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

Abstract

AbstractLigand 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.