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dc.contributor.authorBurke, Kieron
dc.contributor.authorCancio, Antonio
dc.contributor.authorGould, Tim
dc.contributor.authorPittalis, Stefano
dc.date.accessioned2018-09-05T04:01:22Z
dc.date.available2018-09-05T04:01:22Z
dc.date.issued2016
dc.identifier.issn0021-9606
dc.identifier.doi10.1063/1.4959126
dc.identifier.urihttp://hdl.handle.net/10072/142962
dc.description.abstractThe Hohenberg-Kohn density functional was long ago shown to reduce to the Thomas-Fermi (TF) approximation in the non-relativistic semiclassical (or large-Z) limit for all matter, i.e., the kinetic energy becomes local. Exchange also becomes local in this limit. Numerical data on the correlation energy of atoms support the conjecture that this is also true for correlation, but much less relevant to atoms. We illustrate how expansions around a large particle number are equivalent to local density approximations and their strong relevance to density functional approximations. Analyzing highly accurate atomic correlation energies, we show that EC → −AC ZlnZ + BCZ as Z → ∞, where Z is the atomic number, AC is known, and we estimate BC to be about 37 mhartree. The local density approximation yields AC exactly, but a very incorrect value for BC, showing that the local approximation is less relevant for the correlation alone. This limit is a benchmark for the non-empirical construction of density functional approximations. We conjecture that, beyond atoms, the leading correction to the local density approximation in the large-Z limit generally takes this form, but with BC a functional of the TF density for the system. The implications for the construction of approximate density functionals are discussed.
dc.description.peerreviewedYes
dc.languageEnglish
dc.language.isoeng
dc.publisherAmerican Institute of Physics
dc.relation.ispartofpagefrom054112-1
dc.relation.ispartofpageto054112-16
dc.relation.ispartofjournalJournal of Chemical Physics
dc.relation.ispartofvolume145
dc.subject.fieldofresearchPhysical Sciences not elsewhere classified
dc.subject.fieldofresearchPhysical Sciences
dc.subject.fieldofresearchChemical Sciences
dc.subject.fieldofresearchEngineering
dc.subject.fieldofresearchcode029999
dc.subject.fieldofresearchcode02
dc.subject.fieldofresearchcode03
dc.subject.fieldofresearchcode09
dc.titleLocality of correlation in density functional theory
dc.typeJournal article
dc.type.descriptionC1 - Articles
dc.type.codeC - Journal Articles
dc.description.versionVersion of Record (VoR)
gro.rights.copyright© 2016 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in 145, 054112 (2016) and may be found at https://aip.scitation.org/doi/10.1063/1.4959126.
gro.hasfulltextFull Text
gro.griffith.authorGould, Tim J.


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