On non-hydrogen-atom products of thermal decomposition of benzyl radical: A theoretical investigation by the transition state theory/multi-well master equation approach

Benzyl radical (C₇H₇), one of the resonantly stabilized hydrocarbon radicals, is one of the significant precursors of polycyclic aromatic hydrocarbons in interstellar media and combustion engines. The unimolecular decomposition of benzyl radical is still incompletely understood despite of its importance and relatively small molecular size. The decomposition reactions of benzyl radical were investigated in the present study by using the ab initio transition state theory (TST) and the multi-well master equation theory. Specifically, all reaction pathways on the potential energy surface of C₇H₇ was calculated at the level of QCISD(T)/CBS. For the reactions with multireference characters, the CASPT2(9e,7o)/aug-cc-pVTZ method was used to calculate the vibrational frequencies and energies of structures along the one-dimensional reaction coordinate of the breaking bond. The high-pressure limits of rate constants for all the reactions were obtained by using the TST except those for C₇H₆ + H and C₆H₄ + CH₃ by the variational TST. The pressure-dependent rate constants were obtained by using the multi-well master equation simulations. The calculated rate constants agree well with available experimental and theoretical data in the literature. Moreover, the present results identify the composition of the non-hydrogen-atom production observed in previous experiments, which provide new insights into the reactions of aromatic compounds. © 2024 Wiley Periodicals LLC.