Is the Spin-Orbit Coupling Important in the Prediction of the (51)V Hyperfine Coupling Constants of V(IV)O(2+) Species? ORCA Versus Gaussian Performance and Biological Applications
Density functional theory calculations of the V-51 hyperfine coupling (HFC) tensor A, have been completed for eighteen (VO2+)-O-IV complexes with different donor set, electric charge and coordination geometry. A tensor was calculated with ORCA software with several functionals and basis sets taking...
| Published in: | Journal of Computational Chemistry |
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| Main Authors: | , |
| Other Authors: | , |
| Format: | Article in Journal/Newspaper |
| Language: | unknown |
| Published: |
2011
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| Subjects: | |
| Online Access: | http://hdl.handle.net/11388/155533 https://doi.org/10.1002/jcc.21862 |
| Summary: | Density functional theory calculations of the V-51 hyperfine coupling (HFC) tensor A, have been completed for eighteen (VO2+)-O-IV 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 > PBE0 >> B3PW > TPSSh >> B3LYP >> BP86 > VWN5 (for A(iso)), BHandHLYP > PBE0 >> B3PW > TPSSh > B3LYP >> BP86 > VWN5 (for A(z)), B3LYP > PBE0 similar to B3PW similar to BHandHLYP >> TPSSh > BP86 similar to 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) = A(iso) + A(z,anis)), whereas among the hybrid functionals PBE0 performs better than the other ones. BHandHLYP functional and Gaussian software are recommended when the (VO2+)-O-IV species contains only V-O and/ or V-N bonds, whereas PBE0 functional and ORCA software for (VO2+)-O-IV complexes with one or more V-S bonds. Finally, the application of these methods to the coordination environment of (VO2+)-O-IV ion in V-proteins, like vanadyl-substituted insulin, carbonic anhydrase, collagen and S-adenosylmethionine synthetase, was discussed. |
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