The results of a computational study with multiconfigurational quantum chemical methods on actinide monoxides (AnO) and dioxides (AnO₂) for An = Th, Pa, U, Np, Pu, Am, and Cm, are presented. First and second ionization energies were determined and compared with experimental values, when available. The trend along the series is analyzed in terms of the electronic configurations of the various species. The agreement with experiment is excellent in most cases. Of particular interest is the first ionization of PuO₂. We applied cutting-edge theoretical methods to refine the ionization energy, but our computed data fall in the range of ~6 eV and not in the ~7 eV region as the experiment dictates. Such a system requires further computational and experimental attention.

Americium and curium oxides AmO_n and CmO_n (n = 1, 2) were studied using state-of-the-art multiconfigurational, relativistic, quantum chemical methods. Spectroscopic properties for the ground state and several excited states of the four target compounds were determined. The computed dissociation energy of AmO (4.6 eV) agrees fairly well with estimates derived from experimental studies (5.73 ± 0.37 eV) while the computed dissociation energy of CmO (7.1 eV) agrees well with the experimental value (7.5 eV). The computed ionization energy of AmO (6.3 eV) is in good agreement with the current experimental value (5.9 ± 0.2 eV).