| This thesis describes the application of electroabsorption spectroscopy to the study of excited state properties and electron transfer in inorganic mixed-valence complexes. Specifically these measurements address changes in the dipole moments, {dollar}lbrack Deltamusb{lcub}12{rcub}rbrack ,{dollar} and polarizabilities, {dollar}Deltaalphasb{lcub}12{rcub},{dollar} between the ground and the Franck-Condon excited state. These studies show the invalidity of some previous assumptions of about the charge transfer distances {dollar}(Rsb{lcub}rm ab{rcub}){dollar} in cyano-bridged dinuclear complexes, and further lead to a better estimate of some key electron transfer parameters, the adiabatic coupling energy {dollar}(Hsb{lcub}rm ab{rcub}){dollar} and the solvent reorganization energy {dollar}(lambdasb{lcub}rm s{rcub}).{dollar} Electroabsorption studies were also used to interrogate excited state localization versus delocalization of charge in the phenathroline ligands of a ruthenium tris-phenanthroline complex, and to address the extent of electronic coupling in novel porphyrin dimers. Finally, electroabsorption study was used to evaluate state specific contributions to the first hyperpolarizability {dollar}(beta ){dollar} in conjugated porphyrin-based and heteroatomic polyene-based push pull chromophores in the context of Oudar's two state model. |
