Probing actinide electronic structure using fluorescence and multi-photon ionization spectroscopy

The role of the 5f orbitals in actinide bond formation is one of the central issues of actinide chemistry. This question can be explored using relativistic quantum chemistry calculations, but the theoretical methods must be validated using definitive experimental data. For simple ionic compounds such as actinide oxides and halides, the electronic structure can be examined using electronic and photoelectron spectroscopy of gas phase molecules. The present article surveys recent spectroscopic and theoretical studies of the oxides of thorium and uranium. The results show that the 5f-like states are spectators and that the complex patterns of low-lying electronic states for these molecules can be understood in terms of a semi-empirical ligand field model. Comparisons with recent high-level theoretical calculations are presented and discussed.