Improving the calculation of electron paramagnetic resonance hyperfine coupling tensors for d-block metals
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Improving the calculation of electron paramagnetic resonance hyperfine coupling tensors for d-block metals. / Hedegård, Erik Donovan; Kongsted, Jacob; Sauer, Stephan P. A.
In: Physical Chemistry Chemical Physics, Vol. 14, No. 30, 2012, p. 10669-10676.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - Improving the calculation of electron paramagnetic resonance hyperfine coupling tensors for d-block metals
AU - Hedegård, Erik Donovan
AU - Kongsted, Jacob
AU - Sauer, Stephan P. A.
PY - 2012
Y1 - 2012
N2 - 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.
AB - 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.
KW - Faculty of Science
KW - ESR spectroscopy
KW - EPR spectroscopy
KW - Quantum Chemistry
KW - Computational Chemistry
KW - Transition metal complex
U2 - 10.1039/C2CP40969K
DO - 10.1039/C2CP40969K
M3 - Journal article
VL - 14
SP - 10669
EP - 10676
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 30
ER -
ID: 38187740