Excitations électroniques et magnétisme des matériaux : calcul ab initio de l'absorption X et du dichroïsme circulaire magnétique au seuil K

Experimental measurements of X-ray absorption (XAS) and magnetic circular dichroism(XMCD) are widely used to study electronic excitations and magnetism in materials.Theoretical interpretations of those measurements play a crucial role in the understandingof those studies. We have developped new methods to calculate X-ray absorptionand XMCD at the K edge based on the use of the density functionnal theory (DFT), ofpseudopotentials and of the continued fraction approach. Those methods allow a parameterfree treatment of the core hole.We applied those methods on a wide range of materials, from weak to strong electroniccorrelation, in order to see if a monoparticle approximation could describe XAS andXMCD spectra.We rst sudied the X-ray absorption of graphene, a weakly correlated material,in order to determine if the interlayer state responsible for the supraconductivity ofintercalated graphites could be seen in XAS, as suggested by recent experiments. We thencalculated the strongly correlated systems NiO, CoO, CuO, La2CuO4 and Ca2−xCuO2Cl2.We showed the presence of non-local excitations in the dipolar part of the absorption spectrain those systems, and proposed an independant method to measure the charge-transfergap based on the XAS of a hole-doped system. We showed the importance of many-bodyeects in the edge region and attributed them to multi-determinant eects with the helpof a concolution with photoemission formula. Last, we successfully calculated the XMCDspectra of iron and cobalt under pressure, and discussed of the relative importance ofdipole and quadrupole transitions, of anisotropy and of the accuracy of sum rules.Les mesures d'absorption X et de dichroïsme circulaire magnétique sont largementutilisées pour étudier les excitations électroniques et le magnétisme des matériaux. Cesétudes dépendent de manière cruciale de l'interprétation théorique des mesures expérimentales.Nous avons développé de nouvelles méthodes de calcul de l'absorption X (XAS)au seuil K et du dichroïsme magnétique circulaire (XMCD) au seuil K basées sur l'utilisationde la théorie de la fonctionnelle de densité (DFT), des pseudopotentiels et de lafraction continue. Ces méthodes permettent le traitement des eets du trou de coeur dansune approche sans paramètre libre.Nous avons appliqué ces méthodes à toute une gamme de matériaux, en allant de lafaible corrélation vers la forte corrélation électronique, an de voir si une approximationmonoparticule pouvait décrire les spectres XAS et XMCD. Nous avons d'abord étudiéles spectres XAS du graphène, matériau faiblement corrélé, an de déterminer si l'état interlayer , responsable de la supraconductivité dans les graphites intercalés, pouvaitêtre vu en XAS comme suggéré par des mesures récentes. Nous avons ensuite abordé lessystèmes à forte corrélation que sont NiO, CoO, CuO, La2CuO4 et Ca2−xCuO2Cl2. Nousavons montré la présence d'excitations non locales dans la partie dipolaire des spectresXAS dans ces systèmes, ce qui nous a permis de proposer une nouvelle méthode indépendantede mesure de la largeur de la bande interdite basée sur le XAS dans un système dopéavec des trous. Nous avons montré l'importance des effets à N corps dans la région duseuil de ces spectres et avons attribué cela à des effets à plusieurs déterminants de Slaterà l'aide d'une formule de convolution par la photoémission. Enfin, le XMCD du fer et ducobalt sous pression sont calculés avec succès, ce qui permet de discuter de l'importancerelative des transitions dipolaires et quadrupolaires, de l'anisotropie et de la pertinencede l'utilisation des règles de somme

Hole-depletion of ladders in Sr14_{14}Cu24_{24}O41_{41} induced by correlation effects

The hole distribution in Sr$_{14}$Cu$_{24}$O$_{41}$ is studied by low temperature polarization dependent O K Near-Edge X-ray Absorption Fine Structure measurements and state of the art electronic structure calculations that include core-hole and correlation effects in a mean-field approach. Contrary to all previous analysis, based on semi-empirical models, we show that correlations and antiferromagnetic ordering favor the strong chain hole-attraction. For the remaining small number of holes accommodated on ladders, leg-sites are preferred to rung-sites. The small hole affinity of rung-sites explains naturally the 1D - 2D cross-over in the phase diagram of (La,Y,Sr,Ca)$_{14}$Cu$_{24}$O$_{41}$Comment: 6 pages, 8 figure

K-edge X-ray absorption spectra in transition metal oxides beyond the single particle approximation: shake-up many body effects

The near edge structure (XANES) in K-edge X-ray absorption spectroscopy (XAS) is a widely used tool for studying electronic and local structure in materials. The precise interpretation of these spectra with the help of calculations is hence of prime importance, especially for the study of correlated materials which have a complicated electronic structure per se. The single particle approach, for example, has generally limited itself to the dominant dipolar cross-section. It has long been known however that effects beyond this approach should be taken into account, both due to the inadequacy of such calculations when compared to experiment and the presence of shake-up many-body satellites in core-level photoemission spectra of correlated materials. This effect should manifest itself in XANES spectra and the question is firstly how to account for it theoretically and secondly how to verify it experimentally. By using state-of-the-art first principles electronic structure calculations and 1s photoemission measurements we demonstrate that shake-up many-body effects are present in K-edge XAS dipolar spectra of NiO, CoO and CuO at all energy scales. We show that shake-up effects can be included in K-edge XAS spectra in a simple way by convoluting the single-particle first-principles calculations including core-hole effects with the 1s photoemission spectra. We thus describe all features appearing in the XAS dipolar cross-section of NiO and CoO and obtain a dramatic improvement with respect to the single-particle calculation in CuO. These materials being prototype correlated magnetic oxides, our work points to the presence of shake-up effects in K-edge XANES of most correlated transition metal compounds and shows how to account for them, paving the way to a precise understanding of their electronic structure.Comment: 6 pages, 4 picture

Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials

Quantum ESPRESSO is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density-functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave). Quantum ESPRESSO stands for "opEn Source Package for Research in Electronic Structure, Simulation, and Optimization". It is freely available to researchers around the world under the terms of the GNU General Public License. Quantum ESPRESSO builds upon newly-restructured electronic-structure codes that have been developed and tested by some of the original authors of novel electronic-structure algorithms and applied in the last twenty years by some of the leading materials modeling groups worldwide. Innovation and efficiency are still its main focus, with special attention paid to massively-parallel architectures, and a great effort being devoted to user friendliness. Quantum ESPRESSO is evolving towards a distribution of independent and inter-operable codes in the spirit of an open-source project, where researchers active in the field of electronic-structure calculations are encouraged to participate in the project by contributing their own codes or by implementing their own ideas into existing codes.Comment: 36 pages, 5 figures, resubmitted to J.Phys.: Condens. Matte

Orientation and stability of a bi-functional aromatic organic molecular adsorbate on silicon

In this work we combine scanning tunneling microscopy, near-edge X-ray absorption fine structure spectroscopy, X-ray photoemission spectroscopy and density functional theory to resolve a long-standing confusion regarding the adsorption behaviour of benzonitrile on Si(001) at room temperature. We find that a trough-bridging structure is sufficient to explain adsorption at low coverages. At higher coverages when steric hindrance prevents the phenyl ring lying flat on the surface, the 2+2 cycloaddition structure dominates

The electronic structure of iridium oxide electrodes active in water splitting

Iridium oxide based electrodes are among the most promising candidates for electrocatalyzing the oxygen evolution reaction, making it imperative to understand their chemical/electronic structure. However, the complexity of iridium oxide's electronic structure makes it particularly difficult to experimentally determine the chemical state of the active surface species. To achieve an accurate understanding of the electronic structure of iridium oxide surfaces, we have combined synchrotron-based X-ray photoemission and absorption spectroscopies with ab initio calculations. Our investigation reveals a pre-edge feature in the O K-edge of highly catalytically active X-ray amorphous iridium oxides that we have identified as O 2p hole states forming in conjunction with IrIII. These electronic defects in the near-surface region of the anionic and cationic framework are likely critical for the enhanced activity of amorphous iridium oxides relative to their crystalline counterparts

Excitations électroniques et magnétisme des matériaux (clacul ab initio de l'absorption X et du dichroïsme circulaire magnétique au seuil K)

A l'aide de nouvelles méthodes de calcul de l'absorption X (XAS) et du dichroïsme circulaire magnétique (XMCD) au seuil K ne comportant aucun paramètre libre développées durant cette thèse, nous avons d'abord étudié les spectres XAS du graphène, afin de déterminer si l'état interlayer pouvait être vu en XAS comme suggéré par des mesures récentes. Nous avons ensuite abordé les systèmes à forte corrélation que sont NiO, CoO, CuO, La2CuO4 et Ca2-xCuO2Cl2. Nous avons montré la présence d'excitations non locales dans leurs spectres XAS, ce qui nous a permis de proposer une nouvelle méthode de mesure du gap. Nous avons montré l'importance des effets à plusieurs déterminants de Slater à l'aide d'une formule de convolution par la photoémission. Enfin, le XMCD du fer et du cobalt sous pression sont calculés avec succès, ce qui permet de discuter de l'importance relative des transition dipolaires et quadrupolaires, de l'anisotropie et de la pertinence de l'utilisation des règles de somme.PARIS-BIUSJ-Physique recherche (751052113) / SudocSudocFranceF

First-principles calculations of x-ray absorption in a scheme based on ultrasoft pseudopotentials: From !-quartz to high-Tc compounds

International audienceWe develop a first-principles scheme based on the continued-fraction approach and ultrasoft pseudopotentials to calculate K-edge x-ray absorption spectra in solids, allowing such calculations in transition-metal and rare-earth compounds with substantially reduced cutoffs with respect to the norm-conserving case. We validate the method by calculating Si and O K edges in !-quartz, Cu K edge in copper and in La2CuO4. For the case of Si and O edges in !-quartz and in copper, we obtain good agreement with experimental data. In the Cu K-edge spectra of La2CuO4, a material considered a real challenge for density-functional theory, we attribute all the near-edge and far-edge peaks to single-particle excitations