We synthesized two C-S-H compounds from a mixture of carbon and sulfur in hydrogen-C : (H2S)(2)H-2 and from sulfur in mixed methane-hydrogen fluids-(CH4)(x)(H2S)((2-x))H-2 at 4 GPa. X-ray synchrotron single-crystal diffraction and Raman spectroscopy have been applied to these samples up to 58 and 143 GPa, respectively. Both samples show a similar Al-2 Cu-type I4/mcm basic symmetry, while the hydrogen subsystem evolves with pressure via variously ordered molecular and extended modifications. The methane-bearing sample lowers symmetry to an orthorhombic Pnma structure after laser heating to 1400 K at 143 GPa. The results suggest that C-S-H compounds are structurally different from a common Im-3m H3S.

Earth's core is composed of iron (Fe) alloyed with light elements, e.g., silicon (Si). Its thermal conductivity critically affects Earth's thermal structure, evolution, and dynamics, as it controls the magnitude of thermal and compositional sources required to sustain a geodynamo over Earth's history. Here we directly measured thermal conductivities of solid Fe and Fe-Si alloys up to 144GPa and 3300K. 15 at% Si alloyed in Fe substantially reduces its conductivity by about 2 folds at 132GPa and 3000K. An outer core with 15 at% Si would have a conductivity of about 20Wm(-1) K-1, lower than pure Fe at similar pressure-temperature conditions. This suggests a lower minimum heat flow, around 3 TW, across the core-mantle boundary than previously expected, and thus less thermal energy needed to operate the geodynamo. Our results provide key constraints on inner core age that could be older than two billion-years. Thermal conductivity of Earth's core affects Earth's thermal structure, evolution and dynamics. Based on thermal conductivity measurements of iron-silicon alloys at high pressure and temperature conditions, the authors here propose Earth's inner core could be older than previously expected.

The synthesis of polynitrogen compounds is of great importance due to their potential as high-energy-density materials (HEDM), but because of the intrinsic instability of these compounds, their synthesis and stabilization is a fundamental challenge. Polymeric nitrogen units which may be stabilized in compounds with metals at high pressure are now restricted to non-branched chains with an average N-N bond order of 1.25, limiting their HEDM performances. Herein, we demonstrate the synthesis of a novel polynitrogen compound TaN5 via a direct reaction between tantalum and nitrogen in a diamond anvil cell at circa 100 GPa. TaN5 is the first example of a material containing branched all-single-bonded nitrogen chains [N-5(5-)](infinity). Apart from that we discover two novel Ta-N compounds: TaN4 with finite N-4(4-) chains and the incommensurately modulated compound TaN2-x, which is recoverable at ambient conditions.

Following the discovery of high-temperature superconductivity in the La-H system, we studied the formation of new chemical compounds in the barium-hydrogen system at pressures from 75 to 173GPa. Using in situ generation of hydrogen from NH3BH3, we synthesized previously unknown superhydride BaH12 with a pseudocubic (fcc) Ba sublattice in four independent experiments. Density functional theory calculations indicate close agreement between the theoretical and experimental equations of state. In addition, we identified previously known P6/mmm-BaH2 and possibly BaH10 and BaH6 as impurities in the samples. Ab initio calculations show that newly discovered semimetallic BaH12 contains H-2 and H-3(-) molecular units and detached H-12 chains which are formed as a result of a Peierls-type distortion of the cubic cage structure. Barium dodecahydride is a unique molecular hydride with metallic conductivity that demonstrates the superconducting transition around 20K at 140GPa. Metallization of pure hydrogen via overlapping of electronic bands requires high pressure above 3 Mbar. Here the authors study the Ba-H system and discover a unique superhydride BaH12 that contains molecular hydrogen, which demonstrates metallic properties and superconductivity below 1.5 Mbar.

Carbon-bearing phases show a rich variety of structural transitions as an adaptation to pressure. Of particular interest is the crossover from sp(2) carbon to sp(3) carbon, as physical and chemical properties of carbon in these distinct electronic configurations are very different. In this chapter we review pressure-induced sp(2)-sp(3) transitions in elemental carbon, carbonates, and hydrocarbons.

The application of pressure has been speculated to boost the search for high-temperature superconductors, especially in superhydrides. However, the applied pressure as high as hundreds of GPa needed to create superconductivity in those materials limits their technological application. Finding a route to achieve the high-temperature superconductivity at near-ambient conditions is attractive. By choosing a phase-change alloy Ge2Sb2Te5, we study the phase evolution of this material with pressure from the trigonal phase through the amorphous to the body-centered cubic one by the measurements of x-ray diffraction, Raman scattering, resistivity, and Hall coefficient. Superconductivity is observed to take place in the last two phases and can maintain at nearly ambient pressure in the decompression run. Pressure-induced disorder is found to be the key for holding superconductivity in the compressed phase-change alloy.

Nitrogen and water are very abundant in nature; however, the way they chemically react at extreme pressure-temperature conditions is unknown. Below 6 GPa, they have been reported to form clathrate compounds. Here, we present Raman spectroscopy and x-ray diffraction studies in the H2O-N-2 system at high pressures up to 140 GPa. We find that clathrates, which form locally in our diamond cell experiments above 0.3 GPa, transform into a fine grained state above 6 GPa, while there is no sign of formation of mixed compounds. We point out size effects in fine grained crystallites, which result in peculiar Raman spectra in the molecular regime, but x-ray diffraction shows no additional phase or deviation from the bulk behavior of familiar solid phases. Moreover, we find no sign of ice doping by nitrogen, even in the regimes of stability of nonmolecular nitrogen.

Synthesis and characterization of nitrogen-rich materials is important for the design of novel high energy density materials due to extremely energetic low-order nitrogen-nitrogen bonds. The balance between the energy output and stability may be achieved if polynitrogen units are stabilized by resonance as in cyclo-N-5(-) pentazolate salts. Here we demonstrate the synthesis of three oxygen-free pentazolate salts Na2N5, NaN5 and NaN5 center dot N-2 from sodium azide NaN3 and molecular nitrogen N-2 at similar to 50 GPa. NaN5 center dot N-2 is a metal-pentazolate framework (MPF) obtained via a self-templated synthesis method with nitrogen molecules being incorporated into the nanochannels of the MPF. Such self-assembled MPFs may be common in a variety of ionic pentazolate compounds. The formation of Na2N5 demonstrates that the cyclo-N-5 group can accommodate more than one electron and indicates the great accessible compositional diversity of pentazolate salts.

Inspired by the rich physical properties of IV-VI compounds, we choose polycrystalline Pb0.99Cr0.01Se to investigate its structural, vibrational, and electrical transport properties under pressure up to 50 GPa. The structural transitions from the B1 to Pnma phase and then to the B2 phase in this sample are verified by the x-ray diffraction and Raman scattering measurements. The formation of the intermediate phase is suggested to be mediated by Peierls distortion, and the broad hump in the temperature-dependent resistivity in the intermediate phase gives further evidence of this phenomenon. When the material evolves into the B2 phase, superconductivity is observed to emerge, accompanied by suppressing the broad hump of resistivity at intermediate temperatures. Meanwhile, Hall coefficient measurements indicate that the carrier type changes during the structural transitions. These results suggest that the superconductivity in the B2 phase for this material is originated by "melting" the Peierls lattice distortion. By extending the present findings to other similar IV-VI semiconductors, we propose that all group IV-VI compounds could exhibit superconductivity in their B2 phase due to the lattice melting at high pressures.

Most of the studied two-dimensional (2D) materials are based on highly symmetric hexagonal structural motifs. In contrast, lower-symmetry structures may have exciting anisotropic properties leading to various applications in nano-electronics. In this work we report the synthesis of nickel diazenide NiN2 which possesses atomic-thick layers comprised of Ni2N3 pentagons forming Cairo-type tessellation. The layers of NiN2 are weakly bonded with the calculated exfoliation energy of 0.72 J/m(2), which is just slightly larger than that of graphene. The compound crystallizes in the space group of the ideal Cairo tiling (P4/mbm) and possesses significant anisotropy of elastic properties. The single-layer NiN2 is a direct-band-gap semiconductor, while the bulk material is metallic. This indicates the promise of NiN2 to be a precursor of a pentagonal 2D material with a tunable direct band gap.