Vibronic intensities in the electronic spectra of transition metal ions

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Abstract
The relative vibronic intensities of the vibronic origins due to the three odd parity vibrational modes have been calculated for the 2 Eg ↔2 A 2g transition of the octahedral MnF6 2- ion, using a crystal field model. Two methods for treating the sum over the intermediate odd parity states are considered, the closure approximation and the single 4 T 2u d 2 p state method. It is shown that in the latter limit the relative vibronic intensities depend only on the vibrational force field whereas using closure there is also some dependence on the radial functions employed. Calculations using six different force fields and several radial functions are presented several of which reproduce the experimental relative intensity for both methods, although there is a strong dependence of the calculated intensity on the force field.