Polymer Thermophoresis by Mesoscale Simulations

We employ mesoscopic simulations to study the thermophoretic motion of polymers in a solvent via multiparticle collision dynamics (MPCD). As the usual solvent–monomer collision rules employed in MPCD involving polymers fail to cause thermophoresis, we extend the technique by introducing explicit solvent–monomer interactions, while the solvent molecules remain ideal with respect to one another. We find that with purely repulsive polymer–solvent interaction, the polymer exhibits thermophilic behavior, whereas to display thermophobic behavior, the polymer–solvent potential requires the presence of attractions between solvent particles and monomers, in accordance with previous experimental findings. In addition, we observe that the thermophoretic mobility is independent of polymer length in the observed regime, again in agreement with experiments. Finally, we investigate the thermophoretic behavior of block copolymers, demonstrating that the thermophoretic mobility can be obtained by linear interpolation, weighted by the relative lengths of the two blocks.