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.

The conduction of heat through minerals and melts at extreme pressures and temperatures is of central importance to the evolution and dynamics of planets. In the cooling Earth's core, the thermal conductivity of iron alloys defines the adiabatic heat flux and therefore the thermal and compositional energy available to support the production of Earth's magnetic field via dynamo action(1-3). Attempts to describe thermal transport in Earth's core have been problematic, with predictions of high thermal conductivity(4-7) at odds with traditional geophysical models and direct evidence for a primordial magnetic field in the rock record(8-10). Measurements of core heat transport are needed to resolve this difference. Here we present direct measurements of the thermal conductivity of solid iron at pressure and temperature conditions relevant to the cores of Mercury-sized to Earth-sized planets, using a dynamically laser-heated diamond-anvil cell(11,12). Our measurements place the thermal conductivity of Earth's core near the low end of previous estimates, at 18-44 watts per metre per kelvin. The result is in agreement with palaeomagnetic measurements(10) indicating that Earth's geodynamo has persisted since the beginning of Earth's history, and allows for a solid inner core as old as the dynamo.

The only known compound of sodium and hydrogen is archetypal ionic NaH. Application of high pressure is known to promote states with higher atomic coordination, but extensive searches for polyhydrides with unusual stoichiometry have had only limited success in spite of several theoretical predictions. Here we report the first observation of the formation of polyhydrides of Na (NaH3 and NaH7) above 40GPa and 2,000 K. We combine synchrotron X-ray diffraction and Raman spectroscopy in a laser-heated diamond anvil cell and theoretical random structure searching, which both agree on the stable structures and compositions. Our results support the formation of multicenter bonding in a material with unusual stoichiometry. These results are applicable to the design of new energetic solids and high-temperature superconductors based on hydrogen-rich materials.

The search of compounds with CxNy composition holds great promise for creating materials which would rival diamond in hardness due to the very strong covalent C-N bond. Early theoretical and experimental works on CxNy compounds were based on the hypothetical structural similarity of predicted C3N4 phases with known binary A(3)B(4) structural types; however, the synthesis of C3N4 other than g-C3N4 remains elusive. Here, we explore an elemental synthesis at high pressures and temperatures in which the compositional limitations due to the use of precursors in the early works are substantially lifted. Using in situ synchrotron X-ray diffraction and Raman spectroscopy, we demonstrate the synthesis of a highly incompressible Pnnm CN compound (x = y = 1) with sp(3)-hybridized carbon above 55 GPa and 7000 K. This result is supported by first-principles evolutionary search, which finds that CN is the most stable compound above 14 GPa. On pressure release below 6 GPa, the synthesized CN compound amorphizes, maintaining its 1:1 stoichiometry as confirmed by energy-dispersive X-ray spectroscopy. This work underscores the importance of understanding the novel high-pressure chemistry laws that promote extended 3D C-N structures, never observed at ambient conditions. Moreover, it opens a new route for synthesis of superhard materials based on novel stoichiometries

Synthesis of high nitrogen containing materials has been the subject of research interest for use as alternative clean sources of fuel and explosives. Here we present experimental evidence for the photochemical synthesis of new energetic materials from sodium azide (NaN3) at 4.88.1 GPa. We show that excitation into the conduction band generates color centers within the compressed alpha-NaN3 phase lattice with minimal or no molecular N-2 evolution. Photochemical changes to the sample were monitored by X-ray diffraction (XRD), infrared (IR) absorption, and Raman spectroscopy. These high pressure products were found to be stable upon decompression at 300 K down to 1.6 GPa, although it is suspected that the material can be recoverable to ambient pressure with cold decompression.

The ability of Earth's mantle to conduct heat by radiation is determined by optical properties of mantle phases. Optical properties of mantle minerals at high pressure are accessible through diamond anvil cell experiments, but because of the intense thermal radiation at T > 1000 K such studies are limited to lower temperatures. Accordingly, radiative thermal conductivity at mantle conditions has been evaluated with the assumption of the temperature-independent optical properties. Particularly uncertain is the temperature-dependence of optical properties of lower mantle minerals across the spin transition, as the spin state itself is a strong function of temperature. Here we use laser-heated diamond anvil cells combined with a pulsed ultra-bright supercontinuum laser probe and a synchronized time-gated detector to examine optical properties of high and low spin ferrous iron at 45-73 GPa up to 1600 K in an octahedral crystallographic unit (FeO6), one of the most abundant building blocks in the mantle. Siderite (FeCO3) is used as a model for FeO6-octahedra as it contains no ferric iron and exhibits a sharp optically apparent pressure-induced spin transition at 44 GPa, simplifying data interpretation. We find that the optical absorbance of low spin FeO6 increases with temperature due to the partially lifted Laporte selection rule. The temperature-induced low-to-high spin transition, however, results in a dramatic drop in absorbance of the FeO6 unit in siderite. The absorption edge (Fe-O charge transfer) red-shifts (similar to 1 cm(-1)/K) with increasing temperature and at T > 1600 K and P > 70 GPa becomes the dominant absorption mechanism in the visible range, suggesting its superior role in reducing the ability of mantle minerals to conduct heat by radiation. This implies that the radiative thermal conductivity of analogous FeO6-bearing minerals such as ferropericlase, the second most abundant mineral in the Earth's lower mantle, is substantially reduced approaching the core-mantle boundary conditions. (C) 2016 Elsevier B.V. All rights reserved.