Rotational phase transitions in antifluorite-type osmate and iridate compounds.

ABSTRACT

We present temperature-dependent single-crystal diffraction results on seven antifluorite-typeA2MeX6compounds withMe= Os or Ir K2OsCl6,A2OsBr6withA= K, Rb, Cs and NH4, and K2IrX6withX= Cl and Br. The structural transitions in this family arise fromMeX6octahedron rotations that generate a rich variety of symmetries depending on the rotation axis and stacking schemes. In order to search for local distortions in the high-symmetry phase we perform refinements of anharmonic atomic displacement parameters with comprehensive data sets. Even at temperatures close to the onset of structural distortions, these refinements only yield a small improvement indicating only small anharmonic effects. The phase transitions in these antifluorites are essentially of displacive character. However, some harmonic displacement parameters are very large reflecting soft phonon modes with the softening covering large parts of the Brillouin zone. The occurrence of the rotational transitions in the antifluorite-type family can be remarkably well analyzed in terms of a tolerance factor of ionic radii.