Polyelectrolyte Complexation of Two Oppositely Charged Symmetric Polymers: A Minimal Theory

Abstract: Interplay of Coulomb interaction energy, free ion entropy, and conformational elasticity is a fascinating aspect in polyelectrolytes (PEs). We develop a theory for complexation of two oppositely charged PEs, a process known to be the precursor to the formation of complex coacervates in PE solutions, to explore the underlying thermodynamics of complex formation, at low salts. Explicit calculation of the free energy of complexation and its components indicates that the entropy of free counterions and salt ions and the Coulomb enthalpy of bound ion-pairs dictate the equilibrium of PE complexation. This helps decouple the self-consistent dependency of charge and size of the uncomplexed parts of the polyions, derive an analytical expression for charge, and evaluate the free energy components as functions of chain overlap. Complexation is observed to be driven by enthalpy gain at low Coulomb strengths, driven by entropy gain of released counterions but opposed by enthalpy loss due to reduction of ion-pairs at moderate Coulomb strengths, and finally prohibited by enthalpy loss at higher Coulomb strengths. Phase diagrams are constructed which identify the stability of fully-, partially- and un-complexed states as functions of electrostatic strength. Thermodynamic predictions from our model are in good quantitative agreement with simulations in literature, and may motivate simulations and experiments at higher electrostatic strengths at which complexation is found to be unfavourable.