Is the spin-orbit coupling important in the prediction of the 51V hyperfine coupling constants of VIVO2+ species? ORCA versus Gaussian performance and biological applications
✍ Scribed by Giovanni Micera; Eugenio Garribba
- Publisher
- John Wiley and Sons
- Year
- 2011
- Tongue
- English
- Weight
- 204 KB
- Volume
- 32
- Category
- Article
- ISSN
- 0192-8651
No coin nor oath required. For personal study only.
✦ Synopsis
Density functional theory calculations of the 51 V hyperfine coupling (HFC) tensor A, have been completed for eighteen V IV O 2þ complexes with different donor set, electric charge and coordination geometry. A tensor was calculated with ORCA software with several functionals and basis sets taking into account the spin-orbit coupling contribution. The results were compared with those obtained with Gaussian 03 software using the half-and-half functional BHandHLYP and 6-311g(d,p) basis set. The order of accuracy of the functionals in the prediction of A iso , A z and dipolar term A z,anis is BHandHLYP
VWN5 (for A z,anis ). The good agreement in the prediction of A z with BHandHLYP is due to a compensation between the overestimation of A iso and underestimation of A z,anis (A z ¼ A iso þ A z,anis ), whereas among the hybrid functionals PBE0 performs better than the other ones. BHandHLYP functional and Gaussian software are recommended when the V IV O 2þ species contains only V-O and/or V-N bonds, whereas PBE0 functional and ORCA software for V IV O 2þ complexes with one or more VAS bonds. Finally, the application of these methods to the coordination environment of V IV O 2þ ion in V-proteins, like vanadylsubstituted insulin, carbonic anhydrase, collagen and S-adenosylmethionine synthetase, was discussed. V