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

在这项由化学系实验物理化学计划资助的提案中，芝加哥大学的劳里·巴特勒将继续研究光化学反应产物通道上的电子效应。描述了两组实验。第一个将探索异构化选择的碳氢基的竞争性单分子解离通道作为自由基内能的函数。第二组继续以前的工作，以了解化学反应中的产物分支，在化学反应中，从反应物演变到一个或多个产物通道时，电子波函数有很大的必要变化。加州伯克利高级光源(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，然而即使经过几十年的研究，许多关键自由基中间体的反应仍然没有得到直接的实验研究。目前的知识状况可以用粗略来形容。这个项目研究化学反应的基本原理，确定在什么条件下从给定的反应中产生不同的产品。这项工作的结果最终将有助于理解燃烧、光化学烟雾产生和化学气相沉积等各种过程。

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.