Computing Decay Widths of Autoionizing Rydberg States with Complex-Variable Coupled-Cluster Theory.

Abstract

We compute autoionization widths of various Rydberg states of neon and N2 by equation-of-motion coupled-cluster theory combined with complex scaling and complex basis functions. This represents the first time that complex-variable methods are applied to Rydberg states represented in Gaussian basis sets. A new computational protocol based on Kaufmann basis functions is designed to make these methods applicable to atomic and molecular Rydberg states. As a first step, we apply our protocol to the neon atom and compute widths of the 3s, 3p, 4p and 3d Rydberg states. We then proceed to compute the widths of the 3sσg, 3dσg, and 3dπg Rydberg states of N2, which belong to the Hopfield series. Our results demonstrate a decrease in the decay width for increasing angular momentum and principal quantum number within both Rydberg series.