Optical absorption spectra of s2 impurity ions in aqueous halide ion glasses

The optical absorption bands of aqueous 0·05 M Sn²⁺ in 7 M LiI at 77°K appear at 361, 352, 325, 310, 300, 292 and 262 nm. They are considered to be the A₁, A₂, B, C₁, C₂, C₃ and D′ bands since the positions and relative intensities lie within the range of those bands for Sn²⁺-doped alkali iodide crystals. Upon warming the glass there is an uncorrelated increase in the B band and a decrease in the A₁ band. In 3·6, 4·1, 4·6 and 5·1 M CaCl₂ glasses with 5×10^?3 M Sn²⁺ the A₁ and A₂ bands show uncorrelated increases with increasing concentration of Cl^?. Comparable observations are reported for Pb²⁺-doped glasses of lithium halides and CaI₂. In general the spectra of the Sn²⁺- and Pb²⁺-doped glasses correlate well with those of the corresponding crystal systems. The effect of temperature and halide-ion concentration are attributed to shifts in chemical equilibria among the well-known halo complexes, MX_n^2?n MX_n?1^1?n+X^?, each having a characteristic, absorption and emission. Absorptions may be attributed to M²⁺(³P₁ ← ¹S₀) and M²⁺(¹P₁ ← ¹S₀) in the complex, shifted by partially covalent bonding of n halide ions.