Kinetics of the Cyclopentadienyl plus Acetylene, Fulvenallene H, and 1-Ethynylcyclopentadiene plus H Reactions

Abstract

Quantum chemical methods and statistical reaction rate theory are utilized to examine the kinetics and thermochemistry of three reactions occurring on the C(7)H(7) potential energy surface: cyclopentadienyl (C(5)H(5)) + acetylene (C(2)H(2)), fulvenallene + H, and 1-ethynylcyclopentadiene + H. These reactions are relevant to the formation of polyaromatic hydrocarbons (PAHs) and the combustion of alkylated aromatics. Reaction of the resonantly stabilized C(5)H(5) radical with C(2)H(2) is an important PAH growth reaction; here we identify several new low-energy pathways connecting these reactants with fulvenallene + H, 1-ethynylcyclopentadiene + H, and the cycloheptatrienyl and benzyl radicals...