We have generated a set of thermodynamic and kinetic parameters for the reactions involving HO₂ in the very early stages of benzene oxidation at low temperatures using density functional theory (DFT). In particular, we report the rate constants for the reactions of HO₂ with benzene and phenyl. The calculated reaction rate constant for the abstraction of H–C₆H₅ by HO₂ is found to be in good agreement with the limited experimental values. HO₂ addition to benzene is found to be more important than direct abstraction. We show that the reactions of HO₂ with the phenyl radical generate the propagating radical OH in a highly exoergic reaction. The results presented herein should be useful in modeling the oxidation of aromatic compounds at low temperatures.
Combustion and Flame Vol. 157, Issue 7, p. 1325-1330