The pyrite-type high-pressure form of FeOOH.

Water transported into Earth's interior by subduction strongly influences dynamics such as volcanism and plate tectonics. Several recent studies have reported hydrous minerals to be stable at pressure and temperature conditions representative of Earth's deep interior, implying that surface water may be transported as far as the core-mantle boundary. However, the hydrous mineral goethite, α-FeOOH, was recently reported to decompose under the conditions of the middle region of the lower mantle to form FeO2 and release H2, suggesting the upward migration of hydrogen and large fluctuations in the oxygen distribution within the Earth system. Here we report the stability of FeOOH phases at the pressure and temperature conditions of the deep lower mantle, based on first-principles calculations and in situ X-ray diffraction experiments. In contrast to previous work suggesting the dehydrogenation of FeOOH into FeO2 in the middle of the lower mantle, we report the formation of a new FeOOH phase with the pyrite-type framework of FeO6 octahedra, which is much denser than the surrounding mantle and is stable at the conditions of the base of the mantle. Pyrite-type FeOOH may stabilize as a solid solution with other hydrous minerals in deeply subducted slabs, and could form in subducted banded iron formations. Deep-seated pyrite-type FeOOH eventually dissociates into Fe2O3 and releases H2O when subducted slabs are heated at the base of the mantle. This process may cause the incorporation of hydrogen into the outer core by the formation of iron hydride, FeHx, in the reducing environment of the core-mantle boundary.

Equation of State of Liquid Iron under Extreme Conditions.

The density of liquid iron has been determined up to 116 GPa and 4350 K via static compression experiments following an innovative analysis of diffuse scattering from liquid. The longitudinal sound velocity was also obtained to 45 GPa and 2700 K based on inelastic x-ray scattering measurements. Combining these results with previous shock-wave data, we determine a thermal equation of state for liquid iron. It indicates that Earth's outer core exhibits 7.5%-7.6% density deficit, 3.7%-4.4% velocity excess, and an almost identical adiabatic bulk modulus, with respect to liquid iron.

First principles calculation of the elasticity of ice VIII and X.

The elastic constants of ice VIII and ice X phases under pressure have been determined at static 0 K conditions using first principles calculation. A step-like increase of the elastic constants of ice VIII phase occurred at 100-110 GPa due to hydrogen bond symmetrization. The elastic constants, and the pressure dependencies of these constants, of ice X and VIII are completely distinct. Due to these differences, these two phases can be distinguished on the basis of the elastic behavior. Conversely, the experimental elastic constant of C11 of ice VII gradually changes from an ice VIII like asymmetric hydrogen bond to a symmetric bond character within a wide pressure range. This finding suggests that the transition from ice VII to ice X starts around 30 GPa and completes at 110 GPa.

Postperovskite phase transition of ZnGeO3: comparative crystal chemistry of postperovskite phase transition from germanate perovskites.

The postperovskite phase of ZnGeO3 was confirmed by laser heating experiments of the perovskite phase under 110-130 GPa at high temperature. Ab initio calculations indicated that the phase transition occurs at 133 GPa at 0 K. This postperovskite transition pressure is significantly higher than those reported for other germanates, such as MnGeO3 and MgGeO3. The comparative crystal chemistry of the perovskite-to-postperovskite transition suggests that a relatively elongated b-axis in the low-pressure range resulted in the delay in the transition to the postperovskite phase. Similar to most GdFeO3-type perovskites that transform to the CaIrO3-type postperovskite phase, ZnGeO3 perovskite eventually transformed to the CaIrO3-type postperovskite phase at a critical rotational angle of the GeO6 octahedron. The formation of the postperovskite structure at a very low critical rotational angle for MnGeO3 suggests that relatively large divalent cations likely break down the corner-sharing GeO6 frameworks without a large rotation of GeO6 to form the postperovskite phase.

Prediction of a hexagonal SiO2 phase affecting stabilities of MgSiO3 and CaSiO3 at multimegabar pressures.

Ultrahigh-pressure phase relationship of SiO(2) silica in multimegabar pressure condition is still quite unclear. Here, we report a theoretical prediction on a previously uncharacterized stable structure of silica with an unexpected hexagonal Fe(2)P-type form. This phase, more stable than the cotunnite-type structure, a previously postulated postpyrite phase, was discovered to stabilize at 640 GPa through a careful structure search by means of ab initio density functional computations over various structure models. This is the first evidential result of the pressure-induced phase transition to the Fe(2)P-type structure among all dioxide compounds. The crystal structure consists of closely packed, fairly regular SiO(9) tricapped trigonal prisms with a significantly compact lattice. Additional investigation further elucidates large effects of this phase change in SiO(2) on the stability of MgSiO(3) and CaSiO(3) at multimegabar pressures. A postperovskite phase of MgSiO(3) breaks down at 1.04 TPa along an assumed adiabat of super-Earths and yields Fe(2)P-type SiO(2) and CsCl (B2)-type MgO. CaSiO(3) perovskite, on the other hand, directly dissociates into SiO(2) and metallic CaO, skipping a postperovskite polymorph. Predicted ultrahigh-pressure and temperature phase diagrams of SiO(2), MgSiO(3), and CaSiO(3) indicate that the Fe(2)P-type SiO(2) could be one of the dominant components in the deep mantles of terrestrial exoplanets and the cores of gas giants.

Recent progress in the study on phonon heat transport property of Earth's lower mantle minerals.

The lattice thermal conductivities (κlat) of Earth's lower mantle (LM) minerals is a crucial parameter in the study of deep Earth dynamics and its determination is also one of the grand challenges in condensed matter physics. Here, we review recent progress on theoretical and experimental studies for theκlatunder high pressure (P) and high temperature (T) condition up to 150 GPa and 4000 K. After the critical parameters necessary to obtain converged values of theκlatare summarized, the theoreticalκlatof the LM minerals, determined through various computational methodologies, is compiled along with experimental findings. Although significant scattering is found in the experimental results at LMP,T, the quantum anharmonic lattice dynamics theory combined with the phonon Boltzmann transport theory demonstrates a clear relationship in theκlatof the end-member LM phases, MgO, MgSiO3bridgmanite (Brg) and post-perovskite (PPv),κlatMgO>>κlatPPv>κlatBrg, and a discontinuous change in theκlatby ∼20%-50% expected across the Brg-PPv transition. Knowledge on the additional but geophysically important factors, such as the effects of iron solid solution, isotopic mass difference, and higher order crystal anharmonicity are also summarized in detail. Current problems and future perspectives are finally mentioned.

Ab initio lattice thermal conductivity of MgSiO3 perovskite as found in Earth's lower mantle.

The lattice thermal conductivity (κ(lat)) of MgSiO3 perovskite (Mg-Pv) under high-pressure and high-temperature conditions was computed based on the ab initio anharmonic lattice dynamics method with the density functional perturbation theory. κ(lat) of Mg-Pv is found to increase with increasing pressure from 9.8 (at 23.5 GPa) to 43.6 W m(-1) K(-1) (at 136 GPa) at 300 K, while decreasing with increasing temperature from 28.1 (at 300 K) to 2.3 W m(-1) K(-1) (at 4000 K) at 100 GPa. A multiphase composite average yielded a mantle Rayleigh number adequate to promote the vigorous thermal convection of the mantle that is expected geophysically.

Shear response of Fe-bearing MgSiO(3) post-perovskite at lower mantle pressures.

We investigate the shear response of possible slip systems activated in pure and Fe-bearing MgSiO(3) post-perovskite (PPv) through ab initio generalized stacking fault (GSF) energy calculations. Here we show that the [100](001) slip system has the easiest response to plastic shear among ten possible slip systems investigated. Incorporation of Fe(2+) decreases the strength of all slip systems but does not change the plastic anisotropy style. Therefore, pure and Fe-bearing MgSiO(3) PPv should demonstrate similar LPO patterns with a strong signature of the [100](001) slip system. An aggregate with this deformation texture is expected to produce a V(SH) > V(SV) type polarization anisotropy, being consistent with seismological observations.(Communicated by Ikuo KUSHIRO, M.J.A.).

Ab initiolattice thermal conductivity of (Mg,Fe)O ferropericlase at the Earth's lower mantle pressure and temperature.

The effects of iron (Fe) incorporation on the lattice thermal conductivity (κlat) of MgO are investigated under the Earth's lower mantle pressure (P) and temperature (T) condition (P> ∼20 GPa,T> ∼2000 K) based on the density-functional theory combined with the anharmonic lattice dynamics theory. Theκlatof ferropericlase (FP) is determined combining the internally consistent LDA +Umethod and self-consistent approach to solve the phonon Boltzmann transport equation. The calculatedκlatare well fitted to the extended Slack model which is proposed in this study to representκlatin a wide volume andTrange. Results demonstrate that theκlatof MgO decreases strongly by Fe incorporation. This strong negative effect is found due to decreases in phonon group velocity and lifetime. Consequently, theκlatof MgO at the core-mantle boundary condition (P∼ 136 GPa,T∼ 4000 K) is substantially reduced from ∼40 to ∼10 W m-1K-1by the incorporation of Fe (12.5 mol%). The effect of Fe incorporation on theκlatof MgO is found to be insensitive toPandT, and at highT, theκlatof FP obeys a well-establishedTinverse relation unlike the experimental observations.

Temperature profile in the lowermost mantle from seismological and mineral physics joint modeling.

The internal structure of the core-mantle boundary (CMB) region of the Earth plays a crucial role in controlling the dynamics and evolution of our planet. We have developed a comprehensive model based on the radial variations of shear velocity in the D'' layer (the base of the lower mantle) and the high-P,T elastic properties of major candidate minerals, including the effects of post-perovskite phase changes. This modeling shows a temperature profile in the lowermost mantle with a CMB temperature of 3,800 +/- 200 K, which suggests that lateral temperature variations of 200-300 K can explain much of the large velocity heterogeneity observed in D''. A single-crossing phase transition model was found to be more favorable in reproducing the observed seismic wave velocity structure than a double-crossing phase transition model.

A new high-pressure structure of SiO2directly converted fromα-quartz under nonhydrostatic compression.

High-pressure behavior of SiO2is one of the prototypical subjects in several research areas including condensed matter physics, inorganic chemistry, mineralogy, materials science, and crystallography. Therefore, numerous studies have been performed on the structure evolution of SiO2under pressure. Here, we show a new structure directly converted fromα-quartz under uniaxial compression. Ourab initiocalculations elucidate a simple transition pathway fromα-quartz to the Fe2P-type phase, and an intermediate state with the Li2ZrF6-type structure appears in this structure conversion. Some interesting properties are found on this intermediate state. (1) The Li2ZrF6-type phase is metastable probably due to a volumetric unbalance between the Li and Zr sites but becomes more energetically stable thanα-quartz over ∼12 GPa. (2) It is vibrationally stable at 0 GPa, suggesting that this phase can be recovered down to ambient condition once synthesized. (3) The crystal structures of Li2ZrF6-type SiO2and phase D, one of dense magnesium hydrous silicates, are found identical, suggesting the stabilization of their solid solution under high-P,Tcondition.

Theoretical and experimental evidence for a new post-cotunnite phase of titanium dioxide with significant optical absorption.

We report the discovery of a post-cotunnite phase of TiO2 by both density-functional ab initio calculations and high-pressure experiments. A pressure-induced phase transition to a hexagonal Fe2P-type structure (space group P62m) was predicted to occur at 161 GPa and 0 K and successfully observed by in situ synchrotron x-ray diffraction measurements at 210 GPa and 4000 K with a significant increase in opacity. This change in opacity is attributed to a reduction of band gap from 3.0 to 1.9 eV across the phase change. The Fe2P-type structure is proved to be the densest phase in major metal dioxides.

Postperovskite phase equilibria in the MgSiO3-Al2O3 system.

We investigate high-P,T phase equilibria of the MgSiO(3)-Al(2)O(3) system by means of the density functional ab initio computation methods with multiconfiguration sampling. Being different from earlier studies based on the static substitution properties with no consideration of Rh(2)O(3)(II) phase, present calculations demonstrate that (i) dissolving Al(2)O(3) tends to decrease the postperovskite transition pressure of MgSiO(3) but the effect is not significant ( approximately -0.2 GPa/mol% Al(2)O(3)); (ii) Al(2)O(3) produces the narrow perovskite+postperovskite coexisting P,T area (approximately 1 GPa) for the pyrolitic concentration (x(Al2O3) approximately 6 mol%), which is sufficiently responsible to the deep-mantle D'' seismic discontinuity; (iii) the transition would be smeared (approximately 4 GPa) for the basaltic Al-rich composition (x(Al2O3) approximately 20 mol%), which is still seismically visible unless iron has significant effects; and last (iv) the perovskite structure spontaneously changes to the Rh(2)O(3)(II) with increasing the Al concentration involving small displacements of the Mg-site cations.

Dense yttria phase eclipsing the A-type sesquioxide structure: high-pressure experiments and ab initio calculations.

In situ X-ray diffraction experiments and ab initio calculations elucidated the high-pressure phase transition properties of yttrium sesquioxides. The C-, B-, and A-type sesquioxides structure sequence observed in the room-temperature compression does not coincide with the high-pressure phase sequence of yttrium sesquioxides at high temperature. A reconstructive-type transformation taking place at high temperature yields the Gd(2)S(3) structure around 8 GPa with a drastic change in cation-oxygen coordinations. Ab initio structural optimization suggests that a displacive-type transformation from B- to A-type sesquioxides structure metastably occurs under pressure at room temperature. The calculated density of states indicates that the transition to the Gd(2)S(3) structure causes a significant decrease in the band gap. The Gd(2)S(3) phase was also found to be partially recovered at ambient pressure. We briefly discuss the quenchability of the Gd(2)S(3) structure in sesquioxides on the basis of the enthalpy differences between the ambient phase and the recovered products.

Viscosity of hcp iron at Earth's inner core conditions from density functional theory.

The inner core, extending to 1,221 km above the Earth's center at pressures between 329 and 364 GPa, is primarily composed of solid iron. Its rheological properties influence both the Earth's rotation and deformation of the inner core which is a potential source of the observed seismic anisotropy. However, the rheology of the inner core is poorly understood. We propose a mineral physics approach based on the density functional theory to infer the viscosity of hexagonal close packed (hcp) iron at the inner core pressure (P) and temperature (T). As plastic deformation is rate-limited by atomic diffusion under the extreme conditions of the Earth's center, we quantify self-diffusion in iron non-empirically. The results are applied to model steady-state creep of hcp iron. Here, we show that dislocation creep is a key mechanism driving deformation of hcp iron at inner core conditions. The associated viscosity agrees well with the estimates from geophysical observations supporting that the inner core is significantly less viscous than the Earth's mantle. Such low viscosity rules out inner core translation, with melting on one side and solidification on the opposite, but allows for the occurrence of the seismically observed fluctuations in inner core differential rotation.

High-pressure phase transition to the Gd(2)S(3) structure in Sc(2)O(3): a new trend in dense structures in sesquioxides.

In situ X-ray diffraction experiments using a laser-heated diamond anvil cell revealed a novel dense phase with the Gd(2)S(3) structure stabilizing in Sc(2)O(3) at pressures over 19 GPa. Although no phase transformation was induced during room-temperature compression up to 31 GPa, the C rare earth sesquioxide structure transformed into the B rare earth sesquioxide structure at 10 GPa after laser annealing and subsequently into the Gd(2)S(3) structure at 19 GPa. Neither the A rare earth sesquioxide structure nor the U(2)S(3) structure was found in Sc(2)O(3). Static density functional lattice energy calculations demonstrated that the C structure prefers Gd(2)S(3) over U(2)S(3) as the post phase. Sc(2)O(3) is the second sesquioxide, after In(2)O(3), to crystallize into a Gd(2)S(3) structure at high pressures and high temperatures.

The melting points of MgO up to 4 TPa predicted based on ab initio thermodynamic integration molecular dynamics.

The melting curve of MgO is extended up to 4 TPa, corresponding to the Jovian core pressure, based on the one-step thermodynamic integration method implemented on ab initio molecular dynamics. The calculated melting temperatures are 3100 and 16 000 K at 0 and 500 GPa, respectively, which are consistent with previous experimental results, and 20 600 K at 3900 GPa, which is inconsistent with a recent experimental extrapolation, which implies the molten Jovian core. A quite small Clapeyron slope ([Formula: see text]) of [Formula: see text] is found at 3900 GPa due to comparable densities of the liquid and B2 phases under extreme compression. The Mg-O coordination number in the liquid phase is saturated at around 7.5 above 1 TPa and remains smaller than that in the B2 phase (8) even at 4 TPa, suggesting no density crossover between liquid and crystal and thus no further denser crystalline phases. Dynamical properties (atomic diffusivity and viscosity) are also investigated along the melting curve to understand these behaviors in greater detail.

Pressure dependence of transverse acoustic phonon energy in ferropericlase across the spin transition.

We investigated transverse acoustic (TA) phonons in iron-bearing magnesium oxide (ferropericlase) up to 56 GPa using inelastic x-ray scattering (IXS). The results show that the energy of the TA phonon far from the Brillouin zone center suddenly increases with increasing pressure above the spin transition pressure of ferropericlase. Ab initio calculations revealed that the TA phonon energy far from the Brillouin zone center is higher in the low-spin state than in the high spin state; that the TA phonon energy depend weakly on pressure; and that the energy gap between the TA and the lowest-energy-optic phonons is much narrower in the low-spin state than in the high-spin state. This allows us to conclude that the anomalous behavior of the TA mode in the present experiments is the result of gap narrowing due to the spin transition and explains contradictory results in previous experimental studies.

Constraints on Earth's inner core composition inferred from measurements of the sound velocity of hcp-iron in extreme conditions.

Hexagonal close-packed iron (hcp-Fe) is a main component of Earth's inner core. The difference in density between hcp-Fe and the inner core in the Preliminary Reference Earth Model (PREM) shows a density deficit, which implies an existence of light elements in the core. Sound velocities then provide an important constraint on the amount and kind of light elements in the core. Although seismological observations provide density-sound velocity data of Earth's core, there are few measurements in controlled laboratory conditions for comparison. We report the compressional sound velocity (V P) of hcp-Fe up to 163 GPa and 3000 K using inelastic x-ray scattering from a laser-heated sample in a diamond anvil cell. We propose a new high-temperature Birch's law for hcp-Fe, which gives us the V P of pure hcp-Fe up to core conditions. We find that Earth's inner core has a 4 to 5% smaller density and a 4 to 10% smaller V P than hcp-Fe. Our results demonstrate that components other than Fe in Earth's core are required to explain Earth's core density and velocity deficits compared to hcp-Fe. Assuming that the temperature effects on iron alloys are the same as those on hcp-Fe, we narrow down light elements in the inner core in terms of the velocity deficit. Hydrogen is a good candidate; thus, Earth's core may be a hidden hydrogen reservoir. Silicon and sulfur are also possible candidates and could show good agreement with PREM if we consider the presence of some melt in the inner core, anelasticity, and/or a premelting effect.

MgSiO3 postperovskite at D'' conditions.

The postperovskite transition in MgSiO(3) at conditions similar to those expected at the D'' discontinuity of Earth's lower mantle offers a paradigm for interpreting the properties of this region. Despite consistent experimental and theoretical predictions of this phase transformation, the complexity of the D'' region raises questions about its geophysical significance. Here we report the thermoelastic properties of Cmcm postperovskite at appropriate conditions and evidences of its presence in the lowermost mantle. These are (i) the jumps in shear and longitudinal velocities similar to those observed in certain places of the D'' discontinuity and (ii) the anticorrelation between shear and bulk velocity anomalies as detected within the D'' region. In addition, the increase in shear modulus across the phase transition provides a possible explanation for the reported discrepancy between the calculated shear modulus of postperovskite free aggregates and the seismological counterpart in the lowermost mantle.