Description of ligand field splitting in terms of density functional theory: Split levels of the lowest-lying subterms of the 4fn−16s2 (n=3–14) configurations in lanthanide monofluorides LnF (Ln=Pr–Yb)

Abstract

The split levels associated with the lowest-lying subterms of the 4fn−16s2 (n=3–14) configurations of lanthanide monofluorides LnF (Ln=Pr–Yb) were calculated by employing the combined ligand field and density functional theory (CLDT) method recently proposed. The 288 calculated split levels are in excellent agreement with experiment and hence shows that the CLDT method can accurately reproduce the low-lying electronic excited states of lanthanide compounds. To quantitatively describe the low-lying electronic states of a lanthanide compound, therefore, the effective ligand potential must include the Coulomb and exchange-correlation potentials of the compound as well as the pseudopotentials of the ligands.