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Issue 30, 2012
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Improving the calculation of electron paramagnetic resonance hyperfine coupling tensors for d-block metals

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Abstract

Calculation of hyperfine coupling constants (HFCs) of Electron Paramagnetic Resonance from first principles can be a beneficial complement to experimental data in cases where the molecular structure is unknown. We have recently investigated basis set convergence of HFCs in d-block complexes and obtained a set of basis functions for the elements Sc–Zn, which were saturated with respect to both the Fermi contact and spin-dipolar components of the hyperfine coupling tensor [Hedegård et al., J. Chem. Theory Comput., 2011, 7, 4077–4087]. Furthermore, a contraction scheme was proposed leading to very accurate, yet efficient basis sets for the elements Sc–Zn. Here this scheme is tested against a larger test set of molecules and a wider range of DFT functionals. We further investigate the regular aug-cc-pVTZ and core–valence correlation aug-cc-pCVTZ basis sets as well as another core-property basis set, CP(PPP). While aug-cc-pVTZ-J provides hyperfine coupling constants that are almost identical to the converged series (aug-cc-pVTZ-Juc), we observe that not only the regular but also the core–valence correlation basis sets provide results far from the converged results. The usage of specialized core-basis sets leads to a large and highly significant improvement of the calculated hyperfine couplings in comparison with experimental data.

Graphical abstract: Improving the calculation of electron paramagnetic resonance hyperfine coupling tensors for d-block metals

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Supplementary files

Article information


Submitted
26 Mar 2012
Accepted
01 Jun 2012
First published
04 Jun 2012

Phys. Chem. Chem. Phys., 2012,14, 10669-10676
Article type
Paper

Improving the calculation of electron paramagnetic resonance hyperfine coupling tensors for d-block metals

E. D. Hedegård, J. Kongsted and S. P. A. Sauer, Phys. Chem. Chem. Phys., 2012, 14, 10669
DOI: 10.1039/C2CP40969K

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