Relativistic effects on molecular hyperfine interactions: Application to ytterbium fluorides

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Abstract
Dirac scattered-wave (DSW) calculations are presented for YbF3−6 and YbF5−8 clusters that model Yb+3 impurity sites in KMgF3 and CaF3 lattices, respectively. The calculations predict Γ6 and Γ7 ground states for these two cubic geometries and show good agreement with observed g tensors, spin-orbit splittings, and Yb hyperfine interactions, but overestimate the crystal field splittings and the amount of covalency between the metal and the fluorine 2p orbitals. Nevertheless, the fluorine hyperfine tensors are in qualitative agreement with experiment, and confirm the existence of a large p-orbital contribution to the isotropic part of the 19F hyperfine tensor for YbF3−6. The implications of these results for future relativistic calculations on lanthanide complexes are discussed.