Interplay between local structure, vibrational and electronic properties on CuO under pressure
The electronic and local structural properties of CuO under pressure have been investigated by means of X-ray absorption spectroscopy (XAS) at Cu K edge and ab initio calculations, up to 17 GPa. The crystal structure of CuO consists of Cu motifs within CuO4 square planar units and two elongated apical Cu-O bonds. The CuO4 square planar units are stable in the studied pressure range, with Cu-O distances that are approximately constant up to 5 GPa, and then decrease slightly up to 17 GPa. In contrast, the elongated Cu-O apical distances decrease continuously with pressure in the studied range. An anomalous increase of the mean square relative displacement (EXAFS Debye-Waller, s2) of the elong…
Negative thermal expansion in cuprite-type compounds: A combined synchrotron XRPD, EXAFS, and computational study of Cu2O and Ag2O
Cuprite-type oxides (Cu2O and Ag2O) are framework structures composed by two interpenetrated networks of metal-sharing M4O tetrahedra (M = Cu, Ag). Both compounds exhibit a peculiar negative thermal expansion (NTE) behaviour over an extended temperature range (9 240 K for Cu2O, 30-470 K for Ag2O). High-accuracy synchrotron powder diffraction and EXAFS measurements were performed from 10 K up to the decomposition temperature to understand the nature of the NTE effects. The critical comparison of the diffraction and absorption results concerning the temperature dependence of the interatomic distances and of the atomic vibrational parameters proves to be fundamental in defining the local dynam…
Isotopic Effect In Extended X-Ray-Absorption Fine Structure of Germanium
Extended x-ray absorption fine structure has been measured on two powdered samples of 70Ge and 76Ge as a function of temperature from 20 to 300 K. The effect of isotopic mass difference on the amplitude of relative atomic vibrations is neatly evidenced by the temperature dependence of the difference of Debye-Waller factors. The isotopic effect is also detected on the difference of nearest-neighbor average ineratomic distances, thanks to a resolution better than 10 fm. (DOI: 10.1103/PhysRevLett.100.055901)
XANES and EXAFS modelling of configurational disorder in silver borate glasses
The sensitivity of X-ray absorption spectroscopy (XAS) to the local structure around a selected atomic species (symmetry, distances and angles) is commonly exploited to quantitatively describe systems where all the configurations around the absorbing atoms may be approximated by the mean one. However, in many cases of disordered systems a simple description of the local structure with singleconfiguration models cannot be reconciled with experimental spectra. In this paper the necessity to analyse the XAS spectra by considering a multiplicity of atomic structural configurations is demonstrated in the case of silver borate glasses. The local coordination around Ag cations in (Ag2O.nB2O3) glas…