Influence of early-staged energy barrier on stereodynamics of reaction of LiH(ν=0, j=0)+H→Li + H₂

Abstract

Theoretical studies of stereodynamics for reaction LiH(ν=0, j=0)+H→Li+H₂ have been carried out with quasiclassical trajectory method on two potential energy surfaces(PESs) structured as W-PES and P-PES. The main difference of the two PESs is at fixed angle of Li-H-H from 110° to 180°. In this angle range, there is an early-staged energy barrier on the P-PES, but there is no barrier on the W-PES. Some studies have been done to explore the influence of the early-staged energy barrier on this exothermic reaction. Integral cross sections, differential cross sections and product rotational angular momentum of the reaction have been calculated. When E _c<0.48 eV, the dominant influence of barrier is to restrain reacting. However, when E _c>0.48 eV, the dominant influence of barrier is to promote reacting. The angular distribution of the product H₂ is extremely forward on both the PESs, because the lifetime of most complexes is short. Totally, the lifetime on the P-PES is longer than that on W-PES for the existence of the barrier. With the collision energy increasing, on the both PESs, the distribution of the direction of the product H₂ angular momentum changed, and there is a trend that peak at (90°,270°) gets weaker and peak at (90°,90°) gets stronger. The energy barrier weakens the degree of the rotation alignment of the H₂.

Keywords

Stereodynamics / Quasiclassical trajectory method / Product rotational polarization

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