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DOE OSTI · 22415790

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

Kananenka, Alexei A.·Zgid, Dominika
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Abstract

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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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICSCORRELATIONSDENSITY FUNCTIONAL METHODDIAGRAMSELECTRONSERRORSGREEN FUNCTIONIMPLEMENTATIONMATHEMATICAL SOLUTIONSRANDOM PHASE APPROXIMATIONSPIN

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Kananenka, Alexei A., Zgid, Dominika. 2015-05-21. Fractional charge and spin errors in self-consistent Green’s function theory. https://doi.org/10.1063/1.4921259

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