Issue 24, 2023

Influence of intramolecular dynamics on the relaxation spectra of simple liquids

Abstract

The shape of the structural relaxation peak in the susceptibility spectra of liquids is of great interest, as it promises to provide information about the distribution of molecular mobilities and dynamic heterogeneity. However, recent studies suggest a generic shape of this peak near the glass transition temperature irrespective of the liquid under investigation, which somehow reduces the information contained in the peak shape. By contrast, at higher temperatures, say, around the melting point, the situation is different and the peak shape varies strongly between different liquids. In this study, we investigate molecules with a ring-tail structure and address the question how intramolecular dynamics influences the peak shape at these temperatures. Using depolarized light scattering and dielectric spectroscopy, we observe a bimodal relaxation, which we attribute to the fact that the reorientation of the ring group to some extent decouples from the rest of the molecule. This shows that the relaxation spectra are sensitive to details of the molecular motions at high temperatures, whereas in the supercooled state this microscopic information seems to give way to a generic shape, probably due to the onset of cooperativity which extends across different intramolecular moieties.

Graphical abstract: Influence of intramolecular dynamics on the relaxation spectra of simple liquids

Article information

Article type
Paper
Submitted
15 Mar 2023
Accepted
31 May 2023
First published
02 Jun 2023
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2023,25, 16380-16388

Influence of intramolecular dynamics on the relaxation spectra of simple liquids

R. Zeißler, F. Pabst, T. Böhmer and T. Blochowicz, Phys. Chem. Chem. Phys., 2023, 25, 16380 DOI: 10.1039/D3CP01172K

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