The effects of chain conformations on the thermodynamics of polymeric systems: A mean-field theory

Many popular models for macromolecular system thermodynamics, such as the Flory model, assume that chain conformations decouple from system thermodynamics even though it is well known that these two factors are intimately connected. Here we present a single-chain–based, mean-field model that explicitly incorporates the coupling between the conformations of the chains and the thermodynamic behavior of the polymer solutions. The theory predicts a variation of chain conformation and system thermodynamics with polymer concentration, even for athermal solutions, in reasonable agreement with Monte Carlo simulations.