Glassy dynamics in polyalcohols: intermolecular simplicity vs. intramolecular complexity. Issue 30 (26th July 2022)

• Record Type: Journal Article
• Authors: Böhmer, Till; Gabriel, Jan Philipp; Zeißler, Rolf; Richter, Timo; Blochowicz, Thomas
• Is Part Of: Physical chemistry chemical physics. Volume 24:Issue 30(2022)
• Page Start: 18272
• Page End: 18280
• Publication Date: 2022-07-26
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d2cp01969h
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : We show that intramolecular dynamics can induce significant broadening of the spectral shape of the α-process in polyalcohols (PAs). The effect is only observed in long-chained PAs, like sorbitol, and is absent in short-chained PAs, like glycerol. 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 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.