Evidence and Stability Field of fcc Superionic Water Ice Using Static Compression.

Structural transformation of hot dense water ice is investigated by combining synchrotron x-ray diffraction and a laser-heating diamond anvil cell above 25 GPa. A transition from the body-centered-cubic (bcc) to face-centered-cubic (fcc) oxygen atoms sublattices is observed from 57 GPa and 1500 K to 166 GPa and 2500 K. That is the structural signature of the transition to fcc superionic (fcc SI) ice. The sign of the density discontinuity at the transition is obtained and a phase diagram is disclosed, showing an extended fcc SI stability field. Present data also constrain the stability field of the bcc superionic (bcc SI) ice up to 100 GPa at least. The current understanding of warm dense water ice based on ab initio simulations is discussed in the light of present data.

Transformation of Ammonium Azide at High Pressure and Temperature.

The compression of ammonium azide (AA) has been considered to be a promising route for producing high energy-density polynitrogen compounds. So far though, there is no experimental evidence that pure AA can be transformed into polynitrogen materials under high pressure at room temperature. We report here on high pressure (P) and temperature (T) experiments on AA embedded in N2 and on pure AA in the range 0-30 GPa, 300-700 K. The decomposition of AA into N2 and NH3 was observed in liquid N2 around 15 GPa-700 K. For pressures above 20 GPa, our results show that AA in N2 transforms into a new crystalline compound and solid ammonia when heated above 620 K. This compound is stable at room temperature and on decompression down to at least 7.0 GPa. Pure AA also transforms into a new compound at similar P-T conditions, but the product is different. The newly observed phases are studied by Raman spectroscopy and X-ray diffraction and compared to nitrogen and hydronitrogen compounds that have been predicted in the literature. While there is no exact match with any of them, similar vibrational features are found between the product that was obtained in AA + N2 with a polymeric compound of N9H formula.

Melting Curve and Liquid Structure of Nitrogen Probed by X-ray Diffraction to 120 GPa.

Synchrotron x-ray diffraction measurements of nitrogen are performed up to 120 GPa to determine the melting curve and the structural changes of the solid and liquid phases along it. The melting temperature exhibits a monotonic increase up to the triple point where the epsilon molecular solid, the cubic gauche covalent solid, and the fluid meet at 116 GPa, 2080 K. Above, the stability of the cubic gauche phase induces a sharp increase of the melting curve. The structural data on liquid nitrogen show that the latter remains molecular over the whole probed domain, which contradicts the prediction of a liquid-liquid transition at 88 GPa, 2000 K. These findings thus largely revisit the phase diagram of hot dense nitrogen and challenge the current understanding of this model system.

Use of a multichannel collimator for structural investigation of low-Z dense liquids in a diamond anvil cell: validation on fluid H2 up to 5 GPa.

We report the first application of a multichannel collimator (MCC) to perform quantitative structure factor measurements of dense low-Z fluids in a diamond anvil cell (DAC) using synchrotron x-ray diffraction. The MCC design, initially developed for the Paris-Edinburgh large volume press geometry, has been modified for use with diamond anvil cells. A good selectivity of the diffracted signal of the dense fluid sample is obtained due to a large rejection of the Compton diffusion from the diamond anvils. The signal to background ratio is significantly improved. We modify previously developed analytical techniques for quantitative measurement of the structure factor of fluids in DACs [J. H. Eggert, G. Weck, P. Loubeyre, and M. Mezouar, Phys. Rev. B 65, 174105 (2002)] to account for the contribution of the MCC. We present experimental results on liquids argon and hydrogen at 296 K to validate our method and test its limits, respectively.

Structure of polymeric carbon dioxide CO2-V.

The structure of polymeric carbon dioxide (CO2-V) has been solved using synchrotron x-ray powder diffraction, and its evolution followed from 8 to 65 GPa. We compare the experimental results obtained for a 100% CO2 sample and a 1 mol % CO2/He sample. The latter allows us to produce the polymer in a pure form and study its compressibility under hydrostatic conditions. The high quality of the x-ray data enables us to solve the structure directly from experiments. The latter is isomorphic to the ß-cristobalite phase of SiO2 with the space group I42d. Carbon and oxygen atoms are arranged in CO4 tetrahedral units linked by oxygen atoms at the corners. The bulk modulus determined under hydrostatic conditions, B0=136(10) GPa, is much smaller than previously reported. The comparison of our experimental findings with theoretical calculations performed in the present and previous studies shows that density functional theory very well describes polymeric CO2.