Russell, B. A. et al. (2023) A second glass transition observed in single-component homogeneous liquids due to intramolecular vitrification. Journal of the American Chemical Society, 145(48), pp. 26061-26067. (doi: 10.1021/jacs.3c07110) (PMID:37978954) (PMCID:PMC10704603)
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Abstract
On supercooling a liquid, the viscosity rises rapidly until at the glass transition it vitrifies into an amorphous solid accompanied by a steep drop in the heat capacity. Therefore, a pure homogeneous liquid is not expected to display more than one glass transition. Here we show that a family of single-component homogeneous molecular liquids, titanium tetraalkoxides, exhibit two calorimetric glass transitions of comparable magnitude, one of which is the conventional glass transition associated with dynamic arrest of the bulk liquid properties, while the other is associated with the freezing out of intramolecular degrees of freedom. Such intramolecular vitrification is likely to be found in molecules in which low-frequency terahertz intramolecular motion is coupled to the surrounding liquid. These results imply that intramolecular barrier-crossing processes, typically associated with chemical reactivity, do not necessarily follow the Arrhenius law but may freeze out at a finite temperature.
| Item Type: | Articles |
|---|---|
| Additional Information: | K.W. acknowledges funding by a grant from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement no. 832703) and the Engineering and Physical Sciences Research Council (EPSRC) for support through grant EP/N007417/1. K.W. and H.M.S. acknowledge funding by Leverhulme Trust Research Project Grant RPG-2018-350. U.J. and G.M. acknowledge financial support from the Slovenian Research Agency (projectI0-0003). L.H. thanks the Carnegie Trust for a Carnegie Vacation Scholarship. We acknowledge the University of Glasgow for funding and the award of a College of Science and Engineering Ph.D. Scholarshipto T.C. |
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Russell, Dr Ben and Senn, Dr Hans and Farnaby, Dr Joy and Tukachev, Mr Nikita and Wynne, Professor Klaas and Chowdhury, Mr Tajrian and Hayes, Laure-Anne and Gonzalez Jimenez, Dr Mario |
| Authors: | Russell, B. A., González-Jiménez, M., Tukachev, N. V.,, Hayes, L.-A., Chowdhury, T., Javornik, U., Mali, G., Tassieri, M., Farnaby, J. H., Senn, H. M., and Wynne, K. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Journal of the American Chemical Society |
| Publisher: | American Chemical Society |
| ISSN: | 0002-7863 |
| ISSN (Online): | 1520-5126 |
| Published Online: | 18 November 2023 |
| Copyright Holders: | Copyright © 2023 The Authors |
| First Published: | First published in Journal of the American Chemical Society 145(48):26061-26067 |
| Publisher Policy: | Reproduced under a Creative Commons license |
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