First-principles study of structural phase transitions and metallization of XPSe3 (X = Fe, Mn) under high pressure

The pressure-induced structural phase transition and metallization of FePSe3 and MnPSe3 are investigated from ambient pressure to 40 GPa by first-principles calculation. FePSe3 and MnPSe3 undergo reversible structural transitions from R3¯ structure to C2/m structure and then to P3¯1m structure. The structural phase transitions of FePSe3 are at about 6 GPa and 13 GPa, while the pressure points are at approximately 13 GPa and 25 GPa for MnPSe3, reflecting from pressure-dependent enthalpy calculation, cell volume collapses, and sudden changes of lattice parameters. The computed metallization transition is also observed at around 8 GPa and 16 GPa owing to energy-band closure for FePSe3 and MnPSe3, respectively. The metallic character of XPSe3 is strengthened with increasing pressure based on the electronic energy band and electron density of states. The layer sliding of atoms is revealed using the P2-P3 atom pair of XPSe3 during structural phase transitions. The paper is conducive to considering the electronic structure and metallization of transition metal thiophosphates XPSe3-type family under extreme conditions.