A Barrierless Pathway Accessing the C₉H₉ and C₉H₈ Potential Energy Surfaces via the Elementary Reaction of Benzene with 1-Propynyl.

ABSTRACT: The crossed molecular beams reactions of the 1-propynyl radical (CH₃CC; X²A₁) with benzene (C₆H₆; X¹A_1g) and D6-benzene (C₆D₆; X¹A_1g) were conducted to explore the formation of C₉H₈ isomers under single-collision conditions. The underlying reaction mechanisms were unravelled through the combination of the experimental data with electronic structure and statistical RRKM calculations. These data suggest the formation of 1-phenyl-1-propyne (C₆H₅CCCH₃) via the barrierless addition of 1-propynyl to benzene forming a low-lying doublet C₉H₉ intermediate that dissociates by hydrogen atom emission via a tight transition state. In accordance with our experiments, RRKM calculations predict that the thermodynamically most stable isomer - the polycyclic aromatic hydrocarbon (PAH) indene - is not formed via this reaction. With all barriers lying below the energy of the reactants, this reaction is viable in the cold interstellar medium where several methyl-substituted molecules have been detected. Its underlying mechanism therefore advances our understanding of how methyl-substituted hydrocarbons can be formed under extreme conditions such as those found in the molecular cloud TMC-1. Implications for the chemistry of the 1-propynyl radical in astrophysical environments are also discussed.

SUBMITTER: Thomas AM 

PROVIDER: S-EPMC6879741 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature