Solvation Role on Kinetic Processes in Solution

溶剂化作用对溶液动力学过程的作用

• 批准号: 9732910
• 负责人: Harold Friedman
• 金额: $ 9.03万
• 依托单位: SUNY at Stony Brook
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-05-15 至 1999-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9732910&HistoricalAwards=false
• 关键词: Solvation; Role; Kinetic; Processes; Solution

Harold Friedman and Fernando Raineri are supported by a grant from the Theoretical and Computational Chemistry Program to use a combination of integral equation techniques and molecular dynamics simulations to understand the structural, energetic and dynamical aspects of the solvation of complex molecules in a variety of solvent environments. They have developed a Surrogate Hamiltonian theory that employs a renormalized linear response theory for the nonequilibrium distribution function of the solvent in the time-varying field of the solute. The theory has been applied to number of simpler systems and checked with molecular dynamics simulations. In the next phase of the research, particular emphasis will be placed on electron transfer reactions and bond-breaking / bond-forming reactions. The surrogate Hamiltonian theory will be extended to include higher order effects such as multiple moments, solute excluded volume and hydrogen bonding effects. They also plan to develop a molecular interpretation for the parameters used by physical organic chemists to quantify nucleophilic solvent assistance in the solvolysis of aliphatic halides in solution. The aim of this research project is to improve the way in which measurable properties of solutions are interpreted in terms of the interactions among the molecular constituents. This is particularly challenging for ionic solutions since the long range of the forces between the ionic charges strongly affect both the measurable properties and the mathematical tools needed to relate them to the molecular models. The work of Friedman and Raineri should provide fundamental molecular insight into the mechanism and dynamics of solvation.

哈罗德·弗里德曼和费尔南多·雷内里得到了 理论和计算化学计划使用的组合 积分方程技术和分子动力学模拟， 了解的结构，能量和动力方面的 复杂分子在各种溶剂环境中的溶剂化。 他们发展了一种替代哈密顿理论， 非平衡分布的重整化线性响应理论 溶剂在溶质时变场中的作用。 的 理论已被应用到一些简单的系统，并检查与 分子动力学模拟 在下一阶段的研究中， 将特别强调电子转移反应， 键断裂/键形成反应。 代理哈密顿理论 将扩展到包括更高阶的效果，例如多个 矩、溶质排除体积和氢键效应。 他们还 计划对所用参数进行分子解释， 物理有机化学家量化亲核溶剂的援助， 脂肪族卤化物在溶液中的溶剂分解。 该研究项目的目的是改善 解决方案的可测量属性解释的条款， 分子间的相互作用。这是特别 离子溶液具有挑战性，因为力的范围很长， 离子电荷之间的相互作用强烈地影响着 以及将它们与分子模型联系起来的数学工具。 Friedman和Raineri的工作应该提供基本的分子生物学基础。 深入了解溶剂化的机制和动力学。