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dc.contributor.authorHaase, Pi A. B.
dc.contributor.authorRepisky, Michal
dc.contributor.authorKomorovsky, Stanislav
dc.contributor.authorBendix, Jesper
dc.contributor.authorSauer, Stephan P. A.
dc.date.accessioned2022-05-02T11:45:16Z
dc.date.available2022-05-02T11:45:16Z
dc.date.issued2017-10-12
dc.description.abstractThe performance of relativistic density functional theory (DFT) methods has been investigated for the calculation of the recently measured hyperfine coupling constants of hexafluorido complexes [ReF<sub>6</sub> ] <sup>2-</sup> and [IrF<sub>6</sub> ] <sup>2-</sup> . Three relativistic methods were employed at the DFT level of theory: the 2-component zeroth-order regular approximation (ZORA) method, in which the spin–orbit coupling was treated either variationally (EV ZORA) or as a perturbation (LR ZORA), and the 4-component Dirac–Kohn–Sham (DKS) method. The dependence of the results on the basis set and the choice of exchange-correlation functional was studied. Furthermore, the effect of varying the amount of Hartree–Fock exchange in the hybrid functionals was investigated. The LR ZORA and DKS methods combined with DFT led to very similar deviations (about 20%) from the experimental values for the coupling constant of complex [ReF<sub>6</sub> ] <sup>2-</sup> by using hybrid functionals. However, none of the methods were able to reproduce the large anisotropy of the hyperfine coupling tensor of complex [ReF6 ] <sup>2-</sup> . For [IrF<sub>6</sub> ] <sup>2-</sup> , the EV ZORA and DKS methods reproduced the experimental tensor components with deviations of &10 and &5% for the hybrid functionals, whereas the LR ZORA method predicted the coupling constant to be around one order of magnitude too large owing to the combination of large spin–orbit coupling and very low excitation energies.en_US
dc.identifier.citationHaase, Repisky M, Komorovsky S, Bendix J, Sauer SPA. Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF6]2- and [IrF6]2-. Chemistry - A European Journal. 2017;24(20):5124-5133en_US
dc.identifier.cristinIDFRIDAID 1554034
dc.identifier.doi10.1002/chem.201704653
dc.identifier.issn0947-6539
dc.identifier.issn1521-3765
dc.identifier.urihttps://hdl.handle.net/10037/24968
dc.language.isoengen_US
dc.publisherWileyen_US
dc.relation.journalChemistry - A European Journal
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2017 The Author(s)en_US
dc.titleRelativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF6]2- and [IrF6]2-en_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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