Self-Consistent Field Theory of Polyelectrolyte Systems

Abstract

A self-consistent field theory is applied to inhomogeneous polyelectrolyte systems. We consider the smeared and the annealed charge distributions, corresponding to strongly and weakly dissociating polymers, respectively. The electrostatic interactions are described by the nonlinear Poisson−Boltzmann equation, where the dielectric constant of the system is treated as position-dependent to take into account the large difference between those of hydrophobic polymers and water-like solvents. We present results for several systems, including the interface of a phase-separated polyelectrolyte solution in a poor solvent, the lamellar structures of symmetric diblock polyelectrolytes, and the phase behavior of polyelectrolyte blends.

Confinement free energy of flexible polyelectrolytes in spherical cavities

“…These equations are equivalent to those derived by Shi and Noolandi 35 and Wang et al, 36 although the method of derivation is different as briefly outlined in Appendix A. In these equations, ␤ ͑r͒ and ␤ ͑r͒ are, respectively, the macroscopic number density and the field experienced by particles of type ␤, due to excluded volume interactions.…”

Field‐theoretic simulations of polyelectrolyte complexation

“…17 Polyelectrolytes have been the subject of extensive theoretical and computational research for decades. [1][2][3][4][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] Statistical field theory models have played a significant role in these theoretical investigations, and both mean-field and nonmean-field approaches have been employed to gain insights into the structure and thermodynamics of a wide variety of polyelectrolyte systems. [21][22][23][24][25][26][27][28] Prior to this work, however, there has been no general numerical tool for simulating a field theory model of polyelectrolytes without the use of simplifying approximations.…”

Shape instabilities in adsorbed polymer condensates

“…Our SCF model follows the works of Shi and Noolandi 31 and Wang et al 32 We still utilize the earlier prescription for the polymeric behavior but now have to introduce an additional electric potential, w(r), which incorporates electrostatic effects. It is determined via the Poisson equation but it is important to note that we consider a dielectric constant, e(r), which is a function of position, since we assume a strong segregation between polymer and solvent.…”