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A novel perovskite oxide, CaCu3Rh4O12, has been synthesized under high-pressure and high-temperature conditions (15 GPa and 1273 K). Rietveld refinement of synchrotron X-ray powder diffraction data indicates that this compound crystallizes in a cubic AA'3B4O12-type perovskite structure. Synchrotron X-ray absorption and photoemission spectroscopy measurements reveal that the Cu and Rh valences are nearly trivalent. The spectroscopic analysis based on calculations suggests that the appropriate ionic model of this compound is Ca(2+)Cu(∼2.8+)3Rh(∼3.4+)4O12, as opposed to the conventional Ca(2+)Cu(2+)3Rh(4+)4O12. The uncommon valence state of this compound is attributed to the relative energy levels of the Cu 3d and Rh 4d orbitals, in which the large crystal-field splitting energy of the Rh 4d orbitals is substantial.

In this paper we review a variety of spectra for Ce compounds, i.e. valence photoemission and inverse valence photoemission, core-level and resonant photoemission as well as X-ray absorption, X-ray emission and X-ray magnetic circular dichroism (MCD). Those spectra are theoretically analysed by using the single-site Anderson model with various final state interactions. In the first part of the present article we are considering intermetallic Ce compounds, especially several Ce–Pd ordered phases, as well as CeRh3, CeSn3 and CeFe2. In the second part we focus on insulating Ce compounds like CeF3 as well as related systems like Ce oxides. Also we compare Ce hydroxides to other rare-earth hydroxides. Discussions are given on the physical information derived from the analysis, especially through a few key parameters of an extended version of the previously considered Anderson model. Those parameters (i.e. the Coulomb interaction Ufd between 5d and 4f electrons as well as the core hole potential -Udc acting on the 5d electron) have necessarily to be taken into account in order to interpret the experimental L3 X-ray absorption spectra. Another important point stressed in the present paper is the surface/bulk sensitivities of the various spectra to be investigated and theoretically analysed. Also similarities and differences in spectral features between metallic and insulating systems are pointed out. [ABSTRACT FROM AUTHOR]

Abstract: K-edge X-ray absorption and 2p-XPS spectra of 3d-element oxides present spectral features which cannot be explained within a simple one-electron model. These features reveal the fine electronic structure of transition metal (TM) oxides valence states resulting from hybridized TM-3d and O-2p states, and the correlations between these valence electrons. In this paper, we show how resonant electronic spectroscopy (resonant Auger or resonant photoelectron spectroscopy) around the TM K-edge can be used to interpret the structures of the threshold and, with the help of theoretical calculation, to determine the electronic configuration of the excited ion. Quadrupolar transitions towards localized 3d orbitals are hence detected and quantitatively characterized in the titanium K-edge prepeaks in TiO2 and in the Ni K-edge prepeaks in NiO by angular-dependent resonant KLL Auger measurements. Valuable information also seems to be available in the resonant behavior of 2p-XPS spectra of NiO and Fe2O3. [Copyright &y& Elsevier]

In this paper we review a variety of spectra for Ce compounds, i.e. valence photoemission and inverse valence photoemission, core-level and resonant photoemission as well as X-ray absorption, X-ray emission and X-ray magnetic circular dichroism (MCD). Those spectra are theoretically analysed by using the single-site Anderson model with various final state interactions. In the first part of the present article we are considering intermetallic Ce compounds, especially several Ce–Pd ordered phases, as well as CeRh3, CeSn3 and CeFe2. In the second part we focus on insulating Ce compounds like CeF3 as well as related systems like Ce oxides. Also we compare Ce hydroxides to other rare-earth hydroxides. Discussions are given on the physical information derived from the analysis, especially through a few key parameters of an extended version of the previously considered Anderson model. Those parameters (i.e. the Coulomb interaction Ufd between 5d and 4f electrons as well as the core hole potential -Udc acting on the 5d electron) have necessarily to be taken into account in order to interpret the experimental L3 X-ray absorption spectra. Another important point stressed in the present paper is the surface/bulk sensitivities of the various spectra to be investigated and theoretically analysed. Also similarities and differences in spectral features between metallic and insulating systems are pointed out. [ABSTRACT FROM AUTHOR]