Optical Spectra and Electronic Structure

Much of our knowledge of the electronic properties of actinides in solutions and solids is obtained from optical spectroscopy. One of the features that sets actinide spectra apart from those of other elements in the periodic table, aside from the lanthanide series, is that their f-orbitals can be considered both as containing optically active electrons and as belonging to the core of inner shells. As a result of this dominant characteristic, the spectra of these elements, particularly of the lower valence states, are moderately insensitive to changes in the ionic environment. Although ion–ligand interactions shift and split the energy levels of the f-orbitals, the scale of this crystal-field splitting is generally smaller than the intra-ionic Coulomb interaction and spin-orbit coupling. The relative insensitivity of these f-electrons to external forces also means that for these elements there is a close connection between energy levels in compounds and those in gaseous free atoms and ions. Table 18.1 lists the scales of various mechanisms of electronic interactions that will be discussed in this chapter through analysis and modeling of the optical spectra of the various valence states of actinide ions in solutions and compounds.