A laser photolysis/time-resolved Fourier transform infrared emission study of OH(X 2Π, v) produced in the reaction of alkyl radicals with O(3P)

Jörg Lindner, Richard A. Loomis, Jody J. Klaassen, Stephen R. Leone

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Abstract

The emission spectra of vibrationally excited hydroxyl radical products formed in the reactions of alkyl radicals with O(3P) atoms are detected using a laser photolysis/time-resolved Fourier transform infrared spectroscopy technique. For the reaction between oxygen atoms and ethyl, the radicals are produced simultaneously by the 193 nm photolysis of the precursors SO2 and diethyl ketone, respectively. The observed initial OH(v) product vibrational state distribution for the C2H5+O(3P) reaction is 0.18±0.03, 0.23±0.04, 0.29±0.05, 0.23±0.07, and 0.07±0.04 for v = 1 to 5, respectively. The population inversion is best explained by a direct abstraction mechanism for this radical-radical reaction. Vibrationally excited hydroxyl radicals are also observed in the O+ethyl, O+n-propyl, and O+i-propyl reactions when using alkyl iodides as precursors of the alkyl radicals, although quantitative detail is not obtained due to competing reaction processes.

Original languageEnglish
Pages (from-to)1944-1952
Number of pages9
JournalJournal of Chemical Physics
Volume108
Issue number5
DOIs
StatePublished - Feb 1 1998

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