Crystal structure, hydrogen bonding, and high-pressure behavior of the hydroxide perovskite MgSi(OH)6: A phase relevant to deep subduction of hydrated oceanic crust

Abstract

Abstract The structural response to compression of the synthetic high-pressure hydroxide perovskite MgSi(OH)6, the so-called “3.65 Å phase,” has been determined to 8.4 GPa at room temperature using single-crystal XRD in the diamond-anvil cell. Two very similar structures have been determined in space groups P21 and P21/n, for which differences in oxygen donor-acceptor distances indicate that the non-centrosymmetric structure is likely the correct one. This structure has six nonequivalent H sites, of which two are fully occupied and four are half-occupied. Half-occupied sites are associated with a well-defined crankshaft of hydrogen-bonded donor-acceptor oxygens extending parallel to c. Half occupancy of these sites arises from the averaging of two orientations of the crankshaft H atoms (|| ±c) in equal proportions. The P21 and P21/n structures are compared. It is shown that the former is likely the correct space group, which is also consistent with recent spectroscopic studies that recognize six nonequivalent O-H. The structure of MgSi(OH)6 at pressures up to 8.4 GPa was refined in both space groups to see how divergent the two models are. There is a very close correspondence between the responses of the two structures implying that, at least to 8.4 GPa, non-centrosymmetry does not affect compressional behavior. The very different compressional behavior of MgO6 and SiO6 octahedra observed in this study suggests that structural phase transformations or discontinuities likely occur in MgSi(OH)6 above 9 GPa.