Abstract
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 highlighted in 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.
| Original language | English |
|---|---|
| Pages (from-to) | 307-329 |
| Number of pages | 23 |
| Journal | International Reviews in Physical Chemistry |
| Volume | 17 |
| Issue number | 3 |
| Publication status | Published - Jul 1998 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Electroabsorption spectroscopy of molecular inorganic compounds. / Vance, Fredrick W.; Williams, Robert D.; Hupp, Joseph T.
In: International Reviews in Physical Chemistry, Vol. 17, No. 3, 07.1998, p. 307-329.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Electroabsorption spectroscopy of molecular inorganic compounds
AU - Vance, Fredrick W.
AU - Williams, Robert D.
AU - Hupp, Joseph T
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 highlighted in 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 highlighted in 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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M3 - Article
VL - 17
SP - 307
EP - 329
JO - International Reviews in Physical Chemistry
JF - International Reviews in Physical Chemistry
SN - 0144-235X
IS - 3
ER -