The Electronic Structure of the Actinide Oxides and Their Singly and
Doubly Charged Cations: A Ligand Field Approach
Abstract
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.