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AbstractAn investigation of the relative stabilities and equations of state of possible Fe3S polymorphs was conducted using first-principles pseudopotential calculations. These calculations were based on density functional theory and performed using ultrasoft Vanderbilt pseudopotentials within the generalized gradient approximation. In accord with experiment, we found that the tetragonal Fe3P-type polymorph is the only stable phase along the 0 K isotherm as a function of pressure. Fe3S exhibits permanent magnetism at ambient conditions (Fei et al., 2000), but magnetism is suppressed by pressure and temperature, and therefore non-magnetic data are appropriate ones to use for modelling planetary interiors. For this reason, and because the Fe3P-type polymorph of Fe3S contains 32 atoms per unit cell it was impractical to incorporate magnetic properties into the simulations of this phase, we studied the behaviour of the non-magnetic phase. We obtained values of 250 GPa for the bulk modulus, K0, and 4.61 for its first derivative withrespect to pressure, K0', by fitting a 3rdorder Birch-Murnaghan equation of state to the calculated internal energy as a function of volume for the non-magnetic Fe3P-type Fe3S. This suggests that a pressure far greater than that expected in the Martian interior would be needed to achieve a density comparable to that of the Martian core. We therefore conclude that it is unlikely that the core of Mars contains significant amounts of solid Fe3S.

AbstractAn investigation into the relative stabilities and equations of state of stoichiometric FeS was conducted using first-principles pseudopotential calculations. These calculations were based on density functional theory and performed using ultrasoft Vanderbilt pseudopotentials within the generalized gradient approximation. We have identified four stable polymorphs of FeS along the 0 K isotherm as a function of pressure: troilite, an orthorhombic MnP-type structure, a monoclinic structure, and a CsCl-type structure. The calculated internal energy as a function of volume for each polymorph was fitted to 4thorder logarithmic and 3rdorder Birch-Murnaghan equations of state, yielding values for the bulk modulus, K, and its first and second derivatives with respect to pressure, K' and K?. These equations of state may be used to characterize models of planetary cores.

AbstractThe structure and elastic properties of MgSiO3, a major mantle-forming phase, have been simulated using computer models which predict the minimum energy structure by using interatomic pair potentials to describe the net forces acting between the atoms. Four such interatomic potentials were developed in this study, and are compared with potential N1 of Miyamoto and Takeda (1984). The most successful potential (W3) was derived by fitting the short range potential parameters to both the experimentally obtained structural and elastic properties of MgSiO3perovskite. The relative stabilities of some of the possible perovskite polymorphs, the orthorhombic, cubic, and tetragonal phases and hexagonal polytypes, were evaluated at 0 K and between 1 bar and 2 Mbar. The orthorhombic phase is found to be stable at all but the highest pressures, where the cubic phase may be stable. The temperature of the ortho-rhombic to cubic transition may decrease with increasing pressure. The energy of a stacking fault on (110) in the cubic phase was estimated using the ANNNI model and found to be about 1.95 J m-2using potential W3. The distance of separation of partial dislocations of this type is predicted to increase with increasing pressure from 8.4 Å at 1 bar to 9.2 Å at 1 Mbar.

AbstractSvetlozarite, previously described as a new member of the mordenite group of zeolites, is reinterpreted as a multiply twinned and highly faulted dachiardite. X-ray diffraction study and transmission electron microscopy revealed (001) twins and (100) stacking faults. The former are attributed at least mainly to the insertion of a bglide plane between dachiardite sheets at each twin interface, which preserves the 5-ring linkages between the sheets. The latter are associated with loss of the Cface-centring relation, and are attributed to replacement of shared 5-rings by linked 4-rings in the dachiardite sheets. Further study is needed to determine whether the structural faults in the dachiardite structures are chemically controlled.

AbstractIn order to be able to use the nature and scale of the exsolution microstructures developed in titanomagnetites as quantitative indicators of thermal history, it is necessary to have available accurate diffusion data for the system. Diffusion data for pure magnetite and Ti-poor titanomagnetites are available, but no data for diffusion in the centre of the solid-solution series exist. In order to obtain values for the activation energy (?E) and the pre-exponential factor (D0) for the interdiffusion of Fe and Ti in ulvöspinel-rich titanomagnetites, the natural microstructures developed in titanomagnetites from the Taberg intrusion, Sweden, were homogenized over a range of temperatures from 490 to 730 °C. From the model describing homogenization, values of 49.8 kcal mole-1and 2.38 × 10-3cm2s-1were calculated for ?Eand D0respectively. Although the results obtained from these homogenization experiments are slightly less accurate than those which could be obtained by more conventional methods, the homogenization technique has several advantages which outweigh this drawback, namely the ease with which the experiment can be performed and the fact that the diffusion data can be obtained at significantly lower temperatures than is usually possible with more conventional methods.

SummaryChrome spinels from seams in the Rhum layered intrusion, Inner Hebrides, generally contain very fine platelets of exsolved phases. Despite the low bulk Ti content (< 1%) of the spinel grains, analytical electron microscopy shows these platelets to be highly enriched in titanium. Electron diffraction indicates the presence of platelets of two different phases, one a magnesian ilmenite, the other a defect spinel intermediate phase. The platelets are the result of oxidation of the spinel at moderate (c.600 °C) temperatures and their distribution suggests that oxygen fugacity gradients existed across some of the seams.