Benzoxyl radical decomposition kinetics: formation of benzaldehyde H, phenyl CH 2O, and benzene HCO

Abstract

The kinetics of benzoxyl radical decomposition was studied using ab initio computational chemistry and RRKM rate theory. The benzoxyl radical is an important but short-lived intermediate in the combustion of toluene and other alkylated aromatic hydrocarbons. A theoretical study of the thermochemistry and kinetics to products over a range of temperatures and pressures for benzoxyl decomposition is reported. Ab initio calculations with the G3X theoretical method reveal low-energy pathways from the benzoxyl radical to benzaldehyde + H and the phenyl radical + formaldehyde (CH 2O), as well as a novel mechanism to benzene + the formyl radical (HC-O). RRKM simulations were performed for benzoxyl d..