On the Corrections to Strong-Stretching Theory for End-Confined, Charged Polymers in a Uniform Electric Field

Abstract

We investigate the properties of a system of semi-diluted polymers in the presence of charged groups and counter-ions, by means of self-consistent field theory. We study a system of polyelectrolyte chains grafted to a similarly, as well as an oppositely charged surface, solving a set of saddle-point equations that couple the modified diffusion equation for the polymer partition function to the Poisson-Boltzmann equation describing the charge distribution in the system. A numerical study of this set of equations is presented and comparison is made with previous studies. We then consider the case of semi-diluted, grafted polymer chains in the presence of charge-end-groups. We study the problem with self-consistent field as well as strong-stretching theory. We derive the corrections to the Milner-Witten-Cates (MWC) theory for weakly charged chains and show that the monomer-density deviates from the parabolic profile expected in the uncharged case. The corresponding corrections are shown to be dictated by an Abel-Volterra integral equation of the second kind. The validity of our theoretical findings is confirmed comparing the predictions with the results obtained within numerical self-consistent field theory.