Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Comparison of Alternate Approaches for Reversible Geminate Recombination

  • Khokhlova, Svetlana S. (The Fritz Haber Research Center, Institute of Chemistry, The Hebrew University of Jerusalem) ;
  • Agmon, Noam (The Fritz Haber Research Center, Institute of Chemistry, The Hebrew University of Jerusalem)
  • Received : 2011.12.07
  • Accepted : 2012.01.20
  • Published : 2012.03.20
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Abstract

This work compares various models for geminate reversible diffusion influenced reactions. The commonly utilized contact reactivity model (an extension of the Collins-Kimball radiation boundary condition) is augmented here by a volume reactivity model, which extends the celebrated Feynman-Kac equation for irreversible depletion within a reaction sphere. We obtain the exact analytic solution in Laplace space for an initially bound pair, which can dissociate, diffuse or undergo "sticky" recombination. We show that the same expression for the binding probability holds also for "mixed" reaction products. Two different derivations are pursued, yielding seemingly different expressions, which nevertheless coincide numerically. These binding probabilities and their Laplace transforms are compared graphically with those from the contact reactivity model and a previously suggested coarse grained approximation. Mathematically, all these Laplace transforms conform to a single generic equation, in which different reactionless Green's functions, g(s), are incorporated. In most of parameter space the sensitivity to g(s) is not large, so that the binding probabilities for the volume and contact reactivity models are rather similar.

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