title: The Electronic States of U(4+) in U(PO4)Cl: An Example for Angular Overlap Modeling of 5f(n) Systems.
abstract: Detailed experimental data on UPO4Cl comprising single-crystal UV/vis/NIR spectra and temperature-dependent magnetic susceptibilities form the basis for the investigation of the electronic structure of the U(4+) cation in UPO4Cl. For modeling of the observed physical properties the angular overlap model (AOM) was successfully employed. The computations were performed using the newly developed computer program BonnMag. The calculations show that all electronic transitions and the magnetic susceptibility as well as its temperature dependence are well-reproduced within the AOM framework. Using Judd-Ofelt theory BonnMag allows estimation of the relative absorption coefficients of the electronic transitions with reasonable accuracy. Ligand field splitting for states originating from f-electron configurations are determined. Slater-Condon-Shortley parameters and the spin-orbit coupling constant for U(4+) were taken from literature. The good transferability of AOM parameters for U(4+) is confirmed by calculations of the absorption spectra of UP2O7 and (U2O)(PO4)2. The effect of variation of the fit parameters is investigated. AOM parameters for U(4+) (5f) are compared to those of the rare-earth elements (4f) and transition metals (3d).
authors.affiliation: Institute of Inorganic Chemistry, Rheinische Friedrich-Wilhelms-Universität , Gerhard-Domagk-Straße 1, D-53121 Bonn, Germany.
authors.forename: Anna
authors.initials: A
authors.lastname: Bronova
authors.affiliation: Mulliken Center for Theoretical Chemistry, Rheinische Friedrich-Wilhelms-Universität , Beringstr. 4, D-53121 Bonn, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Bredow
authors.affiliation: Institute of Inorganic Chemistry, Rheinische Friedrich-Wilhelms-Universität , Gerhard-Domagk-Straße 1, D-53121 Bonn, Germany.
authors.forename: Robert
authors.initials: R
authors.lastname: Glaum
authors.affiliation: Chemistry Department, University of Fribourg , Chemin du Musée 9, CH-1700 Fribourg, Switzerland.
authors.forename: Werner
authors.initials: W
authors.lastname: Urland