Composition and temperature dependence of cesium-borate glasses by molecular dynamics.

The structural aspects of xCs2O-(1-x)B2O3 glasses have been investigated by molecular dynamics as functions of Cs2O content (x=0.2, 0.3, and 0.4) and temperature (T=300 and 1250 K). The tetrahedral (BØ4-) and triangular (BØ3,BØ2O-, and BØO2 (2-)) short-range order borate units were found to be the structure-building entities of the simulated glasses [Ø=bridging oxygen (BO) and O-=nonbridging oxygen (NBO) atom]. The increase of Cs2O content results in the progressive increase of the NBO-containing triangle population at the expense of the BO4- tetrahedral units. The same effect is caused by temperature increase at a fixed Cs2O content, and this was associated with the "fragile" characteristics of alkali borate glasses. A comparison of simulated Cs and Li borates showed very similar structures at x=0.2, but dissimilar ones when the alkali content exceeds this composition. In particular, for x>0.2 Cs borates exhibit a preference for NBO formation relative to Li borates. Differences in the microstructure of sites hosting Cs ions were found, and this permits their classification into bridging (b type) and nonbridging type (nb type) of sites. b-type sites consist exclusively of BO atoms, while both BO and NBO atoms participate in nb-type sites. These differences in Cs-site local bonding characteristics were found to be reflected on the Cs-O(site) vibration frequencies. Also, the computed Cs-O vibrational responses for simulated Cs borates were found to compare well with experimental far-infrared spectra.