1989 年度実績報告書

分子設計理論

研究課題

研究課題/領域番号	01648005
研究機関	広島大学
研究代表者	今村詮広島大学, 理学部, 教授 (70076991)
研究分担者	大澤映二北海道大学, 理学部, 助教授 (40001763) 山邉時雄京都大学, 工学部, 教授 (80025965) 細矢治夫お茶の水女子大学, 理学部, 教授 (10017204) 西本吉助大阪市立大学, 理学部, 教授 (20046949)
キーワード	Through Space / Band相互作用 / プロペラン / プロトン移動 / 分極による電子遮蔽効果 / 多環芳香族炭化水素 / 極限的反応座標 / ポリシラン / 配座発生法
研究概要	本年度は、実験グループと情報交換をしながら、各自下記のごとく研究をおこなった。 1.プロペラン等の不安定分子種のHOMOのエネルギー準位が、分子構造をどのように反映して決定されるかを、Through Space/Bond相互作用解析で、明らかにした。その結果、HOMOに対して、[1.1.1]と[2.2.2]プロペランでは、周辺の構造の影響は全く異なることをみい出した。これは実験事実と対応する。(今村担当) 2.プロトン移動による分子の発色現象の分子軌道法による研究をおこなった。分子内の電子供与基Dと電子受容基Aの分子内電荷移動相互作用に対する従来の方法の計算値は、実験値より短波長になる。そこで分極による電子遮蔽効果を考慮した反発積分式を用いて、実験値とよく対応する結果を得た。(西本担当) 3.ペリ縮合の多環芳香族炭化水素の安定性が、周辺構造(beach,bay,cove,fjord等)に大きく依存することを、半経験的分子軌道法(PPP法)計算によって確認した。計算した物理量は、1π電子当りのエネルギー、状態密度、部分構造度等である。(細矢担当) 4.極限的反応座標を用いた化学反応理論の展開を行い、化学反応の外部場効果に関する新しい取り扱いを行なった。また、機能性材料の分子設計に関連して、ポリシランのシロキサン結合生成反応の分子論的機構を提案した。(山辺担当) 5.環式分子の配座発生法に関する新しいアルゴリズム「コーナーフラップ法」を展開させ、環式のみならず鎖式分子にたいしても適用可能とし、またフラップ機能を精密化してエッジフリップ、コーナーシフトを付け加えて、マクロライド分子に適用し成功を収めた。(大沢担当)次年度以降、これらの成果を有機的に連関させていく予定である。

研究成果

(28件)

すべてその他

すべて文献書誌 (28件)

[文献書誌] Akira Imamura: "A Theoretical Study of the Ionized State of polymers with the Localized Molecular Orbital Method" Bull.Chem.Soc.Jpn.,. 62. 979-984 (1989)
[文献書誌] Masato Suzuki: "Application of the Recursion Method to the Study of the End Effects on the Bond Length Asternation in polyacetylene" Int.J.Quantum.Chem.,. 35. 613-628 (1989)
[文献書誌] Yuriko Aoki: "An Energyーdecomposition Technique for the Analysis of Band Structure and its Application to Polyphosphazene and its Halogenated Derivatives" J.Mol.Struct.(Theochem),. 188. 321-335 (1989)
[文献書誌] Takashi Ushio: "An Analysis of the Through-bond Interaction Using the Localized Molecular Orbitals with ab initio Calculations--V HOMO Energy Levels of Many Propellane Compounds" Tetrahedron. 45. 7743-7758 (1989)
[文献書誌] Shinichirou Hayashi: "A Study Using a Through Space/Bond Interaction Analysis for the Band Structures of Substituted polyacetyleneーBe System" Synthetic Metals.
[文献書誌] Eijiro Watanabe: "A Study on peierls Instability in QuasiーOneーDimensionalーSystem with InterchainーInteractionsーーーSemiーEmpirical Self-Consistent Field MO Approach" Bull.Chem.Soc.Jpn.,.
[文献書誌] H.Yamamoto: "Ultraviolet photoelectron Spectroscopy of Perylene Anion in Asーperylene Solid" Mol.Cryst.Liq.Cryst.Letters. 6. 171-183 (1989)
[文献書誌] S.Shinkai: "Coenzyme models 47.Synthesis and Reactivity Studies of Novel Flavinophanes and 5ーDeazaflavinophanes:Correlation between Flavine Reactivity and Ring Strain" J.Am.Chem.Soc.111. 4928-4935 (1989)
[文献書誌] Y.Ohta: "Solvent Effect on the Hydrogen Bonds between Guanine and Cytosine and between Hypoxanthine and Cytosine" Bull.Chem.Soc.Jpn.62. 2441-2449 (1989)
[文献書誌] Y.-D.Gao: "Analysis of the πーElectronic Structure of Infinitely Large Networks.III.Branched Polyenes with Bond Alternation." THEOCHEM(J.Mol.Struct.). (1990)
[文献書誌] K.Takano: "Modified Oxidation Number as Applied to Organic Compounds Containing Nitrogen Atoms.Electron Number Analysis with ab initio Molecular Orbital Wave Functions." J.Phys.Chem.94. (1990)
[文献書誌] H.Hosoya: "How Do the polycyclic Aromatic Hydrocarbons Approach Infinity?" Pure & App.Chem.62. 445-450 (1990)
[文献書誌] I.Gutman: "Molecular Graphs with Equal ZーCounting and Independence Polynomials." Z.Naturforsch.45a. (1990)
[文献書誌] H.Hosoya: "Clar's Aromatic Sextet and Sextet Polynomial." Topics in Current Chemistry. No.153. 255-272 (1990)
[文献書誌] Akitomo Tachibana: "Double Proton Transfer in the Dihydroxyenthylene-Glyoxal Complex" J.Mol.Structure(Theochem). 200. 207-217 (1989)
[文献書誌] Akitomo Tachibana: "A String Model for the chemical Reaction Coordinate in Static External Fields" Theor.Chim.Acta. 75. 401-416 (1989)
[文献書誌] Akitomo Tachibana: "Reaction Ergodography for a Model of Siloxane Bond Formation in Organasilane Polymers" J.Am.Chem.Soc.111. 806-810 (1989)
[文献書誌] Akitomo Tachibana: "Theory of"Dynamic"Hydrogen Bonding:Vibronic Effect in ptoton Dynamics" J.Phys.Chem.93. 220-225 (1989)
[文献書誌] Akitomo Tachibana: "String Model for the Rate Constant of Nonadiabatic Solvation in the Hydration Reaction of Carbon Dioxide" Int.J.Quantum Chem.xxx. (1990)
[文献書誌] Akitomo Tachibana: "Reaction Ergodography for Silicon Nitride Bond Formation in the Laser-Driven Gas Phase Reaction" J.Phys.Chem.xxx. (1990)
[文献書誌] H.Goto: "Corner Flapping-A Simple and Fast Algorithm for Exhaustive Generation of Ring Conformation" J.Am.Chem.Soc.111. 8950-8951 (1989)
[文献書誌] K.Imai: "An Extension of Multiparametric Karplus Equation" Tetrahedron Lett.30. 4251-4254 (1989)
[文献書誌] Z.Slanina: "Quantum-Chemically Supported Vibrational Analysis of Giant Molecules:C_<60> and C_<70>" J.Mol.Struct.(Theochem). 202. 169-176 (1989)
[文献書誌] E.Osawa: "1,4-Bishomo[6]prismane(garudana):Molecular Structure and Strain Analysis" J.Chem.Soc.,Perkin Trans.II. 1161-1168 (1989)
[文献書誌] J.M.Rudzinski: "Energy-Minimum Structure of Hydrocarbon Portion of[4_5](1,2,3,4,5)Ferrocenophane" J.Phys.Org.Chem.2. 602-610 (1989)
[文献書誌] E.Osawa: "Application of Molecular Mechanics to Natural Product Chemistry" Pure & Appl.Chem.61. 597-600 (1989)
[文献書誌] 西本吉助: "分子設計のための量子化学" 講談社, 310 (1989)
[文献書誌] 岡田勲: "分子シミュレーション入門" 海文堂, 227 (1990)

1989 年度 実績報告書

分子設計理論

研究代表者

今村 詮 広島大学, 理学部, 教授 (70076991)

研究成果

[文献書誌] Akira Imamura: "A Theoretical Study of the Ionized State of polymers with the Localized Molecular Orbital Method" Bull.Chem.Soc.Jpn.,. 62. 979-984 (1989)

[文献書誌] Masato Suzuki: "Application of the Recursion Method to the Study of the End Effects on the Bond Length Asternation in polyacetylene" Int.J.Quantum.Chem.,. 35. 613-628 (1989)

[文献書誌] Yuriko Aoki: "An Energyーdecomposition Technique for the Analysis of Band Structure and its Application to Polyphosphazene and its Halogenated Derivatives" J.Mol.Struct.(Theochem),. 188. 321-335 (1989)

[文献書誌] Takashi Ushio: "An Analysis of the Through-bond Interaction Using the Localized Molecular Orbitals with ab initio Calculations--V HOMO Energy Levels of Many Propellane Compounds" Tetrahedron. 45. 7743-7758 (1989)

[文献書誌] Shinichirou Hayashi: "A Study Using a Through Space/Bond Interaction Analysis for the Band Structures of Substituted polyacetyleneーBe System" Synthetic Metals.

[文献書誌] Eijiro Watanabe: "A Study on peierls Instability in QuasiーOneーDimensionalーSystem with InterchainーInteractionsーーーSemiーEmpirical Self-Consistent Field MO Approach" Bull.Chem.Soc.Jpn.,.

[文献書誌] H.Yamamoto: "Ultraviolet photoelectron Spectroscopy of Perylene Anion in Asーperylene Solid" Mol.Cryst.Liq.Cryst.Letters. 6. 171-183 (1989)

[文献書誌] S.Shinkai: "Coenzyme models 47.Synthesis and Reactivity Studies of Novel Flavinophanes and 5ーDeazaflavinophanes:Correlation between Flavine Reactivity and Ring Strain" J.Am.Chem.Soc.111. 4928-4935 (1989)

[文献書誌] Y.Ohta: "Solvent Effect on the Hydrogen Bonds between Guanine and Cytosine and between Hypoxanthine and Cytosine" Bull.Chem.Soc.Jpn.62. 2441-2449 (1989)

[文献書誌] Y.-D.Gao: "Analysis of the πーElectronic Structure of Infinitely Large Networks.III.Branched Polyenes with Bond Alternation." THEOCHEM(J.Mol.Struct.). (1990)

[文献書誌] K.Takano: "Modified Oxidation Number as Applied to Organic Compounds Containing Nitrogen Atoms.Electron Number Analysis with ab initio Molecular Orbital Wave Functions." J.Phys.Chem.94. (1990)

[文献書誌] H.Hosoya: "How Do the polycyclic Aromatic Hydrocarbons Approach Infinity?" Pure & App.Chem.62. 445-450 (1990)

[文献書誌] I.Gutman: "Molecular Graphs with Equal ZーCounting and Independence Polynomials." Z.Naturforsch.45a. (1990)

[文献書誌] H.Hosoya: "Clar's Aromatic Sextet and Sextet Polynomial." Topics in Current Chemistry. No.153. 255-272 (1990)

[文献書誌] Akitomo Tachibana: "Double Proton Transfer in the Dihydroxyenthylene-Glyoxal Complex" J.Mol.Structure(Theochem). 200. 207-217 (1989)

[文献書誌] Akitomo Tachibana: "A String Model for the chemical Reaction Coordinate in Static External Fields" Theor.Chim.Acta. 75. 401-416 (1989)

[文献書誌] Akitomo Tachibana: "Reaction Ergodography for a Model of Siloxane Bond Formation in Organasilane Polymers" J.Am.Chem.Soc.111. 806-810 (1989)

[文献書誌] Akitomo Tachibana: "Theory of"Dynamic"Hydrogen Bonding:Vibronic Effect in ptoton Dynamics" J.Phys.Chem.93. 220-225 (1989)

[文献書誌] Akitomo Tachibana: "String Model for the Rate Constant of Nonadiabatic Solvation in the Hydration Reaction of Carbon Dioxide" Int.J.Quantum Chem.xxx. (1990)

[文献書誌] Akitomo Tachibana: "Reaction Ergodography for Silicon Nitride Bond Formation in the Laser-Driven Gas Phase Reaction" J.Phys.Chem.xxx. (1990)

[文献書誌] H.Goto: "Corner Flapping-A Simple and Fast Algorithm for Exhaustive Generation of Ring Conformation" J.Am.Chem.Soc.111. 8950-8951 (1989)

[文献書誌] K.Imai: "An Extension of Multiparametric Karplus Equation" Tetrahedron Lett.30. 4251-4254 (1989)

[文献書誌] Z.Slanina: "Quantum-Chemically Supported Vibrational Analysis of Giant Molecules:C_<60> and C_<70>" J.Mol.Struct.(Theochem). 202. 169-176 (1989)

[文献書誌] E.Osawa: "1,4-Bishomo[6]prismane(garudana):Molecular Structure and Strain Analysis" J.Chem.Soc.,Perkin Trans.II. 1161-1168 (1989)

[文献書誌] J.M.Rudzinski: "Energy-Minimum Structure of Hydrocarbon Portion of[4_5](1,2,3,4,5)Ferrocenophane" J.Phys.Org.Chem.2. 602-610 (1989)

[文献書誌] E.Osawa: "Application of Molecular Mechanics to Natural Product Chemistry" Pure & Appl.Chem.61. 597-600 (1989)

[文献書誌] 西本吉助: "分子設計のための量子化学" 講談社, 310 (1989)

[文献書誌] 岡田勲: "分子シミュレーション入門" 海文堂, 227 (1990)

1989 年度実績報告書

今村詮広島大学, 理学部, 教授 (70076991)