Theoretical Studies of Solvation and Reaction Dynamics in Polar and Nonpolar Solvents

极性和非极性溶剂中溶剂化和反应动力学的理论研究

• 批准号: 0098062
• 负责人: Hyung Kim
• 金额: $ 47.3万
• 依托单位: Carnegie-Mellon University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-03-15 至 2006-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0098062&HistoricalAwards=false
• 关键词: Theoretical; Studies; Solvation; Reaction; Dynamics

Hyung Kim of Carnegie-Mellon University is supported by the Theoretical and Computational Chemistry Program to carry out theoretical studies of solvation and chemical reactions and related electronic spectroscopy in diversified solution environments, such as dipolar and non-dipolar solvents. By incorporating spatial dispersion into reaction field theory with the aid of molecular dynamics (MD) simulations, Kim will construct an accurate continuum theory to describe equilibrium and nonequilibrium solvation in polarizable, non-dipolar, quadrupolar solvents, such as benzene. Quantum chemistry techniques will be applied to solvation of small molecules and various charge-shift processes, such as Menshutkin and excited-state electron transfer reactions in benzene and other quadrupolar solvents. With the combined efforts of MD, quantum chemistry, and continuum theory, this effort will provide the first systematic study of charge-shift reactions in quadrupolar solvents with proper account of nonequilibrium solvation and associated solute-solvent electronic structure variations. In parallel with this effort, the truncated adiabatic basis-set (TAB) solvent electronic description will be improved to study the condensed-phase properties of water. Specifically, the TAB formulation will be extended to incorporate the pairwise-non additive, many-body character of both van der Waals and Coulombic interactions into the simulations. This is expected to allow the short- and long-range interactions to fluctuate with the solvent configurations and vary with the thermodynamic conditions. This method will be applied to study liquid-vapor phase equilibria, solvation dynamics, linear/nonlinear electronic spectroscopy, and ion transport in water under ambient and supercritical conditions. Many chemical reactions occur in condensed phases consisting of reacting solutes that are dissolved in nonreacting liquid solvents. Water, for example, is a solvent of vital interest to chemistry, biochemistry, and chemical engineering. Supercritical water is technologically important, and this research helps provide useful theoretical models that can have long-range impacts on the fundamental understanding of industrially significant solvation effects.

Hyung Kim在理论和计算化学项目的支持下，在偶极和非偶极溶剂等多种溶液环境中开展溶剂化和化学反应以及相关电子光谱的理论研究。 通过将空间色散与分子动力学（MD）模拟的帮助下，反应场理论，金将构建一个准确的连续理论来描述平衡和非平衡溶剂化的极化，非偶极，四极溶剂，如苯。 量子化学技术将应用于小分子的溶剂化和各种电荷转移过程，如Menshutkin和苯和其他四极溶剂中的激发态电子转移反应。 随着MD，量子化学和连续介质理论的共同努力，这项工作将提供第一个系统的研究电荷转移反应在四极溶剂与适当的帐户非平衡溶剂化和相关的溶质-溶剂电子结构的变化。 与此同时，截断绝热基组（TAB）溶剂电子描述将被改进，以研究水的凝聚相性质。 具体而言，TAB配方将扩展到将成对的非添加剂，多体特性的货车德瓦尔斯和库仑相互作用的模拟。 预计这将允许短程和长程相互作用随溶剂构型波动并随热力学条件变化。 这种方法将被应用于研究液-汽相平衡，溶剂化动力学，线性/非线性电子光谱，和离子在环境和超临界条件下在水中的传输。许多化学反应发生在由溶解在非反应性液体溶剂中的反应性溶质组成的凝聚相中。 例如，水是一种对化学、生物化学和化学工程至关重要的溶剂。 超临界水在技术上很重要，这项研究有助于提供有用的理论模型，这些模型可以对工业上重要的溶剂化效应的基本理解产生长期影响。