Thermodynamic insights into polyelectrolyte complexation: A theoretical framework

In this study, we propose a theoretical framework to explore the interactions between flexible polymer chains, specifically polyelectrolytes (PEs). Our analysis reaffirms that the thermodynamic drive for complex coacervation is influenced by key factors such as the number of ions bound to the polymer backbone and the entropy associated with free ions. By calculating the free energy of the system while considering position-dependent mutual interactions and chain conformations, we gain valuable insights into the local dielectricity as PEs overlap. Our findings indicate that global thermodynamic behavior is significantly shaped by local factors such as dielectric constant, providing an explanation for the discrepancies observed between experimental and computational studies. In addition, we found that entropy gain is inversely proportional to the local dielectric constant, provided that the electrostatic temperature remains constant. This relationship underscores the importance of polymer-specific parameters when examining the thermodynamic behavior of charged polymer complexation.