Excited-state mixed valence in transition metal complexes

Mixed valence in the lowest-energy metal-to-ligand charge-transfer excited state of di-(4-acetylpyridine) tetraammineruthenium(II) complexes is defined and analyzed. The excited state has two interchangeably equivalent ligands with different oxidation states. The electronic absorption band energies, selection rules, and bandwidths are analyzed quantitatively in terms of the signs and orientations of the transition dipole moments, sign and magnitude of the coupling, and resonance Raman analysis of displaced normal modes.