Wojnarowska Zaneta, Cheng Shinian, Yao Beibei, Swadzba-Kwasny Malgorzata, McLaughlin Shannon, McGrogan Anne, Delavoux Yoan, Paluch Marian
Institute of Physics, the University of Silesia in Katowice, Silesian Center for Education and Interdisciplinary Research, 75 Pulku Piechoty 1A, 41-500, Chorzow, Poland.
Department of Chemistry, University of Wisconsin-Madison, Madison, WI, 53705, USA.
Nat Commun. 2022 Mar 15;13(1):1342. doi: 10.1038/s41467-022-29021-0.
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] 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) are dramatically elongated, and their distribution becomes broader. This peculiar behavior is induced by isobaric cooling and isothermal compression, with the τ(T,P) 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.
单组分材料两个无序相之间的液-液转变（LLT）仍然是最引人入胜的物理现象之一。在此，我们报道了一系列含有三己基（十四烷基）鏻阳离子[P]和不同尺寸及形状阴离子的离子液体中的一级液-液转变，这为理解控制液-液转变的结构-性质关系提供了见解。除了液-液转变的量热证据外，我们还报道离子动力学在液-液转变过程中表现出异常行为，即电导率弛豫时间（τ）显著延长，且其分布变宽。这种特殊行为是由等压冷却和等温压缩引起的，对于给定系统，τ（T，P）为常数。后一观察结果证明，与液-玻璃转变类似，液-液转变具有等时性特征。最后，利用克劳修斯-克拉佩龙方程估计了液-液转变时比容的不连续幅度。
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