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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

Micera, Giovanni and Garribba, Eugenio (2011) 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. Journal of Computational Chemistry, Vol. 32 (13), p. 2822-2835. ISSN 0192-8651. eISSN 1096-987X. Article.

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DOI: 10.1002/jcc.21862

Abstract

Density functional theory calculations of the 51V hyperfine coupling (HFC) tensor A, have been completed for eighteen VIVO2+ 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 Aiso, Az and dipolar term Az,anis is BHandHLYP > PBE0 >> B3PW > TPSSh >> B3LYP >> BP86 > VWN5 (for Aiso), BHandHLYP > PBE0 >> B3PW > TPSSh > B3LYP >>; BP86 > VWN5 (for Az), B3LYP > PBE0 ∼ B3PW ∼ BHandHLYP >> TPSSh > BP86 ∼ VWN5 (for Az,anis). The good agreement in the prediction of Az with BHandHLYP is due to a compensation between the overestimation of Aiso and underestimation of Az,anis (Az = Aiso +Az,anis), whereas among the hybrid functionals PBE0 performs better than the other ones. BHandHLYP functional and Gaussian software are recommended when the VIVO2+ species contains only V-O and/or V-N bonds, whereas PBE0 functional and ORCA software for VIVO2+ complexes with one or more VAS bonds. Finally, the application of these methods to the coordination environment of VIVO2+ ion in V-proteins, like vanadylsubstituted insulin, carbonic anhydrase, collagen and S-adenosylmethionine synthetase, was discussed.

Item Type:Article
ID Code:6313
Status:Published
Refereed:Yes
Uncontrolled Keywords:Density functional theory, vanadium, EPR spectroscopy, spin-orbit effect, metal proteins
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:Wiley
ISSN:0192-8651
eISSN:1096-987X
Copyright Holders:© 2011 Wiley Periodicals
Deposited On:25 Jul 2011 16:24

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