Aquacomplexes of ions of Group IB-IVB metals in anomalous oxidation states (2S1/2 electron state):: a theoretical study

Ab initio calculations of aquacomplexes of the ions of Group IB-IVB metals in anomalous oxidation states (S-2(1/2) electron state) were carried out by the Becke-Lae-Yang-Parr (BLYP) density functional method using the Dunning-Hay DZ basis set. Optimum geometric parameters and electronic characteristics were determined of aquacomplexes M(H2O)(n)(z+), where Mz+ = Au-0 (n = 2, 4); Ag-0, Cu-0 (n = 2, 4, 6); Zn1+, Cd1+, Hg1+ (n = 4, 6); Ga2+, In2+, Tl2+ (n = 6); and Ge3+, Sn3+, Pb3+ (n = 6). The spin population on the central metal atom decreases as the atomic number increases in the corresponding periods. The energy of transition of the unpaired electron to the first vacant level increases in the same order. The results of calculations are in agreement with experimental data obtained by ESR and optical spectroscopy.