X-ray absorption study of molten yttrium trihalides.

The local structure and structural changes in molten YCl3-LiCl-KCl and molten YBr3-LiBr systems have been investigated by using a high-temperature extended X-ray absorption fine structure (EXAFS) technique. The behaviour of octahedral coordination of the halide ion (Cl(-) and Br(-)) around the Y(3+) ion has been studied by EXAFS of the Y K-absorption edge. The nearest Y(3+)-Cl(-) and Y(3+)-Br(-) distances and coordination numbers of halide ions around the Y(3+) ion do not change by mixing with the alkali halides. The stabilization of the (YCl6)(3-) and (YBr6)(3-) octahedral coordination by adding alkali halides was suggested by decreasing the Debye-Waller factor and the anharmonicity in the nearest Y(3+)-Cl(-) and Y(3+)-Br(-) interactions. The bridging structure of the (YBr6)(3-) octahedra sharing a Br(-) ion in the molten YBr3-LiBr system was studied by EXAFS of the Br K-absorption edge. The coordination number of Y(3+) around the Br(-) ion decreases from 2 in the pure melt to almost 1 in the 30mol% and 15mol% YBr3 melts. This suggests that the bridging is almost broken and the stable octahedron exists freely in the LiBr-rich melts.