Theoretical and Computational Studies of Chemical Reaction Dynamics and Electronic Spectroscopy in Solution

Hyung Kim得到了理论和计算化学计划的资助，继续他在溶液中的化学反应动力学和电子能谱方面的研究。Kim将利用量子化学技术实现Born-Oppenheimer反应场理论，与现有的自洽处理溶剂化的方法进行详细比较。研究了溶质-溶剂电子相关对小分子溶剂化和电荷转移过程的反应自由能的影响。这种方法应该澄清一些与自洽方法有关的缺点，即过高估计2+2环加成的激活障碍。此外，涉及四极极化的反应场方法也将用于处理溶剂系统，如苯和二氧化碳。要研究的溶剂包括醇、胺、烷烃、环烷烃和芳香体系。还将努力了解和量化正常水和超临界水的溶剂化性质。有很好的理论可以用来理解涉及分子间二元接触的气相化学反应。然而，大多数具有重要技术意义的化学反应都发生在缩合相中，缩合相由溶解在非反应溶剂中的反应溶质组成。溶剂对化学反应的影响以及处理这种复杂相互作用的理论方法仍处于发展的早期阶段。然而，这一研究领域的进展可以对我们对工业意义的化学反应的基本理解产生重要的长期影响。Kim的研究有助于为解释溶剂对凝聚相系统化学反应的影响提供理论基础。

Hyung Kim is supported by a grant from the Theoretical and Computational Chemistry Program to continue his research in chemical reaction dynamics and electronic spectroscopy in solution. Kim will implement the Born-Oppenheimer reaction field theory with quantum chemical techniques to make a detailed comparison with existing self-consistent methods for treating solvation. The solute-solvent electronic correlation effects on solvation of small molecules and reaction free energetics of charge shift processes will be investigated. This approach should clarify some of the shortcomings associated with the self-consistent approach with regard to overestimation of activation barriers for 2+2 cycloadditions. Furthermore, a reaction field approach involving quadrupolar polarization will also be developed for treating solvent systems such as benzene and carbon dioxide. Solvents to be studied include alcohols, amines, alkanes, cycloalkanes and aromatic systems. An effort will also be made to understand and quantify the solvation properties of normal and supercritical water. Excellent theories are available for understanding gas phase chemical reactions involving binary encounters between molecules. However, most chemical reactions of technological importance occur in condensed phases consisting of reacting solutes dissolved in non-reacting solvents. The effect which the solvent has on chemical reactions, and theoretical methods for dealing with this complex interaction are still in early stages of development. Nevertheless, progress in this area of research can have an important long range impact on our fundamental understanding of chemical reactions of industrial significance. Kim's research is helping to provide a theoretical basis for the interpretation of solvent effects on chemical reactions in condensed phase systems.