Dynamics of ethyl radical decomposition. 3. Effect of chemical activation vs. microcanonical sampling

William L. Hase, Daniel G. Buckowski, Kandadai N. Swamy

Research output: Contribution to journalArticle

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Abstract

Formation and decomposition of chemically activated ethyl radicals is simulated by the Monte Carlo quasiclassical trajectory method. The results are compared with a previous study of a microcanonical ensemble of ethyl radicals. Chemically activated ethyl radicals have an apparent non-RRKM lifetime distribution as a result of nonrandom excitation. However, rapid intramolecular relaxation processes give a lifetime distribution after approximately 5 × 10-12 s which agrees with that for a microcanonical ensemble. A statistical model for partitioning of energy and angular momenta at the dissociation barrier is given, and the trajectory results agree with the predictions of the model.

Original languageEnglish
Pages (from-to)2754-2763
Number of pages10
JournalJournal of physical chemistry
Volume87
Issue number15
DOIs
StatePublished - 1983

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