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Large coupling-strength expansion of the Møller-Plesset adiabatic connection: From paradigmatic cases to variational
Timothy J Daas1, Juri Grossi1, Stefan Vuckovic2
1Department of Chemistry and Pharmaceutical Sciences, Amsterdam Institute of Molecular and Life Sciences (AIMMS), Faculty of Science, Vrije Universiteit, De Boelelaan 1083, 1081HV Amsterdam, The Netherlands.
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 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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