Quantum chemical calculations of structural properties and spectroscopy of solvated actinide ions: Theory and applications

NUCL 36

Valérie Vallet, valerie.vallet@univ-lille1.fr, Laboratoire de Physique des Lasers Atomes et Molécules (CNRS UMR 8523), Université des Sciences et Technologie de Lille - CNRS, Villeneuve d'Ascq, F-59655, France
Quantum chemical methods enable the calculation of structural models and Debye-Waller factors for single and multiple scattering pathways, from a full ab initio normal mode analysis. The latter values can then be used as fixed parameters in the EXAFS fitting procedure, thus reducing the number of parameters to be varied and improving the chemical conclusions drawn from the experimental data. We will use examples from the chemistry of uranyl(VI) to illustrate how ab initio data can be used to reveal the structure of complexes in solution.

Quantum chemical methods are also very useful for the calculation of spectroscopic properties of heavy ions. In such ions, the manifold of electronic states is very dense and electron correlation and spin-orbit effects are intertwined. We will illustrate the potentialities and limitations of present quantum chemical methods for the calculation of the electronic spectra of bare and solvated early actinide ions.