Charge transfer in Sodium Iodide collisions

Sodium Iodide (NaI) has over the years served as a prototype system in the studies of non-adiabatic dynamics. Here, the charge transfer collision reactions Na+ + I- Na + I (mutual neutralization and ion-pair formation) are studied from an ab initio approach and the total and differential cross sections are calculated for the reactions. This involves electronic structure calculations on NaI to obtain adiabatic potential energy curves, non-adiabatic and spin-orbit couplings followed by nuclear dynamics, treated fully quantum mechanically in a strict diabatic representation. A single avoided crossing at 13.22 a_0 dominates the reactions and the total cross sections are well captured by the semi-classical Landau-Zener model. Compared to measured ion-pair formation cross section, the calculated cross section is about a factor two smaller and the overall shape of the calculated differential cross section is in reasonable agreement with measured ion-pair formation differential cross section. Treating the Landau-Zener coupling as an empirical parameter of 0.05 eV, the measured total and differential cross sections are well captured when doing a full quantum mechanical cross section calculations including rotational coupling. A semi-empirical spin-orbit coupling model is also investigated, giving satisfactory estimation of the effects of spin-orbit interaction for the reactions.