Structural Stability and Anharmonicity of Pr₂Ti₂O₇: Raman Spectroscopic and XRD Studies

Abstract

Herein we report results of pressure- and temperature-dependent Raman scattering studies on Pr 2 Ti 2 O 7 . Pressure-dependent studies performed up to 23 GPa suggest a reversible phase transition above 15 GPa with subtle changes. Temperature-dependent investigations performed in the range of 77–1073 K showed anomalous temperature dependence of some of the Raman modes. Temperature-dependent X-ray diffraction data indicated no structural transition but nonlinear expansion of unit-cell parameters with increasing temperature. With increasing temperature, the structure dilates anisotropically, and volume of coordination polyhedra around all the atoms expands. Also with increasing temperature the distortions in coordination polyhedra around all the atoms decrease, and appreciable decrease is observed in Pr(1)O 10 and Pr(3)O 9 units. The pressure evolution of Raman-mode frequencies was analyzed for both ambient as well as high-pressure phases, and mode Grüneisen parameters for ambient pressure phase were obtained. The temperature evolution of Raman-mode frequencies was analyzed to obtain the explicit and implicit anharmonic components, and it was found that some of the modes attributable to TiO 6 octahedra and PrO n polyhedra have dominating explicit anharmonic component. Comparison of the structural data with the temperature dependence of Raman modes suggests that the anomalous behavior in Raman modes is due to phonon–phonon interaction.