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

Timothy J Daas; Juri Grossi; Stefan Vuckovic; Ziad H Musslimani; Derk P Kooi; Michael Seidl; Klaas J H Giesbertz; Paola Gori-Giorgi

doi:10.1063/5.0029084

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

J Chem Phys. 2020 Dec 7;153(21):214112. doi: 10.1063/5.0029084.

Authors

Timothy J Daas¹, Juri Grossi¹, Stefan Vuckovic², Ziad H Musslimani¹, Derk P Kooi¹, Michael Seidl¹, Klaas J H Giesbertz¹, Paola Gori-Giorgi¹

Affiliations

¹ Department 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.
² Department of Chemistry, University of California, Irvine, California 92697, USA.

PMID: 33291899
DOI: 10.1063/5.0029084

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.