Mode- and Bond-Selected Reaction of H with Local Mode Molecule HDS

Abstract

Understanding mode- and bond-selected dynamics of elementary chemical reactions is of central importance in molecular reaction dynamics. The initial state-selected time-dependent wave packet method is employed to study the mode and bond selectivity, isotopic branching ratio, and temperature dependence of rate constants of the two-channel reaction of H with local mode molecule HDS. For the abstraction channel, fundamental excitation of the HS (DS) bond of the reactant HDS significantly enhances the H-abstraction (D-abstraction) reaction, whose efficacy is higher than the same amount of translational energy except at low energies just above the energy threshold. This is in sharp contrast to the prediction of Polanyi rules: translational energy is more efficient than vibrational energy in enhancing a reaction with an early barrier. The recent sudden vector projection model is then applied to rationalize the observed mode specificity, which, however, shows that the translational mode vector has a larger coupling with the reaction coordinate than the stretching vector of the active bond, implying a reversed relative efficacy on promoting the reaction as well. In contrast, the mode and bond specificity for the exchange channel is not as strong as for the abstraction channel due to the regulation of the shallow well along the reaction path.