2004 Volume 45 Issue 7 Pages 1982-1986
First principles calculations of hydrated polymolybdates complexes have been made with an atomic orbital basis molecular orbital method. Hydration effects are taken into account by the conductor-like screening model (COSMO) using dielectric constant of water. Hydrated heptapolymolybdate, Mo7O246−, shows a low symmetry structure, which agrees well to experimental results, i.e., X-ray diffraction of crystalline salts and X-ray absorption fine structure of the hydrated complex. Contrary to that, the hydrated heteropolymolybdate, NiMo6O2410− prefer to exhibit the high symmetry structure. Inspection of the electronic states found that the Ni ion exhibits trivalent state or d 7 configuration in a formal sense. Jahn-Teller distortion around Ni is therefore evident. Such distortion cannot be found in CrMo6O249− or CoMo6O249−.