent method in the scheme of multireference singly and doubly excited configuration interaction-" Theoret.Chim.Acta. 85. 451-461 (1993)
[文献書誌] K.Yamaguchi,M.Osamura,W.Mori,J.Maki,K.Takada,T.Noro,K.Tanaka: "Comparison between spin restricted and unrestricted post Hartree-Fock calculations in Ising and Heisenberg model" Chem.Phys.Letters. 210. 201-210 (1993)
[文献書誌] H.Tatewaki,K.Tanaka,T.Noro: "Electronic Structure of a Cluster Taken from High-Tc Superconductor of YBa_2Cu_3O_7:(Cu_4O_2)(O_4Ba)(Cu_4O_4)Y(Cu_4O_4)(O_4Ba)(Cu_4O_2)Embedded in Ionic Cage of Point Charges" Japanese J.Appl.Pyhs.(in press). (1994)
[文献書誌] S.Nanbu,M.Gomyo,S.Iwata: "Potential Energy Surfaces of Some Low-Lying States of Fluoroformyl Radical FCO" Chem.Phys.(in press). (1994)
[文献書誌] F.Misazu,M.Sanekata,K.Fuke,S.Iwata: "Photodissociation study on Mg^+(H_2O)_n,n=1-5:Electronic structure and photoinduced intracluster reaction" J.Chem.Phys.(in press). (1994)
[文献書誌] Y.Sonoda,S.Iwata,Y.Osamura: "Molecular orbital study of the ion-molecule reactions producing the hydrocarbons in interstellar space" Bull.Chem.Soc.Japan. 66. 3345-3351 (1993)
[文献書誌] H.Watanabe,M.Aoki,S.Iwata: "Theoretical studies of the aluminum-water clusters Al(H_2O)_n and their ions[Al(H_2O)_n]^+" Bull.Chem.Soc.Japan. 66. 3245-3252 (1993)
[文献書誌] M.Hiyama,S.Iwata: "Theoretical Assignment of the vibronic bands in the photoelecton spectra of N_2 below 30 eV" Chem.Phys.Letters. 211. 319-327 (1993)
[文献書誌] K.Fuke,F.Misaizu,M.Sanekata,K.Tsukamoto,S.Iwata: "Electronic Structure and reactivity of Mg^+(H_2O)_n cluster ions" Z.Phys.D. 26S. 180-183 (1993)
[文献書誌] T.Ikegami,T.Kondow,S.Iwata: "The Photodissociation dynamics of Ar_3^+" J.Chem.Phys.99. 3588-3596 (1993)
[文献書誌] M.Hiyama,S.Iwata: "Assighnment of the Photoelectron Spectrum of HCl above 20 eV" Chem.Phys.Letters. 210. 187-192 (1993)
[文献書誌] T.Ikegami,T.Kondow,S.Iwata: "The geometric and elecronic structures of Ar_n^+(n=3-27)" J.Chem.Phys.98. 3038-3048 (1993)
[文献書誌] K.Hirao: "State-Specific Multireference Moller-Plesset Perturbation Treatment for Singlet and Triplet Excited States,Ionized States and Electron Attached States of H_2O" Chem.Phys.Lett.201. 59-66 (1993)
[文献書誌] S.Yamamoto,K.Hirao: "Molecular Application of the Generalized Symmetry Adapted Cluster Theory" Chem.Phys.Lett.204. 315-319 (1993)
[文献書誌] K.Hirao: "Calculations of Potential Energy Surfaces for Chemical Reactions" Bull.Chem.Soc.Japan. C. 63-68 (1993)
[文献書誌] S.Obara,K.Hirao: "Theoretical Study of the Vibrational Analysis of C_2H_7^+" Bull.Chem.Soc.Japan. 66. 3271-3283 (1993)
[文献書誌] S.Obara,K.Hirao: "Molecular Integrals in the Equation of a Correlated Electronic Wave Function Satisfying the Correlation Cusp Condition" 66. 3300-3309 (1993)
[文献書誌] P.Kebarle,S.Obara,K.Hirao: "Structure and Stability of Meisenheimer Complexes"
[文献書誌] K.Mogi,K.Hirao: "Analytical Derivative Method to Determine the Lowest Energy Point of Avoided Crossing-Seam"
[文献書誌] S.Yamanaka,M.Okumura,K.Yamaguchi,K.Hirao: "CASPT2 and MRMP2 Calculations of Potential Curves and Effective Exchange.Integrals for the Dimer of Triplet Methylene"
[文献書誌] K.Nakamura,Y.Osamura: "Theoretical Study of the Reation Mechanism and Migratory Aptitude of the Pinacol Rearrangement" J.Am.Chem.Soc.115. 9112-9120 (1993)
[文献書誌] S.Yamabe,T.Minato,Y.Osamura: "Dual One-centre Frontier-orbital Interaction in[2+2]Cycloadditions of Ketenes" J.Chem.Soc.,Chem.Commun.1993. 450-452 (1993)
[文献書誌] H.Tokiwa,Y.Osamura,H.Ichikawa: "Energy-Component Analysis along Zero Virial Path" Chem.Phys.(in press).
[文献書誌] K.Miyamoto,H.Ohta,Y.Osamura: "Effect of Conformation of the Substrate on Enzymatic Decarboxylation of a-Arylmalonic Acid" (in press).
[文献書誌] S.Sakaki,K.Kato,T.Miyazaki,Y.Musashi,K.Ohkubo,H.Ihara,C.Hirayama: "Structures and Binding Energies of Benzene-Methane and Benzene-Benzene Complexes" J.Chem.Soc.,Faraday Trans.89. 659-664 (1993)
[文献書誌] S.Sakaki,Y.Musashi,K.Ohkubo: "Decarboxylation of 2-Lactylthiazolium Cation.AM1 and ab initio MO/MP2 Studies" J.Am.Chem.Soc.115. 1515-1519 (1993)
[文献書誌] S.Sakaki,M.Ieki: "Oxidative Addition Reactions of Saturated Si-X Bonds(X=H,F,C,or Si)to Pt(PH_3)_2.An ab initio MO/MP4 Study" J.Am.Chem.Soc.115. 2373-2381 (1993)
[文献書誌] S.Sakaki,K.Mine,D.Taguchi,T.Arai: "Formation of the Oxanichelaccyclopentene Complex from Nickel(O),Carbon dioxide,and Alkyne.An ab initio MO/SD-CI Study" Inorg.Chem.66. 3289 (1993)
[文献書誌] S.Sakaki,M.Ogawa,Y.Musashi,T.Arai: "Reactivity of Pd(PH_3)_2 for Oxidative Additions of the Si-X σ-bonds(X=H,C,or Si).An ab initio MO/MP4 Study" (in press).
[文献書誌] S.Sakaki,Y.Musashi: "An ab initio MO Study of the CO_2 Insertion into the Cu(I)-R Bond(R=H,CH_3,or OH).A Comparison between the CO_2 Insertion and the C_2H_4 Insertion"
[文献書誌] S.Sakaki,Y.Musashi: "An ab initio MO Study of CO_2 Insertion into a Rh(I)-H Bond"

1993 年度 実績報告書

分子系の多電子理論

研究代表者

中辻 博 京都大学, 工学部, 教授 (90026211)

研究成果

[文献書誌] H.Nakatsuji,M.Ehara: "SAC-CI Method Applied to High-Spin Multiplicity" J.Chem.Phys.98. 7179-7184 (1993)

[文献書誌] K.Yasuda,H.Nakatsuji: "Theoretical Study of the Visible and Ultraviolet Spectra of Chromyl Chloride CrO_2Cl_2" J.Chem.Phys.99. 1945-1951 (1993)

[文献書誌] H.Nakatsuji,M.Ehara: "EGCI Method Applied to High-Spin Multiplicity" J.Chem.Phys.99. 1952-1961 (1993)

[文献書誌] Y.Fukunishi,H.Nakatsuji: "Cluster Model Study on GaAs Epitaxial Crystal Growth by As_2 Molecular Beam. I.As_2 Adsorption on GaAs Surface" Surf.Sci.291. 271-280 (1993)

[文献書誌] Y.Fukunishi,H.Nakatsuji: "Cluster Model Study on GaAs Epitaxial Crystal Growth by As_2 Molecular Beam. II.Mechanism Involving GaAs_2 Intermediate" Surf.Sci.291. 281-290 (1993)

[文献書誌] M.Hada,H.Nakatsuji,J.Ushio,M.Izawa,H.Yokono: "Highly Coordinate Germanium and Tin Complexes in the Allylation Reactions of Aldehydes" Organometal.12. 3398-3404 (1993)

[文献書誌] H.Nakatsuji,T.Higashioji,M.Sugimoto: "Theoretical Study of Metal NMR Chemical Shifts.Selenium Compounds" Bull.Chem.Soc.Jap.66. 3235-3240 (1993)

[文献書誌] K.Endo,C.Inoue,N.Kobayashi,T.Higashioji,H.Nakatsuji: "Spectra Analysis of the XPS Core and Valence Energy Levels of Polyvinyl Alcohol by an ab initio MO Method Using the 1,3,5-Hexanetriol Molecule" Bull.Chem.Soc.Jap.66. 3241-3244 (1993)

[文献書誌] H.Nakatsuji,T.Nakao: "Theoretical Study on Metal NMR Chemical Shifts.Germanium Compounds" Intern.J.Quantum Chem.(in press).

[文献書誌] H.Nakatsuji,M.Ehara,T.Momose: "Hyperfine Splitting Constants Studied by the SAC-CI Method" J.Chem.Phys.(in press).

[文献書誌] H.Nakatsuji: "Electronic Mechanisms of Metal Chemical Shifts from Ab Initio Theory" NATO ASI Series C386. 263-278 (1993)

[文献書誌] T.Sakai,K.Tanaka: "A CSF based multi reference coupled pair approximation II-as a size consistent method in the scheme of multireference singly and doubly excited configuration interaction-" Theoret.Chim.Acta. 85. 451-461 (1993)

[文献書誌] K.Yamaguchi,M.Osamura,W.Mori,J.Maki,K.Takada,T.Noro,K.Tanaka: "Comparison between spin restricted and unrestricted post Hartree-Fock calculations in Ising and Heisenberg model" Chem.Phys.Letters. 210. 201-210 (1993)

[文献書誌] H.Tatewaki,K.Tanaka,T.Noro: "Electronic Structure of a Cluster Taken from High-Tc Superconductor of YBa_2Cu_3O_7:(Cu_4O_2)(O_4Ba)(Cu_4O_4)Y(Cu_4O_4)(O_4Ba)(Cu_4O_2)Embedded in Ionic Cage of Point Charges" Japanese J.Appl.Pyhs.(in press). (1994)

[文献書誌] S.Nanbu,M.Gomyo,S.Iwata: "Potential Energy Surfaces of Some Low-Lying States of Fluoroformyl Radical FCO" Chem.Phys.(in press). (1994)

[文献書誌] F.Misazu,M.Sanekata,K.Fuke,S.Iwata: "Photodissociation study on Mg^+(H_2O)_n,n=1-5:Electronic structure and photoinduced intracluster reaction" J.Chem.Phys.(in press). (1994)

[文献書誌] Y.Sonoda,S.Iwata,Y.Osamura: "Molecular orbital study of the ion-molecule reactions producing the hydrocarbons in interstellar space" Bull.Chem.Soc.Japan. 66. 3345-3351 (1993)

[文献書誌] H.Watanabe,M.Aoki,S.Iwata: "Theoretical studies of the aluminum-water clusters Al(H_2O)_n and their ions[Al(H_2O)_n]^+" Bull.Chem.Soc.Japan. 66. 3245-3252 (1993)

[文献書誌] M.Hiyama,S.Iwata: "Theoretical Assignment of the vibronic bands in the photoelecton spectra of N_2 below 30 eV" Chem.Phys.Letters. 211. 319-327 (1993)

[文献書誌] K.Fuke,F.Misaizu,M.Sanekata,K.Tsukamoto,S.Iwata: "Electronic Structure and reactivity of Mg^+(H_2O)_n cluster ions" Z.Phys.D. 26S. 180-183 (1993)

[文献書誌] T.Ikegami,T.Kondow,S.Iwata: "The Photodissociation dynamics of Ar_3^+" J.Chem.Phys.99. 3588-3596 (1993)

[文献書誌] M.Hiyama,S.Iwata: "Assighnment of the Photoelectron Spectrum of HCl above 20 eV" Chem.Phys.Letters. 210. 187-192 (1993)

[文献書誌] T.Ikegami,T.Kondow,S.Iwata: "The geometric and elecronic structures of Ar_n^+(n=3-27)" J.Chem.Phys.98. 3038-3048 (1993)

[文献書誌] K.Hirao: "State-Specific Multireference Moller-Plesset Perturbation Treatment for Singlet and Triplet Excited States,Ionized States and Electron Attached States of H_2O" Chem.Phys.Lett.201. 59-66 (1993)

[文献書誌] S.Yamamoto,K.Hirao: "Molecular Application of the Generalized Symmetry Adapted Cluster Theory" Chem.Phys.Lett.204. 315-319 (1993)

[文献書誌] K.Hirao: "Calculations of Potential Energy Surfaces for Chemical Reactions" Bull.Chem.Soc.Japan. C. 63-68 (1993)

[文献書誌] S.Obara,K.Hirao: "Theoretical Study of the Vibrational Analysis of C_2H_7^+" Bull.Chem.Soc.Japan. 66. 3271-3283 (1993)

[文献書誌] S.Obara,K.Hirao: "Molecular Integrals in the Equation of a Correlated Electronic Wave Function Satisfying the Correlation Cusp Condition" 66. 3300-3309 (1993)

[文献書誌] P.Kebarle,S.Obara,K.Hirao: "Structure and Stability of Meisenheimer Complexes"

[文献書誌] K.Mogi,K.Hirao: "Analytical Derivative Method to Determine the Lowest Energy Point of Avoided Crossing-Seam"

[文献書誌] S.Yamanaka,M.Okumura,K.Yamaguchi,K.Hirao: "CASPT2 and MRMP2 Calculations of Potential Curves and Effective Exchange.Integrals for the Dimer of Triplet Methylene"

[文献書誌] K.Nakamura,Y.Osamura: "Theoretical Study of the Reation Mechanism and Migratory Aptitude of the Pinacol Rearrangement" J.Am.Chem.Soc.115. 9112-9120 (1993)

[文献書誌] S.Yamabe,T.Minato,Y.Osamura: "Dual One-centre Frontier-orbital Interaction in[2+2]Cycloadditions of Ketenes" J.Chem.Soc.,Chem.Commun.1993. 450-452 (1993)

[文献書誌] H.Tokiwa,Y.Osamura,H.Ichikawa: "Energy-Component Analysis along Zero Virial Path" Chem.Phys.(in press).

[文献書誌] K.Miyamoto,H.Ohta,Y.Osamura: "Effect of Conformation of the Substrate on Enzymatic Decarboxylation of a-Arylmalonic Acid" (in press).

[文献書誌] S.Sakaki,K.Kato,T.Miyazaki,Y.Musashi,K.Ohkubo,H.Ihara,C.Hirayama: "Structures and Binding Energies of Benzene-Methane and Benzene-Benzene Complexes" J.Chem.Soc.,Faraday Trans.89. 659-664 (1993)

[文献書誌] S.Sakaki,Y.Musashi,K.Ohkubo: "Decarboxylation of 2-Lactylthiazolium Cation.AM1 and ab initio MO/MP2 Studies" J.Am.Chem.Soc.115. 1515-1519 (1993)

[文献書誌] S.Sakaki,M.Ieki: "Oxidative Addition Reactions of Saturated Si-X Bonds(X=H,F,C,or Si)to Pt(PH_3)_2.An ab initio MO/MP4 Study" J.Am.Chem.Soc.115. 2373-2381 (1993)

[文献書誌] S.Sakaki,K.Mine,D.Taguchi,T.Arai: "Formation of the Oxanichelaccyclopentene Complex from Nickel(O),Carbon dioxide,and Alkyne.An ab initio MO/SD-CI Study" Inorg.Chem.66. 3289 (1993)

[文献書誌] S.Sakaki,M.Ogawa,Y.Musashi,T.Arai: "Reactivity of Pd(PH_3)_2 for Oxidative Additions of the Si-X σ-bonds(X=H,C,or Si).An ab initio MO/MP4 Study" (in press).

[文献書誌] S.Sakaki,Y.Musashi: "An ab initio MO Study of the CO_2 Insertion into the Cu(I)-R Bond(R=H,CH_3,or OH).A Comparison between the CO_2 Insertion and the C_2H_4 Insertion"

[文献書誌] S.Sakaki,Y.Musashi: "An ab initio MO Study of CO_2 Insertion into a Rh(I)-H Bond"

1993 年度実績報告書

中辻博京都大学, 工学部, 教授 (90026211)