Core excitation energies conclusions

As a provisional conclusion, let us merely note that the alkali model works best for optical electrons when the Rydberg spectrum occurs far away in energy from any spectrum involving excitation out of the core. 

For the excited V4 mode, both porphine core motions and side chain motions are predicted to be involved in the VER pathways. We draw similar conclusions for the excited mode. In spite of the distortion of the porphine core, comparable to that observed in Ni-heme, the v-, mode is not predicted to be involved in the energy transfer pathways from the excited V4 mode in NiOEP. The overtone is strongly coupled with the mode in NiOEP, but the third order Fermi resonance parameter is smaller than observed for other pathways. This result is similar to the predictions for the nonplanar Ni-heme (see Table 9.5). 

The second theoretical calculation is by Tatewaki et al. [22] They used four-component relativistic multiconfigurational quasidegenerate perturbation theory to take account of correlation effects between the active core [Ce + 4s. ..5p )F (2s 2p )] and three valence electrons in (4/), (5d), (6s), (6p), and intra-valence correlation effects. For the energy levels of the two excited states they obtained 0.144 eV and 0.351 eV. They did not reach conclusions about the higher excited states because of the limitations of the theory they used. A further study of the CeF excited states using larger RASCI and the/-shell Omega decomposition method (which is described below) is under way. 

---