Structural and bonding changes in cesium iodide at high pressures

Cesium iodide, a simple ionic salt at low pressures, undergoes a second-order transformation at 40 gigapascals (400 kilobars) from the cubic B2 (cesium chloride-type) structure to the body-centered tetragonal structure. Also, the energy gap between valence and conduction bands decreases from 6.4 electron volts at zero pressure to about 1.7 electron volts at 60 gigapascals, transforming cesium iodide from a highly ionic compound to a semiconductor. The structural transition increases the rate at which the band gap closes, and an extrapolation suggests that cesium iodide becomes metallic near (or somewhat above) 100 gigapascals. Similar changes in bonding character are likely to occur in other alkali halides at pressures above 100 gigapascals.     

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.     

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.     

Phase Transition and Thermal Expansion of MgSiO3 Perovskite

Results from in situ x-ray diffraction experiments with a DIA-type cubic anvil apparatus (SAM 85) reveal that MgSiO(3) perovskite transforms from the orthorhombic Pbnm symmetry to another perovskite-type structure above 600 kelvin (K) at pressures of 7.3 gigapascals; the apparent volume increase across the transition is 0.7%. Unit-cell volume increased linearly with temperature, both below (1.44 x 10(-5) K(-1)) and above (1.55 x 10(-5) K(-1)) the transition. These results indicate that the physical properties measured on the Pbnm phase should be used with great caution because they may not be applicable to the earth's lower mantle. A density analysis based on the new data yields an iron content of 10.4 weight percent for a pyrolite composition under conditions corresponding to the lower mantle. All current equation-of-state data are compatible with constant chemical composition in the upper and lower mantle; thus, these data imply that a chemically layered mantle is unnecessary, and whole-mantle convection is possible.     

Crystal Structure of the High-Pressure Phase of Solid CO2

X-ray diffraction study of solid CO(2) at room temperature has shown that the powder pattern of the high-pressure phase, which supersedes the low-pressure cubic Pa3 phase at about 10 gigapascals, is consistently interpreted in terms of an orthorhombic Cmca structure. The orthorhombic cell at 11.8 gigapascals has dimensions of 4.330 +/- 0.015, 4.657 +/- 0.005, 5.963 +/- 0.009 angstroms for its a, b, and c faces, respectively, and a volume of 120.3 +/- 0.5 cubic angstroms. Four molecules contained in the unit cell are located at the base-centered positions with their molecular axes inclined at about 52 degrees with respect to the crystallographic c axis. The volume change associated with the Pa3-Cmca transition is close to zero. The structural dimensions obtained for the high-pressure crystalline phase of CO(2) are of great importance for a theoretical understanding of the role of intermolecular interactions, including quadrupole-quadrupole interactions, in molecular condensation.     

Compressibility of solid c60

Room-temperature powder x-ray diffraction profiles have been obtained at hydrostatic pressures P = 0 and 1.2 gigapascals on the solid phase of cubic C(60) ("fullerite"). Within experimental error, the linear compressibility d(ln a)/dP is the same as the interlayer compressibility d(ln c)/dP of hexagonal graphite, consistent with van der Waals intermolecular bonding. The volume compressibility -d(ln V)/dP is 7.0 +/- 1 x 10(-12) square centimeter per dyne, 3 and 40 times the values for graphite and diamond, respectively.     

Twinning in MgSiO3 Perovskite

Crystals of MgSiO(3) perovskite synthesized at high pressures and temperatures have orthorhombic symmetry under ambient conditions. Examination by transmission electron microscopy shows that the microstructure of crystals synthesized at 26 gigapascals and 1600 degrees C is dominated by a large number of twin domains that are related by reflection operations with respect to {112} and {110} planes. These twins may be associated with the transformations of MgSiO(3) perovskite from the cubic to tetragonal and tetragonal to orthorhombic phases, respectively, upon decreasing pressure and temperature. These observations suggest that under the experimental synthesis conditions, and perhaps in the earth's lower mantle, the stable phase of MgSiO(3) might have the cubic perovskite structure.     

Baddeleyite-Type High-Pressure Phase of TiO2

A high-pressure phase of TiO(2), which had been observed by shock-wave experiments and remained unresolved, has been studied by in situ x-ray diffraction. The single phase was formed at 20 gigapascals and 770 degrees C with the use of sintered-diamond multianvils; it has the same structure as baddeleyite, the stable phase of ZrO(2) at ambient conditions. The coordination number of Ti increases from six to seven across the rutile to baddeleyite transition, and the volume is reduced by approximately 9 percent.     

Synthesis and Equation of State of (Mg,Fe) SiO3 Perovskite to Over 100 Gigapascals

Silicate perovskite of composition (Mg(0.88)Fe(0.12)) SiO(3) has been synthesized in a laser-heated diamond-anvil cell to a pressure of 127 gigapascals at temperatures exceeding 2000 K. The perovskite phase was identified and its unit-cell dimensions measured by in situ x-ray diffraction at elevated pressure and room temperature. An analysis of these data yields the first high-precision equation of state for this mineral, with values of the zero-pressure isothermal bulk modulus and its pressure derivative being K(0T) = 266 +/- 6 gigapascals and K'(0T) = 3.9 +/- 0.4. In addition, the orthorhombic distortion of the silicate-perovskite structure away from ideal cubic symmetry remains constant with pressure: the lattice parameter ratios are b/a = 1.032 +/- 0.002 and c/a = 1.444 +/- 0.006. These results, which prove that silicate perovskite is stable to ultrahigh pressures, demonstrate that perovskite can exist throughout the pressure range of the lower mantle and that it is therefore likely to be the most abundant mineral in Earth.     

Stability of Perovskite (MgSiO3) in the Earth's Mantle

Available thermodynamic data and seismic models favor perovskite (MgSiO3) as the stable phase in the mantle. MgSiO3 was heated at temperatures from 1900 to 3200 kelvin with a Nd-YAG laser in diamond-anvil cells to study the phase relations at pressures from 45 to 100 gigapascals. The quenched products were studied with synchrotron x-ray radiation. The results show that MgSiO3 broke down to a mixture of MgO (periclase) and SiO2 (stishovite or an unquenchable polymorph) at pressures from 58 to 85 gigapascals. These results imply that perovskite may not be stable in the lower mantle and that it might be necessary to reconsider the compositional and density models of the mantle.     

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.     

(Mg,Fe)SiO3-perovskite stability under lower mantle conditions

In three different experiments up to 100 gigapascals and 3000 kelvin, (Mg,Fe)SiO3-perovskite, the major component of the lower mantle, remained stable and did not decompose to its component oxides (Mg, Fe)O and SiO2. Perovskite was formed from these oxides when heated in a diamond anvil cell at pressures up to 100 gigapascals. Both MgSiO3 crystals and glasses heated to 3000 kelvin at 75 gigapascals also formed perovskite as a single phase, as evident from Raman spectra. Moreover, fluorescence measurements on chromium-doped samples synthesized at these conditions gave no indication of the presence of MgO.     

Metallic CsI at pressures of up to 220 gigapascals

Direct electrical transport measurements in a diamond anvil cell provide evidence for the metallization of cesium iodide (CsI) at a pressure of 115 gigapascals. A drop in the temperature dependence of the resistance was found at pressures above 180 gigapascals, indicating that the CsI was superconductive. The superconductivity changed under the influence of a magnetic field to a lower critical temperature and disappeared above 0.3 tesla. The highest critical temperature at which superconductivity was observed was 2 kelvin, and the critical temperature decreased with increasing pressure.     

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.     

X-ray Diffraction to 302 Gigapascals: High-Pressure Crystal Structure of Cesium Iodide

X-ray diffraction measurements have been carried out on cesium iodide (CsI) to 302 gigapascals with a platinum pressure standard. The results indicate that above 200 gigapascals CsI at 300 K has a hexagonal close-packed crystal structure with the ideal c/a ratio of 1.63 +/- 0.01. The crystal structure and pressure-volume relations converge at high pressure with those of solid xenon, which is isoelectronic with CsI. The results indicate a significant loss of ionic bonding in the hexagonal close-packed metallic phase of CsI at ultrahigh pressure.     

Compression of Ice to 210 Gigapascals: Infrared Evidence for a Symmetric Hydrogen-Bonded Phase

Protonated and deuterated ices (H2O and D2O) compressed to a maximum pressure of 210 gigapascals at 85 to 300 kelvin exhibit a phase transition at 60 gigapascals in H2O ice (70 gigapascals in D2O ice) on the basis of their infrared reflectance spectra determined with synchrotron radiation. The transition is characterized by soft-mode behavior of the nu3 O-H or O-D stretch below the transition, followed by a hardening (positive pressure shift) above it. This behavior is interpreted as the transformation of ice phase VII to a structure with symmetric hydrogen bonds. The spectroscopic features of the phase persisted to the maximum pressures (210 gigapascals) of the measurements, although changes in vibrational mode coupling were observed at 150 to 160 gigapascals.     

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.     

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.     

Synchrotron X-ray Diffraction from a Microscopic Single Crystal Under Pressure

Metallic filaments with submicrometer diametere have been fabricated. Standard diffraction techniques with conventional x-ray sources were unsuccessful in identifying the structure of these materials. However, with the use of synchrotron radiation produced on a wiggler beam line, diffraction data were obtained in measurement periods as short as 10 milliseconds. Two cylindrical single crystals of bismuth were studied, each with a diameter of 0.22 +/- 0.02 micrometer. The volume of sample illuminated for these measurements was 0.38 cubic micrometer, less than 0.5 femtoliter. The crystals are grown in glass capillaries, and, because bismuth expands on solidification, they are under a residual hoop stress. The crystallographic data indicate the presence of a linear compressive strain of about 2 percent, which is assumed to be the result of a residual stress of about 2 gigapascals.     

Water as a dense icelike component in silicate glasses

Density and Brillouin-scattering measurements of hydrous andesite glasses at ambient conditions showed that dissolved water has a concentration-independent partial molar volume of 12 +/- 0.5 cubic centimeters per mole and a bulk modulus of 18 +/- 3 gigapascals. Dissolved as hydroxyl ions or as molecular water, water has volume properties similar to those of ice VII, the densest form of ice. These properties point to hydrogen bonding as an important factor in water dissolution, and they indicate that changes of water speciation are driven by the entropy and not by the volume of the system. Water in a concentration greater than 1 percent by weight also causes a marked decrease of the shear modulus of the glass.