Phase transition and thermodynamic properties of BiFeO₃ from first-principles calculations

The first-principles projector-augmented wave method employing quasi-harmonic Debye model, is applied to investigate the thermodynamic properties and the phase transition between the trigonal R3c structure and the orthorhombic Pnma structure. It is found that at ambient temperature, the phase transition from the trigonal R3c phase to the orthorhombic Pnma phase is a first-order antiferromagnetic–nonmagnetic and insulator–metal transition, and occurs at 10.56 GPa, which is in good agreement with experimental data. With increasing temperature, the transition pressure decreases almost linearly. Moreover, the thermodynamic properties including Grüneisen parameter, heat capacity, entropy, and the dependences of thermal expansion coefficient on temperature and pressure are also obtained.