Dynamics of the reaction between the free end of a tethered self-avoiding polymer and a flat penetrable surface: a...

The average time τr for one end of a long, self-avoiding polymer to interact for the first time with a flat penetrable surface to which it is attached at the other end is shown here to scale essentially as the square of the chain's contour length N. This result is obtained within the framework of the Wilemski-Fixman approximation to diffusion-limited reactions, in which the reaction time is expressed as a time correlation function of a "sink" term. In the present work, this sink-sink correlation function is calculated using perturbation expansions in the excluded volume and the polymer-surface interactions, with renormalization group methods being used to resum the expansion into a power law form. The quadratic dependence of τr on N mirrors the behavior of the average time τc of a free random walk to cyclize, but contrasts with the cyclization time of a free self-avoiding walk (SAW), for which τr ∼ N(2.2). A simulation study by Cheng and Makarov [J. Phys. Chem. B 114, 3321 (2010)] of the chain-end reaction time of an SAW on a flat impenetrable surface leads to the same N(2.2) behavior, which is surprising given the reduced conformational space a tethered polymer has to explore in order to react.