title: First-principles calculations of X-ray absorption spectra at the K-edge of 3d transition metals: an electronic structure analysis of the pre-edge.
abstract: We first present an extended introduction of the various methods used to extract electronic and structural information from the K pre-edge X-ray absorption spectra of 3d transition metal ions. The K pre-edge structure is then modelled for a selection of 3d transition metal compounds and analyzed using first-principles calculations based on the density functional theory (DFT) in the local density approximation (LDA). The selected compounds under study are presented in an ascending order of electronic structure complexity, starting with the Ti K-edge of rutile and anatase, and finishing with the Fe K-edge of the cyanomet-myoglobin. In most cases, the calculations are compared to polarized experimental spectra. It is shown that DFT-LDA methods enable us to reproduce satisfactorily the experimental features and to understand the nature of the electronic transitions involved in the pre-edge region. The limiting aspects of such methods in modelling the core-hole electron interaction and the 3d electron-electron repulsion are also pointed out.
authors.affiliation: Institut de Minéralogie et Physique des Milieux Condensés, UMR 7590 CNRS, Université Pierre et Marie Curie, Université Paris Diderot, IPGP, IRD, 140 rue de Lourmel, 75015 Paris, France. delphine.cabaret@impmc.upmc.fr
authors.forename: Delphine
authors.initials: D
authors.lastname: Cabaret
authors.forename: Amélie
authors.initials: A
authors.lastname: Bordage
authors.forename: Amélie
authors.initials: A
authors.lastname: Juhin
authors.forename: Mounir
authors.initials: M
authors.lastname: Arfaoui
authors.forename: Emilie
authors.initials: E
authors.lastname: Gaudry
mesh_terms: D018360:Crystallography, X-Ray; D004583:Electrons; D005296:Ferrous Compounds / Q000737:chemistry; D009211:Myoglobin / Q000737:chemistry; D014025:Titanium / Q000737:chemistry; D028561:Transition Elements / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
chemical_list: D005296:Ferrous Compounds; D009211:Myoglobin; D028561:Transition Elements; C009495:titanium dioxide; D014025:Titanium; C022597:ferrous sulfide