Excited electronic states from a variational approach based on symmetry-projected Hartree–Fock configurations

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dc.citation.articleNumber224110en_US
dc.citation.issueNumber22en_US
dc.citation.journalTitleThe Journal of Chemical Physicsen_US
dc.citation.volumeNumber139en_US
dc.contributor.authorJiménez-Hoyos, Carlos A.en_US
dc.contributor.authorRodríguez-Guzmán, R.en_US
dc.contributor.authorScuseria, Gustavo E.en_US
dc.date.accessioned2017-05-04T19:43:55Zen_US
dc.date.available2017-05-04T19:43:55Zen_US
dc.date.issued2013en_US
dc.description.abstractRecent work from our research group has demonstrated that symmetry-projected Hartree–Fock (HF) methods provide a compact representation of molecular ground state wavefunctions based on a superposition of non-orthogonal Slater determinants. The symmetry-projected ansatz can account for static correlations in a computationally efficient way. Here we present a variational extension of this methodology applicable to excited states of the same symmetry as the ground state. Benchmark calculations on the C2 dimer with a modest basis set, which allows comparison with full configuration interaction results, indicate that this extension provides a high quality description of the low-lying spectrum for the entire dissociation profile. We apply the same methodology to obtain the full low-lying vertical excitation spectrum of formaldehyde, in good agreement with available theoretical and experimental data, as well as to a challenging model C2v insertion pathway for BeH2. The variational excited state methodology developed in this work has two remarkable traits: it is fully black-box and will be applicable to fairly large systems thanks to its mean-field computational cost.en_US
dc.identifier.citationJiménez-Hoyos, Carlos A., Rodríguez-Guzmán, R. and Scuseria, Gustavo E.. "Excited electronic states from a variational approach based on symmetry-projected Hartree–Fock configurations." <i>The Journal of Chemical Physics,</i> 139, no. 22 (2013) American Institute of Physics: https://doi.org/10.1063/1.4840097.en_US
dc.identifier.doihttps://doi.org/10.1063/1.4840097en_US
dc.identifier.urihttps://hdl.handle.net/1911/94186en_US
dc.language.isoengen_US
dc.publisherAmerican Institute of Physicsen_US
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.en_US
dc.titleExcited electronic states from a variational approach based on symmetry-projected Hartree–Fock configurationsen_US
dc.typeJournal articleen_US
dc.type.dcmiTexten_US
dc.type.publicationpublisher versionen_US
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