57Fe-Moessbauer spectra, electronic and crystal structure of members of the CuS2-FeS2 solid solution series

Abstract

Members of the (Cu, Fe)S2 solid solution crystallize in the pyrite structure type, space group Pa 3, Cu and Fe being statistically distributed on the metal sites. Within this series, a semiconductor to metal transition can be detected between 25 and 38 mole% CuS2. Compositional dependent 57Fe-Moessbauer spectra reveal Fe2+ in low-spin configuration. A minimum of the quadrupole splitting and the slope in the 57Fe-isomer shift in the intermediate part of the system, near 30 mole% CuS2, can be correlated with the onset of metallic conductivity, whereas the structural parameters are not influenced by this transition. The analysis of the compositional dependency of the quadrupole splitting, in comparison to the isotypic system (Co, Fe)S2, leads to the conclusion that Cu in solid (Cu, Fe)S2 compounds is Cu+ with an Ar -3 d10 electronic configuration.