Glassy Dynamics in Polyalcohols: Intermolecular Simplicity vs. Intramolecular Complexity

TL;DR

This study investigates how the microscopic origin of relaxation behavior in polyalcohols varies, revealing that intramolecular dynamics can cause deviations from the generic relaxation shape observed in supercooled liquids.

Contribution

It demonstrates that intramolecular dynamics significantly influence relaxation spectra in long-chained polyalcohols, highlighting limitations in observing universal relaxation behavior.

Findings

Short-chained PAs like glycerol follow the generic relaxation shape.

Long-chained PAs like sorbitol show intramolecular dynamic contributions.

The observed relaxation shape depends on whether dynamics reflect intermolecular heterogeneity.

Abstract

Using depolarized light scattering, we have recently shown that structural relaxation in a broad range of supercooled liquids follows, to good approximation, a generic line shape with high-frequency power law $\omega^{-1/2}$. We now continue this study by investigating a systematic series of polyalcohols (PAs), frequently used as model systems in glass-science, i.a., because the width of their respective dielectric loss spectra varies strongly along the series. Our results reveal that the microscopic origin of the observed relaxation behavior varies significantly between different PAs: While short-chained PAs like glycerol rotate as more or less rigid entities and their light scattering spectra follow the generic shape, long-chained PAs like sorbitol display pronounced intramolecular dynamic contributions on the time scale of structural relaxation, leading to systematic deviations from the generic shape. Based on these findings we discuss an important limitation for observing the generic shape in a supercooled liquid: The dynamics that is probed needs to reflect the intermolecular dynamic heterogeneity, and must not be superimposed by effects of intramolecular dynamic heterogeneity.