Molecular theory of solvent effects an chemical reactions

溶剂影响化学反应的分子理论

• 批准号: 12440170
• 负责人: HIRATA Fumio
• 金额: $ 4.61万
• 依托单位: Okazaki National Research Institutes
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440170/
• 关键词: chemical reactions in solutions; electronic structure; solvent effect; RISM theory; solvated electrons; biomolecules; protein folding; vapor-liquid phase transition; 一般化ランジェヴァン; 回転緩和; 圧力効果; モード結合理論; 水の特異性; RISM-SCF理論; 水の粘性; 電子状態理論; 安定性; 部

Primary driving force of chemical reactions including exchange of atoms is the change in electronic structure. However, if a reaction takes place in solution, solvent effect becomes another important factor to determine both the reactivity and reaction rate. The study proposed in the project is to build a new theory of chemical reactions in solution by combining the theories which have been proposed by the principal investigator.Chemical rections take place not only in bulk solutions but also at such interfaces with electrodes and enzymes. Recently, vapor-liquid and liquid-liquid interfaces have been also realized as important reaction fileds. Therefore, we extended our study to the problems related to such solution interfaces, and developed new theories concerning vapor-liquid and liquid-liquid phase separation. Those studies are published in 53 papers in scientific journals. The research subjects are classified into the following five categories.(1)The electronic structure, chemical reaction and solvated electrons in solutions.(2)Stability of biomolecules and protein folding.(3)Dynamics and relaxation processes in solutions.(4)The statistical mechanics of solution at interfaces.(5)Development of the statistical mechanics of molecular liquids, and of phase transition and phase separation.The results of the study are also published in the following book.F.HIRATA Ed., "Molecular Theory of Solvation," Kluwer-Springer Academic, 2003.

包括原子交换在内的化学反应的主要驱动力是电子结构的变化。然而，如果反应发生在溶液中，溶剂效应成为决定反应活性和反应速度的另一个重要因素。该项目提出的研究是结合主要研究者提出的理论，建立一个新的溶液化学反应理论。化学反应不仅发生在溶液中，而且发生在与电极和酶的界面上。近年来，气液界面和液液界面也作为重要的反应领域得到了重视。因此，我们将研究扩展到与这种溶液界面相关的问题，并发展了新的汽液相分离和液液相分离理论。这些研究以53篇论文的形式发表在科学期刊上。研究对象分为以下五类。(1)溶液中的电子结构、化学反应和溶剂化电子。(2)生物分子和蛋白质折叠的稳定性。(3)溶液中的动力学和松弛过程。(4)界面上溶液的统计力学。(5)分子液体统计力学的发展，以及相变和相分离。这项研究的结果也发表在下面的书中。

项目成果

F.Hirata, S-H.Chong: "Collective density fluctuations and dynamics of ions in water studied by the interaction-site model of liquid"Cond.Mat.Phys.. 4. 261-276 (2001)

F.Hirata、S-H.Chong：“通过液体相互作用位点模型研究水中离子的集体密度波动和动力学”Cond.Mat.Phys.. 4. 261-276 (2001)

T.Kimura, N.Matsubayashi, H.sato, F.Hirata, M.Nakahara: "Enthalpy and Entropy Decomposition of Free-Energy Changes for Side-Chain Conformations of Asparatic Acid and Asparagine in Acidic, Neutral, and Basic Aqueous Solutions"J.Phys.Chem., B. 106. 12336-12

T.Kimura、N.Matsubayashi、H.sato、F.Hirata、M.Nakahara：“酸性、中性和碱性水溶液中天冬氨酸和天冬酰胺侧链构象的自由能变化的焓和熵分解”

T.Sumi, F.Hirata: "A density-functional theory for polymer liquids based on interaction site mode"J.Chem.Phys.. 118. 2431-2442 (2003)

T.Sumi, F.Hirata：“基于相互作用位点模式的聚合物液体的密度泛函理论”J.Chem.Phys.. 118. 2431-2442 (2003)

A.Sethia, E.R.Bittner, F.Hirata: "Interplay between the repulsive and attractive interaction and the spacial dimesionality of an excess electron in a simple fluid"J.Theor.ComChem.. 2. 129-138 (2003)

A.Sethia、E.R.Bittner、F.Hirata：“简单流体中排斥和吸引相互作用与多余电子的空间维度之间的相互作用”J.Theor.ComChem.. 2. 129-138 (2003)

A.Kovalenko, F.Hirata: "Towards a Molecular Theory for the Van Der Waals-Maxwell Description of Fluid Phase Transition"J.Theor.ComChem.. 1. 381-406 (2002)

A.Kovalenko、F.Hirata：“迈向流体相变范德华-麦克斯韦描述的分子理论”J.Theor.ComChem.. 1. 381-406 (2002)