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Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF6]2− and [IrF6]2−
| Content Provider | Semantic Scholar |
|---|---|
| Author | Haase, Pi A. B. Repiský, Michal Komorovsky, Stanislav Bendix, Jesper Sauer, Stephan P. A. |
| Copyright Year | 2018 |
| Abstract | The performance of relativistic density functional theory (DFT) methods has been investigated for the calculation of the recently measured hyperfine coupling constants of hexafluorido complexes [ReF6 ]2- and [IrF6 ]2- . 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 [ReF6 ]2- by using hybrid functionals. However, none of the methods were able to reproduce the large anisotropy of the hyperfine coupling tensor of complex [ReF6 ]2- . For [IrF6 ]2- , 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. |
| Starting Page | 5124 |
| Ending Page | 5133 |
| Page Count | 10 |
| File Format | PDF HTM / HTML |
| DOI | 10.1002/chem.201704653 |
| PubMed reference number | 29027277 |
| Journal | Medline |
| Volume Number | 24 |
| Alternate Webpage(s) | https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/5d/81/CHEM-24-5124.PMC5969236.pdf |
| Alternate Webpage(s) | https://doi.org/10.1002/chem.201704653 |
| Journal | Chemistry |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
