1995 Fiscal Year Annual Research Report

局所分子場における溶液のダイナミクス

Research Project

Project/Area Number	07354013
Research Institution	Nagoya University
Principal Investigator	野村浩康名古屋大学, 工学部, 教授 (50023081)
Co-Investigator(Kenkyū-buntansha)	田端正明佐賀大学, 理工学部, 教授 (40039285) 山口敏男福岡大学, 理学部, 教授 (70158111) 平田文男岡崎国立共同研究機構, 分子科学研究所, 教授 (90218785) 中原勝京都大学, 化学研究所, 教授 (20025480) 岡田正大阪大学, 基礎工学部, 教授 (40029442)
Keywords	局所場 / ゆらぎ / 化学反応 / ダイナミクス / 溶媒和
Research Abstract	本研究は、溶液中のゆらぎあるいは局所分子場によって支配される分子集団のダイナミクスを理論及び実験者の共同により調査・研究し溶液化学の分子論的基礎概念を作り出す方法論を集約することを目的とする。溶液中の局所的規則性と集団運動を分子論的に捉え、理論的・実験的に表現し溶液中の化学反応を記述することを目指して溶液中の局所分子場によって支配されるダイナミクスを溶質及び溶媒の物理的、化学的性質を含む形で表現し、溶液化学の分子論的基礎概念を創り出すため、以下の課題取り上げた。 (1)溶液中の局所分子場を規定する基本的相互作用を記述する理論をどのように構築するか (2)溶液中の局所分子場の及ぶ範囲とその時間的発展はどのようになっているか (3)溶液中の局所分子場によって形成された局所構造はどのように伝播し、組織化されいくかこの課題に基づき、以下の4つの調査・研究項目を設定し、各項目間の緊密な協力と有機的な連携のもとに以下の成果を得た。 A.野村、平田を中心としてRISM法を用い統計力学における2つの流れ、即ち、不可逆過程の理論と積分方程式による理論を結合して、液体構造の微視的特徴を反映した溶液の分子論的ダイナミクス理論の展開を模索した。岡田、木下、富永らは、溶媒和、回転・並進・熱(振動エネルギー)の拡散過程を局所的な分子の集団運動(局所フォノン)と関連づけて理解することを目指し、溶液の微視的領域の集団運動によって支配される実験的事実を提示した。山口、樋渡らは、中性子散乱、X線小角散乱の実験とシミュレーション計算によって、過冷却液体の構造とダイナミクス、生体系における水の構造ダイナミクスなど、研究項目Bで取り扱う現象と較べて遙かに遅い時間領域で観測される構造変化を系統的に研究した。澤田、前田らは高分子を含む溶液系のダイナミクスを局所構造だけでなく中距離相互作用まで考慮に入れ検討した。

Research Products

(19 results)

All Other

All Publications (19 results)

[Publications] Shinobu Koda: "Ultrasonic Investigation on the Viscosity Dependence of the Rate Constant of Rotational Isomerism of Dibromoethane and Dibromopropane in Solutions" J.Chem.Soc.,Faraday Trans.91(3). 445-449 (1995)
[Publications] Hiroyasu Nomura: "Dynamics of the Sulfate Ion in Dilute Water-DMF Solutions" Z.Naturforsch. 50a. 7-10 (1995)
[Publications] Masaharu Ohba: "Pressure Dependence of the Limiting Partial Molar Volume of Solute in the Lennard-Jones Systems as Investigated by the RISM Method" J.Phys.Chem. 99. 9258-9262 (1995)
[Publications] Masaharu Ohba: "Statistical Mechanical Theory of the Partial and Other Derivatives of Themodynamic Quantities of Liquid Mixtures" J.Phys.Chem. 99. 12356-12362 (1995)
[Publications] Keiji Yasuda: "Frequency Dependence of Ultrasonically Induced Birefriengence of Rod Like Paricles" J.Phys.Chem. (inpress). (1996)
[Publications] Yoshinori Hirata: "Photodissociation and Geminate Dynamics in solution Phase-Picosecond Transient Absorption Studies of Tetraphenylhydrazines and Diphenyl Disulfides" Res.Chem.Interned.21. 823-836 (1995)
[Publications] Ktsuya Nishiyama: "Soluvation Dynamics of Dye Molecules in Polar Soluvents Studied by Time Resolved Hole Burning Spectroscopy" J.Mol.Liquids. 65/66. 41-48 (1995)
[Publications] Masao Kawata: "Irregular ordert in basicities of ethyamines in aqueous solutions" J.Am.Chem.Soc.117. 1638-1640 (1995)
[Publications] S.Chong: "A nolecular theory for the non-equiilibrium free energy surface in electron transfer rection" J.Phys.Chem.99(26). 10526-10529 (1995)
[Publications] M.Irisa: "Soluvation Free Energies of Non-polar and Polar Solutes Reproduced by the Combination of the Extend Sca led Particle Theory and the Poisson-Boltzmann Equation" Mol.Phys.85(6). 1227-1238 (1995)
[Publications] Toshio Yamaguchi: "Structure and dynamics of supercooled and glassy aqueous ionic solutions" J.Mol.Liquids.65/66. 91-98 (1995)
[Publications] Toshio Yamaguchi: "Structure of Ionic Hydration in Non-ambient conditions" Physica B. 213/214. 480-482 (1995)
[Publications] Masaaki Matsumoto: "Structure of clusters in ethanol-water binary solutions studied by mass spectrometry and X-ray diffraction" Bull.Chem.Soc.Jpn.68. 1775-1783 (1996)
[Publications] Masaru Nakahara: "Jump in the Rotational Mobility of Benzene Induced by the Clathrate Hydrate formation" J.Phys.Chem.99. 1377-1379 (1995)
[Publications] Masaru Nakahara: "Hydrophobic Slowdown and Hydrophilic Speedup of Water Rotation in Supercooled Aqueous Solutions of Benzen and Phenol" J.Phys.Chem.99. 10698-10700 (1995)
[Publications] Chiaki Wakai: "Pressure-and Temperature-variabl Viscocity Dependence of Orientational Correlation Times for Solitary Water Molecules in Organic Soluvents" J.Chem.Phys.103. 2025-2032 (1995)
[Publications] Masaaki Tabata: "Thermochromism of Metal Exchange Reaction between Zinc (II) and Mercury (II) Porpyrins" Z.naturforsch. 50b. 545-550 (1995)
[Publications] Masaaki Tabata: "Kinetics and mechanism of Metal-Substitution Reaction of Homodinuclear Mercury (II) Porphyrin with Zinc (II) with Paticular Reference to a Heterodinuclear Metalloporphyrin Intermediate" J.Phys.Chem.99. 10698-10700 (1995)
[Publications] Masaaki Tabata: "Ion-Pair Extraction of Metalloporphyrins into Acetonitrile for Determination of Copper (II)" Anal.Chem.68. 印刷中 (1996)

1995 Fiscal Year Annual Research Report

局所分子場における溶液のダイナミクス

Principal Investigator

野村 浩康 名古屋大学, 工学部, 教授 (50023081)

Research Products

[Publications] Shinobu Koda: "Ultrasonic Investigation on the Viscosity Dependence of the Rate Constant of Rotational Isomerism of Dibromoethane and Dibromopropane in Solutions" J.Chem.Soc.,Faraday Trans.91(3). 445-449 (1995)

[Publications] Hiroyasu Nomura: "Dynamics of the Sulfate Ion in Dilute Water-DMF Solutions" Z.Naturforsch. 50a. 7-10 (1995)

[Publications] Masaharu Ohba: "Pressure Dependence of the Limiting Partial Molar Volume of Solute in the Lennard-Jones Systems as Investigated by the RISM Method" J.Phys.Chem. 99. 9258-9262 (1995)

[Publications] Masaharu Ohba: "Statistical Mechanical Theory of the Partial and Other Derivatives of Themodynamic Quantities of Liquid Mixtures" J.Phys.Chem. 99. 12356-12362 (1995)

[Publications] Keiji Yasuda: "Frequency Dependence of Ultrasonically Induced Birefriengence of Rod Like Paricles" J.Phys.Chem. (inpress). (1996)

[Publications] Yoshinori Hirata: "Photodissociation and Geminate Dynamics in solution Phase-Picosecond Transient Absorption Studies of Tetraphenylhydrazines and Diphenyl Disulfides" Res.Chem.Interned.21. 823-836 (1995)

[Publications] Ktsuya Nishiyama: "Soluvation Dynamics of Dye Molecules in Polar Soluvents Studied by Time Resolved Hole Burning Spectroscopy" J.Mol.Liquids. 65/66. 41-48 (1995)

[Publications] Masao Kawata: "Irregular ordert in basicities of ethyamines in aqueous solutions" J.Am.Chem.Soc.117. 1638-1640 (1995)

[Publications] S.Chong: "A nolecular theory for the non-equiilibrium free energy surface in electron transfer rection" J.Phys.Chem.99(26). 10526-10529 (1995)

[Publications] M.Irisa: "Soluvation Free Energies of Non-polar and Polar Solutes Reproduced by the Combination of the Extend Sca led Particle Theory and the Poisson-Boltzmann Equation" Mol.Phys.85(6). 1227-1238 (1995)

[Publications] Toshio Yamaguchi: "Structure and dynamics of supercooled and glassy aqueous ionic solutions" J.Mol.Liquids.65/66. 91-98 (1995)

[Publications] Toshio Yamaguchi: "Structure of Ionic Hydration in Non-ambient conditions" Physica B. 213/214. 480-482 (1995)

[Publications] Masaaki Matsumoto: "Structure of clusters in ethanol-water binary solutions studied by mass spectrometry and X-ray diffraction" Bull.Chem.Soc.Jpn.68. 1775-1783 (1996)

[Publications] Masaru Nakahara: "Jump in the Rotational Mobility of Benzene Induced by the Clathrate Hydrate formation" J.Phys.Chem.99. 1377-1379 (1995)

[Publications] Masaru Nakahara: "Hydrophobic Slowdown and Hydrophilic Speedup of Water Rotation in Supercooled Aqueous Solutions of Benzen and Phenol" J.Phys.Chem.99. 10698-10700 (1995)

[Publications] Chiaki Wakai: "Pressure-and Temperature-variabl Viscocity Dependence of Orientational Correlation Times for Solitary Water Molecules in Organic Soluvents" J.Chem.Phys.103. 2025-2032 (1995)

[Publications] Masaaki Tabata: "Thermochromism of Metal Exchange Reaction between Zinc (II) and Mercury (II) Porpyrins" Z.naturforsch. 50b. 545-550 (1995)

[Publications] Masaaki Tabata: "Kinetics and mechanism of Metal-Substitution Reaction of Homodinuclear Mercury (II) Porphyrin with Zinc (II) with Paticular Reference to a Heterodinuclear Metalloporphyrin Intermediate" J.Phys.Chem.99. 10698-10700 (1995)

[Publications] Masaaki Tabata: "Ion-Pair Extraction of Metalloporphyrins into Acetonitrile for Determination of Copper (II)" Anal.Chem.68. 印刷中 (1996)

野村浩康名古屋大学, 工学部, 教授 (50023081)