Semiflexible Polymers Under Good Solvent Conditions Interacting With Repulsive Walls

TL;DR

This study investigates how semiflexible polymers behave near repulsive walls under good solvent conditions, revealing how chain stiffness influences surface tension, monomer distribution, and nematic ordering through theoretical and simulation methods.

Contribution

It provides new insights into the interplay between chain stiffness, confinement, and surface effects in semiflexible polymer solutions using combined density functional theory and molecular dynamics simulations.

Findings

Surface tension increases with chain stiffness.

Stiffer polymers show greater enrichment of chain ends near the wall.

Wall-induced nematic order depends on chain stiffness and confinement.

Abstract

Solutions of semiflexible polymers confined by repulsive planar walls are studied by density functional theory and Molecular Dynamics simulations, to clarify the competition between the chain alignment favored by the wall and the depletion caused by the monomer-wall repulsion. A coarse-grained bead-spring model with bond bending potential is studied, varying both the contour length and the persistence length of the polymers, as well as the monomer concentration in the solution (good solvent conditions are assumed throughout, and solvent molecules are not included explicitly). The profiles of monomer density and pressure tensor components near the wall are studied, and the surface tension of the solution is obtained. While the surface tension slightly decreases with chain length for flexible polymers, it clearly increases with chain length for stiff polymers. Thus, at fixed density and fixed chain length the surface tension also increases with increasing persistence length. Chain ends always are enriched near the wall, but this effect is much larger for stiff polymers than for flexible ones. Also the profiles of the mean square gyration radius components near the wall and the nematic order parameter are studied to clarify the conditions where wall-induced nematic order occurs.