Simulation of the Coronal Dynamics of Polymer-Grafted Nanoparticles.

Polymer-grafted nanoparticles (PGNPs) are an important component of many advanced materials. The interplay between the nanoparticle surface curvature and spatial confinement by neighboring chains produces a complex set of structural and dynamical behaviors in the polymer corona surrounding the nanoparticle. For example, experiments have shown that the inner portion of the corona is more stretched and relaxes more slowly than the outer region. Here, we perform systematic core-modified dissipative particle dynamics (CM-DPD) simulations and analyze the relaxation dynamics using proper orthogonal decomposition (POD) of the monomer coordinates. We find that grafted chains relax more slowly than free chains and that the relaxation time of the grafted chains scales inversely with the confinement strength. For PGNPs in a polymer melt, the relaxation processes are always Rouse-like. However, we observe either Zimm-like or Rouse-like dynamics for PGNPs in solution depending on the confinement strength.