Critical vaporization of MgSiO3.

Inhomogeneous ab initio molecular dynamics simulations show that vaporization of MgSiO3 is incongruent and that the vapor phase is dominated by SiO and O2 molecules. The vapor is strongly depleted in Mg at low temperature and approaches the composition of the liquid near the critical point. We find that the liquid-vapor critical temperature ([Formula: see text] K) is much lower than assumed in hydrodynamic simulations, pointing to much more extensive supercritical fluid after the Moon-forming impact than previously thought. The structure of the near-critical liquid is very different from what has been studied previously and includes a significant fraction (10%) of molecular species SiO and O2.

Electrical conductivity of SiO2 at extreme conditions and planetary dynamos.

Ab intio molecular dynamics simulations show that the electrical conductivity of liquid SiO2 is semimetallic at the conditions of the deep molten mantle of early Earth and super-Earths, raising the possibility of silicate dynamos in these bodies. Whereas the electrical conductivity increases uniformly with increasing temperature, it depends nonmonotonically on compression. At very high pressure, the electrical conductivity decreases on compression, opposite to the behavior of many materials. We show that this behavior is caused by a novel compression mechanism: the development of broken charge ordering, and its influence on the electronic band gap.

Melting of CaSiO3 Perovskite at High Pressure.

Ab initio molecular dynamics simulations predict that CaSiO3 perovskite melts at 5600 K at 136 GPa, and 6400 K at 300 GPa, significantly higher than MgSiO3 perovskite. The entropy of melting (1.8 kB per atom) is much larger than that of many silicates at ambient pressure and of simple liquids and varies little with pressure. The volume of melting decreases rapidly with increasing pressure, to 3 % at 136 GPa, producing a melting slope that diminishes rapidly with pressure. We determine the melting temperature via the ZW method, combining the Z method, for which we clarify the theoretical basis, with a waiting time analysis. The ZW method results are internally confirmed by integrating the Clausius-Clapeyron equation, which also yields our results for the entropy and volume of melting. We find the eutectic composition on the MgSiO3-CaSiO3 join to be x Ca = 0.26 at 136 GPa and that metasilicate melt is denser than coexisting silicates.

Hydrous silicate melt at high pressure.

The structure and physical properties of hydrous silicate melts and the solubility of water in melts over most of the pressure regime of Earth's mantle (up to 136 GPa) remain unknown. At low pressure (up to a few gigapascals) the solubility of water increases rapidly with increasing pressure, and water has a large influence on the solidus temperature, density, viscosity and electrical conductivity. Here we report the results of first-principles molecular dynamics simulations of hydrous MgSiO3 melt. These show that pressure has a profound influence on speciation of the water component, which changes from being dominated by hydroxyls and water molecules at low pressure to extended structures at high pressure. We link this change in structure to our finding that the water-silicate system becomes increasingly ideal at high pressure: we find complete miscibility of water and silicate melt throughout almost the entire mantle pressure regime. On the basis of our results, we argue that a buoyantly stable melt at the base of the upper mantle would contain approximately 3 wt% water and have an electrical conductivity of 18 S m(-1), and should therefore be detectable by means of electromagnetic sounding.

Ultra-low-velocity anomaly inside the Pacific Slab near the 410-km discontinuity.

The upper boundary of the mantle transition zone, known as the "410-km discontinuity", is attributed to the phase transformation of the mineral olivine (α) to wadsleyite (ß olivine). Here we present observations of triplicated P-waves from dense seismic arrays that constrain the structure of the subducting Pacific slab near the 410-km discontinuity beneath the northern Sea of Japan. Our analysis of P-wave travel times and waveforms at periods as short as 2 s indicates the presence of an ultra-low-velocity layer within the cold slab, with a P-wave velocity that is at least ≈20% lower than in the ambient mantle and an apparent thickness of ≈20 km along the wave path. This ultra-low-velocity layer could contain unstable material (e.g., poirierite) with reduced grain size where diffusionless transformations are favored.

Structure of iron to 1 Gbar and 40, 000 K.

First-principles calculations show that compression-induced electronic transitions produce a rich phase diagram featuring reentrant stability of the fcc phase with an extremum on the fcc to hcp boundary at 23 Mbar and 19 000 K, conditions similar to those expected at the center of super-Earth exoplanets. Transformations of hcp to fcc at 57 Mbar due to 4s to 3d electron transfer and from fcc to a body-centered structure at 320 Mbar due to hybridization of the 3d with the core 3p band are experimentally observable along a quasi-isentrope generated by laser-induced ramp compression.

Measuring the melting curve of iron at super-Earth core conditions.

The discovery of more than 4500 extrasolar planets has created a need for modeling their interior structure and dynamics. Given the prominence of iron in planetary interiors, we require accurate and precise physical properties at extreme pressure and temperature. A first-order property of iron is its melting point, which is still debated for the conditions of Earth's interior. We used high-energy lasers at the National Ignition Facility and in situ x-ray diffraction to determine the melting point of iron up to 1000 gigapascals, three times the pressure of Earth's inner core. We used this melting curve to determine the length of dynamo action during core solidification to the hexagonal close-packed (hcp) structure. We find that terrestrial exoplanets with four to six times Earth's mass have the longest dynamos, which provide important shielding against cosmic radiation.

First-principles study of enhancement of transport properties of silica melt by water.

First-principles molecular dynamics simulations show that water (8.25 wt%) dramatically affects the transport properties of SiO2 liquid increasing the diffusivity and decreasing the viscosity by an order of magnitude. At 3000 K, the diffusivity of Si, O, and H, and the viscosity vary anomalously with pressure. Highly mobile protons make the hydrous liquid a potential superionic conductor. The predicted dynamical changes are associated with structural depolymerization and water speciation, which changes from being dominated by hydroxyls at low pressure to extended structures at high pressure.

Thermal conductivity of periclase (MgO) from first principles.

We combine first-principles calculations of forces with the direct nonequilibrium molecular dynamics method to determine the lattice thermal conductivity k of periclase (MgO) up to conditions representative of the Earth's core-mantle boundary (136 GPa, 4100 K). We predict the logarithmic density derivative a=(∂ln k/∂ln ρ)(T)=4.6±1.2 and that k=20±5 Wm(-1) K(-1) at the core-mantle boundary, while also finding good agreement with extant experimental data at much lower pressures.

A silicate dynamo in the early Earth.

The Earth's magnetic field has operated for at least 3.4 billion years, yet how the ancient field was produced is still unknown. The core in the early Earth was surrounded by a molten silicate layer, a basal magma ocean that may have survived for more than one billion years. Here we use density functional theory-based molecular dynamics simulations to predict the electrical conductivity of silicate liquid at the conditions of the basal magma ocean: 100-140 GPa, and 4000-6000 K. We find that the electrical conductivity exceeds 10,000 S/m, more than 100 times that measured in silicate liquids at low pressure and temperature. The magnetic Reynolds number computed from our results exceeds the threshold for dynamo activity and the magnetic field strength is similar to that observed in the Archean paleomagnetic record. We therefore conclude that the Archean field was produced by the basal magma ocean.

Heat and charge transport in H2O at ice-giant conditions from ab initio molecular dynamics simulations.

The impact of the inner structure and thermal history of planets on their observable features, such as luminosity or magnetic field, crucially depends on the poorly known heat and charge transport properties of their internal layers. The thermal and electric conductivities of different phases of water (liquid, solid, and super-ionic) occurring in the interior of ice giant planets, such as Uranus or Neptune, are evaluated from equilibrium ab initio molecular dynamics, leveraging recent progresses in the theory and data analysis of transport in extended systems. The implications of our findings on the evolution models of the ice giants are briefly discussed.

Oceanic plateau of the Hawaiian mantle plume head subducted to the uppermost lower mantle.

The Hawaiian-Emperor seamount chain that includes the Hawaiian volcanoes was created by the Hawaiian mantle plume. Although the mantle plume hypothesis predicts an oceanic plateau produced by massive decompression melting during the initiation stage of the Hawaiian hot spot, the fate of this plateau is unclear. We discovered a megameter-scale portion of thickened oceanic crust in the uppermost lower mantle west of the Sea of Okhotsk by stacking seismic waveforms of SS precursors. We propose that this thick crust represents a major part of the oceanic plateau that was created by the Hawaiian plume head ~100 million years ago and subducted 20 million to 30 million years ago. Our discovery provides temporal and spatial clues of the early history of the Hawaiian plume for future plate reconstructions.

Extrinsic Elastic Anisotropy in a Compositionally Heterogeneous Earth's Mantle.

Several theoretical studies indicate that a substantial fraction of the measured seismic anisotropy could be interpreted as extrinsic anisotropy associated with compositional layering in rocks, reducing the significance of strain-induced intrinsic anisotropy. Here we quantify the potential contribution of grain-scale and rock-scale compositional anisotropy to the observations by (i) combining effective medium theories with realistic estimates of mineral isotropic elastic properties and (ii) measuring velocities of synthetic seismic waves propagating through modeled strain-induced microstructures. It is shown that for typical mantle and oceanic crust subsolidus compositions, rock-scale compositional layering does not generate any substantial extrinsic anisotropy (<1%) because of the limited contrast in isotropic elastic moduli among different rocks. Quasi-laminated structures observed in subducting slabs using P and S wave scattering are often invoked as a source of extrinsic anisotropy, but our calculations show that they only generate minor seismic anisotropy (<0.1-0.2% of Vp and Vs radial anisotropy). More generally, rock-scale compositional layering, when present, cannot be detected with seismic anisotropy studies but mainly with wave scattering. In contrast, when grain-scale layering is present, significant extrinsic anisotropy could exist in vertically limited levels of the mantle such as in a mid-ocean ridge basalt-rich lower transition zone or in the uppermost lower mantle where foliated basalts and pyrolites display up to 2-3% Vp and 3-6% Vs radial anisotropy. Thus, seismic anisotropy observed around the 660-km discontinuity could be possibly related to grain-scale shape-preferred orientation. Extrinsic anisotropy can form also in a compositionally homogeneous mantle, where velocity variations associated with major phase transitions can generate up to 1% of positive radial anisotropy.

Melting in super-earths.

We examine the possible extent of melting in rock-iron super-earths, focusing on those in the habitable zone. We consider the energetics of accretion and core formation, the timescale of cooling and its dependence on viscosity and partial melting, thermal regulation via the temperature dependence of viscosity, and the melting curves of rock and iron components at the ultra-high pressures characteristic of super-earths. We find that the efficiency of kinetic energy deposition during accretion increases with planetary mass; considering the likely role of giant impacts and core formation, we find that super-earths probably complete their accretionary phase in an entirely molten state. Considerations of thermal regulation lead us to propose model temperature profiles of super-earths that are controlled by silicate melting. We estimate melting curves of iron and rock components up to the extreme pressures characteristic of super-earth interiors based on existing experimental and ab initio results and scaling laws. We construct super-earth thermal models by solving the equations of mass conservation and hydrostatic equilibrium, together with equations of state of rock and iron components. We set the potential temperature at the core-mantle boundary and at the surface to the local silicate melting temperature. We find that ancient (∼4 Gyr) super-earths may be partially molten at the top and bottom of their mantles, and that mantle convection is sufficiently vigorous to sustain dynamo action over the whole range of super-earth masses.

Viscosity of MgSiO3 liquid at Earth's mantle conditions: implications for an early magma ocean.

Understanding the chemical and thermal evolution of Earth requires knowledge of transport properties of silicate melts at high pressure and high temperature. Here, first-principles molecular dynamics simulations show that the viscosity of MgSiO3 liquid varies by two orders of magnitude over the mantle pressure regime. Addition of water systematically lowers the viscosity, consistent with enhanced structural depolymerization. The combined effects of pressure and temperature along model geotherms lead to a 10-fold increase in viscosity with depth from the surface to the base of the mantle. Based on these calculations, efficient heat flux from a deep magma ocean may have exceeded the incoming solar flux early in Earth's history.

Structure and freezing of MgSiO3 liquid in Earth's lower mantle.

First-principles molecular-dynamics simulations show that over the pressure regime of Earth's mantle the mean silicon-oxygen coordination number of magnesium metasilicate liquid changes nearly linearly from 4 to 6. The density contrast between liquid and crystal decreases by a factor of nearly 5 over the mantle pressure regime and is 4% at the core-mantle boundary. The ab initio melting curve, obtained by integration of the Clausius-Clapeyron equation, yields a melting temperature at the core-mantle boundary of 5400 +/- 600 kelvins.

First-principles study of illite-smectite and implications for clay mineral systems.

Illite-smectite interstratified clay minerals are ubiquitous in sedimentary basins and they have been linked to the maturation, migration and trapping of hydrocarbons, rock cementation, evolution of porewater chemistry during diagenesis and the development of pore pressure. But, despite the importance of these clays, their structures are controversial. Two competing models exist, each with profoundly different consequences for the understanding of diagenetic processes: model A views such interstratified clays as a stacking of layers identical to endmember illite and smectite layers, implying discrete and independently formed units (fundamental particles), whereas model B views the clays as composed of crystallites with a unique structure that maintains coherency over much greater distances, in line with local charge balance about interlayers. Here we use first-principles density-functional theory to explore the energetics and structures of these two models for an illite-smectite interstratified clay mineral with a ratio of 1:1 and a Reichweite parameter of 1. We find that the total energy of model B is 2.3 kJ atom(-1) mol(-1) lower than that of model A, and that this energy difference can be traced to structural distortions in model A due to local charge imbalance. The greater stability of model B requires re-evaluation of the evolution of the smectite-to-illite sequence of clay minerals, including the nature of coexisting species, stability relations, growth mechanisms and the model of fundamental particles.

Magnetism in dense hexagonal iron.

The magnetic state of hexagonal close-packed iron has been the subject of debate for more than three decades. Although Mössbauer measurements find no evidence of the hyperfine splitting that can signal the presence of magnetic moments, density functional theory predicts an antiferromagnetic (afm) ground state. This discrepancy between theory and experiment is now particularly important because of recent experimental findings of anomalous splitting in the Raman spectra and the presence of superconductivity in hexagonal close-packed iron, which may be caused by magnetic correlations. Here, we report results from first principles calculations on the previously predicted theoretical collinear afm ground state that strongly support the presence of afm correlations in hexagonal close-packed iron. We show that anomalous splitting of the Raman mode can be explained by spin-phonon interactions. Moreover, we find that the calculated hyperfine field is very weak and would lead to hyperfine splitting below the resolution of Mössbauer experiments.