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dc.contributor.authorJiménez-Hoyos, Carlos A.
Henderson, Thomas M.
Tsuchimochi, Takashi
Scuseria, Gustavo E.
dc.date.accessioned 2017-05-03T18:24:04Z
dc.date.available 2017-05-03T18:24:04Z
dc.date.issued 2012
dc.identifier.citation Jiménez-Hoyos, Carlos A., Henderson, Thomas M., Tsuchimochi, Takashi, et al.. "Projected Hartree–Fock theory." The Journal of Chemical Physics, 136, no. 16 (2012) AIP Publishing LLC: https://doi.org/10.1063/1.4705280.
dc.identifier.urihttps://hdl.handle.net/1911/94130
dc.description.abstract Projected 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.
dc.language.iso eng
dc.publisher AIP Publishing LLC
dc.rights Article 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.title Projected Hartree–Fock theory
dc.type Journal article
dc.citation.journalTitle The Journal of Chemical Physics
dc.citation.volumeNumber 136
dc.citation.issueNumber 16
dc.type.dcmi Text
dc.identifier.doihttps://doi.org/10.1063/1.4705280
dc.identifier.pmid 22559472
dc.type.publication publisher version
dc.citation.articleNumber 164109


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