Absorption, fluorescence, and resonance Raman spectroscopy of the hexamethylbenzene/tetracyanoethylene charge-transfer complex: Toward a self-consistent model

Kristen Kulinowski, Ian R. Gould, Anne B. Myers

Research output: Contribution to journalArticle

121 Scopus citations

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
DOIs
StatePublished - 1995
Externally publishedYes

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Absorption, fluorescence, and resonance Raman spectroscopy of the hexamethylbenzene/tetracyanoethylene charge-transfer complex: Toward a self-consistent model'. Together they form a unique fingerprint.

  • Cite this