A density functional theory based study of the microscopic structure and dynamics of aqueous HCl solutions
A density functional theory based study of the microscopic structure and dynamics of aqueous HCl solutions
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DOI：
10.1039/b603059a
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发表时间：
2006-01-01
影响因子：
3.3
通讯作者：
Meijer, E. J.
中科院分区：
文献类型：
--
作者：
Heuft, J. M.;Meijer, E. J.
采用基于密度泛函理论的分子动力学模拟方法研究了两种浓度下盐酸的水溶剂化过程。我们使用的大型模拟箱使我们能够研究更大规模的结构，如水桥氯离子网络。我们发现几乎所有的结构和动力学性质的浓度依赖性很强。过量的质子主要以本征结构和Zundel结构存在，或者作为直接的水合氢离子-氯化物接触离子对，或者作为溶剂分离的离子对。增加浓度对水分子的天然氢键网络具有不利影响。在我们的研究中，这种效应是可见的，因为氯离子周围的溶剂化壳层的持续时间减少。此外，质子跳跃的数量，确定了一个新的和明确定义的识别程序，遭受自然氢键网络的故障。
The aqueous solvation of hydrochloric acid is studied using density functional theory based molecular dynamics simulations at two concentrations. The large simulation boxes that we use allow us to investigate larger-scale structures such as the water-bridged chloride ion network. We find a strong concentration dependence for almost all structural and dynamical properties. Excess protons are mostly present both as Eigen and Zundel structures, either as a direct hydronium-chloride contact-ion pair or a solvent-separated ion pair. Increasing the concentration has a detrimental effect on the natural hydrogen bonded network of water molecules. This effect is visible in our studies as a decrease in the persistence time of the solvation shells around the chloride ions. Also the number of proton hops, determined by a new and well defined identification procedure, suffers from the breakdown of the natural hydrogen bond network.