2025/10/30 by Levi, Gianluca, Kroesbergen, Max, Thirion, Louis +5
#Chemical Physics (physics.chem-ph) #FOS: Physical sciences
paper · doi:10.48550/arxiv.2510.26751
Rydberg excited states of molecules pose a challenge for electronic structure calculations because of their highly diffuse electron distribution. Even large and elaborate atomic basis sets tend to underrepresent the long-range tail, overly confining the Rydberg state. An approach is presented where the molecular orbitals are variationally optimized for the excited state using a plane wave basis set in Hartree-Fock calculations, followed by configuration interaction calculations on the resulting reference. Using excited state optimized plane wave orbitals greatly enhances the convergence of the many-body calculation, as illustrated by a full configuration interaction calculation of the 2s Rydberg state of H2. A neural-network-based selective configuration interaction approach is then applied to calculations of the 3s, 3px and 3py states of H2O and the 3s and 3pz states of NH3. The obtained values of excitation energy are in close agreement with experimental measurements as well as previous many-body calculations based on sufficiently diffuse atomic basis sets. Previously reported high-level calculations limited to atomic basis sets lacking extra diffuse functions, such as aug-cc-pVTZ, give significantly higher estimates due to confinement of the Rydberg states.