Relativistic DFT calculations of hyperfine coupling constants in the 5d hexafluorido complexes: [ReF6]2- and [IrF6]2-
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Relativistic DFT calculations of hyperfine coupling constants in the 5d hexafluorido complexes : [ReF6]2- and [IrF6]2-. / Haase, Pi Ariane Bresling; Repisky, Michal; Komorovsky, Stanislav; Bendix, Jesper; Sauer, Stephan P. A.
I: Chemistry: A European Journal, Bind 24, Nr. 20, 2018, s. 5124-5133.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Relativistic DFT calculations of hyperfine coupling constants in the 5d hexafluorido complexes
T2 - [ReF6]2- and [IrF6]2-
AU - Haase, Pi Ariane Bresling
AU - Repisky, Michal
AU - Komorovsky, Stanislav
AU - Bendix, Jesper
AU - Sauer, Stephan P. A.
PY - 2018
Y1 - 2018
N2 - We have investigated the performance of the most popular relativistic densityfunctional theory methods, zeroth order regular approximation (ZORA) and 4-component Dirac-Kohn-Sham (DKS), in the calculation of the recently measuredhyperfine coupling constants of ReIV and IrIV in their hexafluorido ions. We find that both methods lead to very similar deviations from the experimental values for the [ReF6]2- complex, i.e. ~20% for the coupling constant using hybrid functionals. None of the methods is, however, able to reproduce the large anisotropy of the [ReF6]2- hyperfine tensor. For [IrF6]2- the ZORA method with a variational treatment of spinorbit coupling and the DKS method reproduce the experimental tensor componentswith deviations of ~10% and ~5% for the hybrid functionals, while the ZORA method with a perturbational treatment of spin-orbit coupling wrongly predicts the coupling constant to be around one order of magnitude too large. The reasons for this failure and the basis set and functional dependence of the results are discussed. In addition the manuscript presents for the first time detailed equations for the calculation of hyperfine couplings within the DKS approach as implemented in the Respect program.
AB - We have investigated the performance of the most popular relativistic densityfunctional theory methods, zeroth order regular approximation (ZORA) and 4-component Dirac-Kohn-Sham (DKS), in the calculation of the recently measuredhyperfine coupling constants of ReIV and IrIV in their hexafluorido ions. We find that both methods lead to very similar deviations from the experimental values for the [ReF6]2- complex, i.e. ~20% for the coupling constant using hybrid functionals. None of the methods is, however, able to reproduce the large anisotropy of the [ReF6]2- hyperfine tensor. For [IrF6]2- the ZORA method with a variational treatment of spinorbit coupling and the DKS method reproduce the experimental tensor componentswith deviations of ~10% and ~5% for the hybrid functionals, while the ZORA method with a perturbational treatment of spin-orbit coupling wrongly predicts the coupling constant to be around one order of magnitude too large. The reasons for this failure and the basis set and functional dependence of the results are discussed. In addition the manuscript presents for the first time detailed equations for the calculation of hyperfine couplings within the DKS approach as implemented in the Respect program.
U2 - 10.1002/chem.201704653
DO - 10.1002/chem.201704653
M3 - Journal article
C2 - 29027277
VL - 24
SP - 5124
EP - 5133
JO - Chemistry: A European Journal
JF - Chemistry: A European Journal
SN - 0947-6539
IS - 20
ER -
ID: 184325276