FROZEN-ORBITAL ANALYSIS OF THE EXCITED-STATES OF METAL-COMPLEXES IN HIGH SYMMETRY - O-H CASE

A frozen-orbital analysis (FZOA) is proposed in order to understand th e nature and the ordering of the excited states due to the excitations between degenerate orbitals of metal complexes in high symmetry. The FZOA method represents a direct application of group theory. In the FZ OA approach, only a few two-electron integrals are considered to expla in the ordering and the energy splittings of the excited states, which are brought about by excitations between two degenerate orbitals. Fur thermore, FZOA may be utilized to explain the intensities of the absor ption peaks. Here, we apply FZOA to two series of the excited states o f MoF6. Although there are large discrepancies between the actual exci tation energies by FZOA and those derived by more accurate calculation s, the ordering and the energy splittings are comparable. This relativ e agreement is sufficient to justify an analysis based on FZOA methods . On the basis of the present results, we suggest that FZOA methods wo uld yield some general insight into the nature of the excited states f or molecules of high symmetry.