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

卡耐基梅隆大学的Hyung Kim得到了 理论和计算化学计划，以执行理论 研究溶液中的电荷转移过程。 他将研究 溶质-溶剂电子结构随波动 非平衡溶剂环境及其对电荷迁移的影响 流程. 一种新的量子化学方法将结合 介电连续介质中溶质-溶剂电子关联 说明. 一种改进的溶剂坐标描述， 解释了溶剂对溶质几何形状变化的响应， 反应，也将得到发展。 该理论将应用于 甲醛中的第一单重态电子跃迁，离解 电子附着，超快激发态电子转移和 溶液中的状态依赖旋转动力学。 现在有了很好的理论来理解气相化学 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然非常复杂。 他们的婴儿期 尽管如此，这一研究领域的进展可能会 对我们基本理解的重要长期影响 具有工业意义的化学反应。 金的研究有助于 为解释溶剂效应提供理论依据 凝聚相系统中的化学反应。

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.