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Issue 15, 2020

Generalized single excitation configuration interaction: an investigation into the impact of the inclusion of non-orthogonality on the calculation of core-excited states

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Abstract

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 species with singlet and doublet ground states, and this paper reports the extension to molecules in their triplet ground state. In addition to NOCIS, we present a novel method, one-center NOCIS (1C-NOCIS), for open-shell molecules which is intermediate between NOCIS and the computationally less demanding static exchange approximation (STEX). We explore this hierarchy of spin-pure methods for core excitations of molecules with singlet, doublet, and triplet ground states. We 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.

Graphical abstract: Generalized single excitation configuration interaction: an investigation into the impact of the inclusion of non-orthogonality on the calculation of core-excited states

Article information


Submitted
05 Dec 2019
Accepted
29 Mar 2020
First published
31 Mar 2020

Phys. Chem. Chem. Phys., 2020,22, 8182-8192
Article type
Paper
Author version available

Generalized single excitation configuration interaction: an investigation into the impact of the inclusion of non-orthogonality on the calculation of core-excited states

K. J. Oosterbaan, A. F. White, D. Hait and M. Head-Gordon, Phys. Chem. Chem. Phys., 2020, 22, 8182 DOI: 10.1039/C9CP06592J

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