title: Reactions between resonance-stabilized radicals: propargyl + allyl.
abstract: This article describes a detailed theoretical analysis of the reaction between allyl and propargyl. In this analysis, we employ high-level electronic structure calculations to characterize the potential energy surface and various forms of transition-state theory (TST) to calculate microcanonical, J-resolved rate coefficients-conventional TST for isomerizations, and the variable reaction coordinate form of variational TST for the "barrierless" association/dissociation processes. These rate coefficients are used in a time-dependent, multiple-well master equation to determine phenomenological rate coefficients, k(T,p), for various product channels. The analysis indicates that the formation of (cyclic) c-C(6)H(7) and c-C(6)H(8) species is suppressed by elevated pressure. Overall, the results suggest that the formation of these five-membered rings from the reaction is not as important as previously thought. A simplified description of the kinetics of the reaction is discussed, and corresponding rate coefficients are provided.
authors.affiliation: Combustion Research Facility, Sandia National Laboratories, Livermore, California 94551-0969, USA. jamille@sandia.gov
authors.forename: James A
authors.initials: JA
authors.lastname: Miller
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Klippenstein
authors.forename: Yuri
authors.initials: Y
authors.lastname: Georgievskii
authors.forename: Lawrence B
authors.initials: LB
authors.lastname: Harding
authors.forename: Wesley D
authors.initials: WD
authors.lastname: Allen
authors.forename: Andrew C
authors.initials: AC
authors.lastname: Simmonett