Using resonance Raman spectroscopy to examine vibrational barriers to electron transfer and electronic delocalization

Joseph T Hupp, R. D. Williams

Research output: Contribution to journalArticle

96 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)808-817
Number of pages10
JournalAccounts of Chemical Research
Volume34
Issue number10
DOIs
Publication statusPublished - 2001

Fingerprint

Raman spectroscopy
Electrons
Charge transfer
Raman scattering
Metals
Scattering
Ligands
Kinetics
Chemical analysis
Oxidation-Reduction

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Using resonance Raman spectroscopy to examine vibrational barriers to electron transfer and electronic delocalization. / Hupp, Joseph T; Williams, R. D.

In: Accounts of Chemical Research, Vol. 34, No. 10, 2001, p. 808-817.

Research output: Contribution to journalArticle

@article{78bd7c0e394b4253b31c356c55de1b6c,
title = "Using resonance Raman spectroscopy to examine vibrational barriers to electron transfer and electronic delocalization",
abstract = "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.",
author = "Hupp, {Joseph T} and Williams, {R. D.}",
year = "2001",
doi = "10.1021/ar9602720",
language = "English",
volume = "34",
pages = "808--817",
journal = "Accounts of Chemical Research",
issn = "0001-4842",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Using resonance Raman spectroscopy to examine vibrational barriers to electron transfer and electronic delocalization

AU - Hupp, Joseph T

AU - Williams, R. D.

PY - 2001

Y1 - 2001

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0034772587&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034772587&partnerID=8YFLogxK

U2 - 10.1021/ar9602720

DO - 10.1021/ar9602720

M3 - Article

VL - 34

SP - 808

EP - 817

JO - Accounts of Chemical Research

JF - Accounts of Chemical Research

SN - 0001-4842

IS - 10

ER -