On the prediction of 51V hyperfine coupling constants in VIVO complexes through DFT methods

Abstract

Density functional theory (DFT) calculations of the ⁵¹V hyperfine coupling constants for 22 representative V^IVO complexes with different donor set, electric charge and geometry were performed with Gaussian 03 software. The prediction of A tensor was carried out with five functionals (B3LYP, B3P86, B3PW91, BHandHLYP and BHandH) and four basis sets (6-31g, 6-311g, 6-311+g and 6-311g(d,p)). An excellent agreement with the experimental A_z value (A_z^exptl) was obtained using half-and-half hybrid functionals, such as BHandHLYP or BHandH. They, coupled with the 6-311g(d,p) basis set, yield deviations from |A_z|^exptl lower than 5% and, in most of the cases, lower than 3%.