Hydrogen is expected to display remarkable properties under extreme pressures and temperatures stemming from its low mass and thus propensity to quantum phenomena. Exploring such phenomena remains very challenging even though there was a tremendous technical progress both in experimental and theoretical techniques since the last comprehensive review (McMahon et al.) was published in 2012. Raman and optical spectroscopy experiments including infrared have been extended to cover a broad range of pressures and temperatures (P-T) probing phase stability and optical properties at these conditions. Novel pulsed laser heating and toroidal diamond anvil techniques together with diamond anvil protecting layers drastically improved the capabilities of static compression methods. The electrical conductivity measurements have been also performed to much higher than previously pressures and extended to low temperatures. The dynamic compression techniques have been dramatically improved recently enabling ramp isentropic compression that allows probing a wide range of P-T thermodynamic pathways. In addition, new theoretical methods have been developed beyond a common DFT theory, which make them predictive and in better agreement with experiments. With the development of new theoretical and experimental tools and sample loading methods, the quest for metallic hydrogen accelerated recently delivering a wealth of new data, which are reviewed here. Published under license by AIP Publishing.

Polymeric nitrogen at 120 GPa-180 GPa is known in two monatomic crystalline cubic gauche (cg-N) and layered polymeric (LP-N) phases and one amorphous modification (eta -N), and all these high-pressure phases attract considerable attention for their potential application as a high energy density material. Here, we investigated the stability of these modifications at high pressures in the laser heated diamond anvil cell upon decompression from 161 GPa. Pure LP-N was synthesized above 152 GPa upon laser heating of eta -N to 2500 K, while cg-N forms below 150 GPa. Upon laser heating at 129 GPa and 123 GPa, the LP-N clearly diminished, indicating that the synthesis of cg-N becomes more favorable in a mixed phase region below 129 GPa. Upon unloading, cg-N and LP-N were metastable to at least 71 GPa at up to 2500 K and at room temperature, respectively. These observations clarified a complicated polymorphism of monatomic nitrogen at high pressures and large hysteretic phenomena related to a transition to nonmolecular nitrogen.

Raman and optical spectroscopy are versatile tools for nondestructive characterization of a wide range of properties of novel materials and minerals in situ at extreme and ambient conditions. These techniques are genuinely complementary to X-ray tools (diffraction and spectroscopy) in the probe energy, momentum transfer, and time scale, making concomitant X-ray and optical probes available for advanced sample analysis. We have built a state-of-the-art, user-friendly integrated Raman and optical spectroscopy system at Sector 13 (GeoSoilEnviroCARS, University of Chicago, IL) of the Advanced Photon Source (APS), Argonne National Laboratory (ANL), where optical probes are available now in combination with high resolution in-situ synchrotron X-ray diffraction and spectroscopy tools (XRD, IXS, XES, NFS, and others) for extensive sample investigation. The integrated optical system enables a variety of techniques including multi-colored (five laser lines: 266, 473, 532, 660, and 946 nm) confocal Raman, fluorescence, and optical spectroscopy from ultraviolet (UV) to near infrared (IR) spectral ranges (266-1600 nm), and Coherent Anti-Stokes Raman spectroscopy (CARS) in combination with near IR double sided laser heating.

X-ray synchrotron diffraction (XRD) measurements of single-crystal and powder molybdenum disulfide MoS2 are performed at pressures (P) up to 78 GPa and temperatures (T) of 20 to 298 K in diamond-anvil cells. The results on single crystals demonstrate a sharp pressure induced isosymmetric phase transition of 2H(c) to 2H(a) modification at 23 GPa at 40 and 300 K. The structure of the high-pressure 2H(a) phase previously inferred theoretically and from powder XRD data is confirmed by our single-crystal XRD data solution, which also definitively determines the atomic potions as a function of pressure. No additional periodicity (commensurate or incommensurate) or distortion is found in the whole P-T range of this study. These results suggest that a previously proposed hypothetic charge-density-wave phase does not host pressure induced superconductivity experimentally found above 90 GPa.

We report a new hydrogen clathrate hydrate synthesized at 1.2 GPa and 298 K documented by single-crystal x-ray diffraction, Raman spectroscopy, and first-principles calculations. The oxygen sublattice of the new clathrate hydrate matches that of ice II, while hydrogen molecules are in the ring cavities, which results in the trigonal R3c or R (3) over barc space group (proton ordered or disordered, respectively) and the composition of (H2O)(6)H-2. Raman spectroscopy and theoretical calculations reveal a hydrogen disordered nature of the new phase C-1', distinct from the well-known ordered C-1 clathrate, to which this new structure transforms upon compression and/or cooling. This new clathrate phase can be viewed as a realization of a disordered ice II, unobserved before, in contrast to all other ordered ice structures.

The thermal expansion at constant pressure of solid CD4 III is calculated for the low-temperature region where only the rotational tunneling modes are essential and the effect of phonons and librons can be neglected. It is found that in mK region there is a giant peak of the negative thermal expansion. The height of this peak is comparable or even exceeds the thermal expansion of solid N-2, CO, O-2, or CH4 in their triple points. It is shown that like in the case of light methane, the effect of pressure is quite unusual: as evidenced from the pressure dependence of the thermodynamic Gruneisen parameter (which is negative and large in the absolute value), solid CD4 becomes increasingly quantum with rising pressure.

With the exception of lithium, alkali metals do not react with elemental nitrogen either at ambient conditions or at elevated temperatures, requiring the search for alternative synthetic routes to their nitrogen-containing compounds. Here using a controlled decomposition of sodium azide (NaN3) at high pressure conditions, we synthesize two novel compounds, Na-3(N-2)(4) and NaN2, both containing dinitrogen anions. NaN2 synthesized at 4 GPa might be the common intermediate in high-pressure solid-state metathesis reactions, where NaN3 is used as a source of nitrogen, while Na-3(N-2)(4) opens a new class of compounds, where [N-2] units accommodate a noninteger formal charge of 0.75-. This finding can dramatically extend the expected compositions in other group 1 and 2 metal-nitrogen systems. Electronic structure calculations show the metallic character for both compounds.

Alkaline earth metal peroxides are typical examples of ionic compounds containing polyanions. We herein report a stable BaO2 phase at high pressure up to 130 GPa found via a first-principles computational structure search and high-pressure experimental investigations. The identified monoclinic structure (space group C2/m) can be derived by sublattice distortions of Ba atoms and peroxide groups associated with the phonon mode softening of the lower-pressure Cmmm structure. Contrary to the previous expectation of polymerization of the peroxide group at elevated pressure, this phase retains the peroxide group and, interestingly, exhibits an insulating behavior demonstrating an increase of the band gap under compression. Our synchrotron x-ray diffraction (XRD) measurements could not distinguish between Cmmm and C2/m BaO2 definitively because the difference in XRD patterns is very subtle. However, our data do not show any sign of polymerization transition up to 120 GPa. Raman spectra of the O-O peroxide vibration show a small anomaly in frequency at 110 GPa, which is qualitatively like that predicted theoretically due to the Cmmm to C2/m phase transition, thus supporting the predicted transformation.

The ultrafast synthesis of epsilon-Fe3N1+x in a diamond-anvil cell (DAC) from Fe and N-2 under pressure was observed using serial exposures of an X-ray free electron laser (XFEL). When the sample at 5 GPa was irradiated by a pulse train separated by 443 ns, the estimated sample temperature at the delay time was above 1400 K, confirmed by in situ transformation of alpha- to gamma-iron. Ultimately, the Fe and N-2 reacted uniformly throughout the beam path to form Fe3N1.33, as deduced from its established equation of state (EOS). We thus demonstrate that the activation energy provided by intense X-ray exposures in an XFEL can be coupled with the source time structure to enable exploration of the time-dependence of reactions under high-pressure conditions.

Earth's lowermost mantle displays complex geological phenomena that likely result from its heterogeneous physical interaction with the core. Geophysical models of core-mantle interaction rely on the thermal and electrical conductivities of appropriate geomaterials which, however, have never been probed at representative pressure and temperature (P-T) conditions. Here we report on the opacity of single crystalline bridgmanite and ferropericlase and link it to their radiative and electrical conductivities. Our results show that light absorption in the visible spectral range is enhanced upon heating in both minerals but the rate of change in opacity with temperature is a factor of six higher in ferropericlase. As a result, bridgmanite in the lowermost mantle is moderately transparent while ferropericlase is highly opaque. Our measurements support previous indirect estimates of low (< 1 W/m/K) and largely temperature-independent radiative conductivity in the lowermost mantle. This implies that the radiative mechanism has not contributed significantly to cooling the Earth's core throughout the geologic time. Opaque ferropericlase is electrically conducting and mediates strong core-mantle electromagnetic coupling, explaining the intradecadal oscillations in the length of day, low secular geomagnetic variations in Central Pacific, and the preferred paths of geomagnetic pole reversals. (C) 2021 Elsevier B.V. All rights reserved.