This article reviews recent molecular simulation studies of “collective” properties of aqueous electrolyte solutions, specifically free energies and activity coefficients, solubilities, nucleation rates of crystals, and transport coefficients. These are important fundamental properties for biology and geoscience, but also relevant for many technological applications. Their determination from molecular-scale calculations requires large systems and long sampling times, as well as specialized sampling algorithms. As a result, such properties have not typically been taken into account during optimization of force field parameters; thus, they provide stringent tests for the transferability and range of applicability of proposed molecular models. There has been significant progress on simulation algorithms to enable the determination of these properties with good statistical uncertainties. Comparisons of simulation results to experimental data reveal deficiencies shared by many commonly used models. Moreover, there appear to exist specific tradeoffs within existing modeling frameworks so that good prediction of some properties is linked to poor prediction for specific other properties. For example, non-polarizable models that utilize full charges on the ions generally fail to predict accurately both activity coefficients and solubilities; the concentration dependence of viscosity and diffusivity for these models is also incorrect. Scaled-charge models improve the dynamic properties and could also perform well for solubilities but fail in the prediction of nucleation rates. Even models that do well at room temperature for some properties generally fail to capture their experimentally observed temperature dependence. The main conclusion from the present review is that qualitatively new physics will need to be incorporated in future models of electrolyte solutions to allow the description of collective properties for broad ranges of concentrations, temperatures, and solvent conditions.

中文翻译：

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模拟电解质水溶液的活性，溶解度，传输性能和成核速率。

本文回顾了有关电解质水溶液“集体”性质的最新分子模拟研究，特别是自由能和活度系数，溶解度，晶体的成核速率和传输系数。这些是生物学和地球科学的重要基本属性，但也与许多技术应用相关。通过分子规模计算确定它们需要大型系统和长采样时间，以及专门的采样算法。因此，在优化力场参数期间通常不会考虑这些属性；因此，它们为提出的分子模型的可转移性和适用范围提供了严格的测试。在模拟算法方面取得了重大进展，可以确定具有良好统计不确定性的这些属性。仿真结果与实验数据的比较显示了许多常用模型共有的缺陷。此外，在现有的建模框架中似乎存在特定的权衡，因此某些属性的良好预测与特定其他属性的不良预测相关。例如，利用离子完全电荷的不可极化模型通常无法准确预测活度系数和溶解度。这些模型对粘度和扩散率的浓度依赖性也不正确。比例电荷模型改善了动力学性质，并且对于溶解度也表现良好，但是未能预测成核速率。即使是在室温下对某些性能表现良好的模型，也通常无法捕获其实验观察到的温度依赖性。本综述的主要结论是，定性地将新的物理性质纳入电解质溶液的未来模型中，以描述宽范围的浓度，温度和溶剂条件的集体性质。