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

Nature Physics volume 19, pages 800–806 (2023)Cite this article

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Abstract

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.

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Fig. 1: Simulation and theory of normalized dynamical gradients of the shift of the glass transition temperature and alpha relaxation time relative to the bulk.
Fig. 2: Schematic of the film and key concepts of ECNLE theory, where ‘layers’ are shown only for illustrative reasons and density is homogeneous in all directions within the film.
Fig. 3: Theoretical predictions for the fractional and normalized deviations from bulk of multiple dynamical properties as a function of distance from the vapour interface.

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Data availability

All relevant data are included in the paper and/or its Supplementary Information files. Raw simulation trajectory files, which are prohibitively large, are available upon reasonable request from D.S.S.

Code availability

All results in this paper employed openly available codes and/or standard numerical algorithms.

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Acknowledgements

D.S.S. and A.G. have been supported by the National Science Foundation (NSF) CAREER Award under grant no. DMR-1849594.

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Authors and Affiliations

  1. Department of Chemical, Biological and Materials Engineering, University of South Florida, Tampa, FL, USA

    Asieh Ghanekarade & David S. Simmons

  2. Faculty of Materials Science and Engineering, Phenikaa University, Hanoi, Vietnam

    Anh D. Phan

  3. Departments of Materials Science and Chemistry and Materials Research Laboratory, University of Illinois, Urbana, IL, USA

    Kenneth S. Schweizer

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Contributions

The paper and Supplementary Information were written based on the contributions of all authors. A.G. performed all simulations under the supervision of D.S.S. A.G. and D.S.S. jointly conceived of and analysed all simulations. A.D.P. and K.S.S. performed all ECNLE theory analytical analysis and numerical calculations.

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Correspondence to Anh D. Phan, Kenneth S. Schweizer or David S. Simmons.

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Detailed simulation methods, Supplementary Figs. 1–6 and theory details.

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Ghanekarade, A., Phan, A.D., Schweizer, K.S. et al. Signature of collective elastic glass physics in surface-induced long-range tails in dynamical gradients. Nat. Phys. 19, 800–806 (2023). https://doi.org/10.1038/s41567-023-01995-8

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