Energy shifts in predissociating levels of diatomic molecules: The case of N$_2$ (C$''^5\Pi _u$) and N$_2$(1$^7\Sigma ^+_u$) interacting states

Abstract

This work presents a perturbative calculation methodology for evaluating the energy shifts and broadening of vibrational energy levels, caused by interactions between bound and unbound dissociative electronic states. The method is validated against previously semiclassical analyzed cases, demonstrating remarkable consistency. We successfully applied this approach to the N$_2$ molecule, which exhibits a strong spin-orbit interaction between the bound C$''^5\Pi_u$ and the repulsive 1$^7\Sigma^+_u$ electronic states, around 36 cm$^{-1}$. This interaction constitutes an major pathway for N($^{2}$D) production, important in both excitation and quenching in plasma afterglows. As a result, the maximum absolute shift of 0.15 cm$^{-1}$ was found for the C$''^5\Pi_u$ ($v$ = 7) and maximum broadening of 0.45 cm$^{-1}$ was calculated for $v$ = 8, demonstrating significant perturbation of the C$''^5\Pi_u$ by the 1$^7\Sigma^+_u$ state. The results obtained were compared with direct calculations of the predissociation rates of the C$''^5\Pi_u$ bound state, showing very good agreement.