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

Wojnarowska, Zaneta; Cheng, Shinian; Yao, Beibei; Swadzba-Kwasny, Malgorzata; McLaughlin, Shannon; McGrogan, Anne; Delavoux, Yoan; Paluch, Marian · Nat Commun · 2022

basic_science · Level V

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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 [P<sub>666,14</sub>]<sup>+</sup> 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 (τ<sub>σ</sub>) are dramatically elongated, and their distribution becomes broader. This peculiar behavior is induced by isobaric cooling and isothermal compression, with the τ<sub>σ</sub>(T<sub>LL</sub>,P<sub>LL</sub>) 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.