Non-adiabatic dynamics studies of the H(2S) + LiH(X1Σ+) reaction by time-dependent wave packet method

Abstract

Non-adiabatic dynamics studies of the H + LiH (v₀ = 0, j₀ = 0) reaction are carried out based on the diabatic potential energy surfaces (PESs) reported by He and co-workers (Sci. Rep., 2016, 6, 25083) in the collision energy range from 0.001 to 1.0 eV. The H(²S) + LiH(X¹Σ⁺) → Li(2²S)/Li(2²P) + H₂(X¹Σ_g⁺) depletion reactions and the H′(²S) + LiH(X¹Σ⁺) → H(²S) + LiH′(X¹Σ⁺) exchange reaction are studied at the state-to-state level of theory. The dynamics properties, such as reaction probability, integral cross section, differential cross section, the ro-vibrational state distributions of the product and specific-state rate constant are calculated. In addition, the dynamics values of the H(²S) + LiH(X¹Σ⁺) → Li(2²S) + H₂(X¹Σ_g⁺) depletion reaction are compared with available theoretical results, which are based on the adiabatic PESs. Large discrepancies are found between the adiabatic and diabatic values, especially at low J values, which indicate that the non-adiabatic effect is very great and cannot be simply ignored. Furthermore, the deviations between adiabatic and diabatic values gradually decrease as the collision energy increases.