Field-Theoretic Simulations of Polyelectrolyte Complexation

This viewpoint article is intended as a brief introduction to the emerging subject of field-theoretic simulations (FTS) of charged polymers. While the direct numerical simulation of field theory models has begun to impact several traditional areas of polymer science, including blends and block copolymers, polyelectrolytes have hitherto not been the subject of field-theoretic simulations. Herewe report on a preliminaryFTS study of polyelectrolyte complexation that demonstrates the potential of this novel numerical approach. Polyelectrolytes are ubiquitous in nature and in applications ranging from personal care products to paints, coatings, and processed foods. Indeed, practically all biopolymers are polyelectrolytes. In the application context, the introduction of dissociable groups is one of the most powerful ways to confer water solubility on a polymeric material. Scientifically, the polymer bound charges, which are compensated by a sea of oppositely charged counterions, produce a coupling between chain conformations and electrostatics that leads to an incredible richness of polyelectrolyte phenomena. However, this richness comeswith a price: charged polymers are among the most difficult polymer systems to study theoretically or to simulate on the computer.1–4 The explanation lies in the long