Relativistic and electron correlation effects on thed-d spectrum of transition metal fluorides

Summary The electronic spectra of the transition metal complexes CoF₆^2–, RhF₆^2– and IrF₆^2– that occur in the solids Cs₂MeF₆ are calculated. Hartree-Fock and Dirac-Fock calculations followed by non-relativistic and relativistic CI calculations respectively are used to study the influence of relativity and electron correlation. The calculated transitions are found to agree fairly well with experiment, the largest discrepancies arising from the neglect of differential dynamical electron correlation effects.