Reference Energies for Valence Ionizations and Satellite Transitions.

Abstract

Upon ionization of an atom or a molecule, another electron (or more) can be simultaneously excited. These concurrently generated states are called "satellites" (or shakeup transitions) as they appear in ionization spectra as higher-energy peaks with weaker intensity and larger width than the main peaks associated with single-particle ionizations. Satellites, which correspond to electronically excited states of the cationic species, are notoriously challenging to model using conventional single-reference methods due to their high excitation degree compared to the neutral reference state. This work reports 42 satellite transition energies and 58 valence ionization potentials (IPs) of full configuration interaction quality computed in small molecular systems. Following the protocol developed for the quest database [Véril, M.; Scemama, A.; Caffarel, M.; Lipparini, F.; Boggio-Pasqua, M.; Jacquemin, D.; and Loos, P.-F. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2021, 11, e1517], these reference energies are computed using the configuration interaction using a perturbative selection made iteratively (CIPSI) method. In addition, the accuracy of the well-known coupled-cluster (CC) hierarchy (CC2, CCSD, CC3, CCSDT, CC4, and CCSDTQ) is gauged against these new accurate references. The performances of various approximations based on many-body Green's functions (GW, GF2, and T-matrix) for IPs are also analyzed. Their limitations in correctly modeling satellite transitions are discussed.