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

摘要

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 AnO(2+)) by treating the molecular electronic states as An(m+) free-ion energy levels (where An is an element of Th through Lr and m = 1, 2, 3, or 4) perturbed by the electric field of O(2-)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 S-c, maximum L-c) 5f-core states of An(4+), An(3+), An(2+), and An(+) for the majority of the An(4+)O(2-), An(3+)O(-), An(3+)O(2-), An(2+)O(-), An(2+)O(2-), and An(+)O(-) electronic configurations. Simple linear relationships enabled predictions of the dissociation energies for AnO, AnO(+) and AnO(2+) (where An is an element of Bk through Lr) and ionization energies for AnO and AnO(+) (where An is an element of Bk through Lr), mainly based on recent accurate experimental data for the ionization energies of An atoms (where An is an element of Fm, Md, No, and Lr) and correlations with the energetics of the atoms and ions.