Pressure-induced magnetic, structural, and electronic phase transitions in LaFeO3: A density functional theory (generalized gradient approximation) + U study

We have investigated the behavior of orthoferrite LaFeO3 at ambient conditions and under pressure using DFT (generalized gradient approximation (GGA)) + U approach. Ground state electronic (band gap) and magnetic properties are considerably improved due to the Hubbard correction. Moreover, the experimentally observed pressure-driven phase transition, namely, the simultaneous occurrence of spin crossover, isostructural volume collapse, and drastic reduction in electrical resistance (electronic phase transition) is nicely described by GGA + U calculations. In particular, despite a sharp drop in resistance, a small band gap still remains in the low spin state indicating an insulator to semiconductor phase transition, in good agreement with the experiments but in contrast to GGA, which predicts metallic behavior in low spin state. We discuss the origin of variation in electronic structure of LaFeO3 in low spin state as obtained from GGA to GGA + U methods. These results emphasize the importance of correlation effects in describing the pressure-driven phase transition in LaFeO3 and other rare-earth orthoferrites.