Isothermal equation of state and high-pressure phase transitions of synthetic meridianiite (MgSO4.11D2O) determined by neutron powder diffraction and quasielastic neutron spectroscopy

We have collected neutron powder diffraction data from MgSO4.11D(2)O (the deuterated analogue of meridianiite), a highly hydrated sulfate salt that is thought to be a candidate rock-forming mineral in some icy satellites of the outer solar system. Our measurements, made using the PEARL/HiPr and OSIRIS instruments at the ISIS neutron spallation source, covered the range 0.1 < P < 800 MPa and 150 < T < 280 K. The refined unit-cell volumes as a function of P and T are parameterized in the form of a Murnaghan integrated linear equation of state having a zero-pressure volume V-0 = 706.23 (8) angstrom(3), zero-pressure bulk modulus K-0 = 19.9 (4) GPa and its first pressure derivative, K-0 = 9 (1). The structure's compressibility is highly anisotropic, as expected, with the three principal directions of the unit-strain tensor having compressibilities of 9.6 x 10(-3), 3.4 x 10(-2) and 3.4 x 10(-3) GPa(-1), the most compressible direction being perpendicular to the long axis of a discrete hexadecameric water cluster, (D2O)(16). At high pressure we observed two different phase transitions. First, warming of MgSO4.11D(2)O at 545 MPa resulted in a change in the diffraction pattern at 275 K consistent with partial (peritectic) melting; quasielastic neutron spectra collected simultaneously evince the onset of the reorientational motion of D2O molecules with characteristic time-scales of 20-30 ps, longer than those found in bulk liquid water at the same temperature and commensurate with the lifetime of solvent-separated ion pairs in aqueousMgSO(4). Second, at similar to 0.9 GPa, 240 K, MgSO4.11D(2)O decomposed into high-pressure water ice phase VI and MgSO4.9D(2)O, a recently discovered phase that has hitherto only been formed at ambient pressure by quenching small droplets of MgSO4(aq) in liquid nitrogen. The fate of the high-pressure enneahydrate on further compression and warming is not clear from the neutron diffraction data, but its occurrence indicates that it may also be a rock-forming mineral in the deep mantles of large icy satellites.