Crystal structure, Raman spectrum and lattice dynamics of a new metastable form of tellurium dioxide: γ-TeO2

Abstract The crystal structure of a new metastable form of tellurium dioxide, γ-TeO 2 (orthorhombic, P 2 1 2 1 2 1 (no. 18); a=4.898 A , b=8.576 A , c=4.351 A ; Z =4) was solved ab initio and refined to R B =0.0387 and R p =0.115, on the basis of a Rietveld analysis of its powder X-ray diffraction pattern. Each Te atom is coordinated to four oxygen atoms, and its coordination polyhedron has a view of distorted trigonal bipyramid (disphenoid) TeO 4 E with one equatorial corner occupied by lone pair E. These units frame a three-dimensional network of the same type as the α-TeO 2 one. There exist two different kinds of Te–O–Te bridges in γ-TeO 2 ; one of them is nearly symmetric, and the other is highly asymmetric. The former bridges constitute polymeric chains along the O z -axis. Such a characterization of the γ-TeO 2 structure is supported by the analysis of the Raman spectra using the lattice dynamical model treatment in which the lattice vibrations are considered jointly with the elastic properties. All the longwave frequencies and the elastic constants were thus estimated. Possible relations between the structure of the TeO 2 glass and the γ-phase are discussed.