Electronic structures of greigite (Fe(3)S(4)): A hybrid functional study and prediction for a Verwey transition

Greigite (Fe(3)S(4)) is a ferrimagnetic mineral with vital functions in both the bio-geochemical cycle and novel technological applications. However, the ground state electronic structure of this material has not been fully characterized by either experiment or theory. In the present study, ab initio calculations using the hybrid functional method have been performed to investigate the electronic structure and magnetic properties. It is found that the cubic structure observed under ambient temperature is a half metal and is metastable. A more stable monoclinic structure slightly distorted from the cubic form is found. The structural distortion is induced by charge ordering and associated with a metal-to-insulator transition, resulting in a semiconductive ground state with a bandgap of ~0.8 eV and a magnetic moment of 4 μB per formula unit. The results predict, similar to the magnetite (Fe(3)O(4)), a Verwey transition may exist in greigite, although it has not yet been observed experimentally.