Abstract
| Original language | English |
|---|---|
| Article number | 024111 |
| Journal | Journal of Chemical Physics |
| Volume | 146 |
| Number of pages | 10 |
| ISSN | 0021-9606 |
| DOIs | |
| Publication status | Published - 2017 |
| Externally published | Yes |
Cite this
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Long-range interactions from the many-pair expansion: A different avenue to dispersion in DFT. / de Silva, Piotr; Zhu, Tianyu ; Voorhis, Troy Van.
In: Journal of Chemical Physics, Vol. 146, 024111, 2017.Research output: Contribution to journal › Journal article › Research › peer-review
TY - JOUR
T1 - Long-range interactions from the many-pair expansion: A different avenue to dispersion in DFT
AU - de Silva, Piotr
AU - Zhu, Tianyu
AU - Voorhis, Troy Van
PY - 2017
Y1 - 2017
N2 - 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
AB - 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
U2 - 10.1063/1.4973728
DO - 10.1063/1.4973728
M3 - Journal article
VL - 146
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
M1 - 024111
ER -