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在离子液体中,高局部摩擦取决于与电荷网络的接近程度。

In an ionic liquid, high local friction is determined by the proximity to the charge network.

机构信息

School of Engineering, Benedictine College, Atchison, Kansas 66002, USA.

Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA.

出版信息

J Chem Phys. 2018 Oct 14;149(14):144503. doi: 10.1063/1.5045675.

Abstract

Structural heterogeneity in Ionic Liquids (ILs) is to a large extent defined by nanoscale apolar pockets that act as spacers between strings of positive and negative charges that alternate. In contrast to this, recent work from our group and that of others appear to indicate that dynamic, energetic, and mechanical heterogeneities are governed by the charged part of the liquid. In this article, we study the dynamics of methane, a small apolar solute, in the family of ILs 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ( /NTf ), with n = 2, 4, 8 at temperatures that make the viscosity for each liquid similar and around 8 cP. We do this in an attempt to equalize the effect of the solvent on the dynamics of the solute. In all cases, we find that solute proximity to charge-enhanced regions coincides with translationally caged regimes (high local friction) whereas the opposite is true in charge-depleted regions. In a way, these ILs behave like a liquid within a liquid where the charge network is the high friction component.

摘要

离子液体(ILs)的结构异质性在很大程度上由纳米级非极性口袋定义,这些口袋在交替的正电荷和负电荷串之间起到间隔作用。与这一点形成对比的是,我们小组和其他小组的最近的工作似乎表明,动态、能量和机械异质性受液体的带电部分控制。在本文中,我们研究了甲烷(一种小的非极性溶质)在 1-烷基-3-甲基咪唑双(三氟甲烷磺酰基)亚胺( /NTf )家族的 ILs 中的动力学,其中 n = 2、4、8 在使每种液体的粘度相似且约为 8 cP 的温度下。我们这样做是为了使溶剂对溶质动力学的影响均衡。在所有情况下,我们发现溶质与电荷增强区域的接近度与平移笼区(高局部摩擦)一致,而在电荷耗尽区域则相反。在某种程度上,这些 ILs 表现得像一种液体中的液体,其中电荷网络是高摩擦成分。

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