Anomalous Translational Dynamics of Molecular Probes Near the Polymer Glass Transition

Abstract

The origin of the dramatic slowdown of dynamics near the glass transition temperature (Tg) remains a long-standing fundamental and unresolved issue in soft condensed matter. While single-molecule (SM) experiments using fluorescent probes have provided critical insight for molecular and polymeric glass formers through rotational measurements, translational dynamics remain largely unexplored in such systems at the molecular length scale. Here, we report SM translational dynamics of molecular probes in high molecular weight polystyrene at three temperatures near Tg. The probes exhibit quasi-stationary position fluctuations, non-Gaussian displacement distributions, sub-diffusive transport with anti-correlated displacements, and a characteristic translational relaxation time. The observations are quantitatively described using a microscopic framework based on the generalized Langevin equation and supported by numerical modeling for heterogeneous transport. The translational dynamics of the probes provides direct microscopic evidence of dynamic heterogeneity and suggests a pathway to more fully understand glassy dynamics in glass formers near Tg.

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