Universal diamond edge Raman scale to 0.5 terapascal and implications for the metallization of hydrogen.

The recent progress in generating static pressures up to terapascal values opens opportunities for studying novel materials with unusual properties, such as metallization of hydrogen and high-temperature superconductivity. However, an evaluation of pressure above ~0.3 terapascal is a challenge. We report a universal high-pressure scale up to ~0.5 terapascal, which is based on the shift of the Raman edge of stressed diamond anvils correlated with the equation of state of Au and does not require an additional pressure sensor. According to the new scale, the pressure values are substantially lower by 20% at ~0.5 terapascal compared to the extrapolation of the existing scales. We compare the available data of H2 at the highest static pressures. We show that the onset of the proposed metallization of molecular hydrogen reported by different groups is consistent when corrected with the new scale and can be compared with various theoretical predictions.

Magnetic field screening in hydrogen-rich high-temperature superconductors.

In the last few years, the superconducting transition temperature, Tc, of hydrogen-rich compounds has increased dramatically, and is now approaching room temperature. However, the pressures at which these materials are stable exceed one million atmospheres and limit the number of available experimental studies. Superconductivity in hydrides has been primarily explored by electrical transport measurements, whereas magnetic properties, one of the most important characteristic of a superconductor, have not been satisfactory defined. Here, we develop SQUID magnetometry under extreme high-pressure conditions and report characteristic superconducting parameters for Im-3m-H3S and Fm-3m-LaH10-the representative members of two families of high-temperature superconducting hydrides. We determine a lower critical field Hc1 of ∼0.82 T and ∼0.55 T, and a London penetration depth λL of ∼20 nm and ∼30 nm in H3S and LaH10, respectively. The small values of λL indicate a high superfluid density in both hydrides. These compounds have the values of the Ginzburg-Landau parameter κ ∼12-20 and belong to the group of "moderate" type II superconductors, rather than being hard superconductors as would be intuitively expected from their high Tcs.

Grain size dependent high-pressure elastic properties of ultrafine micro/nanocrystalline grossular.

We have performed sound velocity and unit cell volume measurements of three synthetic, ultrafine micro/nanocrystalline grossular samples up to 50 GPa using Brillouin spectroscopy and synchrotron X-ray diffraction. The samples are characterized by average grain sizes of 90 nm, 93 nm and 179 nm (hereinafter referred to as samples Gr90, Gr93, and Gr179, respectively). The experimentally determined sound velocities and elastic properties of Gr179 sample are comparable with previous measurements, but slightly higher than those of Gr90 and Gr93 under ambient conditions. However, the differences diminish with increasing pressure, and the velocity crossover eventually takes place at approximately 20-30 GPa. The X-ray diffraction peaks of the ultrafine micro/nanocrystalline grossular samples significantly broaden between 15-40 GPa, especially for Gr179. The velocity or elasticity crossover observed at pressures over 30 GPa might be explained by different grain size reduction and/or inhomogeneous strain within the individual grains for the three grossular samples, which is supported by both the pressure-induced peak broadening observed in the X-ray diffraction experiments and transmission electron microscopy observations. The elastic behavior of ultrafine micro/nanocrystalline silicates, in this case, grossular, is both grain size and pressure dependent.

Revealing the Complex Nature of Bonding in the Binary High-Pressure Compound FeO_{2}.

Extreme pressures and temperatures are known to drastically affect the chemistry of iron oxides, resulting in numerous compounds forming homologous series nFeOmFe_{2}O_{3} and the appearance of FeO_{2}. Here, based on the results of in situ single-crystal x-ray diffraction, Mössbauer spectroscopy, x-ray absorption spectroscopy, and density-functional theory+dynamical mean-field theory calculations, we demonstrate that iron in high-pressure cubic FeO_{2} and isostructural FeO_{2}H_{0.5} is ferric (Fe^{3+}), and oxygen has a formal valence less than 2. Reduction of oxygen valence from 2, common for oxides, down to 1.5 can be explained by a formation of a localized hole at oxygen sites.

Superconductivity at 250 K in lanthanum hydride under high pressures.

With the discovery1 of superconductivity at 203 kelvin in H3S, attention returned to conventional superconductors with properties that can be described by the Bardeen-Cooper-Schrieffer and the Migdal-Eliashberg theories. Although these theories predict the possibility of room-temperature superconductivity in metals that have certain favourable properties-such as lattice vibrations at high frequencies-they are not sufficient to guide the design or predict the properties of new superconducting materials. First-principles calculations based on density functional theory have enabled such predictions, and have suggested a new family of superconducting hydrides that possess a clathrate-like structure in which the host atom (calcium, yttrium, lanthanum) is at the centre of a cage formed by hydrogen atoms2-4. For LaH10 and YH10, the onset of superconductivity is predicted to occur at critical temperatures between 240 and 320 kelvin at megabar pressures3-6. Here we report superconductivity with a critical temperature of around 250 kelvin within the [Formula: see text] structure of LaH10 at a pressure of about 170 gigapascals. This is, to our knowledge, the highest critical temperature that has been confirmed so far in a superconducting material. Superconductivity was evidenced by the observation of zero resistance, an isotope effect, and a decrease in critical temperature under an external magnetic field, which suggested an upper critical magnetic field of about 136 tesla at zero temperature. The increase of around 50 kelvin compared with the previous highest critical temperature1 is an encouraging step towards the goal of achieving room-temperature superconductivity in the near future.

Metastable silica high pressure polymorphs as structural proxies of deep Earth silicate melts.

Modelling of processes involving deep Earth liquids requires information on their structures and compression mechanisms. However, knowledge of the local structures of silicates and silica (SiO2) melts at deep mantle conditions and of their densification mechanisms is still limited. Here we report the synthesis and characterization of metastable high-pressure silica phases, coesite-IV and coesite-V, using in situ single-crystal X-ray diffraction and ab initio simulations. Their crystal structures are drastically different from any previously considered models, but explain well features of pair-distribution functions of highly densified silica glass and molten basalt at high pressure. Built of four, five-, and six-coordinated silicon, coesite-IV and coesite-V contain SiO6 octahedra, which, at odds with 3rd Pauling's rule, are connected through common faces. Our results suggest that possible silicate liquids in Earth's lower mantle may have complex structures making them more compressible than previously supposed.

Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains.

Poly-nitrogen compounds have been considered as potential high energy density materials for a long time due to the large number of energetic N-N or N=N bonds. In most cases high nitrogen content and stability at ambient conditions are mutually exclusive, thereby making the synthesis of such materials challenging. One way to stabilize such compounds is the application of high pressure. Here, through a direct reaction between Fe and N2 in a laser-heated diamond anvil cell, we synthesize three ironnitrogen compounds Fe3N2, FeN2 and FeN4. Their crystal structures are revealed by single-crystal synchrotron X-ray diffraction. Fe3N2, synthesized at 50 GPa, is isostructural to chromium carbide Cr3C2. FeN2 has a marcasite structure type and features covalently bonded dinitrogen units in its crystal structure. FeN4, synthesized at 106 GPa, features polymeric nitrogen chains of [N42-]n units. Based on results of structural studies and theoretical analysis, [N42-]n units in this compound reveal catena-poly[tetraz-1-ene-1,4-diyl] anions.

Ice-VII inclusions in diamonds: Evidence for aqueous fluid in Earth's deep mantle.

Water-rich regions in Earth's deeper mantle are suspected to play a key role in the global water budget and the mobility of heat-generating elements. We show that ice-VII occurs as inclusions in natural diamond and serves as an indicator for such water-rich regions. Ice-VII, the residue of aqueous fluid present during growth of diamond, crystallizes upon ascent of the host diamonds but remains at pressures as high as 24 gigapascals; it is now recognized as a mineral by the International Mineralogical Association. In particular, ice-VII in diamonds points toward fluid-rich locations in the upper transition zone and around the 660-kilometer boundary.

Dynamics, thermodynamics and structure of liquids and supercritical fluids: crossover at the Frenkel line.

We review recent work aimed at understanding dynamical and thermodynamic properties of liquids and supercritical fluids. The focus of our discussion is on solid-like transverse collective modes, whose evolution in the supercritical fluids enables one to discuss the main properties of the Frenkel line separating rigid liquid-like and non-rigid gas-like supercritical states. We subsequently present recent experimental evidence of the Frenkel line showing that structural and dynamical crossovers are seen at a pressure and temperature corresponding to the line as predicted by theory and modelling. Finally, we link dynamical and thermodynamic properties of liquids and supercritical fluids by the new calculation of liquid energy governed by the evolution of solid-like transverse modes. The disappearance of those modes at high temperature results in the observed decrease of heat capacity.

Metal fluoride nanotubes featuring square-planar building blocks in a high-pressure polymorph of AgF2.

At a pressure of ca. 15 GPa, AgF2 transforms to an unprecedented orthorhombic polymorph featuring an array of tubular subunits which are built of corner sharing [AgF4] squares. This seems to be the first type of a metal fluoride nanowire and also the only one showing rigid square planar rather than common hexagonal or octahedral moieties.

Structural complexity of simple Fe2O3 at high pressures and temperatures.

Although chemically very simple, Fe2O3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe2O3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe2O3. Decomposition of Fe2O3 and Fe3O4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe5O7 and Fe25O32 phases with release of oxygen. Our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.

High-pressure phase transition in Y3Fe5O12.

Yttrium iron garnet (YIG, Y3Fe5O12) was examined up to 74 GPa and 1800 K using synchrotron x-ray diffraction in a diamond anvil cell. At room temperature, YIG remained in the garnet phase until abrupt amorphization occurred at 51 GPa, consistent with earlier studies. Upon laser heating up to 1800 K, the material transformed to a single-phase orthorhombic GdFeO3-type perovskite of composition (Y(0.75)Fe(0.25))FeO3. No evidence of decomposition of the sample was observed. Both the room-temperature amorphization and high-temperature transformation to the perovskite structure are consistent with the behaviour of other rare earth oxide garnets. The perovskite sample was compressed between 28-74 GPa with annealing to 1450-1650 K every 3-5 GPa. Between 46 and 50 GPa, a 6.8% volume discontinuity was observed without any accompanying change in the number or intensity of diffraction peaks. This is indicative of a high-spin to low-spin electronic transition in Fe(3+), likely in the octahedrally coordinated B-site of the perovskite. The volume change of the inferred spin transition is consistent with those observed in other rare earth ferric iron perovskites at high pressures.

The most incompressible metal osmium at static pressures above 750 gigapascals.

Metallic osmium (Os) is one of the most exceptional elemental materials, having, at ambient pressure, the highest known density and one of the highest cohesive energies and melting temperatures. It is also very incompressible, but its high-pressure behaviour is not well understood because it has been studied so far only at pressures below 75 gigapascals. Here we report powder X-ray diffraction measurements on Os at multi-megabar pressures using both conventional and double-stage diamond anvil cells, with accurate pressure determination ensured by first obtaining self-consistent equations of state of gold, platinum, and tungsten in static experiments up to 500 gigapascals. These measurements allow us to show that Os retains its hexagonal close-packed structure upon compression to over 770 gigapascals. But although its molar volume monotonically decreases with pressure, the unit cell parameter ratio of Os exhibits anomalies at approximately 150 gigapascals and 440 gigapascals. Dynamical mean-field theory calculations suggest that the former anomaly is a signature of the topological change of the Fermi surface for valence electrons. However, the anomaly at 440 gigapascals might be related to an electronic transition associated with pressure-induced interactions between core electrons. The ability to affect the core electrons under static high-pressure experimental conditions, even for incompressible metals such as Os, opens up opportunities to search for new states of matter under extreme compression.

Elastic characterization of platinum/rhodium alloy at high temperature by combined laser heating and laser ultrasonic techniques.

We demonstrate an innovative pump-probe technique combined with laser heating to determine the velocity of a surface Rayleigh wave at high temperature. Laser ultrasonics in a point-source-point-receiver configuration was combined with laser heating to evaluate the elastic properties of micron size specimens. The measurements of the velocity of the surface Rayleigh wave (SRW) were conducted at 1070K.

Importance of correlation effects in hcp iron revealed by a pressure-induced electronic topological transition.

We discover that hcp phases of Fe and Fe(0.9)Ni(0.1) undergo an electronic topological transition at pressures of about 40 GPa. This topological change of the Fermi surface manifests itself through anomalous behavior of the Debye sound velocity, c/a lattice parameter ratio, and Mössbauer center shift observed in our experiments. First-principles simulations within the dynamic mean field approach demonstrate that the transition is induced by many-electron effects. It is absent in one-electron calculations and represents a clear signature of correlation effects in hcp Fe.

BX90: a new diamond anvil cell design for X-ray diffraction and optical measurements.

We present a new design of a universal diamond anvil cell, suitable for different kinds of experimental studies under high pressures. Main features of the cell are an ultimate 90-degrees symmetrical axial opening and high stability, making the presented cell design suitable for a whole range of techniques from optical absorption to single-crystal X-ray diffraction studies, also in combination with external resistive or double-side laser heating. Three examples of the cell applications are provided: a Brillouin scattering of neon, single-crystal X-ray diffraction of α-Cr(2)O(3), and resistivity measurements on the (Mg(0.60)Fe(0.40))(Si(0.63)Al(0.37))O(3) silicate perovskite.

High-pressure behavior of perovskite: FeTiO_{3} dissociation into (Fe_{1-delta},Ti_{delta})O and Fe_{1+delta}Ti_{2-delta}O_{5}.

The stability of perovskite-structured materials at high pressure and temperature is of fundamental interest in solid-state physics, chemistry, and the geosciences. As an alternative to decomposition into oxides or transformation of the CaIrO_{3} postperovskite structure, we observe in situ the breakdown of FeTiO_{3} perovskite into a (Fe_{1-delta},Ti_{delta})O + Fe_{1+delta}Ti_{2-delta}O_{5} assemblage beyond 53 GPa and 2000 K. The high-pressure high-temperature phase of Fe_{1+delta}Ti_{2-delta}O_{5} with a new structure (space group C2/c) could be preserved on decompression to 9 GPa, and amorphizes under further pressure release. Our study demonstrates that perovskite-structured materials can undergo chemical changes and form complex oxides with new structures, rather than only transform to denser polymorphs or decompose to simple oxides.

Portable laser-heating system for diamond anvil cells.

The diamond anvil cell (DAC) technique coupled with laser heating has become the most successful method for studying materials in the multimegabar pressure range at high temperatures. However, so far all DAC laser-heating systems have been stationary: they are linked either to certain equipment or to a beamline. Here, a portable laser-heating system for DACs has been developed which can be moved between various analytical facilities, including transfer from in-house to a synchrotron or between synchrotron beamlines. Application of the system is demonstrated in an example of nuclear inelastic scattering measurements of ferropericlase (Mg(0.88)Fe(0.12))O and h.c.p.-Fe(0.9)Ni(0.1) alloy, and X-ray absorption near-edge spectroscopy of (Mg(0.85)Fe(0.15))SiO(3) majorite at high pressures and temperatures. Our results indicate that sound velocities of h.c.p.-Fe(0.9)Ni(0.1) at pressures up to 50 GPa and high temperatures do not follow a linear relation with density.