State-to-state Rate Constants for the H + LiH(v 0 = 0, j 0 = 0) Reaction: An Accurate Nonadiabatic Dynamical Study

Abstract

Abstract The state-to-state rate constants for hydrogen abstraction, nonadiabatic hydrogen abstraction, and exchange channels of the H + LiH reaction have been studied in the temperature range from 10 to 5000 K by using the nonadiabatic time-dependent wave packet method. The total and vibrational state-resolved rate constants of the H + LiH (v 0 = 0, j 0 = 0) → Li(22S) + H2 reaction are calculated and compared with previous adiabatic values. The results indicated that adiabatic values always overestimate the rate constant due to the nonadiabatic effect not being considered. In addition, the ratio of adiabatic vibrational state-resolved rate constants versus that of nonadiabatic ones is calculated for the hydrogen abstraction channel. This reflects that the nonadiabatic effect is mainly focused on the low-lying vibrational states. Moreover, the rovibrational state-resolved rate constants show that the largest population of product is located at (v′ = 2, j′ = 11), (v′ = 0, j′ = 5), and (v′ = 0, j′ = 6) for the hydrogen abstraction, nonadiabatic hydrogen abstraction and exchange channels, respectively. The total and vibrational state-resolved rate constants of the Li(22P) → Li(22S) quenching process are also calculated in the temperature range up to 5000 K. The results show that when the temperature is lower than 200 K, the quenching efficiency increases rapidly, but with the further increase of temperature, the quenching efficiency hardly changes.