Institute for Solid State Physics and Optics, Wigner Research Centre for Physics, Hungarian Academy of Sciences, Konkoly Thege M. út 29-33, H-1121 Budapest, Hungary.
J Chem Phys. 2012 Nov 28;137(20):204503. doi: 10.1063/1.4767437.
We report on a comparison of three interaction potential models of water (SPC/E, TIP4P-2005, and SWM4-DP) for describing the structure of concentrated aqueous lithium chloride solutions. Classical molecular dynamics simulations have been carried out and total scattering structure factors, calculated from the particle configurations, were compared with experimental diffraction data. Later, reverse Monte Carlo structural modelling was applied for refining molecular dynamics results, so that particle configurations consistent with neutron and X-ray diffraction data could be prepared that, at the same time, were as close as possible to the final stage of the molecular dynamics simulations. Partial radial distribution functions, first neighbors, and angular correlations were analysed further from the best fitting particle configurations. It was found that none of the water potential models describe the structure perfectly; overall, the SWM4-DP model seems to be the most promising. At the highest concentrations the SPC/E model appears to provide the best approximation of the water structure, whereas the TIP4P-2005 model proved to be the most successful for estimating the lithium-oxygen partial radial distribution function at each concentration.
我们报告了三种水分子相互作用势能模型（SPC/E、TIP4P-2005 和 SWM4-DP）在描述浓氯化锂水溶液结构方面的比较。进行了经典分子动力学模拟，并将从粒子构形计算得到的总散射结构因子与实验衍射数据进行了比较。随后，应用反向蒙特卡罗结构建模对分子动力学结果进行了细化，以便准备与中子和 X 射线衍射数据一致的粒子构形，同时尽可能接近分子动力学模拟的最终阶段。从最佳拟合粒子构形进一步分析了部分径向分布函数、最近邻和角关联。结果表明，没有一种水分子势能模型能完美地描述结构；总体而言，SWM4-DP 模型似乎最有前途。在最高浓度下，SPC/E 模型似乎提供了对水结构的最佳近似，而 TIP4P-2005 模型则被证明在估计各浓度下的锂-氧部分径向分布函数方面最为成功。
