High-pressure monoclinic–monoclinic transition in fergusonite-type HoNbO4

Abstract

In this paper we perform a high-pressure (HP) study of fergusonite-type HoNbO4. Powder x-ray diffraction experiments and ab initio density-functional theory (DFT) simulations provide evidence of a phase transition at 18.9(1.1) GPa from the monoclinic fergusonite-type structure (space group I2/a) to another monoclinic polymorph described by space group P21/c. The phase transition is reversible and the HP structural behavior is different than the one previously observed in related niobates. The HP phase remains stable up to 29 GPa. The observed transition involves a change in the Nb coordination number from 4 to 6, and it is driven by mechanical instabilities. We have determined the pressure dependence of unit-cell parameters of both phases and calculated their room-temperature equation of state. For the fergusonite-phase we have also obtained the isothermal compressibility tensor. In addition to the HP studies, we report ambient-pressure Raman and infrared (IR) spectroscopy measurements. We have been able to identify all the active modes of fergusonite-type HoNbO4, which have been assigned based upon DFT calculations. These simulations also provide the elastic constants of the different structures and the pressure dependence of the Raman and IR modes of the two phases of HoNbO4. According to ab initio calculations, the reported phase transition is related to a mechanical instability and a phonon softening.