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

Hyung Kim得到了理论和计算科学基金会的资助。 化学计划继续他在化学反应动力学的研究 和溶液中的电子光谱。 金正恩将实施 玻恩-奥本海默反应场理论与量子化学技术 与现有的自洽方法进行详细比较， 处理溶剂化。 溶质-溶剂电子相关效应对 小分子溶剂化与电荷转移反应自由能 过程将被调查。 这种方法应澄清一些 与自洽办法有关的缺点， 高估了2+2环加成的活化能垒。 此外，反应场的方法，涉及四极极化 也将开发用于处理溶剂系统，如苯和 二氧化碳. 待研究的溶剂包括醇类、胺类， 烷烃、环烷烃和芳族体系。 还将努力 了解和量化的溶剂化性能正常和 超临界水 为理解气相化学反应提供了很好的理论依据 涉及分子间二元碰撞的反应。 但大多数 具有重要技术意义的化学反应发生在凝聚相中 由溶解在非反应溶剂中的反应溶质组成。的 溶剂对化学反应的影响，理论上 处理这种复杂相互作用的方法仍处于早期阶段 发展阶段然而，这一研究领域的进展 会对我们的基本理解产生重要的长期影响 具有工业意义的化学反应。金的研究是 有助于为溶剂的解释提供理论依据 对凝聚相系统中化学反应的影响。

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.