Charge redistribution at Pd surfaces: ab initio grounds for tight-binding interatomic potentials

A simplified tight-binding description of the electronic structure is often necessary for complex studies of surfaces of transition metal compounds. This requires a self-consistent parametrization of the charge redistribution, which is not obvious for late transition series elements (such as Pd, Cu, Au), for which not only d but also s-p electrons have to be taken into account. We show here, with the help of an ab initio FP-LMTO approach, that for these elements the electronic charge is unchanged from bulk to the surface, not only per site but also per orbital. This implies different level shifts for each orbital in order to achieve this orbital neutrality rule. Our results invalidate any neutrality rule which would allow charge redistribution between orbitals to ensure a common rigid shift for all of them. Moreover, in the case of Pd, the power law which governs the variation of band energy with respect to coordination number, is found to differ significantly from the usual tight-binding square root.Comment: 6 pages, 2 figures, Latex; Phys.Rev. B 56 (1997

Analysis of Clean Transition Metal Surfaces by Core Level Spectroscopy

The shifts in the binding energy of core electrons detected by high resolution X-ray photoelectron spectroscopy are a very sensitive probe of the chemical bonding of the excited atom. Since the surface atoms have their geometrical environment perturbed, their core levels are shifted from their bulk positions. A very large number of experiments have been performed on the 4f core level positions of tantalum and tungsten for various orientations of the surface plane. Systematic trends have been put forward and explained by theoretical models. Furthermore, the analysis of the angular variation of the core level line intensities gives structural information when compared with theoretical calculations. In the case of W(100) a single scattering theory is sufficient to reproduce experimental data. Finally we show that, in some particular cases, the core level lineshapes may differ strongly from a Doniach Sunjic model. The temperature dependence of their widths due to core hole-phonon coupling can be reproduced within the independent boson theory

Le cas des marmites modelées e type M4.1. Nouvelles données archéologiques et archéometriques

Póster presentado en XI Congrès AIECM3 sur la céramique médiévale et moderne en Méditerranée, Antalya, Turquía, 19-23 octubre 2015Parmi les mobiliers présents en Méditerranée occidentale durant le haut Moyen Âge, la marmite modelée, à base plane et préhensions en languettes, correspondant au type M4.1 a été mise en évidence par S. Gutiérrez Lloret dans le sud-est de la péninsule Ibérique. Elle semble constituer un marqueur chronologique caractéristique des contextes archéologiques des VIIIe, IXe et Xe s. (Gutiérrez Lloret 1996, 2015). Ce type d’ustensile culinaire, assez générique, est présent sur les deux rives de la Méditerranée occidentale. En Espagne, ces marmites présentes dans de nombreux contextes précoces de la période islamique semble toutefois procéder de formes M.1 et M.2, issues de la tradition tardo antique et wisigothique. Dans le nord de l’Afrique, ce type s’inscrit vraisemblablement dans le prolongement des modèles de la Calcitic Ware de l’Antiquité tardive

Electron-correlation effects in appearance-potential spectra of Ni

Spin-resolved and temperature-dependent appearance-potential spectra of ferromagnetic Nickel are measured and analyzed theoretically. The Lander self-convolution model which relates the line shape to the unoccupied part of the local density of states turns out to be insufficient. Electron correlations and orbitally resolved transition-matrix elements are shown to be essential for a quantitative agreement between experiment and theory.Comment: LaTeX, 6 pages, 2 eps figures included, Phys. Rev. B (in press

On the interpretation of spin-polarized electron energy loss spectra

We study the origin of the structure in the spin-polarized electron energy loss spectroscopy (SPEELS) spectra of ferromagnetic crystals. Our study is based on a 3d tight-binding Fe model, with constant onsite Coulomb repulsion U between electrons of opposite spin. We find it is not the total density of Stoner states as a function of energy loss which determines the response of the system in the Stoner region, as usually thought, but the densities of Stoner states for only a few interband transitions. Which transitions are important depends ultimately on how strongly umklapp processes couple the corresponding bands. This allows us to show, in particular, that the Stoner peak in SPEELS spectra does not necessarily indicate the value of the exchange splitting energy. Thus, the common assumption that this peak allows us to estimate the magnetic moment through its correlation with exchange splitting should be reconsidered, both in bulk and surface studies. Furthermore, we are able to show that the above mechanism is one of the main causes for the typical broadness of experimental spectra. Finally, our model predicts that optical spin waves should be excited in SPEELS experiments.Comment: 11 pages, 7 eps figures, REVTeX fil

Theory of Spin-Resolved Auger-Electron Spectroscopy from Ferromagnetic 3d-Transition Metals

CVV Auger electron spectra are calculated for a multi-band Hubbard model including correlations among the valence electrons as well as correlations between core and valence electrons. The interest is focused on the ferromagnetic 3d-transition metals. The Auger line shape is calculated from a three-particle Green function. A realistic one-particle input is taken from tight-binding band-structure calculations. Within a diagrammatic approach we can distinguish between the \textit{direct} correlations among those electrons participating in the Auger process and the \textit{indirect} correlations in the rest system. The indirect correlations are treated within second-order perturbation theory for the self-energy. The direct correlations are treated using the valence-valence ladder approximation and the first-order perturbation theory with respect to valence-valence and core-valence interactions. The theory is evaluated numerically for ferromagnetic Ni. We discuss the spin-resolved quasi-particle band structure and the Auger spectra and investigate the influence of the core hole.Comment: LaTeX, 12 pages, 8 eps figures included, Phys. Rev. B (in press

Combining Solid State Physics Concepts and X-Ray Absorption Spectroscopy to Understand DeNOx Catalysis

Considering the NO adsorption process, starting from theoretical considerations, evaluation of the variation of the properties of metallic clusters versus their size and composition leads to a prediction of the NO adsorption mode on these nanoentities. Then, based on experimental results obtained mostly through X-ray absorption spectroscopy, we have connected the adsorption mode of the molecule to the behaviour of the metallic cluster following the adsorption process. A simple hypothesis leads us to discuss the catalytic activity of nanometer scale metallic clusters following NO adsorption