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.

K-Cl is a simple system displaying all four main types of bonding, as it contains (i) metallic potassium, (ii) elemental chlorine made of covalently bonded Cl-2 molecules held together by van der Waals forces, and (iii) an archetypal ionic compound KCl. The charge balance rule, assigning classical charges of "+1" to K and "-1" to Cl, predicts that no compounds other than KCl are possible. However, our quantum-mechanical variable-composition evolutionary simulations predict an extremely complex phase diagram, with new thermodynamically stable compounds K3Cl, K2Cl, K3Cl2, K4Cl3, K5Cl4, K3Cl5, KCl3 and KCl7. Of particular interest are 2D-metallic homologs Kn+1Cln, the presence of positively charged Cl atoms in KCl7, and the predicted stability of KCl3 already at nearly ambient pressures at zero Kelvin. We have synthesized cubic Pm (3) over barn -KCl3 at 40-70 GPa and trigonal P (3) over bar c1 -KCl3 at 20-40 GPa in a laser-heated diamond anvil cell (DAC) at temperature exceeding 2000 K from KCl and Cl-2. These phases were identified using in situ synchrotron X-ray diffraction and Raman spectroscopy. Upon unloading to 10 GPa, P (3) over bar c1 -KCl3 transforms to a yet unknown structure before final decomposition to KCl and Cl-2 at near-ambient conditions.

We use fast transient transmission and emission spectroscopies in the pulse laser heated diamond anvil cell to probe the energy-dependent optical properties of hydrogen at pressures of 10-150 GPa and temperatures up to 6000 K. Hydrogen is absorptive at visible to near-infrared wavelengths above a threshold temperature that decreases from 3000 K at 18 GPa to 1700 K at 110 GPa. Transmission spectra at 2400 K and 141 GPa indicate that the absorptive hydrogen is semiconducting or semimetallic in character, definitively ruling out a first-order insulator-metal transition in the studied pressure range.

We spectroscopically investigated the energy gap of the correlated antiferromagnetic insulator LaMnPO1-xFx (x = 0.0 and 0.04) as a function of temperature and pressure, separately, in conjunction with many-body electronic structure calculations. These results show that the electronic structure in all measured regimes is well described by a model that includes both Mott-Hubbard interactions and Hund's rule coupling. Moreover, we find that by applying external pressure, thereby reducing the effective Mott-Hubbard interaction and Hund's coupling, the energy gap in LaMnPO1 xFx can be fully closed, yielding a metallic state.