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Electron localisation descriptors in ONETEP: a tool for interpreting localisation and bonding in large-scale DFT calculations

Electron localisation descriptors in ONETEP: a tool for interpreting localisation and bonding in large-scale DFT calculations
Electron localisation descriptors in ONETEP: a tool for interpreting localisation and bonding in large-scale DFT calculations
Electron localisation descriptors, such as the electron localisation function (ELF) and localisedorbital locator (LOL) provide a visual tool for interpreting the results of electronic structurecalculations. The descriptors produce a quantumvalence shell electron pair repulsion (VSEPR)representation, indicating the localisation of electron pairs into bonding pairs and lone pairs insingle molecules, coordination compounds andcrystalline solids. We have implemented the ELFand LOL within ONETEP, a DFT code designed to perform calculations on systems containingthousands of atoms with plane-wave accuracy. This is possible using a linear-scaling formulation ofDFT in which the Kohn–Sham orbitals are expressed in terms of a set of strictly localisednon-orthogonal generalised Wannier functions (NGWFs), themselves expanded in a psinc basisset. In this paper, we describe our implementation and explore the chemical insights offered byelectron localisation descriptors in ONETEP in a range of bonding and nonbondedsituations.
ONETEP, localised orbital locator, electron localisation function, density functional theory, linear scaling
2516-1075
Clements, Rebecca J.
c92a2d47-ede3-4ce9-bd61-81b8c9681aa6
Womack, James C
ef9e1954-4a38-4e89-bf25-741a0738e85b
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Clements, Rebecca J.
c92a2d47-ede3-4ce9-bd61-81b8c9681aa6
Womack, James C
ef9e1954-4a38-4e89-bf25-741a0738e85b
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61

Clements, Rebecca J., Womack, James C and Skylaris, Chris-Kriton (2020) Electron localisation descriptors in ONETEP: a tool for interpreting localisation and bonding in large-scale DFT calculations. Electronic Structure, 2 (027001). (doi:10.1088/2516-1075/ab8d19).

Record type: Article

Abstract

Electron localisation descriptors, such as the electron localisation function (ELF) and localisedorbital locator (LOL) provide a visual tool for interpreting the results of electronic structurecalculations. The descriptors produce a quantumvalence shell electron pair repulsion (VSEPR)representation, indicating the localisation of electron pairs into bonding pairs and lone pairs insingle molecules, coordination compounds andcrystalline solids. We have implemented the ELFand LOL within ONETEP, a DFT code designed to perform calculations on systems containingthousands of atoms with plane-wave accuracy. This is possible using a linear-scaling formulation ofDFT in which the Kohn–Sham orbitals are expressed in terms of a set of strictly localisednon-orthogonal generalised Wannier functions (NGWFs), themselves expanded in a psinc basisset. In this paper, we describe our implementation and explore the chemical insights offered byelectron localisation descriptors in ONETEP in a range of bonding and nonbondedsituations.

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Accepted/In Press date: 24 April 2020
Published date: 24 June 2020
Keywords: ONETEP, localised orbital locator, electron localisation function, density functional theory, linear scaling

Identifiers

Local EPrints ID: 443467
URI: http://eprints.soton.ac.uk/id/eprint/443467
ISSN: 2516-1075
PURE UUID: ded21919-3943-47ba-a7e3-f49e625576f9
ORCID for James C Womack: ORCID iD orcid.org/0000-0001-5497-4482
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

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Date deposited: 26 Aug 2020 16:35
Last modified: 17 Mar 2024 03:07

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Contributors

Author: Rebecca J. Clements
Author: James C Womack ORCID iD

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