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Title: Disconnecting structure and dynamics in glassy thin films

Abstract

Nanometrically thin glassy films depart strikingly from the behavior of their bulk counterparts. We investigate whether the dynamical differences between a bulk and thin film polymeric glass former can be understood by differences in local microscopic structure. Machine learning methods have shown that local structure can serve as the foundation for successful, predictive models of particle rearrangement dynamics in bulk systems. By contrast, in thin glassy films, we find that particles at the center of the film and those near the surface are structurally indistinguishable despite exhibiting very different dynamics. Next, we show that structure-independent processes, already present in bulk systems and demonstrably different from simple facilitated dynamics, are crucial for understanding glassy dynamics in thin films. Our analysis suggests a picture of glassy dynamics in which two dynamical processes coexist, with relative strengths that depend on the distance from an interface. Here, one of these processes depends on local structure and is unchanged throughout most of the film, while the other is purely Arrhenius, does not depend on local structure, and is strongly enhanced near the free surface of a film.

Authors:
 [1]; ORCiD logo [2];  [3];  [4]
  1. Syracuse Univ., Syracuse, NY (United States)
  2. Google, Mountain View, CA (United States)
  3. Stanford Univ., Stanford, CA (United States)
  4. Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1540262
Grant/Contract Number:  
[FG02-05ER46199]
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
[ Journal Volume: 114; Journal Issue: 40]; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Science & Technology; Other Topics; machine learning; glass; thin film

Citation Formats

Sussman, Daniel M., Schoenholz, Samuel S., Cubuk, Ekin D., and Liu, Andrea J. Disconnecting structure and dynamics in glassy thin films. United States: N. p., 2017. Web. doi:10.1073/pnas.1703927114.
Sussman, Daniel M., Schoenholz, Samuel S., Cubuk, Ekin D., & Liu, Andrea J. Disconnecting structure and dynamics in glassy thin films. United States. doi:10.1073/pnas.1703927114.
Sussman, Daniel M., Schoenholz, Samuel S., Cubuk, Ekin D., and Liu, Andrea J. Tue . "Disconnecting structure and dynamics in glassy thin films". United States. doi:10.1073/pnas.1703927114. https://www.osti.gov/servlets/purl/1540262.
@article{osti_1540262,
title = {Disconnecting structure and dynamics in glassy thin films},
author = {Sussman, Daniel M. and Schoenholz, Samuel S. and Cubuk, Ekin D. and Liu, Andrea J.},
abstractNote = {Nanometrically thin glassy films depart strikingly from the behavior of their bulk counterparts. We investigate whether the dynamical differences between a bulk and thin film polymeric glass former can be understood by differences in local microscopic structure. Machine learning methods have shown that local structure can serve as the foundation for successful, predictive models of particle rearrangement dynamics in bulk systems. By contrast, in thin glassy films, we find that particles at the center of the film and those near the surface are structurally indistinguishable despite exhibiting very different dynamics. Next, we show that structure-independent processes, already present in bulk systems and demonstrably different from simple facilitated dynamics, are crucial for understanding glassy dynamics in thin films. Our analysis suggests a picture of glassy dynamics in which two dynamical processes coexist, with relative strengths that depend on the distance from an interface. Here, one of these processes depends on local structure and is unchanged throughout most of the film, while the other is purely Arrhenius, does not depend on local structure, and is strongly enhanced near the free surface of a film.},
doi = {10.1073/pnas.1703927114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = [40],
volume = [114],
place = {United States},
year = {2017},
month = {9}
}

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