Theoretical Studies of Collision Dynamics

这个由理论和计算化学计划资助的项目涉及化学反应碰撞的理论研究。注意力将集中在阐明当前的基本实验，在这些实验中，一个电子从ClHCl中分离出来，形成中性的ClHCl。该物种不稳定，迅速解离到Cl+HCl。然而，它是亚稳态的，由于共振态的存在，它的寿命很短，但意义重大。这为研究共振对化学反应机理的影响提供了一个重要的原型系统。该项目将利用反应散射的降维理论来表征由从头算电子结构计算确定的过渡态几何构型及其附近的共振。为了与实验结果进行比较，将用振动波函数进行三维Franck-Condon分析。

This project funded in the Theoretical and Computational Chemistry Program involves theoretical studies of chemically reactive collisions. Attention will be focused on elucidation of current fundamental experiments in which an electron is detached from ClHCl- to form neutral ClHCl. This species is not stable, quickly dissociating to Cl+HCl. However it is metastable, with a short but significant lifetime due to the existence of resonance states. This then provides an important prototype system for study of the influence of resonances on the mechanisms of chemical reactions. The project will utilize a reduced dimensionality theory of reactive scattering to characterize the resonances at and near the transition state geometry determined by ab initio electronic structure calculations. The vibrational wave functions will be used to carry out a three-dimensional Franck-Condon analysis for comparison to experimental results.