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

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.