Journal
JOURNAL OF COMPUTATIONAL CHEMISTRY
Volume 24, Issue 16, Pages 2044-2062Publisher
WILEY
DOI: 10.1002/jcc.10360
Keywords
atmospheric chemistry; chlorine; kinetics; radical reactions; reaction mechanisms
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The potential energy surface for the Cl + propene reaction was analyzed at the MP2 level using Pople's 6-31G(d,p) and 6-311 +G(d,p), and Dunning's cc-pVDZ and aug-cc-pVDZ basis sets. Two different channels for the addition reaction leading to chloroalkyl radicals and five alternative channels for the abstraction reaction leading to C3H5 + HCl were explored. The corresponding energy profiles were computed at the QCISD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ level of theory. Theoretical results suggest that the previously established mechanism consisting of (1) direct abstraction and (2) addition-elimination steps is instead made up of (1) addition through an intermediate and (2) two-step abstraction processes. No direct abstraction mechanism exists on the potential energy surface. The kinetic equations derived for the new mechanism are consistent with the pressure dependence experimentally observed for this reaction. (C) 2003 Wiley Periodicals, Inc.
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