Germanium dioxide was found to undergo a transition from the tetragonal rutile-type to the orthorhombic CaCl2-type phase above 25 GPa. The detailed structural evolution of both phases at high pressure in a diamond anvil cell has been investigated by Rietveld refinement using angle-dispersive, X-ray powder-diffraction data. The square of the spontaneous strain (a - b)/(a + b) in the orthorhombic phase was found to be a linear function of pressure and no discontinuities in the cell constants and volume were observed, indicating that the transition is second-order and proper ferroelastic. Compression of the GeO6 octahedra was found to be anisotropic, with the apical Ge-O distances decreasing to a greater extent than the equatorial distances and becoming shorter than the latter above 7 GPa. Above this pressure, the GeO6 octahedron exhibits the common type of tetragonal distortion predicted by a simple ionic model and observed for most rutile-type structures such as those of the heavier group-14 dioxides and the metal difluorides. Above the phase transition, the columns of edge-sharing octahedra tilt about their two fold axes parallel to c and the rotation angle reaches 10.2(5)°by 36(1) GPa so as to yield a hexagonal close-packed oxygen sublattice. The compressibility increases at the phase change as is expected for a second-order transition at which an additional compression mechanism becomes available.
CITATION STYLE
Haines, J., Leger, J. M., Chateau, C., & Pereira, A. S. (2000). Structural evolution of rutile-type and CaCl2-type germanium dioxide at high pressure. Physics and Chemistry of Minerals, 27(8), 575–582. https://doi.org/10.1007/s002690000092
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