posted on 2023-11-30, 22:29authored byJoel Creutzberg, Wojciech Skomorowski, Thomas-C. Jagau
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.