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An FTIR study of tetrahedrally coordinated ferrous iron in the spinel-hercynite solid solution

Department of Mineralogy, Swedish Museum of Natural History, Box 50007, SE-104 05 Stockholm, Sweden

Correspondence: ^* E-mail: henrik.skogby{at}nrm.se

Room-temperature FTIR spectra of ten chemically and structurally well-characterized synthetic spinel-hercynite solid solution single crystals containing between 4 and 98 mol% hercynite component show that absorption in the range 2500–7000 cm^–1 is linearly correlated (R² = 0.995) with ^IVFe²⁺ concentration. The integral molar absorption coefficient for this absorption equals 1.49·10⁸ cm/mol. In addition, the structure of the absorption envelope in this spectral region remains unchanged throughout the entire composition range. These two findings are consistent with assignments to a spin-allowed electronic d-d transition (⁵E ⁵T₂) in ^IVFe²⁺, split by the dynamic Jahn-Teller effect, and demonstrate that next-nearest interactions in Fe clusters have little or no effect on this absorption feature at ambient conditions.

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