Dichalcogenides are known to exhibit layered solid phases, at ambient and high pressures, where 2D layers of chemically bonded formula units are held together by van derWaals forces. These materials are of great interest for solid-state sciences and technology, along with other 2D systems such as graphene and phosphorene. SiS2 is an archetypal model system of the most fundamental interest within this ensemble. Recently, high pressure (GPa) phases with Si in octahedral coordination by S have been theoretically predicted and also experimentally found to occur in this compound. At variance with stishovite in SiO2, which is a 3D network of SiO6 octahedra, the phases with octahedral coordination in SiS2 are 2D layered. Very importantly, this type of semiconducting material was theoretically predicted to exhibit continuous bandgap closing with pressure to a poor metallic state at tens of GPa. We synthesized layered SiS2 with octahedral coordination in a diamond anvil cell at 7.5-9 GPa, by laser heating together elemental S and Si at 1300-1700 K. Indeed, Raman spectroscopy up to 64.4 GPa is compatible with continuous bandgap closing in this material with the onset of either weak metallicity or of a narrow bandgap semiconductor state with a large density of defect-induced, intra-gap energy levels, at about 57 GPa. Importantly, our investigation adds up to the fundamental knowledge of layered dichalcogenides. Published by AIP Publishing.

Thermal conductivity of the lowermost mantle governs the heat flow out of the core energizing planetary-scale geological processes. Yet, there are no direct experimental measurements of thermal conductivity at relevant pressure-temperature conditions of Earth's core-mantle boundary. Here we determine the radiative conductivity of post-perovskite at near core-mantle boundary conditions by optical absorption measurements in a laser-heated diamond anvil cell. Our results show that the radiative conductivity of Mg0.9Fe0.1SiO3 post-perovskite (similar to 11 W/m/K) is almost two times smaller than that of bridgmanite (similar to 2.0 W/m/K) at the base of the mantle. By combining this result with the present-day core-mantle heat flow and available estimations on the lattice thermal conductivity we conclude that post-perovskite is at least as abundant as bridgmanite in the lowermost mantle which has profound implications for the dynamics of the deep Earth. (C) 2017 Elsevier B.V. All rights reserved.

Using in situ synchrotron x-ray diffraction and Raman spectroscopy in concert with first principles calculations we demonstrate the synthesis of stable Xe(Fe; Fe/Ni)(3) and XeNi3 compounds at thermodynamic conditions representative of Earth's core. Surprisingly, in the case of both the Xe-Fe and Xe-Ni systems Fe and Ni become highly electronegative and can act as oxidants. The results indicate the changing chemical properties of elements under extreme conditions by documenting that electropositive at ambient pressure elements could gain electrons and form anions.

The electrical conductivity and Raman spectroscopy measurements have been performed on MoS2 at high pressures up to 80 GPa and variable temperatures down to 5 K. We find that the temperature dependence of the resistance in a mixed phase has an anomaly (a hump) which shifts with pressure to higher temperature. Concomitantly, a different Raman phonon mode appears in the mixed state suggesting that the electrical resistance anomaly may be related to a structural transformation. We suggest that this anomalous behavior is due to a charge-density wave state, the presence of which is indicative for an emergence of superconductivity at higher pressures.

Dense fluid metallic hydrogen occupies the interiors of Jupiter, Saturn, and many extrasolar planets, where pressures reach millions of atmospheres. Planetary structure models must describe accurately the transition from the outer molecular envelopes to the interior metallic regions. We report optical measurements of dynamically compressed fluid deuterium to 600 gigapascals (GPa) that reveal an increasing refractive index, the onset of absorption of visible light near 150 GPa, and a transition to metal-like reflectivity (exceeding 30%) near 200 GPa, all at temperatures below 2000 kelvin. Our measurements and analysis address existing discrepancies between static and dynamic experiments for the insulator-metal transition in dense fluid hydrogen isotopes. They also provide new benchmarks for the theoretical calculations used to construct planetary models.

Hydrogen-rich hydrides attract great attention due to recent theoretical (1) and then experimental discovery of record high-temperature superconductivity in H3S [T-c = 203 K at 155 GPa (2)]. Here we search for stable uranium hydrides at pressures up to 500 GPa using ab initio evolutionary crystal structure prediction. Chemistry of the U-H system turned out to be extremely rich, with 14 new compounds, including hydrogen-rich UH5, UH6, U2H13, UH7, UH8, U2H17, and UH9. Their crystal structures are based on either common face-centered cubic or hexagonal close-packed uranium sublattice and unusual H-8 cubic clusters. Our high-pressure experiments at 1 to 103 GPa confirm the predicted UH7, UH8, and three different phases of UH5, raising confidence about predictions of the other phases. Many of the newly predicted phases are expected to be high-temperature superconductors. The highest-Tc superconductor is UH7, predicted to be thermodynamically stable at pressures above 22 GPa (with T-c = 44 to 54 K), and this phase remains dynamically stable upon decompression to zero pressure (where it has T-c = 57 to 66 K).

Capture of highly volatile radioactive iodine is a promising application of metal-organic frameworks (MOFs), thanks to their high porosity with flexible chemical architecture. Specifically, strong charge-transfer binding of iodine to the framework enables efficient and selective iodine uptake as well as its long-term storage. As such, precise knowledge of the electronic structure of iodine is essential for a detailed modeling of the iodine sorption process, which will allow for rational design of iodophilic MOFs in the future. Here we probe the electronic structure of iodine in MOFs at variable iodine...framework interaction by Raman and optical absorption spectroscopy at high pressure (P). The electronic structure of iodine in the straight channels of SBMOF-1 (Ca-sdb, sdb = 4,4 ' sulfonyldibenzoate) is modified irreversibly at P > 3.4 GPa by charge transfer, marking a polymerization of iodine molecules into a 1D polyiodide chain. In contrast, iodine in the sinusoidal channels of SBMOF-3 (Cd-sdb) retains its molecular (I-2 ) character up to at least 8.4 GPa. Such divergent high-pressure behavior of iodine in the MOFs with similar port size and chemistry illustrates adaptations of the electronic structure of iodine to channel topology and strength of the iodine...framework interaction, which can be used to tailor iodine-immobilizing MOFs.

Half-Heusler compounds have recently been identified as promising thermoelectric materials, but their relatively high thermal conductivities impede the further improvement of thermoelectric performance. The knowledge of phonon vibrational properties provides a fundamental understanding of the thermal transport behavior of solids and thus could serve as a guidance on further suppressing the thermal conductivity. Herein, a highly efficient p-type half-Heusler thermoelectric alloy FeNb0.8Ti0.2Sb is taken as an example to explore its phonon vibrational properties. Phonon spectrum with the frequencies down to 10 cm(-1) and its evolution with pressure for the studied material are provided by Raman scattering. It is found that two vibrational modes with the frequency > 200 cm(-1) display a common mode frequency increase with increasing pressure. Based on the bulk modulus from synchrotron X-ray powder diffraction and phonon frequency shifts, the mode Gruneisen parameters are obtained. Our results establish characteristic phonon vibrational properties of this high-performance half-Heusler thermoelectric alloy. Published by AIP Publishing.

Layered molybdenum dichalchogenides differ from the classic example of bilayer graphene with their unique electronic properties: the application of pressure can continuously tune electronic structure since the band gap is controlled by delicate interlayer interaction. Here, we have performed measurements of Raman scattering, synchrotron x-ray diffraction, electrical conductivity, and Hall coefficient combined with density functional theory calculations to synthetically study the pressure effect on 2H-MoTe2. Both the experiments and calculations consistently demonstrate that MoTe2 undergoes a semiconductor-to-metallic (S-M) transition above 10 GPa. Unlike MoS2, the S-M transition is driven by the gradual tunability of electric structure and band gap without structural transition. The applied pressure also effectively enhances conductivity and carrier concentration while reducing the mobility, which makes MoTe2 more suitable for applications than most other transition-metal dichalchogenides and allows it to be applied in strain-modulated optoelectronic devices.

Diatomic nitrogen is an archetypal molecular system known for its exceptional stability and complex behavior at high pressures and temperatures, including rich solid polymorphism, formation of energetic states, and an insulator-to-metal transformation coupled to a change in chemical bonding. However, the thermobaric conditions of the fluid molecular-polymer phase boundary and associated metallization have not been experimentally established. Here, by applying dynamic laser heating of compressed nitrogen and using fast optical spectroscopy to study electronic properties, we observe a transformation from insulating (molecular) to conducting dense fluid nitrogen at temperatures that decrease with pressure and establish that metallization, and presumably fluid polymerization, occurs above 125 GPa at 2500 K. Our observations create a better understanding of the interplay between molecular dissociation, melting, and metallization revealing features that are common in simple molecular systems.