Exchange-correlation functionals via local interpolation along the adiabatic connection

The construction of density-functional approximations is explored by modeling the adiabatic connection locally, using energy densities defined in terms of the electrostatic potential of the exchange−correlation hole. These local models are more amenable to the construction of size-consistent approxi...

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Main Authors: Vuckovic, Stefan, Irons, Tom J.P., Savin, Andreas, Teale, Andrew M., Gori-Giorgi, Paola
Format: Article
Published: American Chemical Society 2016
Online Access:https://eprints.nottingham.ac.uk/33591/
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author Vuckovic, Stefan
Irons, Tom J.P.
Savin, Andreas
Teale, Andrew M.
Gori-Giorgi, Paola
author_facet Vuckovic, Stefan
Irons, Tom J.P.
Savin, Andreas
Teale, Andrew M.
Gori-Giorgi, Paola
author_sort Vuckovic, Stefan
building Nottingham Research Data Repository
collection Online Access
description The construction of density-functional approximations is explored by modeling the adiabatic connection locally, using energy densities defined in terms of the electrostatic potential of the exchange−correlation hole. These local models are more amenable to the construction of size-consistent approximations than their global counterparts. In this work we use accurate input local ingredients to assess the accuracy of a range of local interpolation models against accurate exchange−correlation energy densities. The importance of the strictly correlated electrons (SCE) functional describing the strong coupling limit is emphasized, enabling the corresponding interpolated functionals to treat strong correlation effects. In addition to exploring the performance of such models numerically for the helium and beryllium isoelectronic series and the dissociation of the hydrogen molecule, an approximate analytic model is presented for the initial slope of the local adiabatic connection. Comparisons are made with approaches based on global models, and prospects for future approximations based on the local adiabatic connection are discussed.
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spelling nottingham-335912020-05-04T17:45:05Z https://eprints.nottingham.ac.uk/33591/ Exchange-correlation functionals via local interpolation along the adiabatic connection Vuckovic, Stefan Irons, Tom J.P. Savin, Andreas Teale, Andrew M. Gori-Giorgi, Paola The construction of density-functional approximations is explored by modeling the adiabatic connection locally, using energy densities defined in terms of the electrostatic potential of the exchange−correlation hole. These local models are more amenable to the construction of size-consistent approximations than their global counterparts. In this work we use accurate input local ingredients to assess the accuracy of a range of local interpolation models against accurate exchange−correlation energy densities. The importance of the strictly correlated electrons (SCE) functional describing the strong coupling limit is emphasized, enabling the corresponding interpolated functionals to treat strong correlation effects. In addition to exploring the performance of such models numerically for the helium and beryllium isoelectronic series and the dissociation of the hydrogen molecule, an approximate analytic model is presented for the initial slope of the local adiabatic connection. Comparisons are made with approaches based on global models, and prospects for future approximations based on the local adiabatic connection are discussed. American Chemical Society 2016-04-26 Article PeerReviewed Vuckovic, Stefan, Irons, Tom J.P., Savin, Andreas, Teale, Andrew M. and Gori-Giorgi, Paola (2016) Exchange-correlation functionals via local interpolation along the adiabatic connection. Journal of Chemical Theory and Computation . ISSN 1549-9626 http://pubs.acs.org/doi/abs/10.1021/acs.jctc.6b00177 doi:10.1021/acs.jctc.6b00177 doi:10.1021/acs.jctc.6b00177
spellingShingle Vuckovic, Stefan
Irons, Tom J.P.
Savin, Andreas
Teale, Andrew M.
Gori-Giorgi, Paola
Exchange-correlation functionals via local interpolation along the adiabatic connection
title Exchange-correlation functionals via local interpolation along the adiabatic connection
title_full Exchange-correlation functionals via local interpolation along the adiabatic connection
title_fullStr Exchange-correlation functionals via local interpolation along the adiabatic connection
title_full_unstemmed Exchange-correlation functionals via local interpolation along the adiabatic connection
title_short Exchange-correlation functionals via local interpolation along the adiabatic connection
title_sort exchange-correlation functionals via local interpolation along the adiabatic connection
url https://eprints.nottingham.ac.uk/33591/
https://eprints.nottingham.ac.uk/33591/
https://eprints.nottingham.ac.uk/33591/