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The sequence of transitions between different phases of BiNbO4 has been thoroughly investigated and clarified using thermal analysis, high-resolution neutron diffraction, and Raman spectroscopy. The theoretical optical phonon modes of the α-phase have been calculated. Based on thermoanalytical data supported by density functional theory (DFT) calculations, the β-phase is proposed to be metastable, while the α- and γ-phases are stable below and above 1040 °C, respectively. Accurate positional parameters for oxygen positions in the three
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