Journal article

A theoretical characterization of covalency in rare earth complexes through their absorption electronic properties: f-f transitions

  • Petit, Laurence Laboratoire de Reconnaissance Ionique, CEA-Grenoble, France - Laboratoire d'Électrochimie et de Chimie Analytique, École Nationale Supérieure de Chimie de Paris, France
  • Borel, Alain Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, Switzerland
  • Daul, Claude Department of Chemistry, University of Fribourg, Switzerland
  • Maldivi, Pascale Laboratoire de Reconnaissance Ionique, CEA-Grenoble, France -
  • Adamo, Carlo Laboratoire d'Électrochimie et de Chimie Analytique, École Nationale Supérieure de Chimie de Paris, France
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    08.08.2006
Published in:
  • Inorganic Chemistry. - 2006, vol. 45, no. 18, p. 7382 -7388
English Experimental uncertainties concerning the coordination mode of trivalent plutonium in concentrated LiCl have led us to theoretically evaluate the f-f transitions of a series of rare earth aquo and chloro complexes. The calculation of Pr(III), U(III), Np(III), and Pu(III) systems' spectra was undertaken using the LFDFT (ligand field density functional theory) route that combines the backgrounds of ligand field (LF) theory with Kohn-Sham orbitals. LF parameters are fitted to previous DFT calculations, thus preventing the use of empirical data. The f-f transitions values are globally well predicted, but the lack of accurate experimental references can sometimes hinder reliable comparisons. Despite this, the nephelauxetic effect from aquo to chloro complexes is clearly observed through both spectral red shifts and the decrease in F2, the Slater-Condon parameter. Accordingly, this work provides the first theoretical characterization of covalency in trivalent f elements through their electronic spectra.
Faculty
Faculté des sciences et de médecine
Department
Département de Chimie
Language
  • English
Classification
Chemistry
License
License undefined
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Persistent URL
https://folia.unifr.ch/unifr/documents/300623
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