Theoretical Studies of Charge Shift Processes in Solution: Role of Solute-Solvent Electronic Structure and Solvation Dynamics

卡内基梅隆大学的Hyung Kim得到了理论和计算化学项目的资助，以执行溶液中电荷移动过程的理论研究。他将研究在波动的非平衡溶剂环境下溶质-溶剂电子结构的变化及其对电荷转移过程的影响。一种新的量子化学方法将溶质-溶剂电子关联结合到介电连续介质溶剂描述中。还将开发一种改进的溶剂坐标描述，该描述适当地考虑了反应过程中溶剂对溶质几何形状变化的响应。该理论将被应用于甲醛中的第一个单重态电子跃迁、解离电子附着、超快激发态电子转移和溶液中依赖于态的转动动力学。现在有了很好的理论来理解涉及分子间二元相遇的气相化学反应。然而，大多数具有重要技术意义的化学反应发生在由溶解在非反应溶剂中的反应溶质组成的凝聚相中。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非常初级的阶段。然而，这一研究领域的进展可能会对我们对具有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凝聚相体系中溶剂对化学反应的影响提供理论基础。

Hyung Kim of Carnegie Mellon University is supported by a grant from the Theoretical and Computational Chemistry Program to perform theoretical studies of charge shift processes in solution. He will study solute-solvent electronic structure variation with a fluctuating nonequilibrium solvent environment and it's effect on charge shift processes. A novel quantum chemical method will incorporate the solute-solvent electron correlation within a dielectric continuum solvent description. An improved solvent coordinate description, which properly accounts for solvent response to variations in the solute geometry during reaction, will also be developed. The theory will be applied to the first singlet electronic transition in formaldehyde, dissociative electron attachment, ultrafast excited-state electron transfer and state-dependent rotational dynamics in solution. Excellent theories are now 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 very much in their infancy. 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.