Pressure-Tuned Fermi Resonance in Ice VII

Fermi resonance was observed between the OH stretch and the overtone of the OH bending modes of HDO molecules contaminated in phase VII of D(2)O ice over the pressure range from 17 to 30 gigapascals. An anharmonic coupling constant, which is related to the potential energy surface on which hydrogen-bonded protons oscillate, was found to range around 50 wave numbers through the resonant pressure range. Its experimentally obtained magnitude and pressure-insensitive behavior will be useful for theoretical studies of the potential energy surface and hence of the nature of hydrogen bonding in ice.     

Pressure-induced enhancement of tc above 150 k in hg-1223

The recently discovered homologous series HgBa(2)Can-1 Cun O2n+2+delta possesses remarkable properties. A superconducting transition temperature, T(c), as high as 133 kelvin has been measured in a multiphase Hg-Ba-Ca-Cu-O sample and found to be attributable to the Hg-1223 compound. Temperature-dependent electrical resistivity measurements under pressure on a (> 95%) pure Hg-1223 phase are reported. These data show that T(c) increases steadily with pressure at a rate of about 1 kelvin per gigapascal up to 15 gigapascals, then more slowly and reaches a T(c) = 150 kelvin, with the onset of the transition at 157 kelvin, for 23.5 gigapascals. This large pressure variation (as compared to the small effects observed in similar compounds with the optimal T(c)) strongly suggests that higher critical temperatures could be obtained at atmospheric pressure.     

Pressure-induced coordination changes in alkali-germanate melts: an in situ spectroscopic investigation

The structure of liquid Na(2)Ge(2)O(5).H(2)O, a silicate melt analog, has been studied with Raman spectroscopy to pressures of 2.2 gigapascals. Upon compression, a peak near approximately 240 wavenumbers associated with octahedral GeO(6) groups grows relative to a peak near approximately 500 wavenumbers associated with tetrahedral GeO(4) groups. This change corresponds to an increase in octahedral germanium in the liquid from near 0% at ambient pressures to >50% at a pressure of 2.2 gigapascals. Silicate liquids plausibly undergo similar coordination changes at depth in the Earth. Such structural changes may generate decreases in the fusion slopes of silicates at high pressures as well as neutrally buoyant magmas within the transition zone of the Earth's mantle.     

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.     

The Phase Boundary Between agr- and beta-Mg2SiO4 Determined by in Situ X-ray Observation

The stability of Mg(2)SiO(4), a major constituent in the Earth's mantle, has been investigated experimentally by in situ observation with synchrotron radiation. A cubic-type high-pressure apparatus equipped with sintered diamond anvils has been used over pressures of 11 to 15 gigapascals and temperatures of 800 degrees to 1600 degrees C. The phase stability of alpha-Mg(2)SiO(4) and beta-Mg(2)SiO(4) was determined by taking account of the kinetic behavior of transition. The phase boundary between alpha-Mg(2)SiO(4) and beta-Mg(2)SiO(4) is approximated by the linear expression P = (9.3 +/- 0.1) + (0.0036 +/- 0.0002)T where P is pressure in gigapascals and T is temperature in degrees Celsius.     

Melting Temperature and Partial Melt Chemistry of H2O-Saturated Mantle Peridotite to 11 Gigapascals

The H2O-saturated solidus of a model mantle composition (Kilborne Hole peridotite nodule, KLB-1) was determined to be just above 1000°C from 5 to 11 gigapascals. Given reasonable H2O abundances in Earth's mantle, an H2O-rich fluid could exist only in a region defined by the wet solidus and thermal stability limits of hydrous minerals, at depths between 90 and 330 kilometers. The experimental partial melts monotonously became more mafic with increasing pressure from andesitic composition at 1 gigapascal to more mafic than the starting peridotite at 10 gigapascals. Because the chemistry of the experimental partial melts is similar to that of kimberlites, it is suggested that kimberlites may be derived by low-temperature melting of an H2O-rich mantle at depths of 150 to 300 kilometers.     

Serpentine stability to mantle depths and subduction-related magmatism

Results of high-pressure experiments on samples of hydrated mantle rocks show that the serpentine mineral antigorite is stable to approximately 720 degrees C at 2 gigapascals, to approximately 690 degrees C at 3 gigapascals, and to approximately 620 degrees C at 5 gigapascals. The breakdown of antigorite to forsterite plus enstatite under these conditions produces 13 percent H(2)O by weight to depths of 150 to 200 kilometers in subduction zones. This H(2)O is in an ideal position for ascent into the hotter, overlying mantle where it can cause partial melting in the source region for calc-alkaline magmas at a depth of 100 to 130 kilometers and a temperature of approximately 1300 degrees C. The breakdown of antigorite in hydrated mantle produces an order of magnitude more H(2)O than does the dehydration of altered oceanic crust.     

Protonic diffusion in high-pressure ice VII

Near ambient pressures, molecular diffusion dominates protonic diffusion in ice. Theoretical studies have predicted that protonic diffusion will dominate at high pressures in ice. We measured the protonic diffusion coefficient for the highest temperature molecular phase of ice VII at 400 kelvin over its entire stable pressure region. The values ranged from 10(-17) to 10(-15) square meters per second at pressures of 10 to 63 gigapascals. The diffusion coefficients extrapolated to high temperatures close to the ice VII melting curve were less by a factor of 10(2) to 10(3) than a superionic criterion of approximately 10(-8) square meters per second, at which protons would diffuse freely.     

Pressure-induced amorphization and negative thermal expansion in ZrW2O8

It has recently been shown that zirconium tungstate (ZrW2O8) exhibits isotropic negative thermal expansion over its entire temperature range of stability. This rather unusual behavior makes this compound particularly suitable for testing model predictions of a connection between negative thermal expansion and pressure-induced amorphization. High-pressure x-ray diffraction and Raman scattering experiments showed that ZrW2O8 becomes progressively amorphous from 1.5 to 3.5 gigapascals. The amorphous phase was retained after pressure release, but the original crystalline phase returned after annealing at 923 kelvin. The results indicate a general trend between negative thermal expansion and pressure-induced amorphization in highly flexible framework structures.     

Body-centered cubic iron-nickel alloy in Earth's core

Cosmochemical, geochemical, and geophysical studies provide evidence that Earth's core contains iron with substantial (5 to 15%) amounts of nickel. The iron-nickel alloy Fe(0.9)Ni(0.1) has been studied in situ by means of angle-dispersive x-ray diffraction in internally heated diamond anvil cells (DACs), and its resistance has been measured as a function of pressure and temperature. At pressures above 225 gigapascals and temperatures over 3400 kelvin, Fe(0.9)Ni(0.1) adopts a body-centered cubic structure. Our experimental and theoretical results not only support the interpretation of shockwave data on pure iron as showing a solid-solid phase transition above about 200 gigapascals, but also suggest that iron alloys with geochemically reasonable compositions (that is, with substantial nickel, sulfur, or silicon content) adopt the bcc structure in Earth's inner core.     

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.     

Pressure-induced landau-type transition in stishovite

A Rietveld structural analysis of stishovite, with angle-dispersive x-ray diffraction synchrotron source at the European Synchrotron Radiation Facility, confirmed a CaCl2 form of stishovite distortion at 54 +/- 1 gigapascals but confirmed no further phase transformation up to 120 gigapascals. The deviatoric stress that is usually encountered at such pressures was relaxed after yttrium-aluminum-garnet-laser heating. A single Birch-Murnaghan equation of state fits volumes of stishovite and a CaCl2 form, showing that the tetragonal distortion occurs without a substantial change in volume. At the 54-gigapascal transition, the pressure-induced lattice modifications were similar to those found in a Landau-type temperature-induced transition. It is proposed that, above the transition pressure, the critical temperature increases above 300 kelvin, so that the lower entropy form becomes stable.     

Moissanite: a window for high-pressure experiments

We achieved a pressure of 52.1 gigapascals with moissanite anvils, which have optical, thermal, electric, magnetic, and x-ray properties that rival those of diamond. The mode-softening of D(2)O toward the pressure-induced hydrogen bond symmetrization and the Raman shifts of diamond under hydrostatic and nonhydrostatic compressions were studied with moissanite anvils in the spectral regions normally obscured by diamond anvils. Moissanite anvil cells allow maximum sample volumes 1000 times larger than those allowed by diamond anvil cells and may enable the next level of advancement in high-pressure experiments.     

Polymorphs of Alumina Predicted by First Principles: Putting Pressure on the Ruby Pressure Scale

Fully optimized quantum mechanical calculations indicate that Al2O3 transforms from the corundum structure to the as yet unobserved Rh2O3 (II) structure at about 78 gigapascals, and it further transforms to Pbnm-perovskite structure at 223 gigapascals. The predicted x-ray spectrum of the Rh2O3 (II) structure is similar to that of the corundum structure, suggesting that the Rh2O3 (II) structure could go undetected in high-pressure x-ray measurements. It is therefore possible that the ruby (Cr3+-doped corundum) fluorescence pressure scale is sensitive to the thermal history of the ruby chips in a given experiment.     

Velocity of sound and equations of state for methanol and ethanol in a diamond-anvil cell

The adaptability of laser-induced phonon spectroscopy to the determination of acoustic velocity and the equation of state in the diamond-anvil high-pressure cell is demonstrated. The technique provides a robust method for measurements at high pressure in both solids and liquids so that important problems in high-pressure elasticity and the earth sciences are now tractable. The velocity of sound and the density of methanol at 25 degrees C have been measured up to a pressure of 6.8 gigapascals. These results imply a higher density (by approximately 5 percent) for liquid methanol above 2.5 gigapascals than that given in existing compilations. The adiabatic bulk modulus increases by a factor of 50 at a maximum compression of 1.8. The thermodynamic Grüneisen parameters of methanol and ethanol both increase with increasing pressure, in contrast to the behavior of most solids.     

Electronic transitions in perovskite: possible nonconvecting layers in the lower mantle

We measured the spin state of iron in magnesium silicate perovskite (Mg(0.9),Fe(0.1))SiO(3) at high pressure and found two electronic transitions occurring at 70 gigapascals and at 120 gigapascals, corresponding to partial and full electron pairing in iron, respectively. The proportion of iron in the low spin state thus grows with depth, increasing the transparency of the mantle in the infrared region, with a maximum at pressures consistent with the D" layer above the core-mantle boundary. The resulting increase in radiative thermal conductivity suggests the existence of nonconvecting layers in the lowermost mantle.     

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.     

Lithium, compression and high-pressure structure

Lithium is found to transform from a body-centered cubic (bcc) to a face-centered cubic (fcc) structure at 6.9 gigapascals (69 kilobars) and 296 kelvin. The relative volume of the bcc structured lithium at 6.9 gigapascals is 0.718, and the fcc structure is 0.25 percent denser. The bulk modulus and its pressure derivative for the bcc structure are 11.57 gigapascals and 3.4, and for the fcc structure are 13.1 gigapascals and 2.8. Extrapolation of the bcc-fcc phase boundary and the melting curve indicate a triple point around 15 gigapascals and 500 kelvin.     

Strength of diamond

The yield strength of diamond is measured under a pressure of 10 gigapascals at temperatures up to 1550 degrees C by the analysis of x-ray peak shapes on diamond diffraction lines in a powdered sample as a function of pressure and temperature. At room temperature, the diamond crystals exhibit elastic behavior with increasing pressure. Significant ductile deformation is observed only at temperatures above 1000 degrees C at this pressure. The differential yield strength of diamond decreases with temperature from 16 gigapascals at 1100 degrees C to 4 gigapascals at 1550 degrees C. Transmission electron microscopy observations on the recovered sample indicate that the dominant deformation mechanism under high pressure and temperature is crystal plasticity.     

Visual Observations of the Amorphous-Amorphous Transition in H2O Under Pressure

The vapor-deposited low-density amorphous phase of H(2)O was directly compressed at 77 kelvin with a diamond-anvil cell, and the boundary between the low-density amorphous phase and the high-density amorphous phase was observed while the sample was warmed under compression. The transition from the low-density amorphous phase to the high-density amorphous phase was distinct and reversible in an apparently narrow pressure range at approximately 130 to approximately 150 kelvin, which provided experimental evidence for polymorphism in amorphous H(2)O.