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Polyamorphism Mirrors Polymorphism in the Liquid–Liquid Transition of a Molecular Liquid

preprint
revised on 01.04.2020 and posted on 03.04.2020 by Finlay Walton, John Bolling, Andrew Farrell, Jamie MacEwen, Christopher Syme, Mario González Jiménez, Hans Martin Senn, Claire Wilson, Gianfelice Cinque, Klaas Wynne
Liquid-liquid transitions between two amorphous phases in a single-component liquid (polyamorphism) have defied explanation and courted controversy. All known examples of liquid–liquid transitions have been observed in the supercooled liquid 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 to 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 discovery of other examples.

Funding

EPSRC EP/J004812/1

EPSRC EP/J004790/1

EPSRC EP/J009733/1

EPSRC EP/J014478/1

EPSRC EP/N007417/1

Leverhulme Trust RPG-2018-350

ERC Advanced Grant 832703

History

Email Address of Submitting Author

klaas.wynne@glasgow.ac.uk

Institution

University of Glasgow

Country

UK

ORCID For Submitting Author

0000-0002-5305-5940

Declaration of Conflict of Interest

None

Exports