Glassy dynamics in polyalcohols: intermolecular simplicity vs. intramolecular complexity.

Autor: Böhmer T; Institute for Condensed Matter Physics, Technical University Darmstadt, Darmstadt, Germany. till.boehmer@pkm.tu-darmstadt.de., Gabriel JP; Glass and Time, IMFUFA, Department of Science and Environment, Roskilde University, Roskilde, Denmark., Zeißler R; Institute for Condensed Matter Physics, Technical University Darmstadt, Darmstadt, Germany. till.boehmer@pkm.tu-darmstadt.de., Richter T; Institute for Condensed Matter Physics, Technical University Darmstadt, Darmstadt, Germany. till.boehmer@pkm.tu-darmstadt.de., Blochowicz T; Institute for Condensed Matter Physics, Technical University Darmstadt, Darmstadt, Germany. till.boehmer@pkm.tu-darmstadt.de.
Jazyk: angličtina
Zdroj: Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2022 Aug 03; Vol. 24 (30), pp. 18272-18280. Date of Electronic Publication: 2022 Aug 03.
DOI: 10.1039/d2cp01969h
Abstrakt: 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 ω -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.
Databáze: MEDLINE