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Название: Diffusion-Influenced Reactions
Автор: Cukier R.I.
We summarize three of our recent results on diffusion-influenced reactions in solutions. All deal with the concentration dependence of the reaction rate when the reactants must first diffuse together before reaction can occur. When one species (the sink species) is not dilute, the rate cannot be obtained by solution of a pair diffusion equation; the correlations among the sinks for the diffusing species must be accounted for. First, we consider fluorescence quenching when the quenchers are not dilute. For charged quenchers and fluorophores we discuss how the solution dielectric constant and ionic strength can strongly influence the deviations from the linear Stern-Volmer behavior (the dilute sink result) which arise due to the sink correlations. Second, we consider heterogeneous catalysis where a reactive species is adsorbed onto a surface and must surface diffuse to reactive sites (the sinks). We find that surface diffusion can be an important factor contributing to the rate of reaction; especially when surface diffusion is rapid relative to the adsorption/desorption rate. Third, we discuss diffusion influenced reactions with sinks which are long ellipsoids. Dilute long ellipsoids provide a large rate enhancement relative to a spherical sink; we show that this rate enhancement survives when nondilute ellipsoids are considered.