Aquacomplexes of ions of Group IB-IVB metals in anomalous oxidation states(S-2(1/2) 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 characterist ics 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+, Tl 2+ (n = 6); and Ge3+, Sn3+, Pb3+ (n = 6). The spin population on the centra l metal atom decreases as the atomic number increases in the corresponding periods. The energy of transition of the unpaired electron to the first vac ant level increases in the same order. The results of calculations are in a greement with experimental data obtained by ESR and optical spectroscopy.