期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 116, 期 32, 页码 9732-9743出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp305469p
关键词
-
资金
- Excellence Initiative by the German federal and state governments to promote science and research at German universities
The structure and diffusion of various linear and ringed solutes are examined in two different solvents, the ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) and SPC/E water, using molecular dynamics (MD) simulations. The formation of distinctly ordered local solvent environments around these solutes is observed. Specifically, spatial distribution functions reveal significant ordering of the solvents around the solutes with chloride hydroxyl group interactions largely dictating these arrangements. Further, a breakdown of the hydrogen bonds that develop between the solute and solvent is provided, showing a relationship between the presence of additional functional groups and the distribution of hydrogen bonds. The diffusivities of the solutes were determined in water at 298 K, 1 bar and [BMIM]Cl at 400 K, 1 bar. The results show that the solutes were approximately 10-100 times more diffusive in water than in [BMIM]Cl. Within [BMIM]Cl, diffusivity appears to decrease with increasing strength of the hydroxyl groups present. Additionally, the free energies of solvation of the solutes are determined with COSMO-RS, providing information about their tendencies in forming aggregates. These results are then compared with MD results in which aggregation is quantified through the use of a dispersion measure. Though all solutes remained relatively dispersed in each of the solvents, those with hydroxyl groups were seen to be the most highly dispersed in the solvent [BMIM]Cl. Further, the dynamic dispersal of a large solute aggregate into [BMIM]Cl was studied, finding that solutes with hydroxyl groups tend to form complexes with the chloride ions. If strong enough, these chlorides can actually bind multiple solutes together into long chains, inhibiting their dispersal in solvent. It is believed that the formation of these chloride solute complexes is largely responsible for the decreased diffusivity and elevated dispersion seen in simulations with [BMIM]Cl.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据