Mode-specific vibrational reorganization energies accompanying photoinduced electron transfer in the hexamethylbenzene/tetracyanoethylene charge-transfer complex

Frances Markel, Nancy S. Ferris, Ian R. Gould, Ian Gould

Research output: Contribution to journalArticle

174 Citations (Scopus)

Abstract

Resonance Raman excitation profiles have been measured across the broad, intense charge-transfer absorption band of the hexamethylbenzene/tetracyanoethyiene complex in CCl4 solution. Nonresonant Raman spectra of the complex and its perdeuterated derivative in the solid state have also been obtained with excitation at 1064 nm. Absorption of light within the charge-transfer band results in electron transfer from hexamethylbenzene to tetracyanoethylene to form a radical-ion pair. The geometry change along each vibrational mode as a result of this photoinduced electron transfer and the accompanying internal reorganization energies have been determined through quantitative simulation of the absorption spectrum and absolute resonance Raman intensities using time-dependent wavepacket propagation methods. The largest individual contributions to the total measured reorganization energy of approximately 3500 cm-1 arise from the presumed donor-acceptor intermolecular stretching mode at 165 cm-1 and the C=C stretch of tetracyanoethylene at 1551 cm-1 with smaller contributions from other modes localized on both tetracyanoethylene and hexamethylbenzene. The importance of these results for understanding trends in the rates of nonphotochemical return electron transfer is discussed.

Original languageEnglish (US)
Pages (from-to)6208-6219
Number of pages12
JournalJournal of the American Chemical Society
Volume114
Issue number15
StatePublished - 1992
Externally publishedYes

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Charge transfer
Electrons
Absorption spectra
Stretching
Raman scattering
Ions
Derivatives
Light
Geometry
tetracyanoethylene
hexamethylbenzene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Mode-specific vibrational reorganization energies accompanying photoinduced electron transfer in the hexamethylbenzene/tetracyanoethylene charge-transfer complex. / Markel, Frances; Ferris, Nancy S.; Gould, Ian R.; Gould, Ian.

In: Journal of the American Chemical Society, Vol. 114, No. 15, 1992, p. 6208-6219.

Research output: Contribution to journalArticle

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N2 - Resonance Raman excitation profiles have been measured across the broad, intense charge-transfer absorption band of the hexamethylbenzene/tetracyanoethyiene complex in CCl4 solution. Nonresonant Raman spectra of the complex and its perdeuterated derivative in the solid state have also been obtained with excitation at 1064 nm. Absorption of light within the charge-transfer band results in electron transfer from hexamethylbenzene to tetracyanoethylene to form a radical-ion pair. The geometry change along each vibrational mode as a result of this photoinduced electron transfer and the accompanying internal reorganization energies have been determined through quantitative simulation of the absorption spectrum and absolute resonance Raman intensities using time-dependent wavepacket propagation methods. The largest individual contributions to the total measured reorganization energy of approximately 3500 cm-1 arise from the presumed donor-acceptor intermolecular stretching mode at 165 cm-1 and the C=C stretch of tetracyanoethylene at 1551 cm-1 with smaller contributions from other modes localized on both tetracyanoethylene and hexamethylbenzene. The importance of these results for understanding trends in the rates of nonphotochemical return electron transfer is discussed.

AB - Resonance Raman excitation profiles have been measured across the broad, intense charge-transfer absorption band of the hexamethylbenzene/tetracyanoethyiene complex in CCl4 solution. Nonresonant Raman spectra of the complex and its perdeuterated derivative in the solid state have also been obtained with excitation at 1064 nm. Absorption of light within the charge-transfer band results in electron transfer from hexamethylbenzene to tetracyanoethylene to form a radical-ion pair. The geometry change along each vibrational mode as a result of this photoinduced electron transfer and the accompanying internal reorganization energies have been determined through quantitative simulation of the absorption spectrum and absolute resonance Raman intensities using time-dependent wavepacket propagation methods. The largest individual contributions to the total measured reorganization energy of approximately 3500 cm-1 arise from the presumed donor-acceptor intermolecular stretching mode at 165 cm-1 and the C=C stretch of tetracyanoethylene at 1551 cm-1 with smaller contributions from other modes localized on both tetracyanoethylene and hexamethylbenzene. The importance of these results for understanding trends in the rates of nonphotochemical return electron transfer is discussed.

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