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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Veröffentlicht in: | The Journal of chemical physics 2020-12, Vol.153 (21), p.214112-214112, Article 214112 |
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Hauptverfasser: | , , , , , , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | 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. |
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ISSN: | 0021-9606 1089-7690 |
DOI: | 10.1063/5.0029084 |