High-pressure single-crystal X-ray diffraction and infrared spectroscopic studies of the C2/m-P21/m phase transition in cummingtonite

Abstract

The structural changes associated with the C2/m-P2 1 /m phase transition in cummingtonite with (Fe+Mn)/(Fe+Mn+Mg) nearly equal 0.50 have been studied with single-crystal X-ray diffraction at various pressures up to 7.90 GPa and infrared spectroscopy up to 8.63 GPa. With increasing pressure, the crystal transforms from C2/m to P2 1 /m symmetry at approximately 1.21 GPa, as determined by the appearance of reflections violating the C2/m space group. Infrared spectra provide additional evidence for the phase transition: A distinct splitting of OH stretching bands results from an increase from one to two nonequivalent OH positions. The C2/m-P2 1 /m transition is of weakly displacive first-order or tricritical character with apparent slope changes in the plots of the axial ratios a/b and a/c as a function of pressure. The unit-cell compression is considerably anisotropic with the a dimension in both C2/m and P2 1 /m phases being the most compressible. Major structural changes for the C2/m-P2 1 /m transition include: (1) One crystallographically distinct silicate chain becomes two discontinuously, coupled by the splitting of the M4-05 bond, as well as M4-06, into two nonequivalent bonds, and (2) the M4-cation coordination increases from sixfold to sevenfold. More importantly, we observed a change in the sense of rotation for the A chain while the crystal structure maintains P2 1 /m symmetry: It is O rotated, as the B chain, at 1.32 GPa, but S-rotated at 2.97 GPa and higher pressures. As pressure increases from 1.32 to 7.90 GPa, there is a switching of the nearest bridging O atoms coordinated with the M4 cation: The M4-O5B distance contracts from 2.944 to 2.551 Aa, whereas the M4-O6B distance increases from 2.754 to 2.903 Aa. Compression mechanisms for the low-and high-pressure polymorphs appear to be slightly different. In the C2/m phase, the behavior of the A and M4 sites controls the compression of the structure, whereas the response of the M1, M2, and M3 octahedra to pressure also plays a role in determining the compression of the P2 1 /m structure. The phase transition is regarded as primarily driven by the differential compression between the M4 and T sites, and the symmetry breaking provides a necessary tighter coordination for the M4 site. Based on our data, the obvious changes in the hyperfine parameters of 57 Fe in grunerite between 1.0 and 3.4 GPa, observed by Zhang and Hafner (1992), are likely to result from the C2/m-P2 1 /m structural transformation.