Impact of the Long-Range Interaction on the Efficiency of the Li + ClH → LiCl + H Reaction.

Quantum and quasiclassical calculations have been performed to compute the low energy efficiency of the Li + ClH → LiCl + H reaction on some potential energy surfaces fitted to ab initio electronic energies using different functional forms. The outcomes of the calculations show marked differences at threshold and in the shape of the excitation function in seeming contrast with the height of the saddle to reaction and the width of the cone of acceptance. The differences in the computed reactive probability and cross section are rationalized in terms of the attractive/repulsive nature of the long-range interaction and the inability of trajectory techniques to deal with threshold effects. The vestiges of these features in the value of the thermal rate coefficients are also commented on.