Synthetic norsethite, BaMg(CO3)2: revised crystal structure, thermal behaviour and displacive phase transition

Abstract

AbstractThe crystal structure of synthetic BaMg(CO3)2whose mineral name is norsethite was re-investigated by single-crystal X-ray diffraction. Complementaryin situhigh- and low-temperature studies by means of vibrational spectroscopy (Raman, IR), powder X-ray diffraction techniques and thermal analyses were performed. Diffraction images (298 K) revealed weak superstructure reflections caused by the displacement of the O atoms in the earlier consideredRmstructure model (a = 5.0212(9), cnew= 2 cold= 33.581(6) Å ,Rc, Z = 6, R1 = 0.011, sinθ/λ < 0.99 Å–1). Thermal analyses reveal decarbonatization in two decomposition steps above 750 K, and the heat-flow curves (difference scanning calorimetry) give clear evidence of a weak and reversible endothermal change at 343±1 K. This agrees with a discontinuity in the IR and single-crystal Raman spectra. The changing trend of thec/aratio supports this discontinuity indicating a temperature-induced structural transition in the range between 343 and 373 K. As the change of the unit-cell volume is almost linear, the character of the transition is apparently second order and matches the mechanism of a subtle displacement of the oxygen atom position. The apparent instability of theRcstructure is also evidenced by the remarkably larger anisotropic displacement of the oxygen atom.