The energetic requirements for electron transfer to the conduction
band of silver bromide from a series of
cyanine dyes have been studied using both picosecond time-resolved and
steady state fluorescence techniques.
The selected dyes exhibit monomeric absorption spectra in the
adsorbed state and have excited state donor
energies that are calculated to span a range about the conduction band
edge of AgBr. Rate constants and
yields for these electron transfers were extracted from the picosecond
fluorescence lifetime measurements.
Yields were also obtained through independent measurements of the
steady state fluorescence of these dyes
and were correlated with estimates of the free energy of the reaction
to depict a threshold for electron transfer
with respect to the conduction band of AgBr. The threshold
compares well with model curves from electron
transfer theory and with literature reports of photographic relative
quantum yield measurements on similar
monomeric systems at silver halide surfaces. This correlation
supports the electron transfer model for spectral
sensitization of the silver halides. Contrasts are drawn with the
sharp energetic thresholds expected for
aggregated dyes.
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