The University of Southampton
University of Southampton Institutional Repository

Linear-scaling calculation of Hartree-Fock exchange energy with non-orthogonal generalised Wannier functions

Linear-scaling calculation of Hartree-Fock exchange energy with non-orthogonal generalised Wannier functions
Linear-scaling calculation of Hartree-Fock exchange energy with non-orthogonal generalised Wannier functions
We present a method for the calculation of four-centre two-electron repulsion integrals in terms of localised non-orthogonal generalised Wannier functions (NGWFs). Our method has been implemented in the ONETEP program and is used to compute the Hartree-Fock exchange energy component of Hartree-Fock and Density Functional Theory (DFT) calculations with hybrid exchange-correlation functionals. As the NGWFs are optimised in situin terms of a systematically improvable basis set which is equivalent to plane waves, it is possible to achieve large basis set accuracy in routine calculations. The spatial localisation of the NGWFs allows us to exploit the exponential decay of the density matrix in systems with a band gap in order to compute the exchange energy with a computational effort that increases linearly with the number of atoms. We describe the implementation of this approach in the ONETEPprogram for linear-scaling first principles quantum mechanical calculations. We present extensive numerical validation of all the steps in our method. Furthermore, we find excellent agreement in energies and structures for a wide variety of molecules when comparing with other codes. We use our method to perform calculations with the B3LYP exchange-correlation functional for models of myoglobin systems bound with O2 and CO ligands and confirm that the same qualitative behaviour is obtained as when the same myoglobin models are studied with the DFT+U approach which is also available in ONETEP. Finally, we confirm the linear-scaling capability of our method by performing calculations on polyethylene and polyacetylene chains of increasing length.
0021-9606
214103
Dziedzic, J.
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Hill, Q.
346651fc-6257-4297-bd1a-e1ab9af3822f
Skylaris, C.-K.
8f593d13-3ace-4558-ba08-04e48211af61
Dziedzic, J.
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Hill, Q.
346651fc-6257-4297-bd1a-e1ab9af3822f
Skylaris, C.-K.
8f593d13-3ace-4558-ba08-04e48211af61

Dziedzic, J., Hill, Q. and Skylaris, C.-K. (2013) Linear-scaling calculation of Hartree-Fock exchange energy with non-orthogonal generalised Wannier functions. The Journal of Chemical Physics, 139 (21), 214103. (doi:10.1063/1.4832338).

Record type: Article

Abstract

We present a method for the calculation of four-centre two-electron repulsion integrals in terms of localised non-orthogonal generalised Wannier functions (NGWFs). Our method has been implemented in the ONETEP program and is used to compute the Hartree-Fock exchange energy component of Hartree-Fock and Density Functional Theory (DFT) calculations with hybrid exchange-correlation functionals. As the NGWFs are optimised in situin terms of a systematically improvable basis set which is equivalent to plane waves, it is possible to achieve large basis set accuracy in routine calculations. The spatial localisation of the NGWFs allows us to exploit the exponential decay of the density matrix in systems with a band gap in order to compute the exchange energy with a computational effort that increases linearly with the number of atoms. We describe the implementation of this approach in the ONETEPprogram for linear-scaling first principles quantum mechanical calculations. We present extensive numerical validation of all the steps in our method. Furthermore, we find excellent agreement in energies and structures for a wide variety of molecules when comparing with other codes. We use our method to perform calculations with the B3LYP exchange-correlation functional for models of myoglobin systems bound with O2 and CO ligands and confirm that the same qualitative behaviour is obtained as when the same myoglobin models are studied with the DFT+U approach which is also available in ONETEP. Finally, we confirm the linear-scaling capability of our method by performing calculations on polyethylene and polyacetylene chains of increasing length.

Full text not available from this repository.

More information

Published date: 2 December 2013
Organisations: Chemistry, Faculty of Natural and Environmental Sciences, Computational Systems Chemistry

Identifiers

Local EPrints ID: 365349
URI: http://eprints.soton.ac.uk/id/eprint/365349
ISSN: 0021-9606
PURE UUID: d210a1cc-f4d6-49d5-b064-9d7703a4035c
ORCID for J. Dziedzic: ORCID iD orcid.org/0000-0003-4786-372X
ORCID for C.-K. Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

Catalogue record

Date deposited: 03 Jun 2014 10:46
Last modified: 29 Oct 2019 01:48

Export record

Altmetrics

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×