Abstract
The structural properties of the perovskite system Ba(Bi 1− x Li x )O 3− y have been investigated for 0.0 < x < 0.25. Over this composition range, the nominal Bi oxidation state varies between +4 and +4.33 and no superconducting propeties were observed. The Li-rich end member of this series, Ba 4Bi 3LiO 11, exhibits a new type of superstructure due to cation order in the octahedral sites—tetragonal P4 mmm , Z = 1, a = 6.101(1), b = 8.628(2) Å. The ordered structure is different from that observed for the analogous Ba 4 M 3LiO 12 phases where M = Sb, Nb, Ta, and possible reasons for this are discussed. In particular, the structures of the Sb and Bi phases are compared in detail using Madelung energy calculations.
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