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

• Published in: Journal of Computational Chemistry
• Main Authors: Micera, Giovanni, Garribba, Eugenio
• Format: Article in Journal/Newspaper
• Language: English
• Published: Wiley 2011
• Subjects: Orca
• Online Access: http://dx.doi.org/10.1002/jcc.21862; https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fjcc.21862; https://onlinelibrary.wiley.com/doi/pdf/10.1002/jcc.21862; https://onlinelibrary.wiley.com/doi/full-xml/10.1002/jcc.21862

Abstract Density functional theory calculations of the 51 V hyperfine coupling (HFC) tensor A , have been completed for eighteen V IV O 2+ 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 ∼ B3PW ∼ BHandHLYP >> TPSSh > BP86 ∼ 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 V IV O 2+ species contains only V‐O and/or V‐N bonds, whereas PBE0 functional and ORCA software for V IV O 2+ complexes with one or more VS bonds. Finally, the application of these methods to the coordination environment of V IV O 2+ ion in V‐proteins, like vanadyl‐substituted insulin, carbonic anhydrase, collagen and S‐adenosylmethionine synthetase, was discussed. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011