Hard x-ray spectroscopy in NaxCoO2 and superconducting NaxCoO2 - yH2O: A view on the bulk Co electronic properties

The electronic properties of Co in bulk Na0.7CoO2 and the superconducting hydrated compound Na0.35CoO2 - y H2O have been investigated by x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS) using hard x-rays. The XAS spectra at the Co K-edge were measured in both compounds with two different polarization directions. The changes in the XAS spectra upon hydration and their polarization dependence are well accounted for by linear muffin- tin orbital calculations in the local density approximation. The underlying electronic structure indicates the strong hybridization between the Co 3d and O 2p states in both compounds, while the electron localization is enhanced in the hydrated compound due to the increase of the Co-Co interplanar distance. The Co K pre-edge further highlights the splitting of the d band as a result of the crystal field effect and demonstrates the Co valency increase when Na0.7CoO2 is hydrated. The RIXS spectra measured at the Co K-edge show an energy loss feature around 10 eV in both compounds in fair agreement with the calculated dynamical structure factor. The RIXS feature is associated to a damped plasmon excitation.Comment: 8 page

Hydrogen bonding and coordination in normal and supercritical water from X-ray inelastic scattering

A direct measure of hydrogen bonding in water under conditions ranging from the normal state to the supercritical regime is derived from the Compton scattering of inelastically-scattered X-rays. First, we show that a measure of the number of electrons $n_e$ involved in hydrogen bonding at varying thermodynamic conditions can be directly obtained from Compton profile differences. Then, we use first-principles simulations to provide a connection between $n_e$ and the number of hydrogen bonds $n_{HB}$. Our study shows that over the broad range studied the relationship between $n_e$ and $n_{HB}$ is linear, allowing for a direct experimental measure of bonding and coordination in water. In particular, the transition to supercritical state is characterized by a sharp increase in the number of water monomers, but also displays a significant number of residual dimers and trimers.Comment: 14 pages, 5 figures, 1 tabl

Characterization of the glass transition in vitreous silica by temperature scanning small-angle X-ray scattering

The temperature dependence of the x-ray scattering in the region below the first sharp diffraction peak was measured for silica glasses with low and high OH content (GE-124 and Corning 7980). Data were obtained upon scanning the temperature at 10, 40 and 80 K/min between 400 K and 1820 K. The measurements resolve, for the first time, the hysteresis between heating and cooling through the glass transition for silica glass, and the data have a better signal to noise ratio than previous light scattering and differential thermal analysis data. For the glass with the higher hydroxyl concentration the glass transition is broader and at a lower temperature. Fits of the data to the Adam-Gibbs-Fulcher equation provide updated kinetic parameters for this very strong glass. The temperature derivative of the observed X-ray scattering matches that of light scattering to within 14%.Comment: EurophysicsLetters, in pres

In situ measurements of density fluctuations and compressibility in silica glass as a function of temperature and thermal history

In this paper, small-angle X-ray scattering measurements are used to determine the different compressibility contributions, as well as the isothermal compressibility, in thermal equilibrium in silica glasses having different thermal histories. Using two different methods of analysis, in the supercooled liquid and in the glassy state, we obtain respectively the temperature and fictive temperature dependences of the isotheraml compressibility. The values obtained in the glass and supercooled liquid states are very close to each other. They agree with previous determinations of the literature. The compressibility in the glass state slightly decreases with increasing fictive temperature. The relaxational part of the compressibility is also calculated and compared to previous determinations. We discussed the small differences between the different determinations

EXAFS study of lead-free relaxor ferroelectric BaTi(1-x)Zr(x)O3 at the Zr K-edge

Extended X-ray absorption fine structure (EXAFS) experiments at the Zr K-edge were carried out on perovskite relaxor ferroelectrics BaTi(1-x)Zr(x)O3 (BTZ) (x = 0.25, 0.30, 0.35), and on BaZrO3 for comparison. Structural information up to 4.5 A around the Zr atoms is obtained, revealing that the local structure differs notably from the average Pm-3m cubic structure deduced from X-ray diffraction. In particular, our results show that the distance between Zr atoms and their first oxygen neighbors is independent of the Zr substitution rate x and equal to that measured in BaZrO3, while the X-ray cubic cell parameter increases linearly with x. Furthermore, we show that the Zr atoms tend to segregate in Zr-rich regions. We propose that the relaxor behavior in BTZ is linked to random elastic fields generated by this particular chemical arrangement, rather than to random electric fields as is the case in most relaxors.Comment: 13 pages, 12 figures, 4 tables. Submitted to Phys. Rev.

Oxide phase characterization in simulated high burn-up UO2 fuels in the early stages of a nuclear severe accident

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FAME : A new beamline for X-ray absorption investigations of very-diluted systems of environmental, material and biological interests

International audienceFAME is the French Absorption spectroscopy beamline in Material and Environmental sciences at the ESRF (France), operational since September 2002. Technically speaking, the source is a 0.85 T bending magnet and the main optical element is a two-crystals monochromator using either Si(111) or Si(220) monocrystals so that the available energy ranges from 4 to 40 keV. The first crystal is liquid nitrogen cooled in order to avoid a thermal bump and thus preserve the energy resolution. The second crystal is dynamically bent during the energy scan in order to focus the beam in the horizontal plane. Two bendable mirrors are located before and after the monochromator, for beam-collimation (to optimize the energy resolution) and vertical focalization, respectively. During scans, the beam on the sample is kept constant in position and size (around 150 × 200 μm2, V × H). The high flux on the sample combined with the sensitivity of our 30-elements fluorescence detector allow to decrease the detection limit down to 10 ppm or around less than a monolayer. Moreover, quick-EXAFS acquisition is operational: the acquisition time may be reduced down to 30s