EPR and Optical Studies of Mo5+ Ions in Lithium Molybdoborate Glasses

Abstract

Electron paramagnetic resonance (EPR) and optical absorption studies of Li2O–MoO3–B2O3 with varying concentrations of Li2O, MoO3 and B2O3 have been carried out at room temperature. Two series of glasses, one with constant MoO3 (CM) and another with constant borate (CB), have been investigated. Characteristic EPR spectra of Mo5+ have been observed centered around g ≅ 2.00, which are attributed to Mo5+ ion in an octahedral coordination sphere with an axial distortion. The spectra also show strong dependence on the concentration of Li2O and B2O3. Spin concentrations (N) and magnetic susceptibilities (χ) have been calculated. In the CM series, the N values decrease with increasing Li2O content up to 30 mol%, while in the CB series variation of N is found to increase initially up to 20 mol%, and with further increase in the Li2O content the N values tend to decrease. The variation of magnetic susceptibilities is almost similar to that observed with the variation of N. From the optical absorption spectra, an absorption edge (α) has been evaluated. In the CM series, the values of α show a blueshift. On the other hand, in the CB series a redshift is observed. The observed variations in spectral parameters are explained by considering the molybdoborate network. Addition of Li2O to the CM and CB series results in modification of [MoO6/2]0 → [MoOO5/2]− and [BO3/2]0 → [BO4/2]− → [BOO2/2]− groups, respectively, leading to creation of nonbridging oxygens. The optical basicity of the glasses has been evaluated in both the CM and the CB glasses. The optical basicity can be used to classify the covalent-to-ionic ratios of the glass, since an increasing optical basicity indicates decreasing covalency. It is observed that the covalency between Mo5+ ions and oxygen ligands increases in the CB series, whereas in the CM series the covalency between Mo5+ ions and oxygen ligands decreases.