Abstract
The simple model for f–d transitions of heavy lanthanide ions in crystals has been extended to more general cases applicable to the octahedral six-fold coordination compounds where the measured spectra involve the low-lying 2t2 component of 5d orbitals, for which the 5d spin–orbit splitting is considerable and can be as large as a few thousand wavenumbers for heavy lanthanide ions. A quasi-angular-momentum technique was employed to deal with the correction caused by the 5d spin–orbit interaction based on the equivalence between the t2 and p orbits. The extended and original models were successfully applied to the interpretations of the f–d excitation spectra of Tm3+ ions in Cs2NaYF6 and CaF2 crystals. The impact of the 5d spin–orbit interaction on the f–d transition spectra was also discussed in more details.
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