Volume 224, 2020

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 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.

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

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
12 Тра 2020
Accepted
09 Чер 2020
First published
09 Чер 2020

Faraday Discuss., 2020,224, 145-165

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

D. P. Kooi and P. Gori-Giorgi, Faraday Discuss., 2020, 224, 145 DOI: 10.1039/D0FD00056F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements