1989 年度実績報告書

溶液の非平衡過程の分子論的アプロ-チ

研究課題

研究課題/領域番号	01307017
研究機関	岡崎国立共同研究機構
研究代表者	大瀧仁志岡崎国立共同研究機構, 分子科学研究所, 教授 (80022549)
研究分担者	山口敏男福岡大学, 理学部, 助教授 (70158111) 冨永敏弘岡山理科大学, 工学部, 教授 (30131618) 舟橋重信名古屋大学, 理学部, 助教授 (30022700) 中原勝京都大学, 理学部, 助教授 (20025480) 野村浩康名古屋大学, 工学部, 教授 (50023081)
キーワード	溶液 / 非平衡過程 / 分子論 / ミクロ集合体のゆらぎ / 拡散過程のダイナミックス / 反応活性種の構造
研究概要	溶液の非平衡の動的過程をミクロなレベルから解明することを目的とする重点領域研究[溶液の非平衡過程の分子論的アプロ-チ]は、平成2年度からの発足を前に、次の三つの研究領域に関して準備を進めた。1.ミクロ集合体のゆらぎ。ラマン散乱、ブリュアン散乱、超音波緩和などを用いて分子集合体の運動やゆらぎ、分子の振動、回転に関する緩和過程やイオン会合のダイナミックスに及ぼす溶媒効果を研究した(野村)。また非電解質の拡散係数の測定から、溶液中の分子の並進運動と溶媒の粘性との関係(富永)、化学反応のゆらぎの効果に関する理論的考察(森田)も併せて検討した。2.拡散過程のダイナミックス。NMRとラマン散乱の方法を組み合わせて水溶液中のイオンの拡散過程を検討し、分子の並進と回転運動の研究を行った(中原)。また蛍光消光過程に及ぼす圧力効果から拡散律速の素反応過程に対する溶媒効果を分子レベルで解明しようと試みた(平山)。さらにシミュレ-ション法を用いて水の集団運動と構造との関係を明らかにした(大峰)。3.反応活性種の構造。二成分混合溶媒に対するx線構造解析から、均一系における分子レベルでの不均一性(クラスタ-生成)を明かにし(大瀧)、また金属イオンの溶媒交換反応及び錯形成反応における活性化体積の測定から、反応活性種の構造を推定し(舟橋)、さらに金属クラスタ-錯体の反応中間体の構造解析法について検討した(佐々木)。またこれらの結果を実験的に確かめるために迅速EXAFS装置開発の準備を進めた(山口)。これらの研究に加えて、国際レベルで我々の研究成果に対する評価を問うために、福岡大学において開催されたミニ国際シンポジウム(平成元年12月)に積極的に協力し、大きな成果を挙げた。さらに、本年度の成果を総括するために、平成2年3月に名古屋において公開シンポジウムを開催した。

研究成果

(22件)

すべてその他

すべて文献書誌 (22件)

[文献書誌] S.Koda: "Study of the Conformational Equilibrium between Rotational Isomers using Ultrasonic Relaxation and Ramar Spectroscopy.Part 3." J.Chem.Soc.Faraday Trans.1. 85. 57-67 (1989)
[文献書誌] S.Koda: "Study on Ionーion and Ionーsolvent Interaction of Thiocyanates in WaterーDMF Mixtures by Means of Raman Spectroscopy." J.Phys.Chem.93. 4959-4963 (1989)
[文献書誌] H.Nomura: "Effects of Molecular Conformation on the Packing Density in Liquid State." J.Phys.Chem.93. 8101-8104 (1989)
[文献書誌] T.Tominaga: "Interactions between the Tris(1,10-phenanthroline)iron (II)Cation and Anionic Surfactants:Diffusion and Conductance Studies." Bull.Chem.Soc.Jpn.62. 1745-1750 (1989)
[文献書誌] M.Katsumoto: "Externally Driven Fluctuation of Concentration in the Secondーorder Chemical Reaction and Dynamic Fluctuation Increase." J.Chem.Soc.Faraday Trans.2. 85. 623-633 (1989)
[文献書誌] K.Ibuki: "Hydrodynamic Interactions and Concentration Dependence of Orientational Relaxation Times of Ions in Dilute Solution." J.Chem.Phys.90. 386-391 (1989)
[文献書誌] A.Adachi: "Raman and NMR Studies on the Concentration Dependence of Orientational Relaxation Times of the Nitrate Ion in Dilute Aqueous Solution." J.Chem.Phys.90. 392-399 (1989)
[文献書誌] Y.Kimura: "Chemical Equilibrium in Argon:Anomaly of Density Dependence of Dimerization Reaction in the Medium Density Region." J.Chem.Phys.90. 2758-2759 (1989)
[文献書誌] Y.Sakai: "Deconvolution of Nonーexponential Emission Decays Arising from Reabsorption of Emitted Light." J.Lumin.42. 317-324 (1989)
[文献書誌] F.Tanaka: "Fluorescence Decays of 9,10ーdichloroanthracence and Its van der Waals Complex." Chem.Phys.131. 435-442 (1989)
[文献書誌] H.Tanaka: "Potential Energy Surfaces for Water Dynamics:Reaction Coordinates,Transition States,and Normal Mode Analysis." J.Chem.Phys.91. 6318-6327 (1989)
[文献書誌] S.Ishiguro: "Solvent Effects on the Formation of Copper(II)Chloro Complexes in AcetonitrileーDimethyl Sulfoxide Mixtures." Bull.Chem.Soc.Jpn.62. 39-44 (1989)
[文献書誌] T.Yamaguchi: "XーRay Diffraction Study of Calcium(II)Chloride Hydrate Melts:CaCl_2・RH_2O(R=4.0,5.6,6.0,and8.6)." Inorg.Chem.28. 2434-2439 (1989)
[文献書誌] T.Radnai: "Intramolecular and Liquid Structure of 2,2,2ーTrifluoroethanol by XーRay Diffraction." J.Solution Chem.18. 771-784 (1989)
[文献書誌] H.Ohtaki: "Dissolution of an NaCl Crystal with the (111)and (ー1ー1ー1)Faces." Pure & Appl.Chem.61. 179-185 (1989)
[文献書誌] H.Suzuki: "Solvation and Complexation of Copper(II)and Chloride Ions in 2,2,2ーTrifluoroethanolーDimethyl Sulfoxide Mixtures." J.Chem.Soc.Faraday Trans.1. 85. 2587-2596 (1989)
[文献書誌] M.Ishii: "VariableーTemperature and VariableーPressure Nitrogenー14 NMR Studies on the Exchange Reaction of Different Nitriles at the Nickel(II)Ion." Bull.Chem.Soc.Jpn.62. 1852-1858 (1989)
[文献書誌] S.Funahashi: "Formation Kinetics of Perpxovanadium(V)Complexes in Strongly Acidic Media as Studied by a Highーpressure Stoppedーflow Technique." Inorg.Chim.Acta.157. 65-71 (1989)
[文献書誌] T.Yamaguchi: "XーRay and Raman Studies of Zine(II)Chloride Hydrate Melts,ZnCl_2・RH_2O(R=1.8,2.5,3.0,4.0 and 6.2)." J.Phys.Chem.93. 2620-2625 (1989)
[文献書誌] S.Yamashita: "A Structual Study of a Series of Bis(2,3ーalkanedione dioximato)nicked(II)Complexes in the Crystal and Liquid States by XーRay Absorption Spectroscopy." Bull.Chem.Soc.Jpn.62. 2902-2907 (1989)
[文献書誌] K.Kabuto: "Consistent Correlation between Absolute Configuration of αーHydroxy Acids and Lanthanoid Induced Shift by an NMR Chiral Shift Reagent in Aqueous Solution." Chem.Lett.385-388 (1989)
[文献書誌] T.Yamauchi: "Facile Regioselective Ligand Substitution for the InーPlane Bridging Acetates in Octakis(μーacetatoーO,O′)ーtetraplatinum(II)." Inorg.Chem.28. 4311-4312 (1989)

1989 年度 実績報告書

溶液の非平衡過程の分子論的アプロ-チ

研究代表者

大瀧 仁志 岡崎国立共同研究機構, 分子科学研究所, 教授 (80022549)

研究成果

[文献書誌] S.Koda: "Study of the Conformational Equilibrium between Rotational Isomers using Ultrasonic Relaxation and Ramar Spectroscopy.Part 3." J.Chem.Soc.Faraday Trans.1. 85. 57-67 (1989)

[文献書誌] S.Koda: "Study on Ionーion and Ionーsolvent Interaction of Thiocyanates in WaterーDMF Mixtures by Means of Raman Spectroscopy." J.Phys.Chem.93. 4959-4963 (1989)

[文献書誌] H.Nomura: "Effects of Molecular Conformation on the Packing Density in Liquid State." J.Phys.Chem.93. 8101-8104 (1989)

[文献書誌] T.Tominaga: "Interactions between the Tris(1,10-phenanthroline)iron (II)Cation and Anionic Surfactants:Diffusion and Conductance Studies." Bull.Chem.Soc.Jpn.62. 1745-1750 (1989)

[文献書誌] M.Katsumoto: "Externally Driven Fluctuation of Concentration in the Secondーorder Chemical Reaction and Dynamic Fluctuation Increase." J.Chem.Soc.Faraday Trans.2. 85. 623-633 (1989)

[文献書誌] K.Ibuki: "Hydrodynamic Interactions and Concentration Dependence of Orientational Relaxation Times of Ions in Dilute Solution." J.Chem.Phys.90. 386-391 (1989)

[文献書誌] A.Adachi: "Raman and NMR Studies on the Concentration Dependence of Orientational Relaxation Times of the Nitrate Ion in Dilute Aqueous Solution." J.Chem.Phys.90. 392-399 (1989)

[文献書誌] Y.Kimura: "Chemical Equilibrium in Argon:Anomaly of Density Dependence of Dimerization Reaction in the Medium Density Region." J.Chem.Phys.90. 2758-2759 (1989)

[文献書誌] Y.Sakai: "Deconvolution of Nonーexponential Emission Decays Arising from Reabsorption of Emitted Light." J.Lumin.42. 317-324 (1989)

[文献書誌] F.Tanaka: "Fluorescence Decays of 9,10ーdichloroanthracence and Its van der Waals Complex." Chem.Phys.131. 435-442 (1989)

[文献書誌] H.Tanaka: "Potential Energy Surfaces for Water Dynamics:Reaction Coordinates,Transition States,and Normal Mode Analysis." J.Chem.Phys.91. 6318-6327 (1989)

[文献書誌] S.Ishiguro: "Solvent Effects on the Formation of Copper(II)Chloro Complexes in AcetonitrileーDimethyl Sulfoxide Mixtures." Bull.Chem.Soc.Jpn.62. 39-44 (1989)

[文献書誌] T.Yamaguchi: "XーRay Diffraction Study of Calcium(II)Chloride Hydrate Melts:CaCl_2・RH_2O(R=4.0,5.6,6.0,and8.6)." Inorg.Chem.28. 2434-2439 (1989)

[文献書誌] T.Radnai: "Intramolecular and Liquid Structure of 2,2,2ーTrifluoroethanol by XーRay Diffraction." J.Solution Chem.18. 771-784 (1989)

[文献書誌] H.Ohtaki: "Dissolution of an NaCl Crystal with the (111)and (ー1ー1ー1)Faces." Pure & Appl.Chem.61. 179-185 (1989)

[文献書誌] H.Suzuki: "Solvation and Complexation of Copper(II)and Chloride Ions in 2,2,2ーTrifluoroethanolーDimethyl Sulfoxide Mixtures." J.Chem.Soc.Faraday Trans.1. 85. 2587-2596 (1989)

[文献書誌] M.Ishii: "VariableーTemperature and VariableーPressure Nitrogenー14 NMR Studies on the Exchange Reaction of Different Nitriles at the Nickel(II)Ion." Bull.Chem.Soc.Jpn.62. 1852-1858 (1989)

[文献書誌] S.Funahashi: "Formation Kinetics of Perpxovanadium(V)Complexes in Strongly Acidic Media as Studied by a Highーpressure Stoppedーflow Technique." Inorg.Chim.Acta.157. 65-71 (1989)

[文献書誌] T.Yamaguchi: "XーRay and Raman Studies of Zine(II)Chloride Hydrate Melts,ZnCl_2・RH_2O(R=1.8,2.5,3.0,4.0 and 6.2)." J.Phys.Chem.93. 2620-2625 (1989)

[文献書誌] S.Yamashita: "A Structual Study of a Series of Bis(2,3ーalkanedione dioximato)nicked(II)Complexes in the Crystal and Liquid States by XーRay Absorption Spectroscopy." Bull.Chem.Soc.Jpn.62. 2902-2907 (1989)

[文献書誌] K.Kabuto: "Consistent Correlation between Absolute Configuration of αーHydroxy Acids and Lanthanoid Induced Shift by an NMR Chiral Shift Reagent in Aqueous Solution." Chem.Lett.385-388 (1989)

[文献書誌] T.Yamauchi: "Facile Regioselective Ligand Substitution for the InーPlane Bridging Acetates in Octakis(μーacetatoーO,O′)ーtetraplatinum(II)." Inorg.Chem.28. 4311-4312 (1989)

1989 年度実績報告書

大瀧仁志岡崎国立共同研究機構, 分子科学研究所, 教授 (80022549)