Publications Repository - Helmholtz-Zentrum Dresden-Rossendorf

The electronical properties of f-elements, especially of the actinides, are a very puzzling topic to investigate. The frontier orbitals (5f, 6d, 7s) all lying in a similar energy regime along with open shells and relativistic effects contribute to a very complex situation, where single-reference methods like DFT and Hartree-Fock may be not suitable any more1. In recent years, the investigation of actinides in combination with organic ligands revealed a very rich chemistry with many forms of coordination and chemical bonding. Besides that, many visually appealing and intuitive tools have been developed, with which the chemical bond can be analysed. These tools for bond analysis include natural-bonding orbitals (NBO) and density-difference plots. The aim of this study is therefore to apply these bond analysis tools to a range of tetravalent actinide complexes with N-donor ligands2, like Schiff bases and amidinates (Figure 1), to elucidate their complicated electronic properties. Thermodynamic computations on the stability of the complexes will also be presented to understand the chemical properties of the actinides and predict yet unknown complexes.