Isomeric Selectivity in Hydrocarbon Radical Reactions and Electronic Nonadiabaticity in Competing Bond Fission and Molecular Elimination Product Channels

在这项由化学部实验物理化学计划资助的提案中，芝加哥大学的劳里巴特勒将继续研究电子效应对光化学反应产物通道的影响。 描述了两组实验。 第一个将探讨竞争的单分子解离通道异构选择的碳氢化合物自由基作为自由基的内能的函数。 第二组继续以前的工作，以了解在化学反应中的产物分支，其中有一个很大的电子波函数的变化，从反应物演变到一个或多个产品的通道。 位于加州伯克利的先进光源（ALS）的化学动力学光束线将用于许多这样的实验。自由基中间体在广泛的化学过程中起着关键作用，但即使经过几十年的研究，许多关键的自由基中间体的反应仍然无法直接进行实验研究。 目前的知识水平可以说是粗糙的。 该项目涉及化学反应的基本原理，确定从给定反应产生不同产物的条件。 这项工作的结果将最终有助于理解燃烧，光化学烟雾的产生和化学气相沉积等不同的过程。

In this proposal funded by the Experimental Physical Chemistry Program of the Chemistry Division, Laurie Butler of the University of Chicago will pursue a program of research to continue studies of electronic effects on photochemical reaction-product channels. Two sets of experiments are described. The first will probe the competing unimolecular dissociation channels of isomerically selected hydrocarbon radicals as a function of internal energy in the radical. The second set continues prior work to understand the product branching in chemical reactions in which there is a large required change in electronic wavefunction in evolving from reactant to one or more of the product channels. The Chemical Dynamics Beam Line at the Advanced Light Source (ALS) in Berkeley, California will be used for many of these experiments.Radical intermediates play a key role in a wide range of chemical processes, yet even after decades of research the reactions of many key radical intermediates elude direct experimental study. The current state of knowledge can be described as crude. This project addresses the basic principles of chemical reactivity, identifying the conditions under which different products are produced from a given reaction. The results of this work will ultimately contribute to understanding of processes as diverse as combustion, photochemical smog production, and chemical vapor deposition.