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High-pressure transitions are thought to modify hydrogen molecules to a molecular metallic solid and finally to an atomic metal1, which is predicted to have exotic physical properties and the topology of a two-component (electron and proton) superconducting superfluid condensate2,3. Therefore, understanding such transitions remains an important objective in condensed matter physics4,5. However, measurements of the crystal structure of solid hydrogen, which provides crucial information about the metallization of hydrogen under compression, are lacking for most high-pressure phases, owing to the considerable technical challenges involved in X-ray and neutron diffraction measurements under extreme conditions. Here we present a single-crystal X-ray diffraction study of solid hydrogen at pressures of up to 254 gigapascals that reveals the crystallographic nature of the transitions from phase I to phases III and IV. Under compression, hydrogen molecules remain in the hexagonal close-packed (hcp) crystal lattice structure, accompanied by a monotonic increase in anisotropy. In addition, the pressure-dependent decrease of the unit cell volume exhibits a slope change when entering phase IV, suggesting a second-order isostructural phase transition. Our results indicate that the precursor to the exotic two-component atomic hydrogen may consist of electronic transitions caused by a highly distorted hcp Brillouin zone and molecular-symmetry breaking. X-ray diffraction measurements of solid hydrogen provide crystallographic information for high-pressure phases of hydrogen and transitions between them, suggesting a series of isostructural transitions under compression before band closure and metallization.

Metallization of hydrogen as a key problem in modern physics is the pressure-induced evolution of the hydrogen electronic band from a wide-gap insulator to a closed gap metal. However, due to its remarkably high energy, the electronic band gap of insulating hydrogen has never before been directly observed under pressure. Using high-brilliance, high-energy synchrotron radiation, we developed an inelastic x-ray probe to yield the hydrogen electronic band information in situ under high pressures in a diamond-anvil cell. The dynamic structure factor of hydrogen was measured over a large energy range of 45 eV. The electronic band gap was found to decrease linearly from 10.9 to 6.57 eV, with an 8.6 times densification ($\ensuremath{\rho}/{\ensuremath{\rho}}_{0}\ensuremath{\sim}8.6$) from zero pressure up to 90 GPa.

Diamond anvil cell techniques have been improved to allow access to the multimegabar ultrahigh-pressure region for exploring novel phenomena in condensed matter. However, the only way to determine crystal structures of materials above 100 GPa, namely, X-ray diffraction (XRD), especially for low Z materials, remains nontrivial in the ultrahigh-pressure region, even with the availability of brilliant synchrotron X-ray sources. In this work, we perform a systematic study, choosing hydrogen (the lowest X-ray scatterer) as the subject, to understand how to better perform XRD measurements of low Z materials at multimegabar pressures. The techniques that we have developed have been proved to be effective in measuring the crystal structure of solid hydrogen up to 254 GPa at room temperature [C. Ji et al., Nature 573, 558-562 (2019)]. We present our discoveries and experiences with regard to several aspects of this work, namely, diamond anvil selection, sample configuration for ultrahigh-pressure XRD studies, XRD diagnostics for low Z materials, and related issues in data interpretation and pressure calibration. We believe that these methods can be readily extended to other low Z materials and can pave the way for studying the crystal structure of hydrogen at higher pressures, eventually testing structural models of metallic hydrogen. (C) 2020Author(s).

Significance The presence of extra reducer was thought to be essential for producing natural diamonds from reduction of carbonates. The present study of the Xiuyan meteoritic crater, however, finds natural diamond formation via a subsolidus self-redox of a ferromagnesian carbonate during shock compression to 25–45 GPa and 800–900 °C without melting, fluid, and another reductant. The ability of carbonate to produce diamond by itself implies that diamond would be a very common mineral in the lower mantle where the carbonates are abundant and pressures and temperatures are sufficiently high., Formation of natural diamonds requires the reduction of carbon to its bare elemental form, and pressures (P) greater than 5 GPa to cross the graphite–diamond transition boundary. In a study of shocked ferromagnesian carbonate at the Xiuyan impact crater, we found that the impact pressure–temperature (P-T) of 25–45 GPa and 800–900 °C were sufficient to decompose ankerite Ca(Fe2+,Mg)(CO3)2 to form diamond in the absence of another reductant. The carbonate self-reduced to diamond by concurrent oxidation of Fe2+ to Fe3+ to form a high-P polymorph of magnesioferrite, MgFe3+2O4. Discovery of the subsolidus carbonate self-reduction mechanism indicates that diamonds could be ubiquitously present as a dominant host for carbon in the Earth’s lower mantle.

High-pressure transitions are thought to modify hydrogen molecules to a molecular metallic solid and finally to an atomic metal

Ubiquitous on Earth, \ensuremath{\alpha}-quartz plays an important role in modern science and technology. However, despite extensive research in the past, the mechanism of the polymorphic transitions of \ensuremath{\alpha}-quartz at high pressures remains poorly understood. Here, combining in situ single-crystal x-ray diffraction experiment and advanced ab initio modeling, we report two stability limits and competing transition pathways of \ensuremath{\alpha}-quartz under high pressure. Under near-equilibrium compression conditions at room temperature, \ensuremath{\alpha}-quartz transits to a new $P2/c$ silica phase via a structural intermediate. If the thermally activated transition is kinetically suppressed, the ultimate stability of \ensuremath{\alpha}-quartz is controlled by its phonon instability and \ensuremath{\alpha}-quartz collapses into a different crystalline phase. Our studies reveal that pressure-induced solid-state transformation of \ensuremath{\alpha}-quartz undergoes a succession of structural stability limits, due to thermodynamic and mechanical catastrophes, and exhibits a hierarchy of transition pathways contingent upon kinetic conditions.

The compression of glassy carbon forms a series of lightweight, ultrastrong, hard, elastic, and conductive carbons., Carbon’s unique ability to have both sp2 and sp3 bonding states gives rise to a range of physical attributes, including excellent mechanical and electrical properties. We show that a series of lightweight, ultrastrong, hard, elastic, and conductive carbons are recovered after compressing sp2-hybridized glassy carbon at various temperatures. Compression induces the local buckling of graphene sheets through sp3 nodes to form interpenetrating graphene networks with long-range disorder and short-range order on the nanometer scale. The compressed glassy carbons have extraordinary specific compressive strengths—more than two times that of commonly used ceramics—and simultaneously exhibit robust elastic recovery in response to local deformations. This type of carbon is an optimal ultralight, ultrastrong material for a wide range of multifunctional applications, and the synthesis methodology demonstrates potential to access entirely new metastable materials with exceptional properties.

Iron isotopes constrain core chemistry The overall composition of Earth's core is an important constraint on the chemistry and evolution of our planet's interior. A longstanding problem has been determining the minor element contribution to its predominately iron-nickel alloy. Based on the iron isotope fractionation of various iron alloys with pressure, Shahar et al. find that carbon and hydrogen are probably not primary components of the core. The fractionation occurs at the high pressures of core formation, suggesting that the stable iron isotope ratios of Earth are a new and independent constraint on core composition. Science , this issue p. 580

Using synchrotron high-pressure X-ray diffraction at cryogenic temperatures, we have established the phase diagram for calcium up to 110 GPa and 5–300 K. We discovered the long-sought for theoretically predicted β-tin structured calcium with I 4 1 /amd symmetry at 35 GPa in a s mall low-temperature range below 10 K, thus resolving the enigma of absence of this lowest enthalpy phase. The stability and relations among various distorted simple-cubic phases in the Ca-III region have also been examined and clarified over a wide range of high pressures and low temperatures.

We have performed measurements of minerals based on the synchrotron source for single crystal and powder X-ray diffraction, inelastic scattering, spectroscopy and radiography by using diamond anvil cells. We investigated the properties of iron (Fe), iron-magnesium oxides (Fe, Mg)O, silica(SiO 2 ), iron-magnesium silicates (Fe, Mg)SiO 3 under simulated high pressure-high temperature extreme conditions of the Earth’s crust, upper mantle, low mantle, core-mantle boundary, outer core, and inner core. The results provide a new window on the investigation of the mineral properties at Earth’s conditions.

The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil cells. The diffraction data for types II (sII) and H (sH) were refined to the known structures with space groups Fd 3 m and P 6 3 / mmc , respectively. Upon compression, sI methane hydrate transforms to the sII phase at 120 MPa, and then to the sH phase at 600 MPa. The sII methane hydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methane hydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm 3 m structure and ice VII ( Pn 3 m ). The results highlight the role of guest (CH 4 )-host (H 2 O) interactions in the stabilization of the hydrate structures under pressure.

The detailing of the intermolecular interactions in dense solid oxygen is essential for an understanding of the rich polymorphism and remarkable properties of this element at high pressure. Synchrotron inelastic x-ray scattering measurements of oxygen K-edge excitations to 38 GPa reveal changes in electronic structure and bonding on compression of the molecular solid. The measurements show that O 2 molecules interact predominantly through the half-filled 1π g * orbital g * orbital in the low-pressure phases, leading to electron delocalization and ultimately intermolecular bonding between O 2 molecules at the transition to the ε-phase. The ε-phase, which consists of (O 2 ) 4 clusters, displays the bonding characteristics of a closed-shell system. Increasing interactions between (O 2 ) 4 clusters develop upon compression of the ε-phase, and provide a potential mechanism for intercluster bonding in still higher-pressure phases.

During the past decade, the radial x-ray diffraction method using a diamond anvil cell (DAC) has been developed at the X17C beamline of the National Synchrotron Light Source. The detailed experimental procedure used with energy dispersive x-ray diffraction is described. The advantages and limitations of using the energy dispersive method for DAC radial diffraction studies are also discussed. The results for FeO at 135 GPa and other radial diffraction experiments performed at X17C are discussed in this report.

Full understanding of atomic arrangement in amorphous oxides both at ambient and high pressure is an ongoing fundamental puzzle. Whereas the structures of archetypal oxide glasses such as v-B2O3 at high pressure are essential to elucidate origins of anomalous macroscopic properties of more complex melts, knowledge of the high-pressure structure and pressure-induced coordination changes of these glasses has remained elusive due to lack of suitable in situ experimental probes. Here, we report synchrotron inelastic X-ray scattering results for v-B2O3 at pressures up to 22.5 GPa, revealing the nature of pressure-induced bonding changes and the structure. Direct in situ measurements show a continuous transformation from tri-coordinated to tetra-coordinated boron beginning at 4–7 GPa with most of the boron tetra-coordinated above 20 GPa, forming dense tetrahedral v-B2O3. After decompression from high pressure the bonding reverts back to tri-coordinated boron but with the data suggesting a permanent densification.

The synchrotron radiation X-ray diffraction technique developed for in situ study at high pressure and temperature has also been used to investigate microscopic mineral inclusions in ultra-high-pressure metamorphic rocks and deep-mantle samples. Present study added two more examples of successful utilization of synchrotron radiation X-ray diffraction technique for in situ investigations of fine-grained (0.5―30 μm in size) minerals in very thin shock melt veins of the Suizhou meteorite: (i) X-ray diffraction measurement of extremely small-sized vein matrix minerals, and (ii) identification of the micron-sized new mineral tuite embedded in the vein matrix. It has been revealed that the fine-grained vein matrix consists of well crystallized garnet, kama-cite and troilite, and the powder diffraction pattern consisting of 17 lines with d-values, intensities ( I ), relative intensities ( I / I o ) and Miller indices, as well as the cell parameters for the new mineral tuite has also been successfully obtained. The result of present investigations has enriched the content of dynamic high-pressure mineralogy and that of Earth’s mantle geochemistry.

The high-pressure, high-temperature behavior of iron has been investigated to 161 GPa and 3000 K by in situ synchrotron X-ray diffraction with double-side laser-heated diamond anvil cells. We found that only α-, γ- and e-Fe can be clearly verified as the stable solid phase in the P–T range studied. Only e-Fe is observed from deep lower mantle (∼1500 km) to outer core conditions. Within the P–T range examined, we did not observe a significant change with pressure or temperature on the c/a ratio of e-Fe. The melting curve of iron has been determined to 105 GPa. A Lindeman law fit gives a melting point of iron at the inner core boundary of 5800 (±200) K, which provides an upper bound on the temperature at that depth. We also examine numerous experimental factors that may complicate the analysis of high P–T diffraction data, and discuss the effects of sample stress on the X-ray diffraction results.

In situ high-pressure synchrotron X-ray diffraction and infrared absorption experiments for gibbsite were performed at room temperature up to 53 and 25 GPa, respectively. A phase transition was confirmed at about 2.5 GPa. The high-pressure phase is indexed as an orthorhombic structure, rather than a triclinic structure as reported in previous studies. The compressibility of gibbsite and its high-pressure polymorph were studied, and their bulk moduli K 0 were determined to be 49 and 75 GPa, respectively with K 0′ as 4. The in situ high-pressure infrared absorption spectra revealed the gradual disordering of hydrogen substructure above 15 GPa in quasihydrostatic compression.

Physical and chemical reactions occurring as a result of the high-velocity impacts of meteorites and micrometeorites and of cosmic rays and solar-wind particles are major causes of space weathering on airless planetary bodies, such as the Moon, Mercury, and asteroids. These weathering processes are responsible for the formation of their regolith and soil. We report here the natural occurrence of the mineral hapkeite, a Fe 2 Si phase, and other associated Fe-Si phases (iron-silicides) in a regolith breccia clast of a lunar highland meteorite. These Fe-Si phases are considered to be a direct product of impact-induced, vapor-phase deposition in the lunar soil, all part of space weathering. We have used an in situ synchrotron energy-dispersive, single-crystal x-ray diffraction technique to confirm the crystal structure of hapkeite as similar to the structure of synthetic Fe 2 Si. This mineral, hapkeite, is named after Bruce Hapke of the University of Pittsburgh, who predicted the presence and importance of vapor-deposited coatings on lunar soil grains some 30 years ago. We propose that this mineral and other Fe-Si phases are probably more common in the lunar regolith than previously thought and are directly related to the formation of vapor-deposited, nanophase elemental iron in the lunar soils.

Tuite, γ-Ca 3 (PO 4 ) 2 , the high-pressure polymorph of whitlockite, was found in a shock melt vein of the Suizhou chondrite. It occurs as polycrystalline aggregates in association with coarse-grained aggregates of ringwoodite, majorite and NaAlSi 3 O 8 -hollandite. These high-pressure mineral assemblages are enclosed in the fine-grained matrix of the vein that consists of majorite-pyrope ss garnet, metal and troilite. This new mineral is trigonal, R 3 m,a = 5.258 A, c = 18.727 A. The tuite is colourless and transparent with vitreous lustre and white streak; it is uniaxial (+) with high refractive indices (ϵ = 1.706, ω = 1.701) and low birefringence (0.005). Microprobe analyses of tuite yield an empirical formula (Ca 2.51 Mg 0.29 ) 2.80 Na 0.28 (P 1.01 O 4 ) 2 . The simplified formula, Ca 3 (PO 4 ) 2 , is the same as whitlockite outside the veins. Stronger reflections on synchrotron radiation X-ray powder diffraction pattern of tuite are d = 2.628 (100), 2.891 (80), 1.945 (47), 1.730 (25) and 1.567(22). The figures in brackets are relative intensities. Tuite in the shock vein of this meteorite was transformed from whitlockite via a shock-produced solid-state reaction, while the pressure and temperature in the shock vein attained 23 GPa and 2000°C. This new mineral and the mineral name (tuite) have been approved by the Commission on New Minerals and Mineral Names of the International Mineralogical Association.

Recent advances in high-pressure diamond anvil cell experiments include high-energy synchrotron x-ray techniques as well as new cell designs and gasketing procedures. The success of high-pressure experiments usually depends on a well-prepared sample, in which the gasket plays an important role. Various gasket materials such as diamond, beryllium, rhenium, and stainless steel have been used. Here we introduce amorphous boron as another gasket material in high-pressure diamond anvil cell experiments. We have applied the boron gasket for laser-heating x-ray diffraction, radial x-ray diffraction, nuclear resonant inelastic x-ray scattering, and inelastic x-ray scattering. The high shear strength of the amorphous boron maximizes the thickness of the sample chamber and increases the pressure homogeneity, improving the quality of high-pressure data. Use of amorphous boron avoids unwanted x-ray diffraction peaks and reduces the absorption of incident and x rays exiting the gasket material. The high quality of the diffraction patterns makes it possible to refine the cell parameters with powder x-ray diffraction data under high pressure and high temperature. The reactivity of boron prevents its use at high temperatures, however. When heated, boron may also react with the specimen to produce unwanted phases. The relatively porous boron starting material at ambient conditions also poses some challenges for sample preparation.

The first natural occurrence of a high-pressure polymorph of chromite has been discovered in the shock-metamorphosed Suizhou meteorite. The composition of this high-pressure polymorph is identical to that of the precursor chromite. The Raman spectrum of this polymorph is distinct from that of chromite. Synchrotron X-ray diffraction analysis revealed that this polymorph has an orthorhombic CaTi2O4- type structure. The cell parameters are: a = 9.462(6) A, b = 9.562(9) A, c = 2.916(1) A, V = 263.8(4) A3 (Z=4), space group = Bbmm, and the density = 5.63 g/cm3 (the numbers in parentheses are standard deviations on the last significant digits). This polymorph is 11.5% denser than chromite. The P-T conditions for the phase transformation from chromite to the CaTi2O4-structured polymorph are estimated at 20–23 GPa and 1800 to 2000 °C, respectively. This dense CaTi2O4-structured FeCr2O4 phase could be a host phase for Cr, Al, Fe, Mg and Mn and other metallic elements in the deep Earth.

Magnesiowustite (Mg0.1Fe0.9)O was studied at ambient temperature under both hydrostatic and quasihydrostatic pressures to 35 GPa. The elastic behaviour, equation of state, transition pressure, and the structure before and after the B1–rhombohedral transition were determined. K0-and K0 '-values for the B1 phase were calculated to be 155 ± 10 and 3.6 ± 0.8 GPa respectively under hydrostatic conditions. The second-order B1–rhombohedral transition occurred at 20 GPa. Quasihydrostatic conditions were used to determine the stress/strain in different crystallographic directions to elucidate the transition mechanism which is triggered by the softening of the c44 in the B1 phase.

The phase transitions and equation of state of cobalt oxide (CoO) have been studied at ambient temperature under non-hydrostatic and hydrostatic high pressures, with the diamond-anvil cell technique. We discovered that under hydrostatic pressure conditions the CoO structure transformed from the low-density rhombohedral to a high-density rhombohedral phase at 90 ± 1 GPa with the molecular volume decreasing by about 2.7%. This phase transition with volume discontinuity may be related to magnetic collapse, which was predicted by theory. The pressure of the phase transition of CoO from face-centred cubic B1 to rhombohedral structure was 43 ± 2 GPa. The decompression spectrum data of CoO under non-hydrostatic pressure showed that these phase transitions are reversible.

A new high-pressure polymorph of merrillite with the structure of trigonal γ-Ca 3 (PO 4 ) 2 was found in the shock-produced veins of the Suizhou meteorite, where it coexists with ringwoodite, majorite, NaAlSi 3 O 8 -hollandite, and majorite-pyrope garnet. The crystallographic nature of this natural γ-Ca 3 (PO 4 ) 2 phase was characterized by Raman spectroscopy and X-ray diffraction, and all data compare favorably to the same data obtained from γ-Ca 3 (PO 4 ) 2 synthesized at 14 GPa and 1400°C. The cell parameters of this new high-pressure mineral are a = 5.258(1) angstroms and c = 18.727(3) angstroms, space group R-3m, and density = 3.447 (g/cm 3 ), where the number in parentheses are standard deviations in the last significant digits. The natural occurrence of the γ-Ca 3 (PO 4 ) 2 phase together with other high-pressure minerals constrains the pressure of the shock veins at about 23 GPa. The Suizhou meteorite provides the first naturally occurring example of γ-Ca 3 (PO 4 ) 2 polymorph.

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) Å and volume V = 5051.3(13) Å 3 ; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) Å, c = 9.992(3) Å, and V = 1241.9(5) Å 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.

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 high-pressure measurements reveal the coupling of strain and order parameter in the pressure-induced ferroelastic transition in dense SiO2. Single-crystal X-ray diffraction measurements in quasi-hydrostatic media reversibly probe the spontaneous strain in the vicinity of the P42=mnm! Pnnm transition near 50 GPa, and indicate weak first-order character. A Landau model is developed that quantitatively relates all of the spectroscopic, elastic, structural, and thermodynamic data for the system. The elastic instability at the transition gives rise to anomalies in the Raman spectrum, which are expected to be a general feature of such pressure-induced transitions. q 2000 Elsevier Science Ltd. All rights reserved.

Solid methane (CH(4)) was compressed up to 202 GPa at 300 K in a diamond-anvil cell. The crystal structure and equation of state over this entire range were determined from angle dispersive X-ray diffraction results. CH(4) undergoes phase transitions from rhombohedral to a simple cubic phase at 19 GPa and from simple cubic to a higher pressure cubic phase at approximately 94 GPa. This higher pressure cubic phase was stable to the maximum pressure investigated. Combined with previous optical measurements, it was found that at room temperature compressed CH(4) remains an insulator with cubic structure to 202 GPa. (C) 2009 Elsevier B. V. All rights reserved.

Lattice strains were measured as a function of the angle ψ between the diffracting plane normal and the stress axis of a diamond anvil cell in a layered sample of molybdenum and gold. The sample was compressed over the range 5–24 GPa and the lattice strains were measured using energy-dispersive x-ray diffraction. As ψ is varied from 0° to 90°, the mean lattice parameter of molybdenum increases by up to 1.2% and that of gold increases by up to 0.7%. A linear relationship between Q(hkl), which is related to the slope of the measured d spacing versus 1−3 cos2 ψ relation, and 3Γ(hkl), a function of the Miller indices of the diffracting plane, is observed for both materials as predicted by theory. The pressure dependence of the uniaxial stress t for gold from this and other recent studies is given by t=0.06+0.015P, where P is the pressure in GPa. The uniaxial stress in molybdenum can be described by t=0.46+0.13P. Using gold as an internal pressure standard, the equation of state of molybdenum depends strongly ...

We report evidence for a preserved magnetic state in FeO up to 143 GPa at room temperature using high-resolution x-ray emission spectroscopy. This observation is based on the spectral line shape of the Fe Kb emission line. Up to the highest pressure, FeO remains a magnetic insulator. Combining our results with previous Mossbauer data, we present a new magnetic phase diagram of FeO. Features like a closed-loop P-T antiferromagnetic domain confirm that high-pressure investigations can reveal new physical properties and unexpected phenomena.

The equations for the lattice strains produced by nonhydrostatic compression are presented for all seven crystal systems in a form convenient for analyzing x-ray diffraction data obtained by newly developed methods. These equations have been used to analyze the data on cubic (bcc α-Fe) and hexagonal (hcp e-Fe) systems. The analysis gives information on the strain produced by the hydrostatic stress component. A new method of estimating the uniaxial stress component from diffraction data is presented. Most importantly, the present analysis provides a general method of determining single crystal elastic constants to ultrahigh pressures.

Raman and infrared spectroscopy of para-H{sub 2} to pressures in excess of 200GPa and to 8K using new ultrapure synthetic diamond anvils reveals numerous new vibrational excitations in the three high-pressure phases. Highly resolved Raman-active librons indicate differences in orientational ordering between phasesII and III, including evidence for changes within phaseII. The librons in phaseIII are strongly pressure dependent and reflect a substantial increase in ordering with pressure. Multiple vibrons in all three phases (I, II, and III) are observed. The results place new bounds on predicted crystal structures and dynamics of the dense molecular solid. {copyright} {ital 1997} {ital The American Physical Society}

The equations for the lattice strains produced by non-hydrostatic compression of the specimen are presented for all seven crystal systems in a form suitable for the analysis of experimental data. Examples of cubic (FeO and bcc iron) and hexagonal (hcp iron) systems are given to demonstrate that the analyses of the data give the estimates of single crystal elastic constants under high pressures. As the lattice strains can be measured at high pressures up to a few megabars using a diamond anvil cell, this approach offers an unique method of estimating the elastic constants at such high pressures. Further, this is the only method of estimating elastic constants of a phase stabilized under pressure. The article also discusses some other interesting specimen-material properties that can be derived at such high pressures.

High-pressure experiments and theoretical calculations demonstrate that an iron-rich ferromagnesian silicate phase can be synthesized at the pressure–temperature conditions near the core–mantle boundary. The iron-rich phase is up to 20% denser than any known silicate at the core–mantle boundary. The high mean atomic number of the silicate greatly reduces the seismic velocity and provides an explanation to the low-velocity and ultra-low-velocity zones. Formation of this previously undescribed phase from reaction between the silicate mantle and the iron core may be responsible for the unusual geophysical and geochemical signatures observed at the base of the lower mantle.

High-pressure energy dispersive X-ray diffraction of wustite has been obtained with three types of diamond cells; each one is designed to optimize a type of in situ study, namely single-crystal X-ray diffraction, deviatoric strain measurement, or simultaneous high-P-T experimentation. The results demonstrate that above 17 GPa at 300 K wustite undergoes a displacive transition from B1 to a rhombohedral structure, and above 90 GPa at 600 K, a second transition to the NiAs structure. Many of the earlier inconsistencies concerning the structure and properties of wustite at high pressures can be attributed to the extreme softening of the C44 elastic modulus at pressures above 10 GPa.

Natural olivine with 12 mol % Fe 2 SiO 4 and synthetic orthopyroxenes with 20% and 40% FeSiO 3 were studied beyond the pressure–temperature conditions of the core–mantle boundary. All samples were found to convert entirely or partially into the CaIrO 3 postperovskite structure, which was recently reported for pure MgSiO 3 . The incorporation of Fe greatly reduces the pressure needed for the transition and establishes the new phase as the major component of the D″ layer. With the liquid core as an unlimited reservoir of iron, core–mantle reactions could further enrich the iron content in this phase and explain the intriguing seismic signatures observed in the D″ layer.

Using in situ high-pressure x-ray diffraction methods, the compressibility of 30nm 3C–SiC nanocrystals was studied under hydrostatic conditions while helium was used as pressure transmitting medium, as well as under nonhydrostatic conditions without pressure medium. No threshold pressure phenomenon was observed for the compressibility of the nanocrystals during compression in hydrostatic conditions, while the critical pressure around 10.5GPa was observed during nonhydrostatic compression. These indicate that the threshold pressure phenomena, recently reported that the nanocrystals initially exhibited much higher bulk modulus below the threshold pressure during compression [Appl. Phys. Lett. 83, 3174 (2003); J. Phys. Chem. 107, 14151 (2003)], were mainly caused by the nonhydrostatic effect instead of a specific feature of nanocrystals upon compression. The bulk modulus of 3C–SiC nanocrystals is estimated as 220.6±0.6GPa based on the hydrostatic compression data.

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.

Two experiments were conducted compressing Ta, Re, Pt, and an Fe-Si alloy to ultrahigh pressures using single-crystal chemical vapor deposition (CVD) and natural diamonds. In situ energy-dispersive and angle-dispersive x-ray diffraction were used to determine pressure from known equations of state. We demonstrate that CVD diamonds can be used in diamond anvil cells to reach pressures of nearly 200 GPa.

Compressed under ambient temperature, graphite undergoes a transition at approximately 17 gigapascals. The near K-edge spectroscopy of carbon using synchrotron x-ray inelastic scattering reveals that half of the pi-bonds between graphite layers convert to sigma-bonds, whereas the other half remain as pi-bonds in the high-pressure form. The x-ray diffraction pattern of the high-pressure form is consistent with a distorted graphite structure in which bridging carbon atoms between graphite layers pair and form sigma-bonds, whereas the nonbridging carbon atoms remain unpaired with pi-bonds. The high-pressure form is superhard, capable of indenting cubic-diamond single crystals.

Effects of pressure on lattice parameters and molar volume of diaspore were studied to 25.5 GPa at 300 K by polycrystalline X-ray diffraction techniques. The pressure-volume data fit with a second-order Birch-Murnaghan equation of state give a bulk modulus K 0 = 167.5 GPa by Ruoff and previously reported, but unsubstantiated, value of K 0 = 85 GPa by Ruoff and Vanderborgh [ Phys. Rev. Lett. 66, 754 (1991)]. Thermodynamic calculation indicates that hydrogen and ruby are stable relative to diaspore and aluminum to pressures above 200 GPa.

Sodium, which has long been regarded as one of the simplest metals, displays a great deal of structural, optical, and electronic complexities under compression. We compressed pure Na in the body-centered cubic structure to 52 GPa and in the face-centered cubic structure from 64 to 97 GPa, and studied the plasmon excitations of both structures using the momentum-dependent inelastic X-ray scattering technique. The plasmon dispersion curves as a function of pressure were extrapolated to zero momentum with a quadratic approximation. As predicted by the simple free-electron model, the square of the zero-momentum plasmon energy increases linearly with densification of the body-centered cubic Na up to 1.5-fold. At further compressions and in face-centered cubic Na above 64 GPa, the linear relation curves progressively toward the density axis up to 3.7-fold densification at 97 GPa. Ab initio calculations indicate that the deviation is an expected behavior of Na remaining a simple metal.

Thorough investigations using Raman spectra of solid methane (CH4) were conducted using moissanite anvil cells in the range of 1−43 GPa at room temperature to identify high-pressure phases. Two interesting phases were uncovered, one with a narrow pressure range of 1 GPa centered at around 12.5 GPa and another with a range of 3 GPa centered at around 40.5 GPa. Our results do not support the existence of a phase transformation around 25 GPa. The high-quality Raman spectra, obtained by using single-crystal samples, narrow the boundaries of seven methane phases at pressures up to 43.2 GPa.

Compressing glassy carbon above 40 GPa, we have observed a new carbon allotrope with a fully $s{p}^{3}$-bonded amorphous structure and diamondlike strength. Synchrotron x-ray Raman spectroscopy revealed a continuous pressure-induced $s{p}^{2}$-to-$s{p}^{3}$ bonding change, while x-ray diffraction confirmed the perseverance of noncrystallinity. The transition was reversible upon releasing pressure. Used as an indenter, the glassy carbon ball demonstrated exceptional strength by reaching 130 GPa with a confining pressure of 60 GPa. Such an extremely large stress difference of $g70\text{ }\text{ }\mathrm{GPa}$ has never been observed in any material besides diamond, indicating the high hardness of this high-pressure carbon allotrope.

Using inelastic x-ray scattering techniques, we have succeeded in probing the high-pressure electronic structure of helium at 300 K. Helium has the widest known valence-conduction band gap of all materials a property whose high-pressure response has been inaccessible to direct measurements. We observed a rich electron excitation spectrum, including a cutoff edge above 23 eV, a sharp exciton peak showing linear volume dependence, and a series of excitations and continuum at 26 to 45 eV. We determined the electronic dispersion along the Γ-M direction over two Brillouin zones, and provided a quantitative picture of the helium exciton beyond the simplified Wannier-Frenkel description.

Ca-III, the first superconducting calcium phase under pressure, was identified as simple-cubic (sc) by previous X-ray diffraction (XRD) experiments. In contrast, all previous theoretical calculations showed that sc had a higher enthalpy than many proposed structures and had an imaginary (unstable) phonon branch. By using our newly developed submicrometer high-pressure single-crystal XRD, cryogenic high-pressure XRD, and theoretical calculations, we demonstrate that Ca-III is neither exactly sc nor any of the lower-enthalpy phases, but sustains the sc-like, primitive unit by a rhombohedral distortion at 300 K and a monoclinic distortion below 30 K. This surprising discovery reveals a scenario that the high-pressure structure of calcium does not go to the zero-temperature global enthalpy minimum but is dictated by high-temperature anharmonicity and low-temperature metastability fine-tuned with phonon stability at the local minimum.

The use of nanoscale x-ray probes overcomes several key limitations in the study of materials up to multimegabar (> 200) pressures, namely, the spatial resolution of measurements of multiple samples, stress gradients, and crystal domains in micron to submicron size samples in diamond-anvil cells. Mixtures of Fe, Pt, and W were studied up to 282 GPa with 250–600 nm size synchrotron x-ray absorption and diffraction probes. The probes readily resolve signals from individual materials, between sample and gasket, and peak pressures, in contrast to the 5-μm-sized x-ray beams that are now becoming routine. The use of nanoscale x-ray beams also enables single-crystal x-ray diffraction studies in nominally polycrystalline samples at ultrahigh pressures, as demonstrated in measurements of (Mg,Fe)SiO 3 postperovskite. These capabilities have potential for driving a push toward higher maximum pressures and further miniaturization of high-pressure devices, in the process advancing studies at extreme conditions.

Using high-pressure synchrotron x-ray absorption spectroscopy, we observed the Ce 4f electron in Ce{sub 75}Al{sub 25} metallic glass transform from its ambient localized state to an itinerant state above 5 GPa. A parallel x-ray diffraction study revealed a volume collapse of about 8.6%, coinciding with 4f delocalization. The transition started from a low-density state below 1.5 GPa, went through continuous densification ending with a high-density state above 5 GPa. This new type of electronic polyamorphism in densely packed metallic glass is dictated by the Ce constituent, and is fundamentally distinct from the well-established structural polyamorphism in which densification is caused by coordination change and atomic rearrangement.