In this article, we report the structural phase transitions in Bi4V2O11 as observed from temperature-dependent Raman scattering and X-ray diffraction measurements. Four different types of highly disordered coordination polyhedra around the vanadium atoms with large dispersion of V–O bond lengths are observed in Bi4V2O11 at ambient temperature. The observed V–O bond lengths could be grouped into two categories, viz. shorter <1.7 Å and longer >1.7 Å. The Raman modes of Bi4V2O11 could be assigned to vibration of these bonds and V–O–V linkages. We could correlate the difference in degree of anharmonicity of the phonon modes with temperature to differences in V–O bond strength. The local structure of vanadium–oxygen network in Bi4V1.8Cu0.2O10.7 was also obtained by similar studies. The effect of highly disordered anion sublattice in the doped compound is reflected in the broadening of the Raman modes.
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