Systematic behaviour in trivalent lanthanide charge transfer energies

Abstract

Information on the energy that is needed to transfer an electron from the valence band of an inorganic compound to a trivalent lanthanide impurity is presented. The energy is a measure of the location of the ground state of the divalent lanthanide relative to the top of the valence band. A variation with type of lanthanide is found that is the same irrespective of the type of compound (fluorides, chlorides, bromides, iodides, oxides, sulfides). The variation is anti-correlated with the known variation in fd transition energies in divalent lanthanides. Because of the anti-correlation, the energy difference between the first 4f n −1 5d state and the bottom of the conduction band is relatively invariant with type of lanthanide ion. The difference is largest for Eu 2+ , and decreases gradually towards the end of the lanthanide series by 0.5 eV for Y b 2+ . Based on the systematic variation in charge transfer energy and fd energy, a three-parameter model is presented to position the energy levels for each divalent lanthanide relative to valence and conduction band states. Using a similar model the levels of trivalent lanthanides are positioned.