We present the results of dielectric measurements for three sizable glass-formers with identical nonpolar cores linked to various dipole-labeled rotors that shed new light on the picture of reorientation of anisotropic systems with significant moment of inertia revealed by broadband dielectric spectroscopy. The dynamics of sizable glass-formers formed by partially rigid molecular cores linked to small polar rotors in many respects differs from that of typical glass-formers. For instance, the extraordinarily large prefactors (τ > 10 s) in the Vogel-Fulcher-Tammann equation were found. The rich and highly diverse relaxation pattern was governed by the location of a dipole, its ability to rotate freely, and the degree of coupling to the motion of the entire sizable system.
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http://dx.doi.org/10.1021/acs.jpclett.1c03088 | DOI Listing |
J Chem Phys
August 2024
August Chełkowski Institute of Physics, University of Silesia, 75 Pulku Piechoty 1, 41-500 Chorzow, Poland.
Sizable glass formers feature numerous unique properties and potential applications, but many questions regarding their glass transition dynamics have not been resolved yet. Here, we have analyzed structural relaxation times measured as a function of temperature and pressure in combination with the equation of state obtained from pressure-volume-temperature measurements. Despite evidence from previous dielectric studies indicating a remarkable sensitivity of supercooled dynamics to compression, and contrary to intuition, our results demonstrated the proof for the almost equivalent importance of thermal energy and free volume fluctuations in controlling reorientation dynamics of sizable molecules.
View Article and Find Full Text PDFJ Phys Chem Lett
November 2021
August Chełkowski Institute of Physics, University of Silesia, 75 Pulku Piechoty 1, 41-500 Chorzow, Poland.
We present the results of dielectric measurements for three sizable glass-formers with identical nonpolar cores linked to various dipole-labeled rotors that shed new light on the picture of reorientation of anisotropic systems with significant moment of inertia revealed by broadband dielectric spectroscopy. The dynamics of sizable glass-formers formed by partially rigid molecular cores linked to small polar rotors in many respects differs from that of typical glass-formers. For instance, the extraordinarily large prefactors (τ > 10 s) in the Vogel-Fulcher-Tammann equation were found.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2021
August Chełkowski Institute of Physics, University of Silesia, 75 Pulku Piechoty 1, 41-500 Chorzow, Poland.
In this Letter we report significant differences in the dielectric behavior of four nonpolymeric and sizable glass-forming molecules with related chemical structures. They belong to the recently constituted class of sizable glass-formers [Jedrzejowska et al. 2020, 101, 010603], for which the pattern of change in dielectric properties with structure has not yet been fully discovered.
View Article and Find Full Text PDFPhys Rev E
January 2020
Institute of Physics, University of Silesia, 75 Pulku Piechoty 1, 41-500 Chorzow, Poland.
In this Rapid Communication we report the unusual dynamics of planar, rigid, and anisotropy glass-forming molecules of unusually large size by dielectric spectroscopy by using two examples. The size of the molecules is much larger than the dipolar moiety located at the end of the longer axis of each molecule. The observed dynamics deviates strongly from the anticorrelation between β_{KWW} (fractional exponent of the Kohlrausch-Williams-Watts function) and dielectric strength, Δɛ(T_{g}), established generally for small van der Waals molecular glass formers.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
October 2014
Laboratoire de Physique Théorique, Ecole Normale Supérieure, UMR 8549 CNRS, 75005 Paris, France.
One of the most actively debated issues in the study of the glass transition is whether a mean-field description is a reasonable starting point for understanding experimental glass formers. Although the mean-field theory of the glass transition--like that of other statistical systems--is exact when the spatial dimension d → ∞, the evolution of systems properties with d may not be smooth. Finite-dimensional effects could dramatically change what happens in physical dimensions,d = 2, 3.
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