Variational analysis of the phenyl O2 and phenoxy O reactions

Abstract

Variational transition state analysis was performed on the barrierless phenyl + O2 and phenoxy + O association reactions. In addition, we also calculated rate constants for the related vinyl radical (C 2H3) + O2 and vinoxy radical (C 2H3O) + O reactions and provided rate constant estimates for analogous reactions in substituted aromatic systems. Potential energy scans along the dissociating C-OO and CO-O bonds (with consideration of C-OO internal rotation) were obtained at the O3LYP/6-31G(d) density functional theory level. The CO-O and C-OO bond scission reactions were observed to be barrierless, in both phenyl and vinyl systems. Potential energy wells were scaled by G3B3 reaction enthalpie..