The order parameter of the liquid-liquid transition in a molecular liquid

Mosses, J., Syme, C. D. and Wynne, K. (2015) The order parameter of the liquid-liquid transition in a molecular liquid. Journal of Physical Chemistry Letters, 6(1), pp. 38-43. (doi: 10.1021/jz5022763)

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Liquid–liquid transitions (LLTs) between amorphous phases of a single (chemically unchanged) liquid were predicted to occur in most molecular liquids but have only been observed in triphenyl phosphite (TPP) and n-butanol, and even these examples have been dismissed as “aborted crystallization”. One of the foremost reasons that LLTs remain so controversial is the lack of an obvious order parameter, that is, a physical parameter characterizing the phase transition. Here, using the technique of fluorescence lifetime imaging, we show for the first time that the LLT in TPP is characterized by a change in polarity linked to changes in molecular ordering associated with crystal polymorphs. We conclude that the LLT in TPP is a phase transition associated with frustrated molecular clusters, explaining the paucity of examples of LLTs seen in nature.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Mosses, Mrs Joanna and Syme, Dr Christopher and Wynne, Professor Klaas
Authors: Mosses, J., Syme, C. D., and Wynne, K.
Subjects:Q Science > QC Physics
Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of Physical Chemistry Letters
Publisher:American Chemical Society
ISSN (Online):1948-7185

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
559071Two-dimensional terahertz/IR spectroscopy: a unique probe of ultrafast hydrogen-bond dynamics of liquid water and model systems.Klaas WynneEngineering & Physical Sciences Research Council (EPSRC)EP/F06926X/1CHEM - CHEMISTRY
571341Liquid-liquid transitions in molecular liquids: from supramolecular structure to phase separationKlaas WynneEngineering & Physical Sciences Research Council (EPSRC)EP/J004790/1CHEM - CHEMISTRY
597872University of Glasgow - Equipment AccountJohn ChapmanEngineering & Physical Sciences Research Council (EPSRC)EP/J014478/1S&E COLLEGE SENIOR MANAGEMENT