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Spin splittings from first-order symmetry-adapted perturbation theory without single-exchange approximation


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dc.contributorJonathan Waldrop, jmw0074@auburn.eduen_US
dc.creatorWaldrop, Jonathan
dc.creatorPatkowski, Konrad
dc.date.accessioned2020-05-20T14:49:50Z
dc.date.available2020-05-20T14:49:50Z
dc.date.created2019
dc.identifier10.1063/1.5086079en_US
dc.identifier.urihttps://aip.scitation.org/doi/10.1063/1.5086079en_US
dc.identifier.urihttp://hdl.handle.net/11200/49807
dc.description.abstractThe recently proposed spin-flip symmetry-adapted perturbation theory (SF-SAPT) first-order exchange energy [Patkowski et al., J. Chem. Phys. 148, 164110 (2018)] enables the standard open-shell SAPT approach to treat arbitrary spin states of the weakly interacting complex. Here, we further extend first-order SF-SAPT beyond the single-exchange approximation to a complete treatment of the exchanges of electrons between monomers. This new form of the exchange correction replaces the single-exchange approximation with a more moderate single-spin-flip approximation. The newly developed expressions are applied to a number of small test systems to elucidate the quality of both approximations. They are also applied to the singlet-triplet splittings in pancake bonded dimers. The accuracy of the single-exchange approximation deteriorates at short intermolecular separations, especially for systems with few electrons and for the high-spin state of the complex. In contrast, the single-spin-flip approximation is exact for interactions involving a doublet molecule and remains highly accurate for any number of unpaired electrons. Because the single-exchange approximation affects the high-spin and low-spin states of pancake bonded complexes evenly, the resulting splitting values are of similar accuracy to those produced by the formally more accurate single-spin-flip approximation. Published under license by AIP Publishing.en_US
dc.formatPDFen_US
dc.publisherAMER INST PHYSICSen_US
dc.relation.ispartofJournal of Chemical Physicsen_US
dc.relation.ispartofseries0021-9606en_US
dc.subjectCONSISTENT BASIS-SETS; QUANTUM-CHEMISTRY; WAVE-FUNCTIONS; PANCAKE; ATOMS; DIMER; SHELLen_US
dc.titleSpin splittings from first-order symmetry-adapted perturbation theory without single-exchange approximationen_US
dc.typeTexten_US
dc.type.genreJournal Article, Academic Journalen_US
dc.citation.volume150en_US
dc.citation.issue7en_US
dc.citation.spage74109en_US
dc.description.statusPublisheden_US
dc.creator.orcid0000-0003-0442-193Xen_US
dc.creator.orcid0000-0002-4468-207Xen_US

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