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The electronic structure of the actinide oxides and their singly and doubly charged cations: A ligand field approach

Ligand field theory (LFT) calculations of energy levels were performed for the neutral actinide monooxides (AnO) and their singly and doubly ionized cations (AnO+ and AnO2+ by treating the molecular electronic states as Anm+ free-ion energy levels (where An ∈ Th through Lr and m=1, 2, 3, or 4) perturbed by the electric field of O2- or O-. LFT parameters obtained from fits to the energy levels of ThO, ThO+, UO, and UO+ were used to compute molecular energy levels for the lowest energy (maximum Sc, maximum Lc) 5f-core states of An4+, An3+, An2+, and An+ for the majority of the An4+O2-, An3+O-, An3+O2-, An2+O-, An2+O2- , and An+O- electronic configurations. Simple linear relationships enabled predictions of the dissociation energies for AnO, AnO+ and AnO2+ (where An ∈ Bk through Lr) and ionization energies for AnO and AnO+ (where An ∈ Bk through Lr), mainly based on recent accurate experimental data for the ionization energies of An atoms (where An ∈ Fm, Md, No, and Lr) and correlations with the energetics of the atoms and ions.