Preparing small Gaussian basis for highly accurate ab initio description of lithium Rydberg states.

Authors

Jan Šmydke, Benjamín Andreides, Simona Dubcová

Published in

Physical chemistry chemical physics : PCCP. Nov 11, 2026. Epub Nov 11, 2026.

Abstract

A new small and highly accurate Gaussian basis set has been developed for the ab initio description of ²Li Rydberg excited states up to n = 7 and S, P, D, F, and G angular momentum symmetry, and the appropriate optimization protocol is presented. The obtained Rydberg excitation energies are compared with results from other highly accurate approaches. At the EOM-CCSD level of theory the new basis exhibits higher than 10^-2 eV accuracy of the excitation energies and the ionization potential and provides superior results compared with an analogous universal Gaussian basis set, while utilizing a smaller number of basis functions. Plots of the 1-dimensional Rydberg-orbital cuts reveal a regular nodal structure along the logarithmic scale of the atomic radius reaching tens of Å far from the nucleus. The presented Rydberg basis set generation methodology is an important step towards routine ab initio Rydberg-state related investigations of more complex systems, such as large atoms and polyatomic molecules.

PMID:
43012854
Bibliographic data and abstract were imported from PubMed on 11 Nov 2026.

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