Communication: direct comparison between theory and experiment for correlated angular and product-state distributions of the ground-state and stretching-excited O((3)P) + CH4 reactions.

Abstract

Motivated by a recent experiment [H. Pan and K. Liu, J. Chem. Phys. 140, 191101 (2014)], we report a quasiclassical trajectory study of the O((3)P) + CH4(vk = 0, 1) → OH + CH3 [k = 1 and 3] reactions on an ab initio potential energy surface. The computed angular distributions and cross sections correlated to the OH(v = 0, 1) + CH3(v = 0) coincident product states can be directly compared to experiment for O + CH4(v3 = 0, 1). Both theory and experiment show that the ground-state reaction is backward scattered, whereas the angular distributions shift toward sideways and forward directions upon antisymmetric stretching (v3) excitation of the reactant. Theory predicts similar behavior for the O + CH4(v1 = 1) reaction. The simulations show that stretching excitation enhances the reaction up to about 15 kcal/mol collision energy, whereas the O + CH4(vk = 1) reactions produce smaller cross sections for OH(v = 1) + CH3(v = 0) than those of O + CH4(v = 0) → OH(v = 0) + CH3(v = 0). The former finding agrees with experiment and the latter awaits for confirmation. The computed cold OH rotational distributions of O + CH4(v = 0) are in good agreement with experiment.