1992 Fiscal Year Annual Research Report

分子系の多電子理論

Research Project

Project/Area Number	04243102
Research Institution	Kyoto University
Principal Investigator	中辻博京都大学, 工学部, 教授 (90026211)
Co-Investigator(Kenkyū-buntansha)	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) 平尾公彦名之屋大学, 教養部, 教授 (70093169) 岩田末廣慶応義塾大学, 理工学部, 教授 (20087505)
Keywords	量子化学 / ab initio MO / 電子相関 / ポテンシャルエネルギー曲面 / 多電子理論 / 摂動論 / 励起状態 / 触媒作用
Research Abstract	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-C1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、高スピン状態に対する理論の一般化とプログラムの開発を行った。また、SAC-C1法を用いて金属錯体の励起状態やイオン化状態の計算を行い、スペクトルの帰属や光化学反応のメカニズム解析を行った。岩田は、N_2,HC1,CO分子の光電子分光スペクトルに対し、ポテンシャル曲線及びフランク・コンドン因子の計算により、曖昧のない帰属に成功した。FCOラジカルのポテンシャル曲面の計算から、その光吸収スペクトルと光解離過程を明らかにした。また、種々の金属クラスターの構造や光化学反応に対する量子化学計算も行った。更に、非縮重系摂動理論を再導出し、その新たな発展を明確にした。平尾は、基底状態・励起状態を問わず、全核配置について信頼できるポテンシャル面を比較的容易に計算できる新しい電子状態理論(多配置メラー・プレセット(MRMP)法)の開発を行った。そして、このMRMP法をいろいろな化学現象に適用し、理論の精度と有用性を確かめた。田中は、先にMRSDCIの枠の中でレイリー・シュレディンガーの摂動法を用いた結合電子対近似(CEPA)様の方程式(MRCPA)を導出しているが、更に波動演算子を用いて再定式化し、見通しの良い表現を得た。これによりMRCPA法はsize-consistencyを満たしていることが示された。榊は、ニッケル錯体を用いたCO_2の電気化学的還元反応に対しab-initio M0/SD-C1研究を行い、中間体の構造や反応性を調ベ、反応機構に関する有用な知見も与えた。また、銅(I)錯体の光化学挙動に関しても有益な理論的知見を与えた。長村は、分極関数がさまざまな分子の波動関数に与える影響を調ベた。また、アルキル置換したC_4H_7^+化学種について、種々の構造異性体並びにそれらの間の異性化プロセスのポテンシャル面を理論的に検討した。

Research Products

(32 results)

All Other

All Publications (32 results)

[Publications] H.Nakatsuji,M.Ehara,M.H.Palmer and M.F.Guest: "Theoretical Study on the Excited and Ionized States of Titanium Tetrachloride" J.Chem.Phys.97. 2561-2570 (1992)
[Publications] H.Nakatsuji and H.Nakai: "Potential Energy Curves of Dioxygen Anion Species:O_2^- and O_2^<2->" Chem.Phys.Letters. 197. 339-345 (1992)
[Publications] H.Nakatsuji and M.Ehara: "SAC-CI Method Applied to High-Spin Multiplicity" J.Chem.Phys.in press.
[Publications] H.Nakatsuji,M.Haka,and A.Kawashima: "Electronic Structures of Dative Metal-Metal Bonds:Ab initio Molecular Orbital Calculations of (OC)_5Os-M(CO)_5(M=W,Cr) in Comparison with (OC)_5(M=Re,Mn)" Inorg.Chem.31. 1740-1744 (1992)
[Publications] H.Nakatsuji and H.Nakai: "Dipped Adcluster Model Study for Molecular and Dissociative Chemisorption of O_2 on an Ag Surface" J.Chem.Phys.98. 2423-2436 (1993)
[Publications] H.Nakatsuji: "Theoretical Model Studies for Surface-Molecule Interacting Systems" Intern.J.Quantum Chemestry,Symposium. 26. 725-736 (1992)
[Publications] T.Ikegami,T.Kondow,S.Iwata: "The geometric and electronec structures of Ar^+_n(n=3-27)." J.Chem.Phys. (1993)
[Publications] F.Misaizu,M.Sanekata,K.Tsukamsto,K.Fuke,S.Iwata: "Photodissociation of Size-selected Mg^+(H_2O)n ions for n=1 and n=2" J.Phys,Chem.96. 8259-8264 (1992)
[Publications] H.Matsuzawa,T.Hanawa K.Suzuki,S.Iwata: "Theoretical study of Aluminum-Sodium bimetallic cluseter I:Geometarical and electronic structures of A1nNa(n=1-4)" Bull.Chem,Soc.JPN.65. 2578-2888 (1992)
[Publications] K.Fan,S.Iwata: "Theoretical studies of new radicals SINNH and SICOH" Chem.Phys.Letters. 195. 475-481 (1992)
[Publications] M.Hiyama,S.Nanbu,S.Iwata: "The excimer emission spectra and the inteteraction potential energy of the ground and excited states of He and alkali metal ion systems" Chem,Phys.Letters. 192. 443-450 (1992)
[Publications] H.Matsuzawa,S.Iwata: "Ab initio study of the infra-red absorption bands and their intensities for ethylene-halogen and amine-halogen complexes" Chem.Phys.163. 297-305 (1992)
[Publications] S.Nanbu,S.Iwata: "Theoretical study of the photodissociation cross sections and the photodissociation dynamics of HOCl" J.Phys.Chem.96. 2103-2111 (1992)
[Publications] K.Fan,S.Iwata: "Theoretical study on the three isomers of the SuNO radical." Chem.Phys.Letters. 189. 401-407 (1992)
[Publications] J.Irisawa,S.Iwata: "Ab initio studies of the low-lying states of BeO" Theor.chim.Acta.81. 223-235 (1992)
[Publications] H.Wasada: "Theoretical Study of the Reactions of Pentacoordinaled Trigonal-Bipyramidal compounds:PH5,PF5,PF4H,PF3H2.PF4CH3,PF3(CH3)2,P(O2C2H4)H3,P(OC3H6)H3 and PO5H4-" J.amer.Chem.Soc.114. 16-27 (1992)
[Publications] K.HIRAO: "Multireference Moller-Plesset Method" Chem.Phys.Lett.190. 374-380 (1992)
[Publications] K.HIRAO: "Floating Functions Satisfying the Hellmann-Feynman Theorem:Single Floating Scheme" J.Comput.Chem.13. 457-467 (1992)
[Publications] K.HIRAO: "Analytic Derivative Theory Based on the Hellmann-Feynman Theorem" Can.J.Chem.70. 434-442 (1992)
[Publications] K.HIRAO: "Multireference Moller-Plesset Perturbation Treatment of Potential Energy curves of N2" Intern.J.Quantum.Chem.S26. 517-526 (1992)
[Publications] K.HIRAO: "Multireference Moller-Plesset Perturbation Theory for High-Spin Open Shell Systems" Chem.Phys.Lett.196. 397-403 (1992)
[Publications] K.Ogasawara,Y.Mochizuki T.Noro,K.Tanaka: "Electronic structure of lower pinglet states of binuclear copper acetete monohydrete" Can.J.Chem.70. 393-398 (1992)
[Publications] T.Yoshida,M.Nakano,T.Tsunekawa,K.Tanaka,K.Yamaguchi: "Ab initio Calculctions of NonlinearOpticel Properties of Silicon Compounds" Molecular Crystal and diquid Crystal. 217. 71-76 (1992)
[Publications] T.Sakai,K.Tanaka: "ACSF based multi reference coulpled pain approximation II-asasiz consitent method in the sdeme of multirefereme sinaly and doublg excited configurations" Theoret.Chim.Acta.
[Publications] 山口兆,田中皓,吉田健: "有機非線形光学:計算でどこまで出来るか" 季刊化学総説. 15. 43-55 (1992)
[Publications] S.Sakaki: "An ab Initio MO/SD-CI Study of Model Complexes of Intermediates in Electrochemical Reduction of CO_2 Catalyzed by Nicl_2 Ccyclam)" J.Am.Chem.Soc.114. 2055-2062 (1992)
[Publications] S.Sakaki,H.Mizutani,Y.Kase: "Geometry,Electronic Structure,and Coordination Ability of [Cu(diN)(PH_3)_2]^+(diN=HN=CHCH=NH)ta the Lowest Energy Triplet Metal-to Ligand Charge-Transfer Excited State.A Theoretical Study" Inorg.Chem.31. 4575-4581 (1992)
[Publications] S.Sakaki,K.Kato,T.Miyazaki,Y.Musashi,K.Ohkubo,H.Ihara,C.Hirayama: "Structure and Binding energies of Benzene-methane and Benzene-benzene Complexes.An ab initio SCF/Mp2 Study" J.Chem.Soc.,Faraday Traus.
[Publications] S.Sakaki,Y.Musashi,K.Onkubo: "Decarboxylation of 2-lactylthiazolium Cation. AMI and ab Intio MO/MP2 Studies" J.Am.Chem.Soc.
[Publications] S.Sakaki,M.Ieki: "Oxidative Addition Reactions of Saturated Si-x Bonds NX=H,F,C or Si) to Pt(PH_3)_2.An ab initio MO/MP4 Study" J.Am.Chem.Soc.
[Publications] 榊茂好: "遷移金属錯体と二.三の小分子との相互作用と反応に関する理論的研究" Organometallic News. 70-75 (1992)
[Publications] 榊茂好: "CO_2の化学ー電子状態を中心として" 化学工業. 43. 617-623 (1992)

1992 Fiscal Year Annual Research Report

分子系の多電子理論

Principal Investigator

中辻 博 京都大学, 工学部, 教授 (90026211)

Research Products

[Publications] H.Nakatsuji,M.Ehara,M.H.Palmer and M.F.Guest: "Theoretical Study on the Excited and Ionized States of Titanium Tetrachloride" J.Chem.Phys.97. 2561-2570 (1992)

[Publications] H.Nakatsuji and H.Nakai: "Potential Energy Curves of Dioxygen Anion Species:O_2^- and O_2^<2->" Chem.Phys.Letters. 197. 339-345 (1992)

[Publications] H.Nakatsuji and M.Ehara: "SAC-CI Method Applied to High-Spin Multiplicity" J.Chem.Phys.in press.

[Publications] H.Nakatsuji,M.Haka,and A.Kawashima: "Electronic Structures of Dative Metal-Metal Bonds:Ab initio Molecular Orbital Calculations of (OC)_5Os-M(CO)_5(M=W,Cr) in Comparison with (OC)_5(M=Re,Mn)" Inorg.Chem.31. 1740-1744 (1992)

[Publications] H.Nakatsuji and H.Nakai: "Dipped Adcluster Model Study for Molecular and Dissociative Chemisorption of O_2 on an Ag Surface" J.Chem.Phys.98. 2423-2436 (1993)

[Publications] H.Nakatsuji: "Theoretical Model Studies for Surface-Molecule Interacting Systems" Intern.J.Quantum Chemestry,Symposium. 26. 725-736 (1992)

[Publications] T.Ikegami,T.Kondow,S.Iwata: "The geometric and electronec structures of Ar^+_n(n=3-27)." J.Chem.Phys. (1993)

[Publications] F.Misaizu,M.Sanekata,K.Tsukamsto,K.Fuke,S.Iwata: "Photodissociation of Size-selected Mg^+(H_2O)n ions for n=1 and n=2" J.Phys,Chem.96. 8259-8264 (1992)

[Publications] H.Matsuzawa,T.Hanawa K.Suzuki,S.Iwata: "Theoretical study of Aluminum-Sodium bimetallic cluseter I:Geometarical and electronic structures of A1nNa(n=1-4)" Bull.Chem,Soc.JPN.65. 2578-2888 (1992)

[Publications] K.Fan,S.Iwata: "Theoretical studies of new radicals SINNH and SICOH" Chem.Phys.Letters. 195. 475-481 (1992)

[Publications] M.Hiyama,S.Nanbu,S.Iwata: "The excimer emission spectra and the inteteraction potential energy of the ground and excited states of He and alkali metal ion systems" Chem,Phys.Letters. 192. 443-450 (1992)

[Publications] H.Matsuzawa,S.Iwata: "Ab initio study of the infra-red absorption bands and their intensities for ethylene-halogen and amine-halogen complexes" Chem.Phys.163. 297-305 (1992)

[Publications] S.Nanbu,S.Iwata: "Theoretical study of the photodissociation cross sections and the photodissociation dynamics of HOCl" J.Phys.Chem.96. 2103-2111 (1992)

[Publications] K.Fan,S.Iwata: "Theoretical study on the three isomers of the SuNO radical." Chem.Phys.Letters. 189. 401-407 (1992)

[Publications] J.Irisawa,S.Iwata: "Ab initio studies of the low-lying states of BeO" Theor.chim.Acta.81. 223-235 (1992)

[Publications] H.Wasada: "Theoretical Study of the Reactions of Pentacoordinaled Trigonal-Bipyramidal compounds:PH5,PF5,PF4H,PF3H2.PF4CH3,PF3(CH3)2,P(O2C2H4)H3,P(OC3H6)H3 and PO5H4-" J.amer.Chem.Soc.114. 16-27 (1992)

[Publications] K.HIRAO: "Multireference Moller-Plesset Method" Chem.Phys.Lett.190. 374-380 (1992)

[Publications] K.HIRAO: "Floating Functions Satisfying the Hellmann-Feynman Theorem:Single Floating Scheme" J.Comput.Chem.13. 457-467 (1992)

[Publications] K.HIRAO: "Analytic Derivative Theory Based on the Hellmann-Feynman Theorem" Can.J.Chem.70. 434-442 (1992)

[Publications] K.HIRAO: "Multireference Moller-Plesset Perturbation Treatment of Potential Energy curves of N2" Intern.J.Quantum.Chem.S26. 517-526 (1992)

[Publications] K.HIRAO: "Multireference Moller-Plesset Perturbation Theory for High-Spin Open Shell Systems" Chem.Phys.Lett.196. 397-403 (1992)

[Publications] K.Ogasawara,Y.Mochizuki T.Noro,K.Tanaka: "Electronic structure of lower pinglet states of binuclear copper acetete monohydrete" Can.J.Chem.70. 393-398 (1992)

[Publications] T.Yoshida,M.Nakano,T.Tsunekawa,K.Tanaka,K.Yamaguchi: "Ab initio Calculctions of NonlinearOpticel Properties of Silicon Compounds" Molecular Crystal and diquid Crystal. 217. 71-76 (1992)

[Publications] T.Sakai,K.Tanaka: "ACSF based multi reference coulpled pain approximation II-asasiz consitent method in the sdeme of multirefereme sinaly and doublg excited configurations" Theoret.Chim.Acta.

[Publications] 山口 兆,田中 皓,吉田 健: "有機非線形光学:計算でどこまで出来るか" 季刊化学総説. 15. 43-55 (1992)

[Publications] S.Sakaki: "An ab Initio MO/SD-CI Study of Model Complexes of Intermediates in Electrochemical Reduction of CO_2 Catalyzed by Nicl_2 Ccyclam)" J.Am.Chem.Soc.114. 2055-2062 (1992)

[Publications] S.Sakaki,H.Mizutani,Y.Kase: "Geometry,Electronic Structure,and Coordination Ability of [Cu(diN)(PH_3)_2]^+(diN=HN=CHCH=NH)ta the Lowest Energy Triplet Metal-to Ligand Charge-Transfer Excited State.A Theoretical Study" Inorg.Chem.31. 4575-4581 (1992)

[Publications] S.Sakaki,K.Kato,T.Miyazaki,Y.Musashi,K.Ohkubo,H.Ihara,C.Hirayama: "Structure and Binding energies of Benzene-methane and Benzene-benzene Complexes.An ab initio SCF/Mp2 Study" J.Chem.Soc.,Faraday Traus.

[Publications] S.Sakaki,Y.Musashi,K.Onkubo: "Decarboxylation of 2-lactylthiazolium Cation. AMI and ab Intio MO/MP2 Studies" J.Am.Chem.Soc.

[Publications] S.Sakaki,M.Ieki: "Oxidative Addition Reactions of Saturated Si-x Bonds NX=H,F,C or Si) to Pt(PH_3)_2.An ab initio MO/MP4 Study" J.Am.Chem.Soc.

[Publications] 榊 茂好: "遷移金属錯体と二.三の小分子との相互作用と反応に関する理論的研究" Organometallic News. 70-75 (1992)

[Publications] 榊 茂好: "CO_2の化学ー電子状態を中心として" 化学工業. 43. 617-623 (1992)

中辻博京都大学, 工学部, 教授 (90026211)

[Publications] 山口兆,田中皓,吉田健: "有機非線形光学:計算でどこまで出来るか" 季刊化学総説. 15. 43-55 (1992)

[Publications] 榊茂好: "遷移金属錯体と二.三の小分子との相互作用と反応に関する理論的研究" Organometallic News. 70-75 (1992)

[Publications] 榊茂好: "CO_2の化学ー電子状態を中心として" 化学工業. 43. 617-623 (1992)