Site occupancy determination for manganese in some spinel-type oxides by Kβ X-ray fluorescence spectra

Site occupancy of cations in spinel-type oxides is sometimes extremely difficult to solve by the conventional crystallographic analysis based on diffraction methods. The present report describes successful determination for manganese spinels by analyzing Kβ X-ray fluorescence spectra, which are essentially sensitive to chemical environments such as oxidation and/or coordination numbers. Instead of looking at peak positions and/or shapes of the spectra, the intensity ratios of Kβ′ satellite and Kβ5 lines were investigated in detail. It has been found that the spectra are apparently classified depending on the manganese site occupancy whether tetrahedral A or octahedral B. Applications to some spinel-type oxides, for which the manganese states have not yet been fully solved so far, were also discussed.