Projected Hartree–Fock theory

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dc.citation.articleNumber164109
dc.citation.issueNumber16en_US
dc.citation.journalTitleThe Journal of Chemical Physicsen_US
dc.citation.volumeNumber136en_US
dc.contributor.authorJiménez-Hoyos, Carlos A.en_US
dc.contributor.authorHenderson, Thomas M.en_US
dc.contributor.authorTsuchimochi, Takashien_US
dc.contributor.authorScuseria, Gustavo E.en_US
dc.date.accessioned2017-05-03T18:24:04Z
dc.date.available2017-05-03T18:24:04Z
dc.date.issued2012en_US
dc.description.abstractProjected Hartree–Fock (PHF) theory has a long history in quantum chemistry. PHF is here understood as the variational determination of an N-electron broken symmetry Slater determinant that minimizes the energy of a projected state with the correct quantum numbers. The method was actively pursued for several decades but seems to have been abandoned. We here derive and implement a “variation after projection” PHF theory using techniques different from those previously employed in quantum chemistry. Our PHF methodology has modest mean-field computational cost, yields relatively simple expressions, can be applied to both collinear and non-collinear spin cases, and can be used in conjunction with deliberate symmetry breaking and restoration of other molecular symmetries like complex conjugation and point group. We present several benchmark applications to dissociation curves and singlet-triplet energy splittings, showing that the resulting PHF wavefunctions are of high quality multireference character. We also provide numerical evidence that in the thermodynamic limit, the energy in PHF is not lower than that of broken-symmetry HF, a simple consequence of the lack of size consistency and extensivity of PHF.en_US
dc.identifier.citationJiménez-Hoyos, Carlos A., Henderson, Thomas M., Tsuchimochi, Takashi, et al.. "Projected Hartree–Fock theory." <i>The Journal of Chemical Physics,</i> 136, no. 16 (2012) AIP Publishing LLC: https://doi.org/10.1063/1.4705280.
dc.identifier.doihttps://doi.org/10.1063/1.4705280en_US
dc.identifier.urihttps://hdl.handle.net/1911/94130
dc.language.isoengen_US
dc.publisherAIP Publishing LLC
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
dc.titleProjected Hartree–Fock theoryen_US
dc.typeJournal articleen_US
dc.type.dcmiTexten_US
dc.type.publicationpublisher versionen_US
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