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.