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Incommensurately modulated ordering of tetrahedral chains in Ca2Fe2O5 at elevated temperatures
Hannes Krüger1, Volker Kahlenberg
1Institut für Mineralogie und Petrographie der Leopold-Franzens-Universität, A-6020 Innsbruck, Austria. hannes.krueger@uibk.ac.at
Abstract:
The basic building units of brownmillerite-type A2B2O5 structures are perovskite-like layers of corner-sharing BO6 octahedra and zweier single chains of BO4 tetrahedra. A three-dimensional framework is formed by alternate stacking of octahedral layers and sheets of tetrahedral chains. The compound Ca2Fe2O5 is known to have Pnma symmetry at ambient conditions. The space group Imma was reported to be evident above 963 K. New high-temperature single-crystal X-ray diffraction experiments at 1100 K revealed that Ca2Fe2O5 forms an incommensurately modulated structure adopting the superspace group Imma(00gamma)s00, with gamma = 0.588 (2). The modulation affects the sequence of the enantiomorphic (right- and left-handed) oriented tetrahedral chains within the layer, breaking the lattice periodicity along c. This ordering can be modelled with crenel occupation modulation functions for the tetrahedrally coordinated Fe, as well as for the O atom interconnecting the tetrahedra.
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