In situ study of the $$ R\overline{3} c \to R\overline{3} m $$ orientational disorder in calcite

The temperature dependences of the crystal structure and intensities of the (113) and (211) reflections in calcite, CaCO₃, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction data. Calcite transforms from to at about T _c = 1,240 K. A CO₃ group occupies, statistically, two positions with equal frequency in the disordered phase, but with unequal frequency in the partially ordered phase. One position for the CO₃ group is rotated by 180° with respect to the other. The unequal occupancy of the two orientations in the partially ordered phase is obtained directly from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x − 1. The a cell parameter shows a negative thermal expansion at low T, followed by a plateau region at higher T, then a steeper contraction towards T _c, where the CO₃ groups disorder in a rapid process. Using a modified Bragg–Williams model, fits were obtained for the order parameter S, and for the intensities of the (113) and (211) reflections. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.