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Fluorescence depolarization by electronic energy transfer in donor-acceptor pairs of like and unlike chromophores

Fluorescence depolarization by energy transfer resulting from dipole–dipole interaction (Förster type) is studied in donor–acceptor pairs of like and unlike chromophores at a fixed distance and with random and uncorrelated static orientations. For unlike chromophores, the acceptor anisotropy decay i...

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Bibliographic Details
Published in:The Journal of chemical physics 1991-12, Vol.95 (11), p.8048-8055
Main Authors: BERBERAN-SANTOS, M. N, VALEUR, B
Format: Article
Language:English
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Summary:Fluorescence depolarization by energy transfer resulting from dipole–dipole interaction (Förster type) is studied in donor–acceptor pairs of like and unlike chromophores at a fixed distance and with random and uncorrelated static orientations. For unlike chromophores, the acceptor anisotropy decay is shown to display three different extreme types of behavior. When the intrinsic decay rate of the acceptor is much faster than both the transfer rate and the donor intrinsic decay rate, the acceptor anisotropy decays from a positive value, then rises and passes through a maximum, and finally tends to a negative limiting value, yielding a zero steady-state value. The existence of a maximum is shown to be due to the peculiar relation between the orientation factor and the average angle formed by the donor and acceptor transition moments. For pairs of like chromophores, the exact anisotropy is calculated and compared with that given by an approximate treatment. It is also shown that the anisotropy of the indirectly excited partner varies with time, tending to zero, in contradiction to previous work, where it is reported to be 4% of that of the directly excited chromophore.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.461285