Single molecule demonstration of Debye-Stokes-Einstein breakdown in polystyrene near the glass transition temperature

Rotational-translational decoupling, in which translational motion is apparently enhanced over rotational motion in violation of Stokes-Einstein (SE) and Debye-Stokes-Einstein (DSE) predictions, has been observed in materials near their glass transition temperatures (T_g). This has been posited to result from ensemble averaging in the context of dynamic heterogeneity. In this work, ensemble and single molecule experiments are performed in parallel on a fluorescent probe in high molecular weight polystyrene near its T_g. Ensemble results show decoupling onset at approximately 1.15T_g, increasing to over three orders of magnitude at T_g. Single molecule measurements also show a high degree of decoupling, with typical molecules at T_g showing translational diffusion coefficients nearly 400 times higher than expected from SE/DSE predictions. At the single molecule level, higher degree of breakdown is associated with particularly mobile molecules and anisotropic trajectories, providing support for anomalous diffusion as a critical driver of rotational-translational decoupling and SE/DSE breakdown.