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

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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.