Effect of vibrations on the pre-edge features of x-ray absorption spectra

The influence of atomic vibrations on x-ray absorption near edge structure (XANES) is calculated by assuming that vibrational energies are small with respect to the instrumental resolution. The resulting expression shows that, at the K-edge, vibrations enable electric dipole transitions to 3s and 3d final states. The theory is applied to the K-edge of Al in Al2O3 corundum and of Ti in TiO2 rutile and compared with experiment. At the Al K-edge, sizeable transitions towards 3s final states are obtained, leading to a clear improvement of the agreement with experimental spectra. At the Ti K-edge, electric dipole transitions towards 3d final states explain the temperature dependence of the pre-edge features.Comment: 4 pages, 2 figure

Structural relaxations around Ti, Cr and Fe impurities in alpha-Al2O3 probed by x-ray absorption near edge structure combined with first-principles calculations

We determine the structural relaxations around paramagnetic impurities (Ti, Cr, Fe) in corundum (alpha-Al2O3), by combining x-ray absorption near edge structure (XANES) experiments and ab initio calculations. The structural relaxations are found to be very local. We then show that XANES is sensitive to small variations in interatomic distances within the coordination shell of the absorbing atom. The experiments were carried out on single crystals of ruby and sapphires. Linear dichroic signals are essential to characterize the geometry of the impurity site. The calculations were performed within a self-consistent ``non muffin-tin'' framework, that uses pseudopotentials, plane-wave basis set, and the continued fraction for the absorption cross section

Structural and electronic relaxations around substitutional Cr3+ and Fe3+ ions in corundum

International audienceThe local arrangement of atoms surrounding a substitutional Cr3+ and Fe3+ ion in α-Al2O3: Cr3+ (ruby) and in α-Al2O3:(Fe−Ti) (blue sapphire) has been studied experimentally using natural x-ray linear dichroism absorption at the Cr and Fe K edge. The isotropic and dichroic signals have been recorded using single crystals and a reliable method has been applied to remove diffraction peaks. Results given by the analysis of both signals are compared with ab initio density functional calculations. This study reveals that the introduction of an impurity ion in the structure leads to relaxations that are very local in nature. The oxygen atoms in the coordination shell relax to an arrangement similar to that for Cr in α-Cr2O3 or for Fe in α-Fe2O3. Aluminum or oxygen atoms at a farther distance are weakly affected by the presence of the impurity

Неоміфологія постсучасної особистості

У статті аналізуються тенденції деміфологізації та деконструкції особистісного буття в умовах сучасного технологічного суспільства. Результатом цих процесів стає підміна глибинності та ієрархічності особистісного само-визначення імітацією та симуляцією у різноманітних формах: імідж, маска, аватар.В статье анализируются тенденции деконструкции и демифологизации личностного бытия в условиях современного технологического общества. Результатом этих процессов стала подмена глубинности и иерархичности личностного самоопределения имитацией и симуляцией в разнообразных формах: имидж, маска, аватар.The trends of demythologization and reconstruction of personality existence in modern technological society circumstances are analyzed in the article. As a result of such processes, an imitation and simulation in their different forms, such as: image, mask, avatar — substitute the depth and hierarchy of personal self-determination

X-ray Linear Dichroism in cubic compounds: the case of Cr3+ in MgAl2O4

The angular dependence (x-ray linear dichroism) of the Cr K pre-edge in MgAl2O4:Cr3+ spinel is measured by means of x-ray absorption near edge structure spectroscopy (XANES) and compared to calculations based on density functional theory (DFT) and ligand field multiplet theory (LFM). We also present an efficient method, based on symmetry considerations, to compute the dichroism of the cubic crystal starting from the dichroism of a single substitutional site. DFT shows that the electric dipole transitions do not contribute to the features visible in the pre-edge and provides a clear vision of the assignment of the 1s-->3d transitions. However, DFT is unable to reproduce quantitatively the angular dependence of the pre-edge, which is, on the other side, well reproduced by LFM calculations. The most relevant factors determining the dichroism of Cr K pre-edge are identified as the site distortion and 3d-3d electronic repulsion. From this combined DFT, LFM approach is concluded that when the pre-edge features are more intense than 4 % of the edge jump, pure quadrupole transitions cannot explain alone the origin of the pre-edge. Finally, the shape of the dichroic signal is more sensitive than the isotropic spectrum to the trigonal distortion of the substitutional site. This suggests the possibility to obtain quantitative information on site distortion from the x-ray linear dichroism by performing angular dependent measurements on single crystals

X-ray magnetic circular dichroïsm provides strong evidence for tetrahedral iron in ferrihydrite

International audience[1] Ferrihydrite is an important iron oxyhydroxide for earth and environmental sciences, biology, and technology. Nevertheless, its mineral structure remains a matter of debate. The stumbling block is whether a significant amount of tetrahedrally coordinated iron is present. Here we present the first X-ray magnetic circular dichroïsm (XMCD) measurements performed on a well characterized synthetic sample of 6-line fer-rihydrite, at both K and L 2,3 energy edges of iron. XMCD results demonstrate unambiguously the presence of tetrahedrally coordinated Fe(III) in the mineral structure, in quantities compatible with the latest extended X-ray absorption fine structure (EXAFS) analyses suggesting a concentration of 20–30%. Moreover , we find an antiferromagnetic coupling between tetrahedral and octahedral sublattices, with the octa-hedral sublattice parallel to the external magnetic field. Components: 5100 words, 3 figures

Kondo screening of the spin and orbital magnetic moments of Fe impurities in Cu

We use x-ray magnetic circular dichroism to evidence the effect of correlations on the local impurity magnetic moment in an archetypal Kondo system, namely, a dilute Cu:Fe alloy. Applying the sum rules on the Fe L2,3 absorption edges, the evolution of the spin and orbital moments across the Kondo temperature are determined separately. The spin moment presents a crossover from a nearly temperature-independent regime below the Kondo temperature to a paramagneticlike regime above. Conversely, the weak orbital moment shows a temperature-independent behavior in the whole temperature range, suggesting different Kondo screening temperature scales for the spin and orbital moments

X-Ray Detected Magnetic Hysteresis of Thermally Evaporated Terbium Double-Decker Oriented Films

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Temperature- and Light-Induced Spin Crossover Observed by X-ray Spectroscopy on Isolated Fe(II) Complexes on Gold

Using X-ray absorption techniques, we show that temperature- and light-induced spin crossover properties are conserved for a submonolayer of the [Fe(H2B(pz)2)2(2,2′-bipy)] complex evaporated onto a Au(111) surface. For a significant fraction of the molecules, we see changes in the absorption at the L2,3 edges that are consistent with those observed in bulk and thick film references. Assignment of these changes to spin crossover is further supported by multiplet calculations to simulate the X-ray absorption spectra. As others have observed in experiments on monolayer coverages, we find that many molecules in our submonolayer system remain pinned in one of the two spin states. Our results clearly demonstrate that temperature- and light-induced spin crossover is possible for isolated molecules on surfaces but that interactions with the surface may play a key role in determining when this can occur

Etude de l'ordre chimique et magnétique d'oxydes spinelles de taille nanométrique par dichroïsme magnétique circulaire des rayons X

PARIS-BIUSJ-Thèses (751052125) / SudocPARIS-BIUSJ-Physique recherche (751052113) / SudocSudocFranceF