Vibronic intensities in the electronic spectra of transition metal complex ions VIII: Vibrational coordinates for octahedral ions and their application to the4 A 2g ?2 E g transition of the MnF 6 2? ion

Abstract

A reexamination of the vibrational coordinates appropriate in vibronic intensity calculations in octahedral coordination compounds is presented. We derive a complete set of symmetry coordinates that is orthonormal and transforms correctly under the group generators. The vibronic hamiltonian for the crystal field and ligand polarization contributions to the intensity are calculated in the basis of these coordinates. The crystal field term is evaluated both using a truncated basis set for the intermediate electronic states and using the closure approximation. These methods have been applied to the calculation of the vibronic intensity distribution for the4A2g ↔2Eg transition of the MnF62− ion and close agreement wtih experiment achieved.