New approaches for the calibration of exchange-energy densities in local hybrid functionals

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dc.contributor.authorMaier, Toni M.
dc.contributor.authorHaasler, Matthias
dc.contributor.authorArbuznikov, Alexey V.
dc.contributor.authorKaupp, Martin
dc.date.accessioned2017-10-24T06:17:05Z
dc.date.available2017-10-24T06:17:05Z
dc.date.issued2016
dc.descriptionDieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.de
dc.descriptionThis publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.en
dc.description.abstractThe ambiguity of exchange-energy densities is a fundamental challenge for the development of local hybrid functionals, or of other functionals based on a local mixing of exchange-energy densities. In this work, a systematic construction of semi-local calibration functions (CFs) for adjusting the exchange-energy densities in local hybrid functionals is provided, which directly links a given CF to an underlying semi-local exchange functional, as well as to the second-order gradient expansion of the exchange hole. Using successive steps of integration by parts allows the derivation of correction terms of increasing order, resulting in more and more complicated but also more flexible CFs. We derive explicit first-and second-order CFs (pig1 and pig2) based on B88 generalized-gradient approximation (GGA) exchange, and a first-order CF (tpig1) based on t-dependent B98 meta-GGA exchange. We combine these CFs with different long-range damping functions and evaluate them for calibration of LDA, B88 GGA, and TPSS meta-GGA exchange-energy densities. Based on a minimization of unphysical nondynamical correlation contributions in three noble-gas dimer potential-energy curves, free parameters in the CFs are optimized, and performance of various approaches in the calibration of different exchange-energy densities is compared. Most notably, the second-order pig2 CF provides the largest flexibility with respect to the diffuseness of the damping function. This suggests that higher-order CFs based on the present integration-by-parts scheme may be particularly suitable for the flexible construction of local hybrid functionals.en
dc.identifier.eissn1463-9084
dc.identifier.issn1463-9076
dc.identifier.pmid27080804
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/6876
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-6215
dc.language.isoen
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titleNew approaches for the calibration of exchange-energy densities in local hybrid functionalsen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c6cp00990e
dcterms.bibliographicCitation.issue31
dcterms.bibliographicCitation.journaltitlePhysical chemistry, chemical physicsen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend21144
dcterms.bibliographicCitation.pagestart21133
dcterms.bibliographicCitation.volume18
tub.accessrights.dnbdomain
tub.affiliationFak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Theoretische Chemiede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Theoretische Chemiede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlin

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