Absorption, fluorescence, and resonance Raman spectroscopy of the hexamethylbenzene/tetracyanoethylene charge-transfer complex

Toward a self-consistent model

Kristen Kulinowski, Ian Gould, Anne B. Myers

Research output: Contribution to journalArticle

121 Citations (Scopus)

Abstract

The weak, far-red fluorescence spectrum of the hexamethylbenzene/tetracyanoethylene charge-transfer complex has been measured in CCl4 and cyclohexane solvents. The total fluorescence quantum yield in CCl4 with 633 nm excitation is about 5 x 10-5. The absorption spectrum, absolute resonance Raman excitation profiles, and fluorescence spectrum in CCl4 are simulated with a common model that explicitly includes the 11 most strongly Franck-Condon-active internal vibrations as well as the solvent, treated as an overdamped Brownian oscillator. The fits to the data require a large (2450 cm-1) "solvent" reorganization energy, which may involve a combination of true solvent motions and very low-frequency intermolecular complex vibrations. The same model is used to calculate the nonphotochemical return electron-transfer rate and compared with previous measurements of the ion-pair lifetime. This represents the first time, to our knowledge, that all four pieces of data (absorption, fluorescence, Raman, and electron-transfer rate) have been simulated with a common model and compared with experimental results.

Original languageEnglish (US)
Pages (from-to)9017-9026
Number of pages10
JournalJournal of Physical Chemistry
Volume99
Issue number22
StatePublished - 1995
Externally publishedYes

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Raman spectroscopy
Charge transfer
Fluorescence
charge transfer
fluorescence
electron transfer
vibration
very low frequencies
Electrons
Quantum yield
Cyclohexane
cyclohexane
excitation
Absorption spectra
oscillators
Ions
absorption spectra
life (durability)
tetracyanoethylene
hexamethylbenzene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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abstract = "The weak, far-red fluorescence spectrum of the hexamethylbenzene/tetracyanoethylene charge-transfer complex has been measured in CCl4 and cyclohexane solvents. The total fluorescence quantum yield in CCl4 with 633 nm excitation is about 5 x 10-5. The absorption spectrum, absolute resonance Raman excitation profiles, and fluorescence spectrum in CCl4 are simulated with a common model that explicitly includes the 11 most strongly Franck-Condon-active internal vibrations as well as the solvent, treated as an overdamped Brownian oscillator. The fits to the data require a large (2450 cm-1) {"}solvent{"} reorganization energy, which may involve a combination of true solvent motions and very low-frequency intermolecular complex vibrations. The same model is used to calculate the nonphotochemical return electron-transfer rate and compared with previous measurements of the ion-pair lifetime. This represents the first time, to our knowledge, that all four pieces of data (absorption, fluorescence, Raman, and electron-transfer rate) have been simulated with a common model and compared with experimental results.",
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T1 - Absorption, fluorescence, and resonance Raman spectroscopy of the hexamethylbenzene/tetracyanoethylene charge-transfer complex

T2 - Toward a self-consistent model

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AU - Gould, Ian

AU - Myers, Anne B.

PY - 1995

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N2 - The weak, far-red fluorescence spectrum of the hexamethylbenzene/tetracyanoethylene charge-transfer complex has been measured in CCl4 and cyclohexane solvents. The total fluorescence quantum yield in CCl4 with 633 nm excitation is about 5 x 10-5. The absorption spectrum, absolute resonance Raman excitation profiles, and fluorescence spectrum in CCl4 are simulated with a common model that explicitly includes the 11 most strongly Franck-Condon-active internal vibrations as well as the solvent, treated as an overdamped Brownian oscillator. The fits to the data require a large (2450 cm-1) "solvent" reorganization energy, which may involve a combination of true solvent motions and very low-frequency intermolecular complex vibrations. The same model is used to calculate the nonphotochemical return electron-transfer rate and compared with previous measurements of the ion-pair lifetime. This represents the first time, to our knowledge, that all four pieces of data (absorption, fluorescence, Raman, and electron-transfer rate) have been simulated with a common model and compared with experimental results.

AB - The weak, far-red fluorescence spectrum of the hexamethylbenzene/tetracyanoethylene charge-transfer complex has been measured in CCl4 and cyclohexane solvents. The total fluorescence quantum yield in CCl4 with 633 nm excitation is about 5 x 10-5. The absorption spectrum, absolute resonance Raman excitation profiles, and fluorescence spectrum in CCl4 are simulated with a common model that explicitly includes the 11 most strongly Franck-Condon-active internal vibrations as well as the solvent, treated as an overdamped Brownian oscillator. The fits to the data require a large (2450 cm-1) "solvent" reorganization energy, which may involve a combination of true solvent motions and very low-frequency intermolecular complex vibrations. The same model is used to calculate the nonphotochemical return electron-transfer rate and compared with previous measurements of the ion-pair lifetime. This represents the first time, to our knowledge, that all four pieces of data (absorption, fluorescence, Raman, and electron-transfer rate) have been simulated with a common model and compared with experimental results.

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