Reactions between resonance-stabilized radicals: propargyl + allyl.
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.
Miller
James A
JA
Combustion Research Facility, Sandia National Laboratories, Livermore, California 94551-0969, USA. jamille@sandia.gov
Klippenstein
Stephen J
SJ
Georgievskii
Yuri
Y
Harding
Lawrence B
LB
Allen
Wesley D
WD
Simmonett
Andrew C
AC