Quantum interference in the mechanism of H + LiH+ → H2 + Li+ reaction dynamics

Abstract

In this work, the detailed reaction mechanism of the astrochemically relevant exoergic and barrierless H + LiH⁺ → H₂ + Li⁺ reaction is investigated by both time-dependent wave packet and quasi-classical trajectory (QCT) methods on the ab initio electronic ground state potential energy surface reported by Martinazzo et al. [Martinazzo et al., J. Chem. Phys., 2003, 119, 11241]. The interference terms due to the coherence between the partial waves are quantified. When plotted along the scattering angle they reveal interference of constructive or destructive nature. Significant interference was found in the differential cross-section (DCS) which is a symbolic of the non-statistical nature of the reaction. This is further complemented by calculating the lifetime of the collision complex by the QCT method. It is found that the reaction follows a direct stripping mechanism at higher collision energies and yields forward scattered products from collisions involving high total angular momentum. At low collision energies, the reaction follows a mixed direct/indirect mechanism but with a dominant indirect contribution. The product state-resolved DCSs reveal that two opposite mechanisms co-exist, both at low and high collision energies. The microscopic scattering mechanism of the reaction is found to be unaffected by the ro-vibrational excitation of the reagent diatom.