Pressure-induced liquid-liquid transition in a family of ionic materials

Zaneta Wojnarowska (), Shinian Cheng, Beibei Yao, Malgorzata Swadzba-Kwasny, Shannon McLaughlin, Anne McGrogan, Yoan Delavoux and Marian Paluch
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Zaneta Wojnarowska: the University of Silesia in Katowice, Silesian Center for Education and Interdisciplinary Research
Shinian Cheng: the University of Silesia in Katowice, Silesian Center for Education and Interdisciplinary Research
Beibei Yao: the University of Silesia in Katowice, Silesian Center for Education and Interdisciplinary Research
Malgorzata Swadzba-Kwasny: The Queen’s University of Belfast
Shannon McLaughlin: The Queen’s University of Belfast
Anne McGrogan: The Queen’s University of Belfast
Yoan Delavoux: The Queen’s University of Belfast
Marian Paluch: the University of Silesia in Katowice, Silesian Center for Education and Interdisciplinary Research

Nature Communications, 2022, vol. 13, issue 1, 1-10

Abstract: Abstract Liquid−liquid transition (LLT) between two disordered phases of single-component material remains one of the most intriguing physical phenomena. Here, we report a first-order LLT in a series of ionic liquids containing trihexyl(tetradecyl)phosphonium cation [P666,14]+ and anions of different sizes and shapes, providing an insight into the structure-property relationships governing LLT. In addition to calorimetric proof of LLT, we report that ion dynamics exhibit anomalous behavior during the LLT, i.e., the conductivity relaxation times (τσ) are dramatically elongated, and their distribution becomes broader. This peculiar behavior is induced by isobaric cooling and isothermal compression, with the τσ(TLL,PLL) constant for a given system. The latter observation proves that LLT, in analogy to liquid-glass transition, has an isochronal character. Finally, the magnitude of discontinuity in a specific volume at LLT was estimated using the Clausius-Clapeyron equation.

Date: 2022
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DOI: 10.1038/s41467-022-29021-0

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