Systematic Investigation of Electronic States and Bond Properties of LnO, LnO⁺, LnS, and LnS⁺ (Ln = La–Lu) by Spin–Orbit Multiconfiguration Perturbation Theory

The electronic structures of lanthanide monoxides (LnO/LnO⁺) and monosulfides (LnS/LnS⁺) for all lanthanide series elements (Ln = La-Lu) have been systematically analyzed with sophisticated quantum chemical calculations. The ground electronic configuration has been determined to be Ln 4f^<i>n</i>6s¹ or 4f^<i>n</i>+1 for the neutral molecules and Ln 4f^<i>n</i> for the cations. The low-lying energy states resulting from spin-orbit coupling and ligand field effects have been resolved using spin-orbit multiconfiguration quasi-degenerate second-order perturbation theory calculations. The ionization energies of LnO (5.20-7.06 eV) are about 0.3-2.2 eV lower than those of LnS (5.54-9.22 eV) due to the difference in the Ln 6s and 4f orbital energies from which an electron is removed during the ionization process. The bond dissociation energies (BDEs) have been computed by the state-averaged general multiconfigurational perturbation theory and the completely renormalized coupled-cluster [CR-CC(2,3)] methods. The BDEs are highly dependent on the lanthanide elements as several factors of the lanthanides affect the bond dissociation. The calculated bond lengths and energies agree well with available experimental values and are systematically predicted for the series of lanthanide monoxides and monosulfides where experimental values are not available. Furthermore, the LS terms of low-lying energy states and their corresponding bond properties have been clarified in detail to systematize the similarities and differences of the lanthanide compounds.