Creating superconductivity in WB2 through pressure-induced metastable planar defects.

High-pressure electrical resistivity measurements reveal that the mechanical deformation of ultra-hard WB2 during compression induces superconductivity above 50 GPa with a maximum superconducting critical temperature, Tcof 17 K at 91 GPa. Upon further compression up to 187 GPa, the Tcgradually decreases. Theoretical calculations show that electron-phonon mediated superconductivity originates from the formation of metastable stacking faults and twin boundaries that exhibit a local structure resembling MgB2 (hP3, space group 191, prototype AlB2). Synchrotron x-ray diffraction measurements up to 145 GPa show that the ambient pressure hP12 structure (space group 194, prototype WB2) continues to persist to this pressure, consistent with the formation of the planar defects above 50 GPa. The abrupt appearance of superconductivity under pressure does not coincide with a structural transition but instead with the formation and percolation of mechanically-induced stacking faults and twin boundaries. The results identify an alternate route for designing superconducting materials.

Ordering of hydrogen bonds in high-pressure low-temperature H2O.

The near K-edge structure of oxygen in liquid water and ices III, II, and IX at 0.25 GPa and several low temperatures down to 4 K has been studied using inelastic x-ray scattering at 9884.7 eV with a total energy resolution of 305 and 175 meV. A marked decrease of the preedge intensity from the liquid phase and ice III to ices II and IX is attributed to ordering of the hydrogen bonds in the proton-ordered lattice of the latter phases. Density functional theory calculations including the influence of the Madelung potential of the ice IX crystal correctly account for the remaining preedge feature. Furthermore, we obtain spectroscopic evidence suggesting a possible new phase of ice at temperatures between 4 and 50 K.

Formation and structure of a dense octahedral glass.

We have performed in situ x-ray and neutron-diffraction measurements, and molecular dynamics simulations, of GeO2, an archetypal network-forming glass under pressure. Below 5 GPa, additional atoms encroaching on the first tetrahedral shell are seen to be a precursor of local coordination change. Between 6 and 10 GPa, we observe structures with a constant average coordination of approximately 5, indicating a new metastable, intermediate form of the glass. At 15 GPa, the structure of a fully octahedral glass has been measured. This structure is not retained upon decompression and, therefore, must be studied in situ.

Polymerization of nitrogen in sodium azide.

The high-pressure behavior of nitrogen in NaN(3) was studied to 160 GPa at 120-3300 K using Raman spectroscopy, electrical conductivity, laser heating, and shear deformation methods. Nitrogen in sodium azide is in a molecularlike form; azide ions N(3-) are straight chains of three atoms linked with covalent bonds and weakly interact with each other. By application of high pressures we strongly increased interaction between ions. We found that at pressures above 19 GPa a new phase appeared, indicating a strong coupling between the azide ions. Another transformation occurs at about 50 GPa, accompanied by the appearance of new Raman peaks and a darkening of the sample. With increasing pressure, the sample becomes completely opaque above 120 GPa, and the azide molecular vibron disappears, evidencing completion of the transformation to a nonmolecular nitrogen state with amorphouslike structure which crystallizes after laser heating up to 3300 K. Laser heating and the application of shear stress accelerates the transformation and causes the transformations to occur at lower pressures. These changes can be interpreted in terms of a transformation of the azide ions to larger nitrogen clusters and then polymeric nitrogen net. The polymeric forms can be preserved on decompression in the diamond anvil cell but transform back to the starting azide and other new phases under ambient conditions.

Structural transformation of molecular nitrogen to a single-bonded atomic state at high pressures.

The transformation of molecular nitrogen to a single-bonded atomic nitrogen is of significant interest from a fundamental stand point and because it is the most energetic non-nuclear material predicted. We performed an x-ray diffraction of nitrogen at pressures up to 170 GPa. At 60 GPa, we found a transition from the rhombohedral (R3c) epsilon-N(2) phase to the zeta-N(2) phase, which we identified as orthorhombic with space group P222(1) and with four molecules per unit cell. This transition is accompanied by increasing intramolecular and decreasing intermolecular distances. The major transformation of this diatomic phase into the single-bonded (polymeric) phase, recently determined to have the cubic gauche structure (cg-N), proceeds as a first-order transition with a volume change of 22%.

Nuclear inelastic x-ray scattering of FeO to 48 GPa.

The partial density of vibrational states has been measured for Fe in compressed FeO (wüstite) using nuclear resonant inelastic x-ray scattering. Substantial changes have been observed in the overall shape of the density of states close to the magnetic transition around 20 GPa from the paramagnetic (low pressure) to the antiferromagnetic (high pressure) state. The results indicate that strong magnetoelastic coupling in FeO is the driving force behind the changes in the phonon spectrum of FeO. The paper presents the first observation of changes in the density of terahertz acoustic phonon states under magnetic transition at high pressure.

Spectroscopic studies of the vibrational and electronic properties of solid hydrogen to 285 GPa.

We report Raman scattering and visible to near-infrared absorption spectra of solid hydrogen under static pressure up to 285 GPa between 20 and 140 K. We obtain pressure dependences of vibron and phonon modes consistent with results previously determined to lower pressures. The results indicate the stability of the ordered molecular phase III to the highest pressure reached and provide constraints on the insulator-to-metal transition pressure.

Novel broken symmetry phase from N(2)O at high pressures and high temperatures.

Simple molecular solids become unstable at high pressures, typically transforming to dense framework and/or metallic structures. We report formation of an unusual ionic solid NO(+)NO(3)(-) (nitrosonium nitrate) from N(2)O at pressures above 20 GPa and temperatures above 1000 K. Synchrotron x-ray diffraction indicates that the compound crystallizes with a structure related to the aragonite form of CaCO(3) and NaNO(3). Raman and infrared spectroscopic data indicate that the structure is noncentrosymmetric and exhibits a strong pressure dependent charge transfer and orientational order.

New transformations of CO(2) at high pressures and temperatures.

CO(2) laser heating of solid CO(2) at pressures between 30 and 80 GPa shows that this compound breaks down to oxygen and diamond along a boundary having a negative P-T slope. This decomposition occurs at temperatures much lower than predicted in theory or inferred from previous experiment. Raman spectroscopy and x-ray diffraction were used as structural probes. At pressures higher than 40 GPa the decomposition is preceded by the formation of a new CO(2) phase (CO(2)-VI). These findings limit the stability of nonmolecular CO(2) phases to moderate temperatures and provide a new topology of the CO(2) phase diagram.

Superconductivity in boron.

Metals formed from light elements are predicted to exhibit intriguing states of electronic order. Of these materials, those containing boron are of considerable current interest because of their relatively high superconducting temperatures. We have investigated elemental boron to very high pressure using diamond anvil cell electrical conductivity techniques. We find that boron transforms from a nonmetal to a superconductor at about 160 gigapascals (GPa). The critical temperature of the transition increases from 6 kelvin (K) at 175 GPa to 11.2 K at 250 GPa, giving a positive pressure derivative of 0.05 K/GPa. Although the observed metallization pressure is compatible with the predictions of first-principles calculations, superconductivity in boron remains to be explored theoretically. The present results constitute a record pressure for both electrical conductivity studies and investigations of superconductivity in dense matter.

Phonon density of states of iron up to 153 gigapascals.

We report phonon densities of states (DOS) of iron measured by nuclear resonant inelastic x-ray scattering to 153 gigapascals and calculated from ab initio theory. Qualitatively, they are in agreement, but the theory predicts density at higher energies. From the DOS, we derive elastic and thermodynamic parameters of iron, including shear modulus, compressional and shear velocities, heat capacity, entropy, kinetic energy, zero-point energy, and Debye temperature. In comparison to the compressional and shear velocities from the preliminary reference Earth model (PREM) seismic model, our results suggest that Earth's inner core has a mean atomic number equal to or higher than pure iron, which is consistent with an iron-nickel alloy.

Semiconducting non-molecular nitrogen up to 240 GPa and its low-pressure stability.

The triple bond of diatomic nitrogen has among the greatest binding energies of any molecule. At low temperatures and pressures, nitrogen forms a molecular crystal in which these strong bonds co-exist with weak van der Waals interactions between molecules, producing an insulator with a large band gap. As the pressure is raised on molecular crystals, intermolecular interactions increase and the molecules eventually dissociate to form monoatomic metallic solids, as was first predicted for hydrogen. Theory predicts that, in a pressure range between 50 and 94 GPa, diatomic nitrogen can be transformed into a non-molecular framework or polymeric structure with potential use as a high-energy-density material. Here we show that the non-molecular phase of nitrogen is semiconducting up to at least 240 GPa, at which pressure the energy gap has decreased to 0.4 eV. At 300 K, this transition from insulating to semiconducting behaviour starts at a pressure of approximately 140 GPa, but shifts to much higher pressure with decreasing temperature. The transition also exhibits remarkably large hysteresis with an equilibrium transition estimated to be near 100 GPa. Moreover, we have succeeded in recovering the non-molecular phase of nitrogen at ambient pressure (at temperatures below 100 K), which could be of importance for practical use.

Elasticity of MgO and a primary pressure scale to 55 GPa.

We have studied the elasticity and pressure-density equation of state of MgO in diamond cells to 55 GPa and have doubled the previous pressure limit of accurate elasticity determinations for crystals. Integrating single-crystal velocity data from Brillouin scattering measurements and density data from polycrystalline x-ray diffraction, we obtained the three principal elastic tensor elements (C(11), C(12), and C(44)) and various secondary elasticity parameters, including single-crystal elastic anisotropy, Cauchy relation, aggregate sound velocities, and Poisson's ratio, as functions of pressure. The present study also provides a direct determination of pressure without recourse to any prior pressure standard, thus creating a primary pressure scale. The commonly used ruby fluorescence pressure scale has thus been improved to 1% accuracy by the new MgO scale.

Transformations in methane hydrates.

Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A and volume V = 5051.3(13) A(3); structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A, c = 9.992(3) A, and V = 1241.9(5) A(3). The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

Effects of high pressure on molecules.

Recent high-pressure studies reveal a wealth of new information about the behavior of molecular materials subjected to pressures well into the multimegabar range (several hundred gigapascal), corresponding to compressions in excess of an order of magnitude. Under such conditions, bonding patterns established for molecular systems near ambient conditions change dramatically, causing profound effects on numerous physical and chemical properties and leading to the formation of new classes of materials. Representative systems are examined to illustrate key phenomena, including the evolution of structure and bonding with compression; pressure-induced phase transitions and chemical reactions; pressure-tuning of vibrational dynamics, quantum effects, and excited electronic states; and novel states of electronic and magnetic order. Examples are taken from simple elemental molecules (e.g. homonuclear diatomics), simple heteronuclear species, hydrogen-bonded systems (including H2O), simple molecular mixtures, and selected larger, more complex molecules. There are many implications that span the sciences.

Fossilized high pressure from the Earth's deep interior: the coesite-in-diamond barometer.

Mineral inclusions in diamonds provide an important source of information about the composition of the continental lithosphere at depths exceeding 120-150 km, i.e., within the diamond stability field. Fossilized high pressures in coesite inclusions from a Venezuela diamond have been identified and measured by using laser Raman and synchrotron x-ray microanalytical techniques. Micro-Raman measurements on an intact inclusion of remnant vibrational band shifts give a high confining pressure of 3.62 (+/-0.18) GPa. Synchrotron single-crystal diffraction measurements of the volume compression are in accord with the Raman results and also revealed direct structural information on the state of the inclusion. In contrast to olivine and garnet inclusions, the thermoelasticity of coesite favors accurate identification of pressure preservation. Owing to the unique combination of physical properties of coesite and diamond, this "coesite-in-diamond" geobarometer is virtually independent of temperature, allowing an estimation of the initial pressure of Venezuela diamond formation of 5.5 (+/-0.5) GPa.

New ortho-para conversion mechanism in dense solid hydrogen.

Analysis of recent measurements of striking changes in the rate of ortho-para conversion of solid H(2) up to 58 GPa shows that the conversion mechanism must differ from that at ambient pressure. A new conversion mechanism is identified in which the emerging excitations are coupled to the converting molecules via electric quadrupole-quadrupole rather than nuclear spin-spin interactions. The latter only initiates conversion while the coupling enhancement associated with the new mechanism is ensured by high compression and a gap closing, with the conversion energy diminishing strongly with increasing pressure.

Pressure-enhanced ortho-para conversion in solid hydrogen up to 58 GPa.

We measured the ortho-para conversion rate in solid hydrogen by using Raman scattering in a diamond-anvil cell, extending previous measurements by a factor of 60 in pressure. We confirm previous experiments that suggested a decrease in the conversion rate above about 0.5 GPa. We observe a distinct minimum at 3 GPa followed by a drastic increase in the conversion rate to our maximum pressure of 58 GPa. This pressure enhancement of conversion is not predicted by previous theoretical treatments and must be due to a new conversion pathway.

Sound velocities in dense hydrogen and the interior of jupiter.

Sound velocities in fluid and crystalline hydrogen were measured under pressure to 24 gigapascals by Brillouin spectroscopy in the diamond anvil cell. The results provide constraints on the intermolecular interactions of dense hydrogen and are used to construct an intermolecular potential consistent with all available data. Fluid perturbation theory calculations with the potential indicate that sound velocities in hydrogen at conditions of the molecular layer of the Jovian planets are lower than previously believed. Jovian models consistent with the present results remain discrepant with recent free oscillation spectra of the planet by 15 percent. The effect of changing interior temperatures, the metallic phase transition depth, and the fraction of high atomic number material on Jovian oscillation frequencies is also investigated with the Brillouin equation of state. The present data place strong constraints on sound velocities in the Jovian molecular layer and provide an improved basis for interpreting possible Jovian oscillations.