Crystal field in rare-earth fluorides—I. Molecular orbital calculation of PrF3 parameters

Crystal field parameters have been calculated, using ab initio LCAO-MO theory, for the ion pair Pr³⁺—F⁻ at five metal ligand distances appropriate to Pr³⁺:LaF₃. The parameters are found to be twice as large as in PrCl₃, but with only half the distance dependence. In the absence of precise Pr³⁺:LaF₃ experimental parameters only qualitative agreement with experiment can be recorded. However, very good numerical agreement is obtained with the experimental covalency parameters for Yb³⁺:CaF₂, which provides a check on the methods adopted for calculating energy denominators.