Infrared spectroscopy of CaGeO₃ perovskite to 24 GPa and thermodynamic implications

Far-infrared absorbance spectra were collected from CaGeO₃ with a metastable orthorhombic perovskite structure from 0 to 24.4 GPa. The absorbance data are compatible with a reflectance spectrum which was collected at ambient conditions from a polished, densely compacted polycrystal. The reflectance spectrum shows 18 IR modes from 155 to 786 cm⁻¹. A detailed model for the density of states constructed from these new data results in accurate calculation of heat capacity and new data on entropy. Peak positions increase linearly with pressure. Mode Grüneisen parameters (ranging from 0.72–1.56) decrease almost linearly with increasing mode frequency which is consistent with deformations of the oxygen sublattice dominating the lattice vibrations. Neither discontinuous changes in the number of modes nor in these frequencies nor in band widths are observed at pressures up to 24.4 GPa. Thus, conversion to the tetragonal phase at ∼12 GPa is not indicated.