Abstract

The dynamic crystal field operators, corresponding to the normal point-charge displacements in an octahedral complex are analyzed in detail. The strict equivalence of absolute versus relative coordinate treatments is established. The resulting formalism is applied to the intensity distribution in the vibronic side bands of the sharp line luminescence spectra ofd3 complexes. Thereby special attention is given to the role of spin-orbit coupling and to the elastic properties of the molecular force field. Using the closure procedure, the relative intensities of the side bands may be expressed in terms of a single dynamic crystal field parameter. These expressions provide a simple rationalization of the observed vibronic selection rules, entirely within the framework of dynamic crystal field theory.

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