London dispersion forces without density distortion: a path to first principles inclusion in density functional theory

Faraday Discuss. 2020 Dec 4;224(0):145-165. doi: 10.1039/d0fd00056f.

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 necessary features of a density functional approximation for the exchange-correlation holes of the monomers, the optimal choice of the one-electron basis (named "dispersals"), and the functional derivative with respect to monomer density variations.

Publication types

  • Research Support, Non-U.S. Gov't