Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 14, Issue 30, Pages 10669-10676Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2cp40969k
Keywords
-
Funding
- Danish Center for Scientific Computing (DCSC)
- Lundbeck Foundation
- Villum Kann Rasmussen Foundation
- Danish Councils for Independent Research (STENO program)
- Danish Councils for Independent Research (Sapere Aude program)
Ask authors/readers for more resources
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 [Hedegard 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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available