Products of the benzene + O(3P) reaction

C.A. Taatjes, D.L. Osborn, T.M. Selby, G. Meloni, A.J. Trevitt, E. Epifanovsky, A.I. Krylov, B. Sirjean, E. Dames, and H. Wang
J. Phys. Chem. A 114, 3355 – 3370 (2010)

The gas-phase reaction of benzene with O(3P) is of considerable interest for modeling of aromatic oxidation as well as because of fundamental questions about the prominence of intersystem crossing in the reaction. While its overall rate constant has been studied extensively, there are still significant uncertainties about the product distribution. The reaction proceeds mainly through the addition of the O atom to benzene, forming initially a triplet diradical adduct, which can either dissociate to form the phenoxy radical and H atom, or undergo intersystem crossing onto a singlet surface, followed by a multiplicity of internal isomerizations, leading to several possible reaction products. In this work, we examined the product branching ratios of the reaction between benzene and O(3P) over the temperature range of 300 to 1000 K and pressure from 1 to 10 Torr. The reactions were initiated by pulsed-laser photolysis of NO2 in the presence of benzene and helium buffer in a slow-flow reactor, and reaction products were identified by using the multiplexed chemical kinetics photoionization mass spectrometer that operates at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory. Phenol and phenoxy radical were detected and quantified. Cyclopentadiene and cyclopentadienyl radical were directly identified for the first time. Finally, ab initio calculations and master equation/RRKM modeling were used to reproduce the experimental branching ratios, yielding pressure-dependent rate expressions for the reaction channels, including phenoxy + H, phenol, cyclopentadiene + CO, which are proposed for kinetic modeling of benzene oxidation.

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