Signature of collective elastic glass physics in surface-induced long-range tails in dynamical gradients

Large-system molecular dynamics simulations of films of glass-forming polymers reveal spatially long-range tails of interface-driven gradients of the glass transition temperature, suggestive of a combined local caging and long-range collective elasticity origin of relaxation and vitrification in glass-forming liquids. Understanding the underlying nature of dynamical correlations believed to drive the bulk glass transition is a long-standing problem. Here we show that the form of spatial gradients of the glass transition temperature and structural relaxation time near an interface indeed provide signatures of the nature of relaxation in bulk glass-forming liquids. We report the results of long-time, large-system molecular dynamics simulations of thick glass-forming polymer films with one vapour interface, supported on a dynamically neutral substrate. We find that gradients in the glass transition temperature and logarithm of the structural relaxation time nucleated at a vapour interface exhibit two distinct regimes: a medium-ranged, large-amplitude exponential gradient, followed by a long-range slowly decaying tail that can be described by an inverse power law. This behaviour disagrees with multiple proposed theories of glassy dynamics but is predicted by the 'elastically collective nonlinear Langevin equation' theory as a consequence of two coupled mechanisms: a medium-ranged interface-nucleated gradient of surface-modified local caging constraints, and an interfacial truncation of a long-ranged collective elastic field. These findings support a coupled spatially local-nonlocal mechanism of activated glassy relaxation and kinetic vitrification in both the isotropic bulk and in broken-symmetry films.

Automated summary

Large-system molecular dynamics simulations reveal long-range tails of interface-driven gradients of the glass transition temperature in glass-forming polymer films, suggesting a combined local caging and long-range collective elasticity origin of relaxation and vitrification. The spatial gradients of the glass transition temperature and structural relaxation time near an interface provide signatures of relaxation in bulk glass-forming liquids. Thick glass-forming polymer films with one vapour interface exhibited two distinct regimes in the gradients of the glass transition temperature and relaxation time: a medium-ranged, large-amplitude exponential gradient, followed by a long-range tail described by an inverse power law. These findings support a coupled spatially local-nonlocal mechanism of relaxation and vitrification in both bulk and broken-symmetry films.