Interfacial mobility scale determines the scale of collective motion and relaxation rate in polymer films.

Thin polymer films are ubiquitous in manufacturing and medical applications, and there has been intense interest in how film thickness and substrate interactions influence film dynamics. It is appreciated that a polymer-air interfacial layer with enhanced mobility plays an important role in the observed changes and recent studies suggest that the length scale ξ of this interfacial layer is related to film relaxation. In the context of the Adam-Gibbs and random first-order transition models of glass formation, these results provide indirect evidence for a relation between ξ and the scale of collective molecular motion. Here we report direct evidence for a proportionality between ξ and the average length L of string-like particle displacements in simulations of polymer films supported on substrates with variable interaction strength and rigidity. This relation explicitly links ξ to the theoretical scale of cooperatively rearranging regions, offering a promising route to experimentally determine this scale of cooperative motion.