Origin of pressure‐induced insulator‐to‐metal transition in the van der Waals compound FePS3 from first‐principles calculations

Pressure‐induced insulator‐to‐metal transition (IMT) has been studied in the van der Waals compound iron thiophosphate (FePS3) using first‐principles calculations within the periodic linear combination of atomic orbitals method with hybrid Hartree–Fock‐DFT B3LYP functional. Our calculations reproduce correctly the IMT at ∼15 GPa, which is accompanied by a reduction of the unit cell volume and of the vdW gap. We found from the detailed analysis of the projected density of states that the 3p states of phosphorus atoms contribute significantly at the bottom of the conduction band. As a result, the collapse of the band gap occurs due to changes in the electronic structure of FePS3 induced by relative displacements of phosphorus or sulfur atoms along the c‐axis direction under pressure. Pressure‐induced phase transitions in iron thiophosphate (FePS3) at ∼4 GPa and ∼15 GPa were studied using first‐principles calculations. The calculations reproduce the insulator‐to‐metal transition (IMT) at ∼15 GPa, accompanied by a reduction of the unit cell volume and of the van der Waals gap. The origin of the IMT is attributed to the pressure‐induced changes in the FePS3 electronic structure caused by the relative displacement of phosphorus or sulfur atoms along the c‐axis direction.