由结构因子计算化学势：II. 带电多组分混合物
Chemical potentials from structure factors: II. Charged multi-component mixtures
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中文总结 AI 辅助
本文扩展S0方法至带电多组分混合物，结合组成空间框架与库仑处理，计算了多卤化物盐水溶液化学势及熔盐混合自由能，阐明离子效应并证明长波长静电关联的重要性。
中文摘要 AI 辅助
带电多组分混合物的化学势是电解质热力学的核心，但仍难以从原子模拟中计算。S0方法可从平衡分子动力学模拟中计算混合物的化学势，本文将其扩展到带电混合物，结合了第一部分（中性多组分混合物）提出的组成空间框架与静态结构因子小波数极限的库仑处理方法。该方法将热力学相关的中性组成涨落与被禁止的宏观电荷涨落分离，并进一步考虑电中性约束。我们用该方法计算了多卤化物盐水溶液的化学势，阐明了离子特异性热力学效应；还计算了熔盐混合物的混合自由能，证明了正确描述长波长静电关联的重要性。
英文摘要
The chemical potentials of charged multi-component mixtures are central to electrolyte thermodynamics, but remain difficult to compute from atomistic simulations. The S0 method enables computing chemical potentials of mixtures from equilibrium molecular dynamics simulations. Here we extend the S0 method to charged mixtures by combining the composition-space framework developed in Part I: Neutral Multi-component Mixtures with a Coulombic treatment of the small-wavenumber limits of static structure factors. This approach separates thermodynamically relevant neutral composition fluctuations from forbidden macroscopic charge fluctuations, and further accounts for charge-neutrality constraints. We use the method to compute the chemical potentials of multiple-halide aqueous salt solutions, elucidating the ion-specific thermodynamic effects. We also calculate the mixing free energies of molten salt mixtures, demonstrating the importance of correctly describing long-wavelength electrostatic correlations.
发表机构
- Department of Chemistry, UC Berkeley（加州大学伯克利分校化学系）
- Chemical Sciences Division, Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室化学科学部）
- Bakar Institute of Digital Materials for the Planet, UC Berkeley（加州大学伯克利分校巴克拉行星数字材料研究所）
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