The Influence of Electronic Nonadiabaticity on Competing Chemical Reaction Pathways

在这个由实验物理化学计划支持的项目中， 化学部，巴特勒将继续研究电子 非绝热化学反应途径 一组实验将 试图预测绝热和非绝热反应通道， 分子官能团的电子激发。 作为一个例子， 光碎片速度和角分布测量， 交叉激光分子束光解硝酸 从头计算将确定所有的产品渠道， 激光激发产生的硝酸。 其他分子 包括硝基甲烷、硝酸甲酯和硝酰胺。 在另一 光碎片速度和角分布实验 一系列酰胺的光解离通道的分析将使用 解离分子的发射光谱来表征形状 在弗兰克-康登区域的势能面。 详细 深入了解众所周知的光诱导键断裂通道将 得到了 本项目中的实验测量与计算相结合 将帮助我们了解复杂的光化学反应性 分子。 例如，有些反应是禁止的，即使有 有足够的能量供它们继续前进 该项目将 提供了一个基础，我们可以解释这些意外的结果，

In this project supported by the Experimental Physical Chemistry Program of the Chemistry Division, Butler will continue studies of electronically nonadiabatic chemical reaction pathways. One set of experiments will seek to predict adiabatic and nonadiabatic reaction channels upon local electronic excitation of a molecular functional group. As an example, photofragment velocity and angular distribution measurements from crossed-laser molecular beam photodissociation of nitric acid together with ab initio calculations will identify all the product channels of nitric acid resulting from laser excitation. Other molecules to be examined include nitromethane, methyl nitrate, and nitramide. In another set of experiments photofragment velocity and angular distribution analysis of the photodissociation channels of a series of amides will use emission spectroscopy of dissociating molecules to characterize the shape of the potential energy surface in the Franck-Condon region. Detailed insight into well-known photo-induced bond cleavage channels will be obtained. The experimental measurements in this project combined with calculations will help us understand the photochemical reactivity of complex molecules. For example, some reactions are forbidden even though there is enough energy available for them to proceed. This project will provide a basis by which we can explain some of these unexpected outcomes