Disorder in BaThF6 – refinement of anharmonic displacement parameters from high-pressure single-crystal X-ray diffraction data

Abstract

The structure of BaThF₆ has been investigated as a function of temperature and pressure with single-crystal X-ray diffraction using synchrotron radiation. The compound crystallizes in the tysonite structure, space groupP6₃/mmc (a = 4.296(1) Å and c = 7.571(1) Å at ambient conditions). It is stable at least down to 150 K and up to 4 GPa. In the entire range of pressures and temperatures studied here, the compound is characterized by a high degree of disorder, both on the cationic and anionic positions. Despite the different valence states and sizes, both cations occupy the same crystallographic site in the ideal tysonite structure. The cationic disorder is described by two alternative approaches. The first model corresponds to a split-atom position model in which Ba²⁺ is maintained on a special position with site symmetry m2, while Th⁴⁺ is slightly displaced from the respective position. In the second model, both cations are maintained on the ideal position and anharmonic displacement parameters using a tensor of third order are introduced. Anharmonic displacement parameters have been refined from high-pressure single-crystal X-ray data measured in situ in a diamond anvil cell for the first time. The feasibility and general problems of anharmonic refinements of high-pressure X-ray data are further commented.