Long-range interactions from the many-pair expansion: A different avenue to dispersion in DFT
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deSilva17JCP.pdf
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Author(s)
de Silva, Piotr
Zhu, Tianyu
Van Voorhis, Troy
Date Issued
January 2017
Journal
Journal of Chemical Physics
Publisher
American Institute of Physics (AIP)
Citation
De Silva, Piotr et al. “Long-Range Interactions from the Many-Pair Expansion: A Different Avenue to Dispersion in DFT.” The Journal of Chemical Physics 146, 2 (January 2017): 024111
Version
Final published version
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1063/1.4973728
