The high-pressure behavior of manganese-rich carbonate, rhodochrosite, has been characterized up to 62GPa by synchrotron-based midinfrared spectroscopy and X-ray diffraction. Modifications in both the infrared spectra and the X-ray diffraction patterns were observed above similar to 35GPa, indicating the presence of a high-pressure phase transition at these pressures. We found that rhodochrosite adopts a structure close to CaCO3-VI with a triclinic unit cell (a=2.87 angstrom, b=4.83 angstrom, c=5.49 angstrom, =99.86 degrees, =94.95 degrees, and =90.95 degrees at 62GPa). Using first-principles calculations based on density functional theory, we confirmed these observations and assigned modes in the new infrared signature of the high-pressure phase. These results suggest that high-pressure metastable phase of calcite may play an important role in carbon storage and transport in the deep Earth.

The phase diagram of H2O is extremely complex; in particular, it is believed that a second critical point exists deep below the supercooled water (SCW) region where two liquids of different densities coexist. The problem, however, is that SCW freezes at temperatures just above this hypothesized liquid liquid critical point (LLCP), so direct experimental verification of its existence has yet to be realized. Here, we report two anomalies in the complex dielectric constant during warming in the form of a peak anomaly near T-p = 203 K and a sharp minimum near T-m = 210 K from ice samples prepared from SCW under hydrostatic pressures of up to 760 MPa. The same features were observed about 4 K higher in heavy ice. T-p is believed to be associated with the nucleation process of metastable cubic ice Ic, and T-m, is the transitioning of ice Ic to either ice Ih or II depending on the pressure. Given that T-p and T-m, are nearly isothermal, present up to at least 620 MPa, and end as a critical point near 33-50 MPa, it is deduced that two types of SCWs with different density concentrations exist, which affects the surface energy of ice Ic nuclei in the "no man's land" region of the phase diagram. Our results are consistent with the LLCP theory and suggest that a metastable critical point exists in the region of 33-50 MPa and T-c >= 210 K.

Rocky planets are thought to comprise compounds of Mg and O as these are among the most abundant elements, but knowledge of their stable phases may be incomplete. MgO is known to be remarkably stable to very high pressure and chemically inert under reduced condition of the Earth's lower mantle. However, in exoplanets oxygen may be a more abundant constituent. Here, using synchrotron x-ray diffraction in laser-heated diamond anvil cells, we show that MgO and oxygen react at pressures above 96 GPa and T = 2150 K with the formation of I4/mcm MgO2. Raman spectroscopy detects the presence of a peroxide ion (O-2(2-)) in the synthesized material as well as in the recovered specimen. Likewise, energy-dispersive x-ray spectroscopy confirms that the recovered sample has higher oxygen content than pure MgO. Our finding suggests that MgO2 may be present together or instead of MgO in rocky mantles and rocky planetary cores under highly oxidized conditions.

Lattice thermal conductivity of ferropericlase and radiative thermal conductivity of iron bearing magnesium silicate perovskite (bridgmanite) - the major mineral of Earth's lower mantle have been measured at room temperature up to 30 and 46 GPa, respectively, using time-domain thermoreflectance and optical spectroscopy techniques in diamond anvil cells. The results provide new constraints for the pressure dependencies of the thermal conductivities of Fe bearing minerals. The lattice thermal conductivity of ferropericlase Mg0.9Fe0.1O is 5.7(6) W/(m*K) at ambient conditions, which is almost 10 times smaller than that of pure MgO; however, it increases with pressure much faster (6.1(7)%/GPa vs 3.6(1)%/GPa). The radiative conductivity of a Mg(0.94)Pe(0.06)SiO(3) bridgmanite single crystal agrees with previously determined values for powder samples at ambient pressure; it is almost pressure-independent in the investigated pressure range. Our results confirm the reduced radiative conductivity scenario for the Earth's lower mantle, while the assessment of the heat flow through the core-mantle boundary still requires in situ measurements at the relevant pressure temperature conditions. (C) 2015 Elsevier B.V. All rights reserved.

The transport properties of matter at high pressure and temperature are critical components in planetary interior models, yet are challenging to measure or predict at relevant conditions. Using a novel flash-heating method for in-situ high-temperature and high-pressure thermal conductivity measurement, we study the transport properties of platinum to 55 GPa and 2300 K. Experimental data reveal a simple high-pressure and high-temperature behavior of the thermal conductivity that is linearly dependent on both pressure and temperature. The corresponding electrical resistivity evaluated through the Wiedemann-Franz-Lorenz law is nearly constant along the melting curve, experimentally confirming the prediction of Stacey for an ideal metal. This study together with prior first-principles predictions of transport properties in Al and Fe at extreme conditions suggests a broad applicability of Stacey's law to diverse metals, supporting a limit on the thermal conductivity of iron at the conditions of Earth's outer core of 90 W/mK or less. (C) 2015 Elsevier B.V. All rights reserved.

Raman spectroscopy and powder x-ray diffraction methods have been used to characterize a novel phase of nitrogen which forms on compression from ambient pressure at low temperatures. The new,lambda, phase exhibits an exceptionally wide range of pressure stability from below 1 to 140 GPa, overlapping nine other known phases. On heating, its transformations are different to those observed in other phases, implying that the phase nitrogen adopts depends not only on P-T path, but also on the initial structural configuration, which greatly complicates its phase diagram.

Manganese fluoride (MnF2) with the tetragonal rutile-type structure has been studied using a synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy in a diamond anvil cell up to 60 GPa at room temperature combined with first-principles density functional calculations. The experimental data reveal two pressure-induced structural phase transitions with the following sequence: rutile. SrI2 type (3 GPa). alpha-PbCl2 type (13 GPa). Complete structural information, including interatomic distances, has been determined in the case of MnF2 including the exact structure of the debated first high-pressure phase. First-principles density functional calculations confirm this phase transition sequence, and the two calculated transition pressures are in excellent agreement with the experiment. Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phases. The results are discussed in line with the possible practical use of rutile-type fluorides in general and specifically MnF2 as a model compound to reveal the HP structural behavior of rutile-type SiO2 (Stishovite).

Measurements of the resistivity, Hall coefficient, and Raman spectroscopy are performed on a Rashba semiconductor BiTeCl single crystal at high pressures up to 50 GPa. We find that applying pressure first induces a theoretically predicted insulating state, followed by a superconducting phase with an insulating normal state. Upon heavy compression, another different superconducting phase is entered into with a metallic normal state. A domelike evolution of the superconducting transition temperature with pressure is obtained with a crossover from the electron to hole carriers across the boundary of the two superconducting phases. These findings imply the possible realization of a topological state of the insulating and superconducting phases in this material.

Hydrogen sulfide (H2S) was studied by x-ray synchrotron diffraction and Raman spectroscopy up to 150 GPa at 180-295 K and by quantum-mechanical variable-composition evolutionary simulations. The experiments show that H2S becomes unstable with respect to formation of compounds with different structure and composition, including Cccm and a body-centered cubic like (R3m or Im-3m) H3S, the latter one predicted previously to show a record-high superconducting transition temperature, a T-c of 203 K. These experiments provide experimental ground for understanding of this record-high T-c. The experimental results are supported by theoretical structure searches that suggest the stability of H3S, H4S3, H5S8, H3S5, and HS2 compounds that have not been reported previously at elevated pressures.

We have performed measurements of Raman scattering, synchrotron x-ray diffraction, and visible transmission spectroscopy combined with density functional theory calculations to study the pressure effect on solid triphenylene. The spectroscopic results demonstrate substantial change of the molecular configuration at 1.4 GPa from the abrupt change of splitting, disappearance, and appearance of some modes. The structure of triphenylene is found be to stable at high pressures without any evidence of structural transition from the x-ray diffraction patterns. The obtained lattice parameters show a good agreement between experiments and calculations. The obtained band gap systematically decreases with increasing pressure. With the application of pressure, the molecular planes become more and more parallel relative to each other. The theoretical calculations indicate that this organic compound becomes metallic at 180 GPa, fueling the hope for the possible realization of superconductivity at high pressure.