Theoretical and Computational Chemistry

Generalized Single Excitation Configuration Interaction: An Investigation into the Impact of the Inclusion of Non-Orthogonality on the Calculation of Core-Excited States



In this paper, we investigate different non-orthogonal generalizations of the configuration interaction with single substitutions (CIS) method for the calculation of core-excited states. Fully non-orthogonal CIS (NOCIS) has been described previously for singlets and doublets and this paper reports the extension to triplet molecules. In addition to NOCIS, we present a novel method, 1C-NOCIS(1C-NOCIS), for open-shell molecules which is intermediate between NOCIS and the static exchange approximation (STEX). We explore this hierarchy of spin-pure methods for singlet, doublet, and triplet molecules and conclude that, while NOCIS provides the best results and preserves the spatial symmetry of the wavefunction, 1C-NOCIS retains much of the accuracy of NOCIS at a dramatically reduced cost. For molecules with closed-shell ground states, STEX and 1C-NOCIS are identical.


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