Accurate Modeling of Bromide and Iodide Hydration with Data-Driven Many-Body Potentials
Accurate Modeling of Bromide and Iodide Hydration with Data-Driven Many-Body Potentials
复制标题
利用数据驱动的多体势对溴化物和碘化物水合进行精确建模
DOI：
10.1021/acs.jpcb.2c04698
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Paesani, Francesco
中科院分区：
文献类型：
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作者：
Caruso, Alessandro;Zhu, Xuanyu;Fulton, John L.;Paesani, Francesco
离子-水的相互作用在确定水系统在各种环境中的性质方面起着核心作用。然而，离子的水化性质是如何从小的水簇演变成整体溶液和界面的定量理解仍然是难以捉摸的。在这里，我们介绍了第二代数据驱动的多体能（MB-nrg）势能函数（pef），代表了溴化物-水和碘化物-水的相互作用。MB-nrg PEFs使用置换不变多项式再现理论耦合簇水平计算的二体和三体能量，并使用经典多体极化隐式表示所有高体能量。对小Br - (H2O)nand I - (H2O) n团簇水化结构的系统分析表明，MB-nrg pef预测的相互作用能与“金标准”耦合团簇参考值在定量上一致。重要的是，当用于液态水中单个溴化离子和碘化离子的等温-等压系系的分子动力学模拟时，MB-nrg PEFs预测的扩展x射线吸收精细结构（EXAFS）光谱准确地再现了实验光谱，从而可以高可信度地表征这两种离子的水化结构。
Ion–water interactions play a central role in determining the properties of aqueous systems in a wide range of environments. However, a quantitative understanding of how the hydration properties of ions evolve from small aqueous clusters to bulk solutions and interfaces remains elusive. Here, we introduce the second generation of data-driven many-body energy (MB-nrg) potential energy functions (PEFs) representing bromide–water and iodide–water interactions. The MB-nrg PEFs use permutationally invariant polynomials to reproduce two-body and three-body energies calculated at the coupled cluster level of theory, and implicitly represent all higher-body energies using classical many-body polarization. A systematic analysis of the hydration structure of small Br–(H2O)nand I–(H2O)nclusters demonstrates that the MB-nrg PEFs predict interaction energies in quantitative agreement with “gold standard” coupled cluster reference values. Importantly, when used in molecular dynamics simulations carried out in the isothermal–isobaric ensemble for single bromide and iodide ions in liquid water, the MB-nrg PEFs predict extended X-ray absorption fine structure (EXAFS) spectra that accurately reproduce the experimental spectra, which thus allows for characterizing the hydration structure of the two ions with a high level of confidence.