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Low-Cost Molecular Excited States from a State-Averaged Resonating Hartree-Fock Approach

preprint
submitted on 20.03.2019 and posted on 21.03.2019 by Jacob Nite, Carlos A. Jimenez-Hoyos
Quantum chemistry methods that describe excited states on the same footing as the ground state are generally scarce. In previous work, Gill et al. (J. Phys. Chem. A 112, 13164 (2008)) and later Sundstrom and Head-Gordon (J. Chem. Phys. 140, 114103 (2014)) considered excited states resulting from a non-orthogonal configuration interaction (NOCI) on stationary solutions of the Hartree–Fock equations. We build upon those contributions and present the state-averaged resonating Hartree–Fock (sa-ResHF) method, which differs from NOCI in that spin-projection and orbital relaxation effects are incorporated from the onset. Our results in a set of small molecules (alanine, formaldehyde, acetaldehyde, acetone, formamide, and ethylene) suggest that sa-ResHF excitation energies are a notable improvement over configuration interaction singles (CIS), at a mean-field computational cost. The orbital relaxation in sa-ResHF, in the presence of a spin-projection operator, generally results in excitation energies that are closer to the experimental values than the corresponding NOCI ones.

History

Email Address of Submitting Author

cjimenezhoyo@wesleyan.edu

Institution

Wesleyan University

Country

United States of America

ORCID For Submitting Author

0000-0001-7425-6795

Declaration of Conflict of Interest

The authors declare that they have no conflict of interest.

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in Journal of Chemical Theory and Computation

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