Abstract
A simple theoretical model of the effect of specific ion-pairing with a chemically inert counterion on the rate of intramolecular charge transfer reactions is presented. The counterion motion is treated as corresponding to a separate reaction coordinate on the two-dimensional free energy surface. For the limiting case of strong ion-pairing and low driving force, i.e. | E pair |>;|Δ G 0|> k B T, the dependence of the effect on the donor-acceptor separation, r DA, and on the Δ G 0 of reaction are discussed in detail. In this limit the counterion dynamics effectively controls the rate of the intramolecular electron transfer over a broad range of donor-acceptor distances. For the limiting case of fast counterion motion the analytical relationship between the reorganization energy and activation energy along the Coulomb coordinate of the free energy surface has been derived.
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