Band-shape analysis of the charge-transfer fluorescence in barrelene-based electron donor-acceptor compounds

José Cortés, Hans Heitele*, Joshua Jortner

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

141 Scopus citations


In this paper we analyze the band shapes of the stationary fluorescence spectra for the radiative charge transfer recombination D+-A- → D-A + hv in a series of barrelene-based organic bridged donor (D)-acceptor (A) molecules D-A, exploring solvent polarity and temperature effects on the band shape. Free energy changes for charge recombination, medium reorganization energies, and intramolecular reorganization energies (for high- and medium-frequency vibrational modes) were evaluated from the band maximum energies and the full widths at half-maximum and from the fits of standard Franck-Condon factors to the entire fluorescence band shape. Utilization of a single high-frequency intramolecular model (ℏωi = 1300 cm-1) in conjunction with solvent modes provided a satisfactory fit of the band shape; however, such an analysis results in unphysically large medium reorganization energies for nonpolar solvents (0.30-0.45 eV) and their large temperature dependence. The inclusion of medium-frequency (ℏω ≃ 500 cm-1) intramolecular modes in the band-shape analysis is important for the proper distinction between solvent and intramolecular reorganization.

Original languageEnglish
Pages (from-to)2527-2536
Number of pages10
JournalJournal of Physical Chemistry
Issue number10
StatePublished - 1994


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