Photoinduced Reaction Dynamics in Weakly Bound Complexes

俄亥俄州立大学的Anne McCoy在理论和计算化学计划的支持下，从理论上研究了弱束缚星团中的光引发过程。我们将考察以下三类过程：(1)二元络合物的紫外光解离，其中离解引起双分子反应；(2)通过振动激发其中一个团簇分子在络合物中光诱导的反应动力学；(3)团簇尺寸对IHI与Ar原子簇合的过渡态动力学的影响以及水团簇与Ar原子的光解离。团簇中光引发过程的研究在理论和计算上都提出了严峻的挑战。这项研究的一个重要组成部分将涉及开发近似方法，以便能够处理动力学研究中经典的至少一些自由度，以及研究传播动力学的量子/经典混合方法。分子簇提供了一个实验室，通过它可以从实验和理论上检验分子之间的相互作用。团簇不能简单地视为其组成分子的总和，因为团簇环境通常会改变复杂分子的化学反应。这项研究将从理论上探索团簇化学反应，其中许多可以与当前感兴趣的相关实验结果进行比较。

Anne McCoy of the Ohio State University is supported by the Theoretical and Computational Chemistry Program to investigate photoinitiated processes in weakly bound clusters theoretically. The following three categories of processes will be examined: (1) ultraviolet photodissociation of binary complexes in which the dissociation induces a bimolecular reaction, (2) reaction dynamics photoinduced in complexes by vibrationally exciting one of the cluster molecules, and (3) cluster size effects on transition state dynamics of IHI clustered with argon atoms and the photodissociation of water clusters with argon atoms. Studies of photoinitiated processes in clusters pose serious challenges theoretically and computationally. A significant component of this research will involve developing approximate approaches that will enable treatments of at least some of the degrees of freedom classically in the dynamics studies, as well as investigating hybrid quantum/classical methods for propagating the dynamics. Clusters of molecules provide a laboratory through which interactions between molecules can be examined both experimentally and theoretically. Clusters cannot be considered simply as the sum of their constituent molecules, as the cluster environment generally changes chemical reactions of the complexed molecules. This research will explore theoretically cluster chemical reactions, many of which can be compared to related experimental results of current interest.