Glass spectrum, excess wing phenomenon, and master curves in molecular glass formers : A multi-method approach

Titelangaben

Rössler, Ernst A. ; Becher, Manuel:
Glass spectrum, excess wing phenomenon, and master curves in molecular glass formers : A multi-method approach.
In: The Journal of Chemical Physics. Bd. 160 (2024) Heft 7 . - 074501.
ISSN 0021-9606
DOI der Verlagsversion: https://doi.org/10.1063/5.0181187

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Abstract

The relaxation spectra of glass formers solely displaying an α-peak and excess wing contribution collected by various methods are reanalyzed to pin down their different spectral evolution. We show that master curve construction encompassing both α-peak and emerging excess wing works for depolarized light scattering (DLS) and nuclear magnetic resonance (NMR) relaxometry. It reveals the self-part of the slow dynamics’ spectrum. Master curves are to be understood as a result of a more extensive scaling covering all temperatures instead of strict frequency–temperature superposition. DLS and NMR display identical relaxation spectra; yet, comparing different systems, we do not find a generic structural relaxation at variance with recent claims. Dielectric spectroscopy (DS) spectra show particularities, which render master curve construction obsolete. The DS α-peak is enhanced or suppressed with respect to that of DLS or NMR, yet, not correlated to the polarity of the liquid. Attempting to single out the excess wing from the overall spectrum discloses a stronger exponential temperature dependence of its amplitude compared to that below Tg and a link between its exponent and that of the fast dynamics’ spectrum. Yet, such a decomposition of α-peak and excess wing appears to be unphysical. Among many different glasses, the amplitude of the excess wing power-law spectrum is found to be identical at Tg, interpreted as a relaxation analog to the Lindemann criterion.