Abstract
The valence state of iron in Cu12−xFexSb4S13 tetrahedrites have been revisited by the combination of the crystallographic results, Mössbauer spectroscopy, and magnetization measurements. The crystal structure solution for Cu11.0Fe1.0Sb4S13 (space group I4¯3m, a=10.3253(12), z=2, R=0.011) proved that iron substitutes for copper only in the Cu1 position. At the iron content of x=0.8, 1.0, and 1.2, the presence of two nonequivalent and non-interacting Fe3+ cations was inferred from Mössbauer spectra. At higher levels of substitution (x=1.5 and 2.0), room-temperature Mössbauer spectra indicate the electron hopping between part of Fe3+ and Fe2+ centers, whereas the rest of iron atoms exists as valence-localized Fe3+ and Fe2+ cations. Electron transfer is frozen out at 77K, where a combination of two Fe3+ sites and one high-spin Fe2+ site is observed. Paramagnetic effective moments extracted from the magnetic susceptibility data point at the Fe3+ state of iron at x=0.8, while a mixture of Fe2+ and Fe3+ is presumed in the samples with higher Fe content.
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