A combined theoretical and experimental investigation of uranium dioxide under high static pressure.

We have investigated the behavior of uranium dioxide (UO2) under high static pressure using a combination of experimental and theoretical techniques. We have made Raman spectroscopic measurements up to 87 GPa, electrical transport measurements up to 50 GPa from 10 K to room temperature, and optical transmission measurements up to 28 GPa. We have also carried out theoretical calculations within the GGA + U framework. We find that Raman frequencies match to a large extent, theoretical predictions for the cotunnite (Pnma) structure above 30 GPa, but at higher pressures some behavior is not captured theoretically. The Raman measurements also imply that the low-pressure fluorite phase coexists with the cotunnite phase up to high pressures, consistent with earlier reports. Electrical transport measurements show that the resistivity decreases by more than six orders of magnitude with increasing pressure up to 50 GPa but that the material never adopts archetypal metallic behavior. Optical transmission spectra show that while UO2 becomes increasingly opaque with increasing pressure, a likely direct optical band gap of more than 1 eV exists up to at least 28 GPa. Together with the electrical transport measurements, we conclude that the high pressure electrical conductivity of UO2 is mediated by variable-range hopping.

The chemistry of cyanuric acid (H3C3N3O3) under high pressure and high temperature.

We have studied cyanuric acid (H(3)C(3)N(3)O(3)) at static pressures up to 8.1 GPa and simultaneous temperatures up to 750 K, using primarily infrared absorption spectroscopy and visual observation. The corresponding phase diagram compares favorably with theoretical predictions of metastable organic materials. Two reactions were observed and characterized; both are irreversible. Below 2 GPa, melting is accompanied by a decomposition reaction, and upon cooling, cyanuric acid is not recovered. Above 2 GPa, heating results in a solid product recoverable at ambient conditions. Corresponding infrared spectra suggest that pressure leads to the formation of heterocycles of increasing complexity and biological potential, with the composition determined by the pressure of formation. Cyanuric acid is of interest at these conditions because it and its monomer, isocyanic acid, are "prebiotic" compounds found in stellar dust clouds, meteorites, and other remnants of the early Earth.

Melting curve and high-pressure chemistry of formic acid to 8 GPa and 600 K.

We have determined the melting temperature of formic acid (HCOOH) as a function of pressure to 8.5 GPa using infrared absorption spectroscopy, Raman spectroscopy and visual observation of samples in a resistively heated diamond-anvil cell. The experimentally determined incongruent melting curve compares favorably with a two-phase thermodynamic model. Decomposition reactions were observed above the melting temperature up to a pressure of 6.5 GPa, with principal products being CO2, H2O, and CO. At pressures above 6.5 GPa, decomposition led to reaction products that could be quenched as solids to zero pressure, and infrared and Raman spectra indicate that pressure leads to the presence of sp3 carbon-carbon bonding in these reaction products.

Sound velocities in olivine at Earth mantle pressures.

The independent elastic constants of an upper mantle mineral, San Carlos olivine [(Mg(1.8)Fe(0.2))SiO(4)], were measured from 0 to 12.5 gigapascals. Evidence is offered in support of the proposition that the explicit temperature dependence of the bulk modulus is small over the range of temperatures and pressures thought to prevail above the 400-kilometer discontinuity, and thus the data can be extrapolated to estimate the properties of olivine under mantle conditions at a depth of 400 kilometers. In the absence of high-temperature data at high pressures, estimates are made of the properties of olivine under mantle conditions to a depth of 400 kilometers. In contrast with low-pressure laboratory data, the predicted covariance of shear and compressional velocities as a function of temperature nearly matches the seismically estimated value for the lower mantle.