Polyamorphism mirrors polymorphism in the liquid-liquid transition of a molecular liquid

Walton, F. , Bolling, J., Farrell, A., MacEwen, J., Syme, C. D. , Gonzalez Jimenez, M. , Senn, H. M. , Wilson, C. , Cinque, G. and Wynne, K. (2020) Polyamorphism mirrors polymorphism in the liquid-liquid transition of a molecular liquid. Journal of the American Chemical Society, 142(16), pp. 7591-7597. (doi: 10.1021/jacs.0c01712) (PMID:32249557)

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Abstract

Liquid–liquid transitions between two amorphous phases in a single-component liquid have courted controversy. All known examples of liquid–liquid transitions in molecular liquids have been observed in the supercooled state, suggesting an intimate connection with vitrification and locally favored structures inhibiting crystallization. However, there is precious little information about the local molecular packing in supercooled liquids, meaning that the order parameter of the transition is still unknown. Here, we investigate the liquid–liquid transition in triphenyl phosphite and show that it is caused by the competition between liquid structures that mirror two crystal polymorphs. The liquid–liquid transition is found to be between a geometrically frustrated liquid and a dynamically frustrated glass. These results indicate a general link between polymorphism and polyamorphism and will lead to a much greater understanding of the physical basis of liquid–liquid transitions and allow the systematic discovery of other examples.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Walton, Mr Finlay and Gonzalez Jimenez, Dr Mario and Wilson, Dr Claire and Senn, Dr Hans and Syme, Dr Christopher and Farrell, Andrew and Wynne, Professor Klaas and Bolling, John
Authors: Walton, F., Bolling, J., Farrell, A., MacEwen, J., Syme, C. D., Gonzalez Jimenez, M., Senn, H. M., Wilson, C., Cinque, G., and Wynne, K.
College/School:College of Science and Engineering > School of Chemistry
College of Science and Engineering > School of Engineering > Biomedical Engineering
College of Medical Veterinary and Life Sciences > Institute of Infection Immunity and Inflammation
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Published Online:04 April 2020
Copyright Holders:Copyright © 2020 American Chemical Society
First Published:First published in Journal of the American Chemical Society 142(16): 7591-7597
Publisher Policy:Reproduced under a Creative Commons licence

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