Vibrational mode-specific dynamics of the F(2P3/2) + C2H6 → HF + C2H5 reaction.

Abstract

We investigate the competing effect of vibrational and translational excitation and the validity of the Polanyi rules in the early- and negative-barrier F(2P3/2) + C2H6 → HF + C2H5 reaction by performing quasi-classical dynamics simulations on a recently developed full-dimensional multi-reference analytical potential energy surface. The effect of five normal-mode excitations of ethane on the reactivity, the mechanism, and the post-reaction energy flow is followed through a wide range of collision energies. Promoting effects of vibrational excitations and interaction time, related to the slightly submerged barrier, are found to be suppressed by the early-barrier-induced translational enhancement, in contrast to the slightly late-barrier Cl + C2H6 reaction. The excess vibrational energy mostly converts into ethyl internal excitation while collision energy is transformed into product separation. The substantial reaction energy excites the HF vibration, which tends to show mode-specificity and translational energy dependence as well. With increasing collision energy, direct stripping becomes dominant over the direct rebound and indirect mechanisms, being basically independent of reactant excitation.