Excited electronic states from a variational approach based on symmetry-projected Hartree–Fock configurations
dc.citation.articleNumber | 224110 | |
dc.citation.issueNumber | 22 | |
dc.citation.journalTitle | The Journal of Chemical Physics | |
dc.citation.volumeNumber | 139 | |
dc.contributor.author | Jiménez-Hoyos, Carlos A. | |
dc.contributor.author | Rodríguez-Guzmán, R. | |
dc.contributor.author | Scuseria, Gustavo E. | |
dc.date.accessioned | 2017-05-04T19:43:55Z | |
dc.date.available | 2017-05-04T19:43:55Z | |
dc.date.issued | 2013 | |
dc.description.abstract | Recent 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. | |
dc.identifier.citation | Jiménez-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. | |
dc.identifier.doi | https://doi.org/10.1063/1.4840097 | |
dc.identifier.uri | https://hdl.handle.net/1911/94186 | |
dc.language.iso | eng | |
dc.publisher | American Institute of Physics | |
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 | Excited electronic states from a variational approach based on symmetry-projected Hartree–Fock configurations | |
dc.type | Journal article | |
dc.type.dcmi | Text | |
dc.type.publication | publisher version |
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