Stability of magnesiowustite in Earth's lower mantle.

Magnesiowüstite [(Mg,Fe)O] is the second most abundant mineral of Earth's lower mantle. Understanding its stability under lower mantle conditions is crucial for interpreting the physical and chemical properties of the whole Earth. Previous studies in an externally heated diamond anvil cell suggested that magnesiowüstites decompose into two components, Fe-rich and Mg-rich magnesiowüstites at 86 GPa and 1,000 K.

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.

Nuclear inelastic x-ray scattering of FeO to 48 GPa.

The partial density of vibrational states has been measured for Fe in compressed FeO (wüstite) using nuclear resonant inelastic x-ray scattering. Substantial changes have been observed in the overall shape of the density of states close to the magnetic transition around 20 GPa from the paramagnetic (low pressure) to the antiferromagnetic (high pressure) state. The results indicate that strong magnetoelastic coupling in FeO is the driving force behind the changes in the phonon spectrum of FeO.

Spectroscopic studies of the vibrational and electronic properties of solid hydrogen to 285 GPa.

We report Raman scattering and visible to near-infrared absorption spectra of solid hydrogen under static pressure up to 285 GPa between 20 and 140 K. We obtain pressure dependences of vibron and phonon modes consistent with results previously determined to lower pressures. The results indicate the stability of the ordered molecular phase III to the highest pressure reached and provide constraints on the insulator-to-metal transition pressure.

Novel broken symmetry phase from N(2)O at high pressures and high temperatures.

Simple molecular solids become unstable at high pressures, typically transforming to dense framework and/or metallic structures. We report formation of an unusual ionic solid NO(+)NO(3)(-) (nitrosonium nitrate) from N(2)O at pressures above 20 GPa and temperatures above 1000 K. Synchrotron x-ray diffraction indicates that the compound crystallizes with a structure related to the aragonite form of CaCO(3) and NaNO(3).

New transformations of CO(2) at high pressures and temperatures.

CO(2) laser heating of solid CO(2) at pressures between 30 and 80 GPa shows that this compound breaks down to oxygen and diamond along a boundary having a negative P-T slope. This decomposition occurs at temperatures much lower than predicted in theory or inferred from previous experiment. Raman spectroscopy and x-ray diffraction were used as structural probes.

Superconductivity in boron.

Metals formed from light elements are predicted to exhibit intriguing states of electronic order. Of these materials, those containing boron are of considerable current interest because of their relatively high superconducting temperatures. We have investigated elemental boron to very high pressure using diamond anvil cell electrical conductivity techniques.

Semiconducting non-molecular nitrogen up to 240 GPa and its low-pressure stability.

The triple bond of diatomic nitrogen has among the greatest binding energies of any molecule. At low temperatures and pressures, nitrogen forms a molecular crystal in which these strong bonds co-exist with weak van der Waals interactions between molecules, producing an insulator with a large band gap. As the pressure is raised on molecular crystals, intermolecular interactions increase and the molecules eventually dissociate to form monoatomic metallic solids, as was first predicted for hydrogen.

Phonon density of states of iron up to 153 gigapascals.

We report phonon densities of states (DOS) of iron measured by nuclear resonant inelastic x-ray scattering to 153 gigapascals and calculated from ab initio theory. Qualitatively, they are in agreement, but the theory predicts density at higher energies. From the DOS, we derive elastic and thermodynamic parameters of iron, including shear modulus, compressional and shear velocities, heat capacity, entropy, kinetic energy, zero-point energy, and Debye temperature.

New ortho-para conversion mechanism in dense solid hydrogen.

Analysis of recent measurements of striking changes in the rate of ortho-para conversion of solid H(2) up to 58 GPa shows that the conversion mechanism must differ from that at ambient pressure. A new conversion mechanism is identified in which the emerging excitations are coupled to the converting molecules via electric quadrupole-quadrupole rather than nuclear spin-spin interactions. The latter only initiates conversion while the coupling enhancement associated with the new mechanism is ensured by high compression and a gap closing, with the conversion energy diminishing strongly with increasing pressure.

Elasticity of MgO and a primary pressure scale to 55 GPa.

We have studied the elasticity and pressure-density equation of state of MgO in diamond cells to 55 GPa and have doubled the previous pressure limit of accurate elasticity determinations for crystals. Integrating single-crystal velocity data from Brillouin scattering measurements and density data from polycrystalline x-ray diffraction, we obtained the three principal elastic tensor elements (C(11), C(12), and C(44)) and various secondary elasticity parameters, including single-crystal elastic anisotropy, Cauchy relation, aggregate sound velocities, and Poisson's ratio, as functions of pressure. The present study also provides a direct determination of pressure without recourse to any prior pressure standard, thus creating a primary pressure scale.

Effects of high pressure on molecules.

Recent high-pressure studies reveal a wealth of new information about the behavior of molecular materials subjected to pressures well into the multimegabar range (several hundred gigapascal), corresponding to compressions in excess of an order of magnitude. Under such conditions, bonding patterns established for molecular systems near ambient conditions change dramatically, causing profound effects on numerous physical and chemical properties and leading to the formation of new classes of materials. Representative systems are examined to illustrate key phenomena, including the evolution of structure and bonding with compression; pressure-induced phase transitions and chemical reactions; pressure-tuning of vibrational dynamics, quantum effects, and excited electronic states; and novel states of electronic and magnetic order.

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).

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.

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.

Raman spectroscopy of iron to 152 gigapascals: implications for Earth's inner core.

Raman spectra of hexagonal close-packed iron (varepsilon-Fe) have been measured from 15 to 152 gigapascals by using diamond-anvil cells with ultrapure synthetic diamond anvils. The results give a Gruneisen parameter gamma(0) = 1.68 (+/-0.

In situ observations of a high-pressure phase of H2O Ice.

A previously unknown solid phase of H2O has been identified by its peculiar growth patterns, distinct pressure-temperature melting relations, and vibrational Raman spectra. Morphologies of ice crystals and their pressure-temperature melting relations were directly observed in a hydrothermal diamond-anvil cell for H2O bulk densities between 1203 and 1257 kilograms per cubic meter at temperatures between -10 degrees and 50 degreesC. Under these conditions, four different ice forms were observed to melt: two stable phases, ice V and ice VI, and two metastable phases, ice IV and the new ice phase.

Multivariable dependence of Fe-Mg partitioning in the lower mantle.

High-pressure diamond-cell experiments indicate that the iron-magnesium partitioning between (Fe,Mg)SiO3-perovskite and magnesiowustite in Earth's lower mantle depends on the pressure, temperature, bulk iron/magnesium ratio, and ferric iron content. The perovskite stability field expands with increasing pressure and temperature. The ferric iron component preferentially dissolves in perovskite and raises the apparent total iron content but had little effect on the partitioning of the ferrous iron.

High-Pressure Iron-Sulfur Compound, Fe3S2, and Melting Relations in the Fe-FeS System.

An iron-sulfur compound (Fe3S2) was synthesized at pressures greater than 14 gigapascals in the system Fe-FeS. The formation of Fe3S2 changed the melting relations from a simple binary eutectic system to a binary system with an intermediate compound that melted incongruently. The eutectic temperature in the system at 14 gigapascals was about 400°C lower than that extrapolated from Usselman's data, implying that previous thermal models of Fe-rich planetary cores could overestimate core temperature.

Magnetic Collapse in Transition Metal Oxides at High Pressure: Implications for the Earth.

Magnetic collapse in transition metal ions is predicted from first-principles computations at pressures reached in the Earth's lower mantle and core. Magnetic collapse would lead to marked changes in geophysically important properties, such as elasticity and conductivity, and also to different geochemical behavior, such as element partitioning, than estimated by extrapolating low-pressure data, and thus change the understanding of Earth's structure and evolution. Magnetic collapse results from band widening rather than from changes in crystal field splitting under 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.

High-Pressure Framework Silicates.

Recent syntheses of high-pressure alkali and alkaline earth silicates reveal a class of framework structures with corner-linked 4- and 6-coordinated silicon. These compounds possess the structural formula (A4-2x1+Bx2+)SimVI(SinIVO2(m+n)+2), where x, m, and n specify the amounts of alkaline earth, 6-coordinated silicon, and 4-coordinated silicon, respectively. Appropriate values of m and n yield a range of high-pressure structures, from fully 4-coordinated to fully 6-coordinated silicate frameworks.