Voroshylova Iuliia V, Chaban Vitaly V
CIQ/REQUIMTE - Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto , Rua do Campo Alegre 687, 4169-007, Porto, Portugal.
J Phys Chem B. 2014 Sep 11;118(36):10716-24. doi: 10.1021/jp5054875. Epub 2014 Aug 29.
Reliable force field (FF) is a central issue in successful prediction of physical chemical properties via computer simulations. This work introduces refined FF parameters for six popular ionic liquids (ILs) of the pyridinium family (butylpyridinium tetrafluoroborate, bis(trifluoromethanesulfonyl)imide, dicyanamide, hexafluorophosphate, triflate, chloride). We elaborate a systematic procedure, which allows accounting for specific cation-anion interactions in the liquid phase. Once these interactions are described accurately, all experimentally determined transport properties can be reproduced. We prove that three parameters per interaction site (atom diameter, depth of potential well, point electrostatic charge) provide a sufficient basis to predict thermodynamics (heat of vaporization, density), structure (radial distributions), and transport (diffusion, viscosity, conductivity) of ILs at room conditions and elevated temperature. The developed atomistic models provide a systematic refinement upon the well-known Canongia Lopes-Pádua (CL&P) FF. Together with the original CL&P parameters the present models foster a computational investigation of ionic liquids.
可靠的力场（FF）是通过计算机模拟成功预测物理化学性质的核心问题。这项工作介绍了吡啶鎓家族六种常见离子液体（ILs）（四氟硼酸丁基吡啶鎓、双（三氟甲磺酰）亚胺、双氰胺、六氟磷酸根、三氟甲磺酸根、氯离子）的精细FF参数。我们阐述了一种系统的程序，该程序能够考虑液相中特定的阳离子-阴离子相互作用。一旦准确描述了这些相互作用，所有实验测定的传输性质都可以再现。我们证明，每个相互作用位点的三个参数（原子直径、势阱深度、点静电电荷）为预测室温及高温下离子液体的热力学（汽化热、密度）、结构（径向分布）和传输（扩散、粘度、电导率）提供了充分的基础。所开发的原子模型在著名的卡诺尼亚·洛佩斯-帕杜阿（CL&P）FF的基础上进行了系统的改进。与原始的CL&P参数一起，目前的模型促进了对离子液体的计算研究。
