PubMed Health⌕ Search

Biomedical subjects

Russell J Hemley

Publications and source records attributed to Russell J Hemley.

At least 19 recordsLinked to original sources
PubMed2007

High-pressure vibrational spectroscopy of energetic materials: hexahydro-1,3,5-trinitro-1,3,5-triazine.

Vibrational spectroscopy has been used to investigate the room-temperature high-pressure phases of the energetic material hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The pressure-induced alterations in the spectral profiles were studied in a compression sequence to 30.2 GPa using Raman spectroscopy and to 26.6 GPa using far-infrared spectroscopy. At pressures near 4.0 GPa, several changes become immediately apparent in the Raman spectrum, such as large frequency shifts, mode splittings, and intensity changes, which are associated with a phase transition from alpha-RDX to gamma-RDX. Our study extends the kinetic stability of gamma-RDX to pressures near 18.0 GPa. Evidence for a new phase was found at pressures between 17.8 and 18.8 GPa and is based on the appearance of new vibrational bands and associated changes in intensity patterns. The new phase has vibrational characteristics that are similar to those of beta-RDX, suggesting the two polymorphs share a related crystal structure.

Journal Article↗
PubMed2006

X-ray-induced dissociation of H2O and formation of an O2-H2 alloy at high pressure.

When subjected to high pressure and extensive x-radiation, water (H2O) molecules cleaved, forming O-O and H-H bonds. The oxygen (O) and hydrogen (H) framework in ice VII was converted into a molecular alloy of O2 and H2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrated that this crystalline solid differs from previously known phases. It remained stable with respect to variations in pressure, temperature, and further x-ray and laser exposure, thus opening new possibilities for studying molecular interactions in the hydrogen-oxygen binary system.

Journal Article↗
PubMed2006

Hydrogen-bond dynamics and Fermi resonance in high-pressure methane filled ice.

High-pressure, variable temperature infrared spectroscopy and first-principles calculations on the methane filled ice structure (MH-III) at high pressures are used to investigate the vibrational dynamics related to pressure induced modifications in hydrogen bonding. Infrared spectroscopy of isotopically dilute solutions of H(2)O in D(2)O is employed together with first-principles calculations to characterize proton dynamics with the pressure induced shortening of hydrogen bonds. A Fermi resonance is identified and shown to dominate the infrared spectrum in the pressure region between 10 and 30 GPa. Significant differences in the effects of the Fermi resonance observed between 10 and 300 K arise from the double-well potential energy surface of the hydrogen bond and quantum effects associated with the proton dynamics.

Journal Article↗
PubMed2006

Probing hydrogen-rich molecular systems at high pressures and temperatures.

Information on the behavior of hydrogen-containing simple molecular systems at high pressures and temperatures is central to many problems in chemistry and allied sciences. The combination of increasing pressure and temperature causes a redistribution of the electronic density, and the resulting alterations in interatomic interactions give rise to changes in macroscopic properties. Experimental studies of hydrogen-rich systems under extreme conditions have advanced considerably in recent years as a result of improvements in diamond anvil cell technology in combination with resistive- and laser-heating techniques. These experimental methods are combined with spectroscopic and diffraction techniques, and the results interpreted with the aid of molecular simulations. In this tutorial review we discuss recent findings in hydrogen, water, and other selected hydrogen-rich systems including compounds formed from these materials. The results are examined in terms of the evolution of effective potentials and interatomic vibrational coupling, molecular dissociation and recombination, ionization and polymerization, quantum effects, and order-disorder phenomena.

Journal Article↗
PubMed2006

Pressure-induced phase transformations in LiAlH4.

The pressure-induced phase transformations in pure LiAlH4 have been studied using in situ Raman spectroscopy up to 7 GPa. The analyses of Raman spectra reveal a phase transition at approximately 3 GPa from the ambient pressure monoclinic alpha-LiAlH4 phase (P2(1)/c) to a high pressure phase (beta-LiAlH4, reported recently to be monoclinic with space group I4(1)/b) having a distorted [AlH4]- tetrahedron. The Al-H stretching mode softens and shifts dramatically to lower frequencies beyond the phase transformation pressure. The high pressure beta-LiAlH4 phase was pressure quenchable and can be recovered at lower pressures ( approximately 1.2 GPa). The Al-H stretching mode in the quenched state further shifts to lower frequencies, suggesting a weakening of the Al-H bond.

Journal Article↗
PubMed2006

Iron-rich post-perovskite and the origin of ultralow-velocity zones.

The boundary layer between the crystalline silicate lower mantle and the liquid iron core contains regions with ultralow seismic velocities. Such low compressional and shear wave velocities and high Poisson's ratio are also observed experimentally in post-perovskite silicate phase containing up to 40 mol% FeSiO3 endmember. The iron-rich post-perovskite silicate is stable at the pressure-temperature and chemical environment of the core-mantle boundary and can be formed by core-mantle reaction. Mantle dynamics may lead to further accumulation of this material into the ultralow-velocity patches that are observable by seismology.

Journal Article↗
PubMed2006

Synthesis of novel transition metal nitrides IrN2 and OsN2.

Two new transition metal nitrides, IrN2 and OsN2, were synthesized at high pressures and temperatures using laser-heated diamond-anvil cell techniques. Synchrotron x-ray diffraction was used to determine the structures of novel nitrides and the equations of states of both the parent metals as well as the newly synthesized materials. The compounds have bulk moduli comparable with those of the traditional superhard materials. For IrN2, the measured bulk modulus [K0 = 428(12) GPa] is second only to that of diamond (K0 = 440 GPa). Ab initio calculations indicate that both compounds have a metal:nitrogen stoichiometry of 1:2 and that nitrogen intercalates in the lattice of the parent metal in the form of single-bonded N-N units.

Journal Article↗
PubMed2006

Valence band x-ray emission spectra of compressed germanium.

We report measurements of the valence band width in compressed Ge determined from x-ray emission spectra below the Ge K edge. The width of the valence band does not show any pressure dependence in the semiconducting diamond-type structure of Ge below 10 GPa. On the other hand, in the metallic beta-Sn phase above 10 GPa the valence band width increases under compression. Density-functional calculations show an increasing valence band width under compression both in the semiconducting phase (contrary to experiment) and in the metallic beta-Sn phase of Ge (in agreement with observed pressure-induced broadening). The pressure-independent valence band width in the semiconducting phase of Ge appears to require theoretical advances beyond the density-functional theory or the GW approximation.

Journal Article↗
PubMed2006

High-pressure x-ray diffraction and Raman spectroscopy of ice VIII.

In situ high-pressure/low-temperature synchrotron x-ray diffraction and optical Raman spectroscopy were used to examine the structural properties, equation of state, and vibrational dynamics of ice VIII. The x-ray measurements show that the pressure-volume relations remain smooth up to 23 GPa at 80 K. Although there is no evidence for structural changes to at least 14 GPa, the unit-cell axial ratio ca undergoes changes at 10-14 GPa. Raman measurements carried out at 80 K show that the nu(Tz)A(1g)+nuT(x,y)E(g) lattice modes for the Raman spectra of ice VIII in the lower-frequency regions (50-800 cm(-1)) disappear at around 10 GPa, and then a new peak of approximately 150 cm(-1) appears at 14 GPa. The combined data provide evidence for a transition beginning near 10 GPa. The results are consistent with recent synchrotron far-IR measurements and theoretical calculations. The decompressed phase recovered at ambient pressure transforms to low-density amorphous ice when heated to approximately 125 K.

Journal Article↗
PubMed2006

High-pressure Brillouin scattering of amorphous BeH2.

High-pressure micro-Brillouin scattering is employed to investigate the pressure dependence of the sound velocity, refractive index, equation of state, and mechanical properties of amorphous BeH2. The refractive index n has been determined by using two scattering geometries (70 degrees and 180 degrees). The equation of state is deduced from the pressure dependences of the sound velocity. The bulk modulus is 14.2 (+/-3.0) GPa and its pressure derivative is 5.3 (+/-0.5). The polarizability is calculated from the refractive index and the density of the material. It increases with pressure while Poisson's ratio decreases with pressure.

Journal Article↗
PubMed2005

Morphology-tuned wurtzite-type ZnS nanobelts.

Nanometre-sized inorganic dots, wires and belts have a wide range of electrical and optical properties, and variable mechanical stability and phase-transition mechanisms that show a sensitive dependency on size, shape and structure. The optical properties of the semiconductor ZnS in wurtzite structures are considerably enhanced, but the lack of structural stability limits technological applications. Here, we demonstrate that morphology-tuned wurtzite ZnS nanobelts show a particular low-energy surface structure dominated by the +/-[210] surface facets. Experiments and calculations show that the morphology of ZnS nanobelts leads to a very high mechanical stability to approximately 6.8 GPa, and also results in an explosive mechanism for the wurtzite-to-sphalerite phase transformation together with in situ fracture of the nanobelts. ZnS wurtzite nanobelts provide a model that is useful not only for understanding the morphology-tuned stability and transformation mechanism, but also for improving synthesis of metastable nanobelts with quantum effects for electronic and optical devices.

Atmospheric Pressure↗
PubMed2005

X-ray emission spectroscopy with a laser-heated diamond anvil cell: a new experimental probe of the spin state of iron in the Earth's interior.

Synchrotron-based X-ray emission spectroscopy (XES) is well suited to probing the local electronic structure of 3d transition metals such as Fe and Mn in their host phases. The laser-heated diamond anvil cell technique is uniquely capable of generating ultra-high static pressures and temperatures in excess of 100 GPa and 3000 K. Here X-ray emission spectroscopy and X-ray diffraction have been interfaced with the laser-heated diamond cell for studying the electronic spin states of iron in magnesiowüstite-(Mg0.75,Fe0.25)O and its crystal structure under lower-mantle conditions. X-ray emission spectra of the ferrous iron in a single crystal of magnesiowüstite-(Mg0.75,Fe0.25)O indicate that a high-spin to low-spin transition of ferrous iron occurs at 54 to 67 GPa and 300 K and the ferrous iron remains in the high-spin state up to 47 GPa and 1300 K. This pilot study points to the unique capability of the synchrotron-based XES and X-ray diffraction techniques for addressing the issue of electronic spin transition or crossover in 3d transition metals and compounds under extreme high-P-T conditions.

Journal Article↗
PubMed2005

Single-crystal synchrotron X-ray diffraction study of wüstite and magnesiowüstite at lower-mantle pressures.

This study demonstrates the use of monochromatic synchrotron X-ray radiation of 40 keV for high-precision equation-of-state studies on sets of single crystals analysed individually in the same diamond-anvil pressure cell. Angle-dispersive zone-axis diffraction patterns were obtained from crystals of wustite-Fe0.93O and magnesiowüstite-(Mg0.73Fe0.27)O to 51 GPa in a hydrostatic helium pressure medium. The rhombohedral phase of Fe0.93O was observed above 23 GPa, and its isothermal bulk modulus (K0) was determined to be 134 (+/-4) GPa, assuming K'=4. The rhombohedral phase of Fe(0.93)O is more compressible than B1-structured Fe0.93O, with K0=146 (+/-2) GPa. Magnesiowüstite-(Mg0.73Fe0.27)O remains cubic over the experimental pressure range, and has a bulk modulus of 154 (+/-3) GPa with K'=4.0 (+/-0.1).

Journal Article↗
PubMed2005

Spin transition of iron in magnesiowüstite in the Earth's lower mantle.

Iron is the most abundant transition-metal element in the mantle and therefore plays an important role in the geochemistry and geodynamics of the Earth's interior. Pressure-induced electronic spin transitions of iron occur in magnesiowüstite, silicate perovskite and post-perovskite. Here we have studied the spin states of iron in magnesiowüstite and the isolated effects of the electronic transitions on the elasticity of magnesiowüstite with in situ X-ray emission spectroscopy and X-ray diffraction to pressures of the lowermost mantle. An observed high-spin to low-spin transition of iron in magnesiowüstite results in an abnormal compressional behaviour between the high-spin and the low-spin states. The high-pressure, low-spin state exhibits a much higher bulk modulus and bulk sound velocity than the low-pressure, high-spin state; the bulk modulus jumps by approximately 35 percent and bulk sound velocity increases by approximately 15 percent across the transition in (Mg0.83,Fe0.17)O. Although no significant density change is observed across the electronic transition, the jump in the sound velocities and the bulk modulus across the transition provides an additional explanation for the seismic wave heterogeneity in the lowermost mantle. The transition also affects current interpretations of the geophysical and geochemical models using extrapolated or calculated thermal equation-of-state data without considering the effects of the electronic transition.

Journal Article↗
PubMed2005

Iron-rich silicates in the Earth's D'' layer.

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.

Journal Article↗
PubMed2005

Sound velocities of hot dense iron: Birch's law revisited.

Sound velocities of hexagonal close-packed iron (hcp-Fe) were measured at pressures up to 73 gigapascals and at temperatures up to 1700 kelvin with nuclear inelastic x-ray scattering in a laser-heated diamond anvil cell. The compressional-wave velocities (VP) and shear-wave velocities (VS) of hcp-Fe decreased significantly with increasing temperature under moderately high pressures. VP and VS under high pressures and temperatures thus cannot be fitted to a linear relation, Birch's law, which has been used to extrapolate measured sound velocities to densities of iron in Earth's interior. This result means that there are more light elements in Earth's core than have been inferred from linear extrapolation at room temperature.

Journal Article↗