Smith Alexander M, Lee Alpha A, Perkin Susan
Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, Oxford OX1 3QZ, United Kingdom.
Department of Inorganic and Analytical Chemistry, University of Geneva, 1205 Geneva, Switzerland.
Phys Rev Lett. 2017 Mar 3;118(9):096002. doi: 10.1103/PhysRevLett.118.096002.
The structure and interactions in electrolytes at high concentration have implications from energy storage to biomolecular interactions. However, many experimental observations are yet to be explained in these mixtures, which are far beyond the regime of validity of mean-field models. Here, we study the structural forces in a mixture of ionic liquid and solvent that is miscible in all proportions at room temperature. Using the surface force balance to measure the force between macroscopic smooth surfaces across the liquid mixtures, we uncover an abrupt increase in the wavelength above a threshold ion concentration. Below the threshold concentration, the wavelength is determined by the size of the solvent molecule, whereas above the threshold, it is the diameter of a cation-anion pair that determines the wavelength.
高浓度电解质中的结构和相互作用在从能量存储到生物分子相互作用等方面都有影响。然而,这些混合物中的许多实验观察结果仍有待解释,因为它们远远超出了平均场模型的有效范围。在这里,我们研究了一种离子液体与溶剂的混合物在室温下以任意比例互溶时的结构力。通过使用表面力天平测量横跨液体混合物的宏观光滑表面之间的力,我们发现高于阈值离子浓度时波长会突然增加。在阈值浓度以下,波长由溶剂分子的大小决定,而在阈值以上,则是阳离子 - 阴离子对的直径决定波长。