Acta Crystallographica Section B

Structural Science

Volume 53, Part 1 (February 1997)

research papers

Acta Cryst. (1997). B53, 102-112 [ doi:10.1107/S0108768196010403 ]

Distortion Characteristics Across the Structural Phase Transition in (Cu_1-xZn_x)WO₄

P. F. Schofield, K. S. Knight, S. A. T. Redfern and G. Cressey

Abstract: Rietveld analysis of neutron powder diffraction data on the sanmartinite (ZnWO₄)-cuproscheelite (CuWO₄) solid solution has enabled the comparison of microscopic and macroscopic order parameters associated with the P2/c-P $\overline 1$ structural phase transition. The macroscopic spontaneous strain, calculated from the lattice parameters, conforms well with a second-order Landau model. Furthermore, this is also true of the symmetry-related atomistic M-O order parameter and the quadratic elongation of the MO6 octahedra. It is clear that the Jahn-Teller effect, associated with the divalent Cu cation, is the driving force for the phase transition and the excess elongation evident in the M-O(2) bond giving rise to the non-symmetry predicted strain element e₂₂. The existence of a large region of order parameter saturation at the copper-rich end of the solid solution is also associated with the MO6 elongation and the breakdown of the homogeneous strain field of the zinc solute atoms.