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

Abstract

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 case, 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.

References in corpus (4)

• Fractional spins and static correlation error in density functional theory
• Double-hybrid density-functional theory made rigorous
• Ions in solution: Density Corrected Density Functional Theory (DC-DFT)
• The interaction-strength interpolation method for main-group chemistry: benchmarking, limitations, and perspectives

Cited by in corpus (4)

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