Semiflexible polymers confined in a slit pore with attractive walls: two-dimensional liquid crystalline order versus capillary nematization.
Semiflexible polymers under good solvent conditions interacting with attractive planar surfaces are investigated by Molecular Dynamics (MD) simulations and classical Density Functional Theory (DFT). A bead-spring type potential complemented by a bending potential is used, allowing variation of chain stiffness from completely flexible coils to rod-like polymers whose persistence length by far exceeds their contour length. Solvent is only implicitly included, monomer-monomer interactions being purely repulsive, while two types of attractive wall-monomer interactions are considered: (i) a strongly attractive Mie-type potential, appropriate for a strictly structureless wall, and (ii) a corrugated wall formed by Lennard-Jones particles arranged on a square lattice. It is found that in dilute solutions the former case leads to the formation of a strongly adsorbed surface layer, and the profile of density and orientational order in the z-direction perpendicular to the wall is predicted by DFT in nice agreement with MD. While for very low bulk densities a Kosterlitz-Thouless type transition from the isotropic phase to a phase with power-law decay of nematic correlations is suggested to occur in the strongly adsorbed layer, for larger densities a smectic-C phase in the surface layer is detected. No "capillary nematization" effect at higher bulk densities is found in this system, unlike systems with repulsive walls. This finding is attributed to the reduction of the bulk density (in the center of the slit pore) due to polymer adsorption on the attractive wall, for a system studied in the canonical ensemble. Consequently in a system with two attractive walls nematic order in the slit pore can occur only at a higher density than for a bulk system.
Institute for Physical Chemistry, Bulgarian Academia of Sciences, 1113 Sofia, Bulgaria. milchev@ipc.bas.bg and Institut für Physik, Johannes Gutenberg Universität Mainz, 55099 Mainz, Germany.
Andrey
http://orcid.org/0000-0003-1991-0648
A
Milchev
Institut für Physik, Johannes Gutenberg Universität Mainz, 55099 Mainz, Germany and Department of Chemistry, University of Virginia, Charlottesville, VA 22901, USA.
Sergei A
SA
Egorov
Institut für Physik, Johannes Gutenberg Universität Mainz, 55099 Mainz, Germany.
Kurt
K
Binder