In this paper, we present a self-consistent field theory of macroscopic forces in spatially inhomogeneous flexible chain polyelectrolyte solutions. We derive an analytical expression for a stress tensor which consists of three terms: isotropic hydrostatic stress, electrostatic (Maxwell) stress, and stress rising from conformational entropy of polymer chains—conformational stress. We apply our theory to the description of polyelectrolyte solutions confined in a conductive slit nanopore and observe anomalous behavior of disjoining pressure and electric differential capacitance.

• Received 24 September 2022
• Accepted 1 February 2023

DOI:https://doi.org/10.1103/PhysRevE.107.024503