Gradient Expansions for the Large-Coupling Strength Limit of the Møller-Plesset Adiabatic Connection

Timothy J. Daas, Derk P. Kooi, Arthur J.A.F. Grooteman, Michael Seidl, Paola Gori-Giorgi*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

The adiabatic connection that has, as weak-interaction expansion, the Møller-Plesset perturbation series has been recently shown to have a large coupling-strength expansion, in terms of functionals of the Hartree-Fock density with a clear physical meaning. In this work, we accurately evaluate these density functionals and we extract second-order gradient coefficients from the data for neutral atoms, following ideas similar to the ones used in the literature for exchange, with some modifications. These new gradient expansions will be the key ingredient for performing interpolations that have already been shown to reduce dramatically MP2 errors for large noncovalent complexes. As a byproduct, our investigation of neutral atoms with large number of electrons N indicates that the second-order gradient expansion for exchange grows as N log(N) rather than as N, as often reported in the literature.

Original languageEnglish
Pages (from-to)1584-1594
Number of pages11
JournalJournal of chemical theory and computation
Volume18
Issue number3
Early online date18 Feb 2022
DOIs
Publication statusPublished - 8 Mar 2022

Bibliographical note

Funding Information:
We thank Kieron Burke and Nathan Argaman for confirming our numerical findings of and , for sharing a preliminary version of their independent work on the logarithmic contribution of the second-order gradient term for exchange, and for insightful discussions. This work was funded by The Netherlands Organisation for Scientific Research, under Vici grant 724.017.001. A.G. is grateful to the Vrije Universiteit for the opportunity to contribute to this paper using the University Research Fellowship.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

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