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

Derk Pieter Kooi; Paola Gori-Giorgi

doi:10.1039/d0fd00056f

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

Derk Pieter Kooi^*
, Paola Gori-Giorgi

^*Corresponding author for this work

AIMMS

Research output: Contribution to Journal › Article › Academic › peer-review

106 Downloads (Pure)

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.

Original language	English
Pages (from-to)	145-165
Number of pages	21
Journal	Faraday Discussions
Volume	224
Early online date	9 Jun 2020
DOIs	https://doi.org/10.1039/d0fd00056f
Publication status	Published - 1 Dec 2020

Funding

This work was funded by the Netherlands Organisation for Scientic Research under Vici grant 724.017.001.

Funders	Funder number
Netherlands Organisation for Scientic Research	724.017.001
Horizon 2020 Framework Programme	648932

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Access to Document

10.1039/d0fd00056f

London dispersion forces without density distortionFinal published version, 530 KBLicence: Article 25fa Dutch Copyright Act

Persistent URL (handle)

Persistent link

Cite this

@article{2796e7194b3b4c809390b94f20912364,

title = "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.",

author = "Kooi, \{Derk Pieter\} and Paola Gori-Giorgi",

year = "2020",

month = dec,

day = "1",

doi = "10.1039/d0fd00056f",

language = "English",

volume = "224",

pages = "145--165",

journal = "Faraday Discussions",

issn = "1359-6640",

publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - London dispersion forces without density distortion

T2 - A path to first principles inclusion in density functional theory

AU - Kooi, Derk Pieter

AU - Gori-Giorgi, Paola

PY - 2020/12/1

Y1 - 2020/12/1

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85097928322

UR - https://www.scopus.com/pages/publications/85097928322#tab=citedBy

U2 - 10.1039/d0fd00056f

DO - 10.1039/d0fd00056f

M3 - Article

C2 - 32969448

AN - SCOPUS:85097928322

SN - 1359-6640

VL - 224

SP - 145

EP - 165

JO - Faraday Discussions

JF - Faraday Discussions

ER -

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

Abstract

Funding

UN SDGs

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Cite this