Long-range interactions from the many-pair expansion: A different avenue to dispersion in DFT

Piotr de Silva, Tianyu Zhu, Troy Van Voorhis

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

One of the several problems that plague majority of density functional theory calculations is their inability to properly account for long-range correlations giving rise to dispersion forces. The recently proposed many-pair expansion (MPE) [T. Zhu et al., Phys. Rev. B 93, 201108(R) (2016)] is a hierarchy of approximations that systematically corrects any deficiencies of an approximate functional to finally converge to the exact energy. This is achieved by decomposing the total density into a sum of two-electron densities and accounting for successive two-, four-, six-,… electron interactions. Here, we show that already low orders of MPE expansion recover the dispersion energy accurately. To this end, we employ the Pariser-Parr-Pople Hamiltonian and study the behavior of long-range interactions in trans-polyacetylene as well as stacks of ethylene and benzene molecules. We also show how convergence of the expansion is affected by electron conjugation and the choice of the density partitioning
Original languageEnglish
Article number024111
JournalJournal of Chemical Physics
Volume146
Number of pages10
ISSN0021-9606
DOIs
Publication statusPublished - 2017
Externally publishedYes

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