Molecular modeling of intermolecular and intramolecular excluded volume interactions for polymers at interfaces

摘要

hybrid modeling approach is proposed for inhomogeneous polymer solutions. The method is illustrated for the depletion problem with polymer chains up to N=10~3 segments in semidilute solutions and good solvent conditions. In a three-dimensional volume, a set of freely jointed chains is considered for which the translational degrees of freedom are sampled using a coarse grained Monte Carlo simulation and the conformational degrees of freedom of the chains are computed using a modified self-consistent field theory. As a result, both intramolecular and intermolecular excluded volume effects are accounted for, not only for chains near the surface, but in the bulk as well. Results are consistent with computer simulations and scaling considerations. More specifically, the depletion thickness, which is a measure for the bulk correlation length, scales as δ∝φ~(-0.75) and converges to the mean field result in the concentrated regime.