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Determination of the bimolecular rate constant of photoinduced charge separation in the energy gap region where the reaction is diffusion controlled — analysis of the transient effect in the course of fluorescence quenching reaction

Authors
Journal
Chemical Physics Letters
0009-2614
Publisher
Elsevier
Publication Date
Volume
185
Identifiers
DOI: 10.1016/s0009-2614(91)85054-z

Abstract

Abstract The photoinduced intermolecular charge separation (CS) rate constant ( k CS) at the encounter in acetonitrile solution has been evaluated for various donor—acceptor pairs by analyzing the transient effect in the fluorescence decay curves, in the energy gap region −Δ G 0=0.37–2.21 eV, where the reaction is diffusion controlled. Although the obtained k CS values are larger than the diffusion rate constant, they do not show the typical bell-shaped −Δ G 0 dependence as observed in the charge recombination reaction of the geminate ion pairs produced by fluorescence quenching reaction, but show a rather flat shape.

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