The effects of collision energy and reagent vibrational excitation on the reactivity of the reaction H+LiH: A quasiclassical trajectory study

摘要

Quasi-classical trajectory (QCT) calculations are carried out for the reaction H + LiH (ν= 0-3, j= 0) using a recent analytical potential energy surface (PES) of Prudente et al. [F.V. Prudente, J.M.C. Marques, A.M. Maniero, Time-dependent wave packet calculation of the LiH + H reactive scattering on a new potential energy surface, Chem. Phys. Lett. 474 (2009) 18-22]. The reaction H + LiH proceeds through the highly exothermic LiH depletion and thermoneutral hydrogen-exchange channels. State-selected and energy-resolved reaction probability and integral reaction cross sections are reported and compared with the recent available literature data. The QCT-calculated probabilities are in good agreement with the previous quantum-mechanical (QM) results, meanwhile, the vibrational excitation of the reagent LiH molecule decreases the reactivity of the LiH depletion channel and increases the reactivity of the hydrogen-exchange channel. Moreover, this decrease and increase can be explained by examining the representative reactive trajectories for the different vibrational excitation of the reagent and the topology of the HHLi PES. Our calculated results indicate that the collision energy and the vibrational excitation of the reagent play an important role on the reactivity of this system.