Theoretica chimica acta

, Volume 56, Issue 1, pp 45–60 | Cite as

Subduced selection rules for vibronic transitions ind3 octahedral complexes

  • Bryan R. Hollebone
Original Investigations
Received:

Abstract

Forbidden electronic transitions are often weakly allowed through vibronic coupling to normal modes of the molecule. In transition metal complexes, the first order strong coupling appears in many cases to select specifically one of the available asymmetric modes. In this work the Intermediate Ligand Field model has been extended to vibronic coupling. The basis functions and tensor operators are described as species subduced from the vibronic generative group SU(3) which results from the diagonal restriction of the direct product of the electronic generative group SU(2) with the three dimensional harmonic oscillator group SU(3). This model implies that transitions between strongly coupled bases are permitted only through an overall octupole operator. All lower multipoles are forbidden and in particular the dipole is eliminated by the requirement for a translationally invariant centre of mass. The model permits any combination of multipole operators for separate electronic and vibrational transitions which result in the overall octupole. This theory is applied to two cases ofd3 complex spectra. It provides an unambiguous assignment of the4A2g-4T2g transition in the absorption spectrum of solid [MnF6]4− and of the MCD spectrum of the4A2g-(2T1g,4T2g) region in [Cr(H2O)6]3+. In the latter complex, the observed exclusive coupling of the2T1g state tot1u (stretch) and the4T2g state tot1u (twist) is predicted by the model.

Key words

Vibronic transitions Metal complexes Intermediate Ligand Field model 
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Copyright information

© Springer-Verlag 1980

Authors and Affiliations

  • Bryan R. Hollebone
    • 1
  1. 1.Department of ChemistryCarleton UniversityOttawaCanada

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