Energy barriers and cooperative motion at the surface of freestanding glassy polystyrene films

We investigate the near-surface relaxation of freestanding atactic polystyrene films with molecular dynamics simulations. As in previous coarse-grained simulations, relaxation times for backbone segments and phenyl rings are linked to their bulk relaxation times via a power-law coupling relation. Variation of the coupling exponent with distance from the surface is consistent with depth-dependent activation barriers. We also quantify a reduction in dynamical heterogeneity at the interface, which can be interpreted in the framework of cooperative models for glassy dynamics.