Phonon softening induced cubic-to-tetragonal phase transition in ReO3

Within density functional theory, the structural, electronic and lattice dynamical properties of ReO3 in cubic Pm-3m and tetragonal P4/mbm phases are studied by using quasiharmonic approximation. The enthalpy-pressure curves show that a phase transition may take place at 5.0 kbar and the nonexistence of imaginary frequency in phonon dispersions demonstrates the two phases are dynamically stable under proper conditions. With the increase of pressure, an obvious softening of M3 mode at M point appears in cubic phase, and a cubic-to-tetragonal phase transition is accompanied with the presence of negative frequency in M3 mode at 5.0 kbar. In detail, one type of O atoms displaced from x=0.2500 to x=0.2401, which corresponds to the softening of M3 mode, are responsible for the phase transition. Our theoretical results show that ReO3 can exist in the tetragonal P4/mbm phase, and a cubic-to-tetragonal phase transition will appear at around 5.0 kbar.