OH-initiated oxidation of toluene. 1. Quantum chemistry investigation of the reaction path

Abstract

In this paper we present the results of a detailed quantum chemistry investigation of the toluene-OH-O2 system, mostly at the B3LYP/6-311G(2df,2pd) level. We focus on OH addition followed by H abstraction to O2, a mechanism based on that proposed by Klotz et al. [Phys. Chem. Chem. Phys. 2000, 2, 227] to explain the experimentally observed photolysis products. A notable feature of the calculated minimum energy pathway is the formation of ketone intermediates during the isomerization from the toluene oxides to the cresols. The quantum chemistry results largely support the plausibility of the mechanism proposed by Klotz et al. The system provides a rich set of reactions with which to test statistical kinetic theories.