Focusing polycapillary to reduce parasitic scattering for inelastic x-ray measurements at high pressure.

The double-differential scattering cross-section for the inelastic scattering of x-ray photons from electrons is typically orders of magnitude smaller than that of elastic scattering. With samples 10-100 µm size in a diamond anvil cell at high pressure, the inelastic x-ray scattering signals from samples are obscured by scattering from the cell gasket and diamonds. One major experimental challenge is to measure a clean inelastic signal from the sample in a diamond anvil cell. Among the many strategies for doing this, we have used a focusing polycapillary as a post-sample optic, which allows essentially only scattered photons within its input field of view to be refocused and transmitted to the backscattering energy analyzer of the spectrometer. We describe the modified inelastic x-ray spectrometer and its alignment. With a focused incident beam which matches the sample size and the field of view of polycapillary, at relatively large scattering angles, the polycapillary effectively reduces parasitic scattering from the diamond anvil cell gasket and diamonds. Raw data collected from the helium exciton measured by x-ray inelastic scattering at high pressure using the polycapillary method are compared with those using conventional post-sample slit collimation.

Polymorphic phase transition mechanism of compressed coesite.

Silicon dioxide is one of the most abundant natural compounds. Polymorphs of SiO2 and their phase transitions have long been a focus of great interest and intense theoretical and experimental pursuits. Here, compressing single-crystal coesite SiO2 under hydrostatic pressures of 26-53 GPa at room temperature, we discover a new polymorphic phase transition mechanism of coesite to post-stishovite, by means of single-crystal synchrotron X-ray diffraction experiment and first-principles computational modelling. The transition features the formation of multiple previously unknown triclinic phases of SiO2 on the transition pathway as structural intermediates. Coexistence of the low-symmetry phases results in extensive splitting of the original coesite X-ray diffraction peaks that appear as dramatic peak broadening and weakening, resembling an amorphous material. This work sheds light on the long-debated pressure-induced amorphization phenomenon of SiO2, but also provides new insights into the densification mechanism of tetrahedrally bonded structures common in nature.

Icosahedral AlCuFe quasicrystal at high pressure and temperature and its implications for the stability of icosahedrite.

The first natural-occurring quasicrystal, icosahedrite, was recently discovered in the Khatyrka meteorite, a new CV3 carbonaceous chondrite. Its finding raised fundamental questions regarding the effects of pressure and temperature on the kinetic and thermodynamic stability of the quasicrystal structure relative to possible isochemical crystalline or amorphous phases. Although several studies showed the stability at ambient temperature of synthetic icosahedral AlCuFe up to ~35 GPa, the simultaneous effect of temperature and pressure relevant for the formation of icosahedrite has been never investigated so far. Here we present in situ synchrotron X-ray diffraction experiments on synthetic icosahedral AlCuFe using multianvil device to explore possible temperature-induced phase transformations at pressures of 5 GPa and temperature up to 1773 K. Results show the structural stability of i-AlCuFe phase with a negligible effect of pressure on the volumetric thermal expansion properties. In addition, the structural analysis of the recovered sample excludes the transformation of AlCuFe quasicrystalline phase to possible approximant phases, which is in contrast with previous predictions at ambient pressure. Results from this study extend our knowledge on the stability of icosahedral AlCuFe at higher temperature and pressure than previously examined, and provide a new constraint on the stability of icosahedrite.

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.

Uncovering a pressure-tuned electronic transition in Bi(1.98)Sr(2.06)Y(0.68)Cu(2)O(8+delta) using Raman scattering and x-ray diffraction.

We report pressure-tuned Raman and x-ray diffraction data of Bi(1.98.)Sr(2.06)Y(0.68)Cu(2)O(8+delta) revealing a critical pressure at 21 GPa with anomalies in electronic Raman background, electron-phonon coupling lambda, spectral weight transfer, density dependent behavior of phonons and magnons, and a compressibility change in the c axis. For the first time in a cuprate, mobile charge carriers, lattice, and magnetism all show anomalies at a distinct critical pressure in the same experimental setting. Furthermore, the spectral changes suggest that the critical pressure at 21 GPa is related to the critical point at optimal doping.

Pressure-tuned spin and charge ordering in an itinerant antiferromagnet.

Elemental chromium orders antiferromagnetically near room temperature, but the ordering temperature can be driven to zero by applying large pressures. We combine diamond anvil cell and synchrotron x-ray diffraction techniques to measure directly the spin and charge order in the pure metal at the approach to its quantum critical point. Both spin and charge order are suppressed exponentially with pressure, well beyond the region where disorder cuts off such a simple evolution, and they maintain a harmonic scaling relationship over decades in scattering intensity. By comparing the development of the order parameter with that of the magnetic wave vector, it is possible to ascribe the destruction of antiferromagnetism to the growth in electron kinetic energy relative to the underlying magnetic exchange interaction.

Anomalous compression behavior in lanthanum/cerium-based metallic glass under high pressure.

In situ high-pressure x-ray diffraction, low-temperature resistivity, and magnetization experiments were performed on a La(32)Ce(32)Al(16)Ni(5)Cu(15) bulk metallic glass (BMG). A sudden change in compressibility at approximately 14 GPa and a rapid increase of resistivity at approximately 12 K were detected, whereas magnetic phase transformation and magnetic field dependence of the low-temperature resistivity do not occur at temperatures down to 4.2 K. An interaction between conduction electrons and the two-level systems is suggested to explain the temperature and field dependences of resistivity of the BMG alloy. Although the cause of the unusual change in compressibility at approximately 14 GPa is not clear, we believe that it could be linked with the unique electron structure of cerium in the amorphous matrix. An electronic phase transition in BMG alloys, most likely a second-order amorphous-to-amorphous phase transition, is suggested.

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.

Space weathering on airless planetary bodies: clues from the lunar mineral hapkeite.

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 Fe2Si 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 Fe2Si. 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.

High-pressure transformations in xenon hydrates.

A high-pressure investigation of the Xe*H(2)O chemical system was conducted by using diamond-anvil cell techniques combined with in situ Raman spectroscopy, synchrotron x-ray diffraction, and laser heating. Structure I xenon clathrate was observed to be stable up to 1.8 GPa, at which pressure it transforms to a new Xe clathrate phase stable up to 2.5 GPa before breaking down to ice VII plus solid xenon. The bulk modulus and structure of both phases were determined: 9 +/- 1 GPa for Xe clathrate A with structure I (cubic, a = 11.595 +/- 0.003 A, V = 1,558.9 +/- 1.2 A(3) at 1.1 GPa) and 45 +/- 5 GPa for Xe clathrate B (tetragonal, a = 8.320 +/- 0.004 A, c = 10.287 +/- 0.007 A, V = 712.1 +/- 1.2 A(3) at 2.2 GPa). The extended pressure stability field of Xe clathrate structure I (A) and the discovery of a second Xe clathrate (B) above 1.8 GPa have implications for xenon in terrestrial and planetary interiors.

High-pressure elasticity of alpha-quartz: instability and ferroelastic transition

The single-crystal elastic moduli of alpha-quartz were measured to above 20 GPa in a diamond-anvil cell by Brillouin spectroscopy. The behavior of the elastic moduli indicates that the high-pressure phase transition in quartz is ferroelastic in nature and is driven by softening of C44 through one of the Born stability criteria. The trends in elastic moduli confirm theoretical predictions, but there are important differences, particularly with respect to the magnitudes of the B(i). The quartz I-II transition occurs prior to complete softening of the mode and amorphization.

Electrical conductivity of xenon at megabar pressures

The electrical transport properties of solid xenon were directly measured at pressures up to 155 GPa and temperatures from 300 K to 27 mK. The temperature dependence of resistance changed from semiconducting to metallic at pressures between 121 and 138 GPa, revealing direct proof of metallization of a rare-gas solid by electrical transport measurements. Anomalies in the conductivity are observed at low temperatures in the vicinity of the transition such that purely metallic behavior is observed only at 155 GPa over the entire temperature range.

Optical evidence for a nonmolecular phase of nitrogen above 150 GPa

Optical spectroscopy techniques, including visible and near infrared (IR) Raman and synchrotron IR methods have been applied to study solid nitrogen at megabar pressures. We find that nitrogen becomes totally opaque above 150 GPa, accompanied by the disappearance of Raman and IR vibrational excitations, while new broad IR and Raman bands become visible. Optical absorption measurements reveal that the semiconducting absorption edge responsible for the change of color is characterized by the presence of a wide Urbach-like tail and a high-energy (Tauc) region. These data are consistent with the dissociation of molecular nitrogen into a nonmolecular (possibly amorphous) phase.

The plastic deformation of iron at pressures of the Earth's inner core

Soon after the discovery of seismic anisotropy in the Earth's inner core, it was suggested that crystal alignment attained during deformation might be responsible. Since then, several other mechanisms have been proposed to account for the observed anisotropy, but the lack of deformation experiments performed at the extreme pressure conditions corresponding to the solid inner core has limited our ability to determine which deformation mechanism applies to this region of the Earth. Here we determine directly the elastic and plastic deformation mechanism of iron at pressures of the Earth's core, from synchrotron X-ray diffraction measurements of iron, under imposed axial stress, in diamond-anvil cells. The epsilon-iron (hexagonally close packed) crystals display strong preferred orientation, with c-axes parallel to the axis of the diamond-anvil cell. Polycrystal plasticity theory predicts an alignment of c-axes parallel to the compression direction as a result of basal slip, if basal slip is either the primary or a secondary slip system. The experiments provide direct observations of deformation mechanisms that occur in the Earth's inner core, and introduce a method for investigating, within the laboratory, the rheology of materials at extreme pressures.

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.