First-order liquid-liquid phase transition in cerium.

We report the first experimental observation of a liquid-liquid phase transition in the monatomic liquid metal cerium, by means of in situ high-pressure high-temperature x-ray diffraction experiments. At 13 GPa, upon increasing temperature from 1550 to 1900 K high-density liquid transforms to a low-density liquid, with a density difference of 14%. Theoretic models based on ab initio calculations are built to investigate the observed phase behavior of the liquids at various pressures. The results suggest that the transition primarily originates from the delocalization of f electrons and is deemed to be of the first order that terminates at a critical point.

Stability and strength of transition-metal tetraborides and triborides.

Using density functional theory, we show that the long-believed transition-metal tetraborides (TB(4)) of tungsten and molybdenum are in fact triborides (TB(3)). This finding is supported by thermodynamic, mechanical, and phonon instabilities of TB(4), and it challenges the previously proposed origin of superhardness of these compounds and the predictability of the generally used hardness model. Theoretical calculations for the newly identified stable TB(3) structure correctly reproduce their structural and mechanical properties, as well as the experimental x-ray diffraction pattern. However, the relatively low shear moduli and strengths suggest that TB(3) cannot be intrinsically stronger than c-BN. The origin of the lattice instability of TB(3) under large shear strain that occurs at the atomic level during plastic deformation can be attributed to valence charge depletion between boron and metal atoms, which enables easy sliding of boron layers between the metal ones.

Anomalous optical and electronic properties of dense sodium.

Synchrotron infrared spectroscopy on sodium shows a transition from a high reflectivity, nearly free-electron metal to a low-reflectivity, poor metal in an orthorhombic phase at 118 GPa. Optical spectra calculated within density functional theory (DFT) agree with the experimental measurements and predict a gap opening in the orthorhombic phase at compression beyond its stability field, a state that would be experimentally attainable by appropriate choice of pressure-temperature path. We show that a transition to an incommensurate phase at 125 GPa results in a partial recovery of good metallic character up to 180 GPa, demonstrating the strong relationship between structure and electronic properties in sodium.

High-pressure physics: sustained static generation of 1.36 to 1.72 megabars.

The pressure in experiments with the diamond-window pressure cell exceeded 1.7 megabars (at 25 degrees C). This is the highest sustained pressure ever generated under static conditions where the pressure in the sample itself was measured. At 1.72 megabars, macroscopic flow of one of the diamond pressure faces was observed.

In Situ Determination of the NiAs Phase of FeO at High Pressure and Temperature.

In situ synchrotron x-ray diffraction measurements of FeO at high pressures and high temperatures revealed that the high-pressure phase of FeO has the NiAs structure (B8). The lattice parameters of this NiAs phase at 96 gigapascals and 800 kelvin are a = 2.574(2) angstroms and c = 5.172(4) angstroms (the number in parentheses is the error in the last digit). Metallic behavior of the high-pressure phase is consistent with a covalently and metallically bonded NiAs structure of FeO. Transition to the NiAs structure of FeO would enhance oxygen solubility in molten iron. This transition thus provides a physiochemical basis for the incorporation of oxygen into the Earth's core.

High-Temperature Phase Transition and Dissociation of (Mg, Fe)SiO3 Perovskite at Lower Mantle Pressures.

To study the crystallography of Earth's lower mantle, techniques for measuring synchrotron x-ray diffraction from a laser-heated diamond anvil cell have been developed. Experiments on samples of (Mg, Fe)SiO(3) show that silicate perovskite maintains its orthorhombic symmetry at 38 gigapascals and 1850 kelvin. Measurements at 65 and 70 gigapascals provide evidence for a temperature-induced orthorhombic-to-cubic phase transition and dissociation to an assemblage of perovskite and mixed oxides. If these phase transitions occur in Earth, they will require a significant change in mineralogical models of the lower mantle.

Observations of Hydrogen at Room Temperature (25{degrees}C) and High Pressure (to 500 Kilobars).

Hydrogen becomes a solid at 25 degrees C when subjected to a pressure of 57 kilobars. The high-pressure phase appears as a transparent crystalline mass. The refractive index of the high-pressure phase increases sharply with pressure, indicating a density increase of similar magnitude. At 360 kilobars the calculated density of the high-pressure phase is 0.6 to 0.7 grams per cubic centimeter.

Lead: X-ray Diffraction Study of a High-Pressure Polymorph.

An x-ray diffraction study of lead under pressure has shown that face-centered cubic structure transforms to the hexagonal close-packed structure at room temperature and a pressure of 130+/- 10 kilobars. The volume change for the transformation is -0.18+/- 0.06 cubic centimeter per mole.

Ultrahigh pressure: beyond 2 megabars and the ruby fluorescence scale.

A new design of the diamond-window, high-pressure cell has permitted static pressure of 2.8 megabars to be generated for the first time. The design is unusually stable mechanically, and thus it should be possible to use the new cell to study most materials, including hydrogen, in the unexplored pressure region above 1 megabar.

A High-Pressure Polymorph of Troilite, FeS.

A new polymorph of FeS was produced in a diamond-anvil cell and observed at high pressure both optically and by x-ray diffraction. Fourteen x-ray reflections of the high-pressure FeS were recorded; however, the crystal structure is unknown. This form of FeS is stable at 25 degrees C only at pressures above approximately 55 kilobars. The transition to the lower pressure polymorph, troilite, is rapid and reversible.

Critical behavior in the hydrogen insulator-metal transition.

The vibrational Raman spectrum of solid hydrogen has been measured from 77 to 295 K in the vicinity of the recently observed insulator-metal transition and low-temperature phase transition at 150 gigapascals (1.5 megabars). The measurements provide evidence for a critical point in the pressure-temperature phase boundary of the low-temperature transition. The result suggests that below the critical temperature the insulator-metal transition changes from continuous to discontinuous, consistent with the general criteria originally proposed by Mott for metallization by band-gap closure. The effect of temperature on hydrogen metallization closely resembles that of the lower pressure insulator-metal transitions in doped V(2)O(3) alloys.

High-pressure physics: the 1-megabar mark on the ruby r1 static pressure scale.

Ruby crystals were subjected to a static pressure greater than 1 megabar in a diamond-windowed pressure cell. The pressure was monitored continuously by observing the spectral shift of the sharp fluorescent R(1) ruby line excited with a cadmium-helium gas-diffusion laser beam. One megabar appears to be the highest pressure ever reported for a static experiment in which an internal calibration was employed.

Electrical conductivity and the red shift of absorption in olivine and spinel at high pressure.

Above 100 kilobars the apparent absorption edges (approximately 3 electron volts) of single-crystal and polycrystalline samples of the metastable olivine and stable spinel forms of Fe(2)SiO(4) shift rapidly with pressure from the near-ultraviolet into the lower-energy infrared region. Simultaneously, an exponential increase in electrical conductivity occurs. These effects are reversible as pressure is reduced or reapplied and are not accompanied by a first-order phase change in olivine or spinel. These observations relate to fundamental concepts of electrical conductivity and photon absorption in complex transition-metal silicates in that they cannot be readily interpreted in terms of an intrinsic band-gap model. The intensity and energy changes are too great and the effect occurs at too low a pressure to be explained by processes such as spin-pairing and other crystal-field effects. The results suggest that a new mechanism of conduction, perhaps symbiotic and employing an efficient charge-transfer process, is induced at high pressure.

High-pressure chemistry of hydrogen in metals: in situ study of iron hydride.

Optical observations and x-ray diffraction measurements of the reaction between iron and hydrogen at high pressure to form iron hydride are described. The reaction is associated with a sudden pressure-induced expansion at 3.5 gigapascals of iron samples immersed in fluid hydrogen. Synchrotron x-ray diffraction measurements carried out to 62 gigapascals demonstrate that iron hydride has a double hexagonal close-packed structure, a cell volume up to 17% larger than pure iron, and a stoichiometry close to FeH. These results greatly extend the pressure range over which the technologically important iron-hydrogen phase diagram has been characterized and have implications for problems ranging from hydrogen degradation and embrittlement of ferrous metals to the presence of hydrogen in Earth's metallic core.

Laser techniques in high-pressure geophysics.

Laser techniques in conjunction with the diamond-anvil cell can be used to study high-pressure properties of materials important to a wide range of problems in earth and planetary science. Spontaneous Raman scattering of crystalline and amorphous solids at high pressure demonstrates that dramatic changes in structure and bonding occur on compression. High-pressure Brillouin scattering is sensitive to the pressure variations of single-crystal elastic moduli and acoustic velocities. Laser heating techniques with the diamond-anvil cell can be used to study phase transitions, including melting, under deep-earth conditions. Finally, laser-induced ruby fluorescence has been essential for the development of techniques for generating the maximum pressures now possible with the diamond-anvil cell, and currently provides a calibrated in situ measure of pressure well above 100 gigapascals.

High-pressure ruby and diamond fluorescence: observations at 0.21 to 0.55 terapascal.

A diamond-anvil, high-pressure apparatus was used to extend the upper pressure limit of static laboratory experiments. Shifts of the R(1) strong fluorescent line of ruby were observed that correspond to static pressures of 0.21 to 0.55 terapascal (2.1 to 5.5 megabars) at 25 degrees C. Sensitive spectroscopic techniques in the pressure range 0.15 to 0.28 terapascal were used to observe ruby and diamond fluorescence separately; these two fluorescent emissions overlap strongly at high pressures. At pressures greater than approximately 0.28 terapascal, the diamond fluorescence diminished and the ruby fluorescence reappeared strongly. Pressure was determined by extrapolation of the calibrated shift of the ruby R(1) line.

Thermoelasticity of Silicate Perovskite and Magnesiowustite and Stratification of the Earth's Mantle.

Analyses of x-ray-diffraction measurements on (Mg,Fe)SiO(3) perovskite and (Mg,Fe)O magnesiowüstite at simultaneous high temperature and pressure are used to determine pressure-volume-temperature equations of state and thermoelastic properties of these lower mantle minerals. Detailed comparison with the seismically observed density and bulk sound velocity profiles of the lower mantle does not support models of this region that assume compositions identical to that of the upper mantle. The data are consistent with lower mantle compositions consisting of nearly pure perovskite (>85 percent), which would indicate that the Earth's mantle is compositionally, and by implication, dynamically stratified.

Structure and Density of FeS at High Pressure and High Temperature and the Internal Structure of Mars.

In situ x-ray diffraction measurements revealed that FeS, a possible core material for the terrestrial planets, transforms to a hexagonal NiAs superstructure with axial ratio (c/a) close to the ideal close-packing value of 1.63 at high pressure and high temperature. The high-pressure-temperature phase has shorter Fe-Fe distances than the low-pressure phase. Significant shortening of the Fe-Fe distance would lead to metallization of FeS, resulting in fundamental changes in physical properties of FeS at high pressure and temperature. Calculations using the density of the high-pressure-temperature FeS phase indicate that the martian core-mantle boundary occurs within the silicate perovskite stability field.

B1-b2 transition in calcium oxide from shock-wave and diamond-cell experiments.

Volume and structural data obtained by shock-wave and diamond-cell techniques demonstrate that calcium oxide transforms from the B1 (sodium chloride type) to the B2 (cesium chloride type) structure at 60 to 70 gigapascals (0.6 to 0.7 megabar) with a volume decrease of 11 percent. The agreement between the shockwave and diamond-cell results independently confirms the ruby-fluorescence pressure scale to about 65 gigapascals. The shock-wave data agree closely with ultrasonic measurements on the B1 phase and also agree satisfactorily with equations of state derived from ab initio calculations. The discovery of this B1-B2 transition is significant in that it allows considerable enrichment of calcium components in the earth's lower mantle, which is consistent with inhomogeneous accretion theories.

Synchrotron X-ray Study of Iron at High Pressure and Temperature.

X-ray synchrotron experiments with in situ laser heating of iron in a diamond-anvil cell show that the high-pressure epsilon phase, a hexagonal close-packed (hcp) structure, transforms to another phase (possibly a polytype double-layer hcp) at a pressure of about 38 gigapascals and at temperatures between 1200 and 1500 kelvin. This information has implications for the phase relations of iron in Earth's core.