Fractional charge and spin errors in self-consistent Green’s function theory

Kananenka, Alexei A.; Zgid, Dominika

doi:10.1063/1.4921259

Title: Fractional charge and spin errors in self-consistent Green’s function theory

Journal Article · Thu May 21 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4921259· OSTI ID:22415790

Kananenka, Alexei A.; Zgid, Dominika ^[1]

Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109 (United States)

We examine fractional charge and spin errors in self-consistent Green’s function theory within a second-order approximation (GF2). For GF2, it is known that the summation of diagrams resulting from the self-consistent solution of the Dyson equation removes the divergences pathological to second-order Møller-Plesset (MP2) theory for strong correlations. In the language often used in density functional theory contexts, this means GF2 has a greatly reduced fractional spin error relative to MP2. The natural question then is what effect, if any, does the Dyson summation have on the fractional charge error in GF2? To this end, we generalize our previous implementation of GF2 to open-shell systems and analyze its fractional spin and charge errors. We find that like MP2, GF2 possesses only a very small fractional charge error, and consequently minimal many electron self-interaction error. This shows that GF2 improves on the critical failings of MP2, but without altering the positive features that make it desirable. Furthermore, we find that GF2 has both less fractional charge and fractional spin errors than typical hybrid density functionals as well as random phase approximation with exchange.

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OSTI ID:: 22415790

Journal Information:: Journal of Chemical Physics, Vol. 142, Issue 19; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606

Country of Publication:: United States

Language:: English

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Title: Fractional charge and spin errors in self-consistent Green’s function theory

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