TY - JOUR
T1 - Electroabsorption spectroscopy of molecular inorganic compounds
AU - Vance, Fredrick W.
AU - Williams, Robert D.
AU - Hupp, Joseph T.
N1 - Funding Information:
We wish to express our gratitude to our co-workers, whose names appear in the references. W e also acknowledge Professor S. Boxer and co-workers for providing preprints of their work and communicating useful comments on our recent work. We thank the US Department of Energy, O ce of Research, Division of Chemical Sciences (Grant No. DE-FG02-87ER 13808) for support of the work done at Northwestern. W e additionally thank the US National Science Foundation (graduate traineeship program (CHE-9256486) and M RSEC program (DM R-9632472)) for partial stipend and scholarship support for F. W . V.
PY - 1998/7
Y1 - 1998/7
N2 - Electroabsorption spectroscopy is known to report directly on the changes in dipole moment and molecular polarizability accompanying electronic excited state formation. Because ground-state/excited-state dipole moment changes can be equated with effective one-electron transfer distances, experimental electroabsorption spectroscopy holds exceptional promise as a methodology for investigating light-induced charge transfer processes within inorganic systems. A survey of the available studies, including metal-to-ligand charge transfer, ligand- to-metal charge transfer and localized and delocalized ‘intervalence’ charge transfer studies, is presented. Also surveyed are electroabsorption studies aimed at illuminating selected molecular nonlinear optical responses. A general observation from electroabsorption studies has been that experimentally determined one- electron transfer distances are less than simple geometric descriptions would predict. Mononuclear transition-metal systems have proven to be good models for unravelling the complicating effects of ground-state localization and many-electron polarization. The capability of electroabsorption spectroscopy to resolve fundamental questions relating to electronic localization and delocalization has been highlightedin a series of studies in bridged dinuclear and tris(diimine) systems. The available electroabsorption data have also been used to reassess a number of molecular charge-transfer related parameters such as the electronic coupling energies and solvent reorganization energies. Very recent studies of putative octupolar complexes and donor-acceptor porphyrinic structures have highlighted the utility of electroabsorption spectroscopy for evaluating second-order nonlinear optical response mechanisms and for providing detailed information about state- specific contributions to overall molecular hyperpolarizabilities.
AB - Electroabsorption spectroscopy is known to report directly on the changes in dipole moment and molecular polarizability accompanying electronic excited state formation. Because ground-state/excited-state dipole moment changes can be equated with effective one-electron transfer distances, experimental electroabsorption spectroscopy holds exceptional promise as a methodology for investigating light-induced charge transfer processes within inorganic systems. A survey of the available studies, including metal-to-ligand charge transfer, ligand- to-metal charge transfer and localized and delocalized ‘intervalence’ charge transfer studies, is presented. Also surveyed are electroabsorption studies aimed at illuminating selected molecular nonlinear optical responses. A general observation from electroabsorption studies has been that experimentally determined one- electron transfer distances are less than simple geometric descriptions would predict. Mononuclear transition-metal systems have proven to be good models for unravelling the complicating effects of ground-state localization and many-electron polarization. The capability of electroabsorption spectroscopy to resolve fundamental questions relating to electronic localization and delocalization has been highlightedin a series of studies in bridged dinuclear and tris(diimine) systems. The available electroabsorption data have also been used to reassess a number of molecular charge-transfer related parameters such as the electronic coupling energies and solvent reorganization energies. Very recent studies of putative octupolar complexes and donor-acceptor porphyrinic structures have highlighted the utility of electroabsorption spectroscopy for evaluating second-order nonlinear optical response mechanisms and for providing detailed information about state- specific contributions to overall molecular hyperpolarizabilities.
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U2 - 10.1080/014423598230072
DO - 10.1080/014423598230072
M3 - Article
AN - SCOPUS:0001318490
VL - 17
SP - 307
EP - 329
JO - International Reviews in Physical Chemistry
JF - International Reviews in Physical Chemistry
SN - 0144-235X
IS - 3
ER -