Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4+6, D-53115 Bonn, Germany.
Phys Chem Chem Phys. 2014 Aug 28;16(32):16880-90. doi: 10.1039/c4cp01177e.
In this paper we show by using static DFT calculations and classical molecular dynamics simulations that the charge transfer between ionic liquid ions plays a major role in the observed discrepancies between the overall mobility of the ions and the observed conductivities of the corresponding ionic liquids, while it also directly suppresses the association of oppositely charged ions, thus the ion pairing. Accordingly, in electrochemical applications of these materials it is important to consider this reduction of the total charges on the ions, which can greatly affect the performance of the given process or device in which the ionic liquid is used. By slightly shifting from the salt-like to a molecular liquid-like system via the decreased charges, the charge transfer also fluidizes the ionic liquid. We believe that this vital information on the molecular level structure of ionic liquids offers a better understanding of these materials, and allows us to improve the a priori design of ionic liquids for any given purpose.
在本文中，我们通过使用静态 DFT 计算和经典分子动力学模拟表明，离子液体离子之间的电荷转移在观察到的离子整体迁移率与相应离子液体的观察电导率之间的差异中起着主要作用，同时它也直接抑制了相反电荷离子的缔合，从而抑制了离子对的形成。因此，在这些材料的电化学应用中，重要的是要考虑到离子总电荷的减少，这会极大地影响其中使用离子液体的给定过程或装置的性能。通过通过降低电荷从类似于盐的系统略微转变为类似于分子液体的系统，电荷转移也使离子液体流动化。我们相信，关于离子液体的分子水平结构的这一重要信息提供了对这些材料的更好理解，并使我们能够改进任何给定目的的离子液体的预先设计。
