The understanding of the chemistry and the physical properties of f-element complexes, and in particular of the actinyl species (AnO22+), is of great importance. These 5f open-shell systems, due to the comparable magnitudes of spin-orbit coupling and crystal field splitting, exhibit relatively complicated electronic structures, often with a large number of low-energy electronic states. This presents a challenge for quantum chemistry to obtaine an accurate description of the electronic structures of such complexes, and hence of their physical properties. The aim of this presentation is thus to discuss applications of a variety of theoretical procedures, using density functional theory (DFT) and multi-reference wavefunction (CASSCF) methods, to describe magnetic properties (mainly EPR g-factors) of selected molecules. To this purpose, we will first discuss the electronic structures and the g-factors of some actinyls, UO2+, NpO22+ and PuO22+, which are extremely stable entities and form the the basis for many coordination complexes. We will then report calculations on selected coordinated actinyls where the influence of the ligands (nitrate, carbonate, �) on the nature of the ground and the first excited states will be detailed.Figure 1.  Non-Collinear spin density of [NpO2(NO3)]-.

Computational studies of magnetic properties of actinyl complexes

247th National Meeting (2014)

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