Thermophoresis of Polymers: Nondraining vs Draining Coil

Present theories for the thermophoretic mobility of polymers in dilute solution without long-ranged electrostatic interaction are based on a draining coil model with short-ranged segment–solvent interaction. We show that the characteristic thermophoretic interaction decays as r –2 with the distance from the chain segment, which is of much longer range than the underlying rapidly decaying binary van der Waals interaction (∝ r –6). As a consequence, thermophoresis on the monomer level is governed by volume forces, resulting in hydrodynamic coupling between the chain segments. The inner parts of the nondraining coil do not actively participate in thermophoresis. The flow lines penetrate only into a thin surface layer of the coil and cause tangential stresses along the surface of the entire coil, not the individual segments. This model is motivated by recent experimental findings for thermoresponsive polymers and core–shell particles, and it explains the well-known molar mass independent thermophoretic mobility of polymers in dilute solution.