Computing decay widths of autoionizing Rydberg states with complex-variable coupled cluster theory

2023/10/30 by Joel Creutzberg, Creutzberg, Joel, Wojciech Skomorowski +3 · 1 citation
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Molecular spectroscopy and chirality #Spectroscopy and Quantum Chemical Studies

paper · pdf · doi:10.48550/arxiv.2310.19377

openalex publication_date 2023/10/30 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01

Abstract

We compute autoionization widths of various Rydberg states of neon and dinitrogen 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 computed widths of the 3s, 3p, 4p and 3d Rydberg states. We then proceed to compute the widths of the 3sσ_g, 3dσ_g, and 3dπ_g Rydberg states of dinitrogen, 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.

Cited by

• Complex-Energy Second-Order Approximate Coupled-Cluster Methods for Electronic Resonances

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