Structural relaxation around substitutional Cr3+ in MgAl2O4

The structural environment of substitutional Cr3+ ion in MgAl2O4 spinel has been investigated by Cr K-edge Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES) spectroscopies. First-principles computations of the structural relaxation and of the XANES spectrum have been performed, with a good agreement to the experiment. The Cr-O distance is close to that in MgCr2O4, indicating a full relaxation of the first neighbors, and the second shell of Al atoms relaxes partially. These observations demonstrate that Vegard's law is not obeyed in the MgAl2O4-MgCr2O4 solid solution. Despite some angular site distortion, the local D3d symmetry of the B-site of the spinel structure is retained during the substitution of Cr for Al. Here, we show that the relaxation is accomodated by strain-induced bond buckling, with angular tilts of the Mg-centred tetrahedra around the Cr-centred octahedron. By contrast, there is no significant alteration of the angles between the edge-sharing octahedra, which build chains aligned along the three four-fold axes of the cubic structure.Comment: 7 pages, 4 figure

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

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

Structural relaxation around substitutional Cr3+ in pyrope garnet

The structural environment of substitutional Cr3+ ion in a natural pyrope Mg3Al2Si3O12 has been investigated by Cr K-edge Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES) coupled with first-principles computations. The Cr-O distance is close to that in knorringite Mg3Cr2Si3O12, indicating a full relaxation of the first neighbors. The local C3i symmetry of the octahedral Y site is retained during Cr-Al substitution. The second and third shells of neighbors (Mg and Si) relax only partially. Site relaxation is accommodated by strain-induced bond buckling, with angular tilts of the Si-centered tetrahedra around the Cr-centered octahedron, and by a radial deformation of the Mg-centered dodecahedra

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

XANES determination of chromium oxidation states in glasses: comparison with optical absorption spectroscopy

The oxidation state of chromium in glasses melted in an air atmosphere with and without refining agents was investigated by Cr K-edge X-ray Absorption Near-Edge Structure (XANES) and optical absorption spectroscopy. A good agreement in the relative proportion of Cr(III) and Cr(VI) is obtained between both methods. We show that the chemical dependence of the absorption coefficient of Cr(III) is less important in XANES than in optical absorption spectroscopy. The comparison of glasses melted under different conditions provides an indirect assessment of the molar extinction coefficient of Cr(VI) in glasses

A new view on gold speciation in sulfur-bearing hydrothermal fluids from in situ X-ray absorption spectroscopy and quantum-chemical modeling

International audienc

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