London dispersion forces without density distortion: a path to first principles inclusion in density functional theory
Abstract
We analyse a path to construct density functionals for the dispersion interaction energy from an expression in terms of the ground state densities and exchange-correlation holes of the isolated fragments. The expression is based on a constrained search formalism for a supramolecular wavefunction that is forced to leave the diagonal of the many-body density matrix of each fragment unchanged, and is exact for the interaction between one-electron densities. We discuss several aspects: the needed features a density functional approximation for the exchange-correlation holes of the monomers should have, the optimal choice of the one-electron basis needed (named "dispersals"), and the functional derivative with respect to monomer density variations.
Keywords
Cite
@article{arxiv.2005.05900,
title = {London dispersion forces without density distortion: a path to first principles inclusion in density functional theory},
author = {Derk P. Kooi and Paola Gori-Giorgi},
journal= {arXiv preprint arXiv:2005.05900},
year = {2021}
}
Comments
12 pages, 4 figures