Peerless James S, Bowers G Hunter, Kwansa Albert L, Yingling Yaroslava G
Department of Materials Science and Engineering, North Carolina State University , 911 Partners Way, Raleigh, North Carolina 27695, United States.
J Phys Chem B. 2015 Dec 10;119(49):15344-52. doi: 10.1021/acs.jpcb.5b09386. Epub 2015 Nov 25.
In this work, an all-atom molecular dynamics simulation technique was employed to gain insight into the dynamic structure of the solvation shell formed around C60 and phenyl-C61-butyric acid methyl ester (PCBM) in nine aromatic solvents. A new method was developed to visualize and quantify the distribution of solvent molecule orientations in the solvation shell. A strong positive correlation was found between the regularity of solvent molecule orientations in the solvation shell and the experimentally obtained solubility limits for both C60 and PCBM. This correlation was extended to predict a solubility of 36 g/L for PCBM in 1,2,4-trimethylbenze. The relationship between solvation-shell structure and solubility provided detailed insight into solvate formation of C60 and solvation in relation to solvent molecular structure and properties. The determined dependence of the solvation-shell structure on the geometric shape of the solvent might allow for enhanced control of fullerene solution-phase behavior during processing by chemically tailoring the solvent molecular structure, potentially diminishing the need for costly and environmentally harmful halogenated solvents and/or additives.
在这项工作中，采用全原子分子动力学模拟技术来深入了解在九种芳香族溶剂中围绕C60和苯基-C61-丁酸甲酯（PCBM）形成的溶剂化壳层的动态结构。开发了一种新方法来可视化和量化溶剂化壳层中溶剂分子取向的分布。发现溶剂化壳层中溶剂分子取向的规律性与实验得到的C60和PCBM的溶解度极限之间存在很强的正相关性。这种相关性被扩展以预测PCBM在1,2,4-三甲基苯中的溶解度为36 g/L。溶剂化壳层结构与溶解度之间的关系为C60的溶剂化物形成以及与溶剂分子结构和性质相关的溶剂化提供了详细的见解。所确定的溶剂化壳层结构对溶剂几何形状的依赖性可能允许通过化学剪裁溶剂分子结构来增强对富勒烯溶液相行为在加工过程中的控制，从而有可能减少对昂贵且对环境有害的卤化溶剂和/或添加剂的需求。
