On the prediction of V-51 hyperfine coupling constants in (VO)-O-IV complexes through DFT methods

Density functional theory (DFT) calculations of the V-51 hyperfine coupling constants for 22 representative VIVO 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%.