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arXiv · 2105.07506

Variations of the Hartree-Fock fractional-spin error for one electron

Hugh G. A. Burton·Clotilde Marut·Timothy J. Daas·Paola Gori-Giorgi·Pierre-François Loos
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Abstract

Fractional-spin errors are inherent in all current approximate density functionals, including Hartree-Fock theory, and their origin has been related to strong static correlation effects. The conventional way to encode fractional-spin calculations is to construct an ensemble density that scales between the high-spin and low-spin densities. In this article, we explore the variation of the Hartree-Fock fractional-spin (or ghost-interaction) error in one-electron systems using restricted and unrestricted ensemble densities, and the exact generalized Hartree-Fock representation. By considering the hydrogen atom and H$_2^+$ cation, we analyze how the unrestricted and generalized Hartree-Fock schemes minimize this error by localizing the electrons or rotating the spin coordinates. We also reveal a clear similarity between the Coulomb hole of He-like ions and the density depletion near the nucleus induced by the fractional-spin error in the unpolarized hydrogen atom. Finally, we analyze the effect of the fractional-spin error on the Møller-Plesset adiabatic connection, excited states, and functional- and density-driven errors.

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Hugh G. A. Burton, Clotilde Marut, Timothy J. Daas, Paola Gori-Giorgi, Pierre-François Loos. 2021-06-30. Variations of the Hartree-Fock fractional-spin error for one electron. https://doi.org/10.1063/5.0056968

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