Quantum dynamics of H + LiH reaction and its isotopic variants

Abstract

Time-dependent quantum wave packet dynamics study is carried out to investigate the initial state selected channel specific reactivity of H + LiH collisional system on a new and more accurate ab initio potential energy surface developed by Wernli et al. [J. Phys. Chem. A113, 1121 (2009)]. The H + LiH reaction proceeds through LiH depletion and H-exchange paths. While the former path is highly exoergic (by ∼2.258 eV), the latter path is thermoneutral. State selected and energy resolved integral reaction cross sections and thermal rate constants are reported and compared with the literature data. The reactivity of the LiH depletion channel is found to be greater than the H-exchange channel. Rotational excitation of the reagent LiH molecule causes a decrease of reactivity of both the channels. On the other hand, the vibrational excitation of the reagent LiH decreases the reactivity of the LiH depletion channel and increases the reactivity of the H-exchange channel. The effect of isotopic substitution (H by D) on the reaction dynamics is also examined.