He+ +N2 Charge Transfer Reaction: An Ab initio Analysis

Abstract

An ab initio analysis on the involved potential energy surfaces is presented for the investigation of the charge transfer mechanism for the He⁺ +N₂ system. At high collision energy, as many as seven low-lying electronic states are observed to be involved in the charge transfer mechanism. Potential energy surfaces for these low-lying electronic states have been computed in the Jacobi scattering coordinates, applying multireference configuration interaction level of theory and aug-cc-pVQZ basis sets. Asymptotes for the ground and various excited states are assigned to mark the entrance (He⁺ +N₂ ) and charge transfer channels (He+N₂ ⁺ ). Nonadiabatic coupling matrix elements and quasi-diabatic potential energy surfaces have been computed for all seven states to rationalize the available experimental data on the charge transfer processes and to facilitate dynamics studies.

Keywords: ab initio analysis; charge transfer reactions; nonadiabatic coupling matrix elements; potential energy surfaces; quasidibatization procedure.