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)

[img]
Preview
Text
213422.pdf - Published Version
Available under License Creative Commons Attribution.

4MB

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:Senn, Dr Hans and Syme, Dr Christopher and Farrell, Andrew and Wynne, Professor Klaas and Wilson, Dr Claire and Walton, Mr Finlay and Bolling, John and Gonzalez Jimenez, Dr Mario
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
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

University Staff: Request a correction | Enlighten Editors: Update this record

Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
166308Liquid-liquid transitions in molecular liquids: from supramolecular structure to phase separationKlaas WynneEngineering and Physical Sciences Research Council (EPSRC)EP/J004790/1Chemistry
166776The structure and dynamics of water confined in nanoscale pools: the dynamic crossoverKlaas WynneEngineering and Physical Sciences Research Council (EPSRC)EP/J009733/1Chemistry
190480University of Glasgow - Equipment AccountMuffy CalderEngineering and Physical Sciences Research Council (EPSRC)EP/J014478/1S&E - College Senior Management
172399Mapping and controlling nucleationKlaas WynneEngineering and Physical Sciences Research Council (EPSRC)EP/N007417/1Chemistry
303917Delocalised phonon-like modes in organic and bio-moleculesKlaas WynneLeverhulme Trust (LEVERHUL)RPG-2018-350Chemistry
304469CONTROLKlaas WynneEuropean Commission (EC)832703Chemistry