Theoretical investigations of actinide complexes with organic ligands
For a safe disposal of highly radioactive actinides a complete understanding of the interactions with the chemical environment is needed. Experiments alone can’t deliver a full insight of these interactions, therefore theoretical investigations followed by comparison with experimental results have to be done as well. Geometry optimisations, molecular dynamical simulations and computation of spectral parameters like UV/VIS, NMR, ESR, XAS, IR and so on can be used to understand, describe and predict chemical compounds and processes. Besides anorganic ligands in the natural environment of the actinides, they also are in contact with organic ligands, having a variaty of functional groups. The main focus of this Ph.D. lies on theoretical investigations of actinide complexes with polydentate ligands, having oxygen and nitrogen as electron donors. Of special interest is the bonding analysis of the actinides because of the complex electronic structure of the valence electrons.
HF- and DFT-based methods will be used in the framework of relativistic quantum chemistry. Dependent on the size and complexity of the systems more sophisticated methods like perturbation theory (MP2), explicitly correlated methods (configuration interaction, coupled-cluster methods) and multi-reference methods (CASPT2, NEVPT2) will be used. On the field of bonding analysis especially the tools derived in the framework of real-space bonding analysis, e.g. ELI-D, QTAIM, NCI plots and density difference analyses, will be used.