Compression mechanism of GaF₃ and FeF₃: a high-pressure X-ray diffraction study

Abstract

The VF₃-type compounds MF₃ with M = Fe and Ga have been studied by high-pressure energy-dispersive X-ray diffraction. The compression mechanism was found to be highly anisotropic for both compounds, with the c-axis showing little pressure dependence. The volume reduction is mainly achieved through coupled rotations of the MF₆ octahedra around the c-axis, which reduces the length of the a-axis. The compression mechanism of both compounds is reasonably well described in terms of deformation of an 8/3/c2 sphere-packing model up to the pressures where the fluorine atoms become hexagonally close-packed. It is proposed that both compounds enter a phase with the fluorine atom arranged in a “super-dense” sphere packing at higher pressures. The zero pressure bulk modulus of FeF₃ and GaF₃ was determined as 12(2) and 37(3) GPa, respectively, and a scaling relation between the zero pressure bulk modulus and unit cell volumes was found for TiF₃, CrF₃, FeF₃ and GaF₃.

Keywords:

• compressibility
• crystal structure
• X-ray diffraction

Acknowledgements

The authors thank HASYLAB-DESY for permission to use the synchrotron radiation facility. DanScatt is gratefully acknowledged for financial support.