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A simple method for constructing effective Hamiltonians for the 4fN and4fN-15d energy levels of lanthanide ions in crystals from quantum-chemicalcalculations is presented. The method is demonstrated by deriving crystal-fieldand spin-orbit parameters for Ce3+ ions doped in LiYF4, Cs2NaYCl6, CaF2, KY3F10and YAG host crystals from quantum chemical calculations based on theDV-X{\alpha} method. Good agreement between calculated and fitted values of thecrystal-field parameters is obtained. The method can be used to calculateparameters even for low-symmetry sites where there are more parameters thanenergy levels.

Extraction of crystal-field parameters for lanthanide ions from quantum-chemical calculations