Charge-Transfer-Induced Predissociation in Rydberg States of Molecular Cations: MgAr

Very little is known about the Rydberg states of molecular cations, i.e., Rydberg states having a doubly charged ion core. With the example of MgAr⁺, we present general features of the structure and dynamics of the Rydberg states of molecular cations, which we find are subject to the process of charge-transfer-induced predissociation. Our study focuses on the spectrum of low-n Rydberg states with potential-energy functions associated with the Mg⁺(3d and 4s) + Ar(¹S₀) dissociation asymptotes. In particular, we have recorded spectra of the 3dπ_Ω' (Ω' = ¹/₂, ³/₂) Rydberg states, extending from the lowest (v' = 0) vibrational levels to their dissociation limits. This spectral range encompasses the region where the onset of predissociation by interaction with the mostly repulsive ²Σ and ²Π charge-transfer states associated with the Mg(3s²) + Ar⁺(²P_1/2,3/2) dissociation asymptotes is observed. This interaction leads to very strong perturbations of the 3dπ Rydberg states of MgAr⁺, revealed by vibrational progressions exhibiting large and rapid variations of the vibrational intervals, line widths, and spin-orbit splittings. We attribute the anomalous sign and magnitude of the spin-orbit coupling constant of the 3dπ state to the interaction with a ²Π Rydberg state correlating to the Mg⁺(4p) + Ar(¹S₀) dissociation limit. To analyze our spectra and elucidate the underlying process of charge-transfer-induced predissociation, we implemented a model that allowed us to derive the potential-energy functions of the charge-transfer states and to quantitatively reproduce the experimental results. This analysis characterizes the main features of the dynamics of the Rydberg series converging to the ground state of MgAr²⁺. We expect that the results and analysis reported here are qualitatively valid for a broader range of singly charged molecular cations, which are inherently prone to charge-transfer interactions.