DEPENDENCE OF THE PHOTOFRAGMENTATION OF THE PERDEUTEROMETHOXY RADICAL ON THE C-O BOND EXTENSION

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 Title: DEPENDENCE OF THE PHOTOFRAGMENTATION OF THE PERDEUTEROMETHOXY RADICAL ON THE C-O BOND EXTENSION Creators: Applegate, Brian E.; Pushkarsky, Michael B.; Miller, Terry A. Issue Date: 1998 Publisher: Ohio State University Abstract: Predissociation in the $\tilde{A}^{2}A_{1}$ state of perdeuteromethoxy has been probed in a jet-cooled expansion by two techniques, fluorescence temporal decay and fluorescence depletion spectroscopy. The rate of photodissociation appears to not only be a function of total excitation energy but also of the vibrational mode excited. A threshold for the photodissociation is established at six quanta of the C-O stretch, $\nu_{3}. Ab initio$ calculations of the bond length extension as a function of each vibrational mode of this radical allows us to compare the absolute bond extension to the rate of photofragmentation. This comparison establishes a clear threshold for C-O bond extension to achieve bond fission. Similar results have been obtained for clearly related radicals $CH_{3}O$ and $CF_{3}S$, where the C-X (X=O, S) bond breaking is again highly correlated with the extension of the C-X bond. Description: Author Institution: The Ohio State University, Dept. of Chemistry URI: http://hdl.handle.net/1811/18814 Other Identifiers: 1998-MG-08