Crystal chemistry of iron-containing perovskites

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Abstract
A review of existing and new structural and Mössbauer data for iron-containing perovskites is presented. A systematic trend between mean M-O bond length and centre shift is determined for Fe2+ and Fe3+ in oxide minerals and silicates, which can be used to determine the valence and site distribution for iron in perovskites where this information is not yet known. Existing centre shift data recorded at different temperatures for rare earth orthoferrites and for bernalite, Fe(OH)3, are fit to a Debye model to determine values for the intrinsic isomer shift and the characteristic Mössbauer temperature. High-pressure phases of FeTiO3 and Fe2O3 with the perovskite structure are discussed with respect to the valence and site distribution of iron. Using systematics between bond length and centre shift, the valence and site distribution of iron are determined for some phases where iron is a minor component, including naturally-occurring perovskites and the high-pressure phase (Mg,Fe)SiO3 perovskite. The latter phase is discussed with respect to the stabilisation of iron in the perovskite structure with the presence of Al3+.

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