Free Energy Profiles of Water Confined between Hydrophobic Surfaces with Grafted Polymeric Segments: A Molecular Simulation Study

Many naturally occurring particles have dangling polymeric segments on their surfaces, which play an important role in their self-assembly. We have investigated the effect of grafted polymeric segments on the behavior of confined water using molecular simulations. Our results show that the presence of polymeric segments has a significant effect on the condensation free energy barrier but has little effect on the evaporation free energy barrier of confined water. Furthermore, we find that the flexibility of the polymeric segments does not affect the free energy profiles of confined water. We invoke macroscopic thermodynamic theory to explain our simulation results.