Large coupling-strength expansion of the Møller–Plesset adiabatic connection: From paradigmatic cases to variational expressions for the leading terms

We study in detail the first three leading terms of the large coupling-strength limit of the adiabatic connection that has as weak-interaction expansion the Møller–Plesset perturbation theory. We first focus on the H atom, both in the spin-polarized and the spin-unpolarized cases, reporting numerica...

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Bibliographic Details
Published in:The Journal of chemical physics 2020-12, Vol.153 (21), p.214112-214112
Main Authors: Daas, Kimberly J., Grossi, Juri, Vuckovic, Stefan, Musslimani, Ziad H., Kooi, Derk P., Seidl, Michael, Giesbertz, Klaas J. H., Gori-Giorgi, Paola
Format: Article
Language:English
Subjects:
Adiabatic flow
Asymptotic properties
Coupling
Electron gas
Electron spin
Exact solutions
Perturbation theory
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Summary:We study in detail the first three leading terms of the large coupling-strength limit of the adiabatic connection that has as weak-interaction expansion the Møller–Plesset perturbation theory. We first focus on the H atom, both in the spin-polarized and the spin-unpolarized cases, reporting numerical and analytical results. In particular, we derive an asymptotic equation that turns out to have simple analytical solutions for certain channels. The asymptotic H atom solution for the spin-unpolarized case is then shown to be variationally optimal for the many-electron spin-restricted closed-shell case, providing expressions for the large coupling-strength density functionals up to the third leading order. We also analyze the H2 molecule and the uniform electron gas.
ISSN:0021-9606
1089-7690
DOI:10.1063/5.0029084