Electroabsorption spectroscopy of molecular inorganic compounds

Fredrick W. Vance, Robert D. Williams, Joseph T Hupp

Research output: Contribution to journalArticle

63 Citations (Scopus)

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 languageEnglish
Pages (from-to)307-329
Number of pages23
JournalInternational Reviews in Physical Chemistry
Volume17
Issue number3
Publication statusPublished - Jul 1998

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Inorganic compounds
inorganic compounds
Charge transfer
charge transfer
Spectroscopy
spectroscopy
Dipole moment
Excited states
Ground state
Electrons
electron transfer
dipole moments
Metals
electronics
Ligands
ligands
ground state
illuminating
metals
excitation

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 journalArticle

Vance, Fredrick W. ; Williams, Robert D. ; Hupp, Joseph T. / Electroabsorption spectroscopy of molecular inorganic compounds. In: International Reviews in Physical Chemistry. 1998 ; Vol. 17, No. 3. pp. 307-329.
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