Kinetics of the benzyl O(3P) reaction: A quantum chemical/statistical reaction rate theory study

Abstract

The resonance stabilized benzyl radical is an important intermediate in the combustion of aromatic hydrocarbons and in polycyclic aromatic hydrocarbon (PAH) formation in flames. Despite being a free radical, benzyl is relatively stable in thermal, oxidizing environments, and is predominantly removed through bimolecular reactions with open-shell species other than O2. In this study the reaction of benzyl with ground-state atomic oxygen, O(3P), is examined using quantum chemistry and statistical reaction rate theory. C 7H7O energy surfaces are generated at the G3SX level, and include several novel pathways. Transition state theory is used to describe elementary reaction kinetics, with canonica..