Separation of dynamic and nondynamic correlation
dc.contributor.author
dc.date.accessioned
2016-11-22T08:35:56Z
dc.date.available
2016-11-22T08:35:56Z
dc.date.issued
2016-07-29
dc.identifier.issn
1463-9076
dc.identifier.uri
dc.description.abstract
The account of electron correlation and its efficient separation into dynamic and nondynamic parts plays a key role in the development of computational methods. In this paper we suggest a physically-sound matrix formulation to split electron correlation into dynamic and nondynamic parts using the two-particle cumulant matrix and a measure of the deviation from idempotency of the first-order density matrix. These matrices are applied to a two-electron model, giving rise to a simplified electron correlation index that (i) depends only on natural orbitals and their occupancies, (ii) can be straightforwardly decomposed into orbital contributions and (iii) splits into dynamic and nondynamic correlation parts that (iv) admit a local version. These expressions are shown to account for dynamic and nondynamic correlation in a variety of systems containing different electron correlation regimes, thus providing the first separation of dynamic and nondynamic correlation using solely natural orbital occupancies
dc.description.sponsorship
This research has been funded by the Spanish MINECO Projects No. CTQ2014-52525-P and CTQ2014-59212-P, and the Basque Country Consolidated Group Project No. IT588-13. ERC acknowledges funding from the European Union’s Horizon 2020 research
and innovation programme under the Marie Sklodowska-Curie grant agreement No. 660943
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2014-52525-P/ES/FUNCIONALES DFT PARA EL CALCULO DE PROPIEDADES OPTICAS NO LINEALES/
info:eu-repo/grantAgreement/MINECO//CTQ2014-59212-P/ES/SPIN STATE AND ENZYMATIC CATALYSIS BASED ON BOTTOM-UP COMPUTATIONAL DESIGN/
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Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c6cp03072f
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Physical Chemistry Chemical Physics, 2016, vol. 18, p. 24015-24023
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Articles publicats (D-Q)
dc.rights
Attribution 3.0 Spain
dc.rights.uri
dc.subject
dc.title
Separation of dynamic and nondynamic correlation
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
Cap
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
025666
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1463-9084