Dynamic ligand polarization contributions to 4f → 4f magnetic dipole transition moments and rotatory strengths: 7F 0 → 5D 2 and 7F 2 ← 5D 0 transitions in Eu (oxydiacetate) 33−

Abstract

Radiation-induced (dynamic) polarizations of electronic charge distributions on ligands may contribute to both the electric- and magnetic-dipole moments of 4f → 4f transitions in lanthanide complexes. The influence of these dynamic ligand polarizations on 4f → 4f electric-dipole intensities has been studied extensively, but their possible influence on magnetic-dipole transition moments (and intensities) has only recently been investigated. In the present study, dynamic ligand-polarization contributions to magnetic-dipole transition moments and rotatory strengths are examined for two transition manifolds of a chiral europium(III) complex. It is shown that these contributions to the magnetic-dipole transition moments may be as large as (or larger than) those associated with static crystal field perturbations on the 4f → 4f transitions examined here. It is likely that the dynamic ligand-polarization mechanism for magnetic-dipole transition moments will be important only for 4f → 4f transitions with vanishingly small ΔJ = 0, ± 1 character.