Abstract
This paper reports a vibrational spectroscopic study of a series of glasses composed of Li-Ba-Th-Zr-fluoride in which Th/sup 4 +/ is progressively replaced by Zr/sup 4 +/. In these glasses, Zr/sup 4 +/ shows a more pronounced variation in coordination number than previously observed. Distinct infrared reflectance and polarized Raman bonds due to Th/sup 4 +/ polyhedra are present only in the glasses containing less than 10 mole% ZrF/sub 4/. In the glasses containing 10 or more mole% ZrF/sub 4/, Raman and infrared bands due to Zr/sup 4 +/ polyhedra dominate the vibrational spectra, even in glasses where the ThF/sub 4/ concentration is greater than the ZrF/sub 4/ concentration. The difference in structural behavior or the Th/sup 4 +/ polyhedra as compared to the Zr/sup 4 +/ polyhedra is believed to be due to the smaller electric field intensity of the Th/sup 4 +/ and to the relatively restricted ability of Th/sup 4 +/ to vary its coordination number in response to the availability of F/sup 1 -/.
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