Cargando…

Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF(6)](2−) and [IrF(6)](2−)

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 [ReF(6)](2−) and [IrF(6)](2−). Three relativistic methods were employed at the DFT level of theory: the 2‐...

Descripción completa

Detalles Bibliográficos
Autores principales: Haase, Pi A. B., Repisky, Michal, Komorovsky, Stanislav, Bendix, Jesper, Sauer, Stephan P. A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5969236/
https://www.ncbi.nlm.nih.gov/pubmed/29027277
http://dx.doi.org/10.1002/chem.201704653
_version_ 1783325930507206656
author Haase, Pi A. B.
Repisky, Michal
Komorovsky, Stanislav
Bendix, Jesper
Sauer, Stephan P. A.
author_facet Haase, Pi A. B.
Repisky, Michal
Komorovsky, Stanislav
Bendix, Jesper
Sauer, Stephan P. A.
author_sort Haase, Pi A. B.
collection PubMed
description 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 [ReF(6)](2−) and [IrF(6)](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 [ReF(6)](2−) by using hybrid functionals. However, none of the methods were able to reproduce the large anisotropy of the hyperfine coupling tensor of complex [ReF(6)](2−). For [IrF(6)](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.
format Online
Article
Text
id pubmed-5969236
institution National Center for Biotechnology Information
language English
publishDate 2017
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-59692362018-05-30 Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF(6)](2−) and [IrF(6)](2−) Haase, Pi A. B. Repisky, Michal Komorovsky, Stanislav Bendix, Jesper Sauer, Stephan P. A. Chemistry Full Papers 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 [ReF(6)](2−) and [IrF(6)](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 [ReF(6)](2−) by using hybrid functionals. However, none of the methods were able to reproduce the large anisotropy of the hyperfine coupling tensor of complex [ReF(6)](2−). For [IrF(6)](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. John Wiley and Sons Inc. 2017-12-04 2018-04-06 /pmc/articles/PMC5969236/ /pubmed/29027277 http://dx.doi.org/10.1002/chem.201704653 Text en © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Full Papers
Haase, Pi A. B.
Repisky, Michal
Komorovsky, Stanislav
Bendix, Jesper
Sauer, Stephan P. A.
Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF(6)](2−) and [IrF(6)](2−)
title Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF(6)](2−) and [IrF(6)](2−)
title_full Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF(6)](2−) and [IrF(6)](2−)
title_fullStr Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF(6)](2−) and [IrF(6)](2−)
title_full_unstemmed Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF(6)](2−) and [IrF(6)](2−)
title_short Relativistic DFT Calculations of Hyperfine Coupling Constants in 5d Hexafluorido Complexes: [ReF(6)](2−) and [IrF(6)](2−)
title_sort relativistic dft calculations of hyperfine coupling constants in 5d hexafluorido complexes: [ref(6)](2−) and [irf(6)](2−)
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5969236/
https://www.ncbi.nlm.nih.gov/pubmed/29027277
http://dx.doi.org/10.1002/chem.201704653
work_keys_str_mv AT haasepiab relativisticdftcalculationsofhyperfinecouplingconstantsin5dhexafluoridocomplexesref62andirf62
AT repiskymichal relativisticdftcalculationsofhyperfinecouplingconstantsin5dhexafluoridocomplexesref62andirf62
AT komorovskystanislav relativisticdftcalculationsofhyperfinecouplingconstantsin5dhexafluoridocomplexesref62andirf62
AT bendixjesper relativisticdftcalculationsofhyperfinecouplingconstantsin5dhexafluoridocomplexesref62andirf62
AT sauerstephanpa relativisticdftcalculationsofhyperfinecouplingconstantsin5dhexafluoridocomplexesref62andirf62