Trajectory Surface Hopping Study of the Li + Li2(X1Σg+) Dissociation Reaction

Abstract

Trajectory surface hopping calculations are reported for the Li + Li2(X1Σg+) dissociation reaction over the range of translational energies 13 ≤ Etr/kcal mol-1 ≤ 80. Both potential energy surfaces for ground doublet Li3, which have been modeled from the double many-body expansion method (DMBE III), have been employed in the dynamics calculations. For the initial internal state (v = 0, j = 10), the behavior of the dissociative cross sections as a function of translational energy shows that nonadiabatic effects are important over the whole range of energies studied. Concerning the role of initial vibration, it has been found that, for Etr = 25 kcal mol-1 and j = 10, the adiabatic dissociative cross sections are enhanced as v increases from 0 to 20, while the nonadiabatic ones just slightly increase with the vibrational quantum number.