Crossed-Beam and Theoretical Studies of the O(3P, 1D) + Benzene Reactions: Primary Products, Branching Fractions, and Role of Intersystem Crossing

Reliable modeling of hydrocarbon oxidation relies critically on knowledge of the branching fractions (BFs) as a function of temperature (T) and pressure (p) for the products of the reaction of the hydrocarbon with atomic oxygen in its ground state, O(P-3). During the past decade, we have performed in-depth investigations of the reactions of O(P-3) with a variety of small unsaturated hydrocarbons using the crossed molecular beam (CMB) technique with universal mass spectrometric (MS) detection and time-of-flight (TOF) analysis, combined with synergistic theoretical calculations of the relevant potential energy surfaces (PESs) and statistical computations of product BFs, including intersystem crossing (ISC). This has allowed us to determine the primary products, their BFs, and extent of ISC to ultimately provide theoretical channel-specific rate constants as a function of T and p. In this work, we have extended this approach to the oxidation of one of the most important species involved in the combustion of aromatics: the benzene (C6H6) molecule. Despite extensive experimental and theoretical studies on the kinetics and dynamics of the O( P-3) + C6H6 reaction, the relative importance of the C6H5O (phenoxy) + H open-shell products and of the spin-forbidden C6H6 (cyclopentadiene) + CO and phenol adduct closed-shell products are still open issues, which have hampered the development of reliable benzene combustion models. With the CMB technique, we have investigated the reaction dynamics of O(P-3) + benzene at a collision energy (E-c) of 8.2 kcal/mol, focusing on the occurrence of the phenoxy + H and spin-forbidden C5H6 + CO and phenol channels in order to shed further light on the dynamics of this complex and important reaction, including the role of ISC. Concurrently, we have also investigated the reaction dynamics of O(D-1) + benzene at the same E-c. Synergistic high-level electronic structure calculations of the underlying triplet/singlet PESs, including nonadiabatic couplings, have been performed to complement and assist the interpretation of the experimental results. Statistical (RRKM)/master equation (ME) computations of the product distribution and BFs on these PESs, with inclusion of ISC, have been performed and compared to experiment. In light of the reasonable agreement between the CMB experiment, literature kinetic experimental results, and theoretical predictions for the O(P-3) + benzene reaction, the so-validated computational methodology has been used to predict (i) the BF between the C6H5O + H and C5H6 + CO channels as a function of collision energy and temperature (at 0.1 and 1 bar), showing that their increase progressively favors radical (phenoxy + H)-forming over molecule (C5H6 + CO and phenol stabilization)-forming channels, and (ii) channelspecific rate constants as a function of T and p, which are expected to be useful for improved combustion models.

Automated summary

The article presents investigations on the products, branching fractions, and rate constants of the phenoxylation reaction through experimental and theoretical studies to enhance the accuracy and reliability of combustion models.