Using Resonance Raman Spectroscopy To Examine Vibrational Barriers to Electron Transfer and Electronic Delocalization

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A time-dependent approach to the interpretation of resonance Raman scattering intensities has been used to obtain quantitative vibrational mode displacement information from scattering intensities associated with charge-transfer excitation. The displacements and associated frequencies are the key parameters needed to understand Franck-Condon effects in electron-transfer kinetics, and to delineate in a mode-specific way the composition of vibrational reorganization energies. Application of the approach to a number of types of electron-transfer reactions is described, including symmetrical and unsymmetrical intervalence electron transfers in inorganic and organic redox systems, metal-to-ligand charge-transfer reactions, and interfacial electron-transfer reactions. Also described is how the approach can be used to elucidate mechanisms for valence delocalization in strongly interacting redox systems.