Improving the calculation of electron paramagnetic resonance hyperfine coupling tensors for d-block metals
Research output: Contribution to journal › Journal article › Research › peer-review
Calculation of hyperfine coupling constants (HFCs) of Electron Paramagnetic Resonance from first principles can be a beneficial compliment 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 [Hedeg°ard et al., J. Chem. Theory Comput., 2011, 7, pp. 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.
Original language | English |
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Journal | Physical Chemistry Chemical Physics |
Volume | 14 |
Issue number | 30 |
Pages (from-to) | 10669-10676 |
Number of pages | 8 |
ISSN | 1463-9076 |
DOIs | |
Publication status | Published - 2012 |
- Faculty of Science - ESR spectroscopy, EPR spectroscopy, Quantum Chemistry, Computational Chemistry, Transition metal complex
Research areas
ID: 38187740