量化钠和钾离子的水合结构：在Jacob梯子上采取其他步骤。,Physical Chemistry Chemical Physics

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量化钠和钾离子的水合结构：在Jacob梯子上采取其他步骤。
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2020-01-02 , DOI: 10.1039/c9cp06161d
Timothy T Duignan ₁ , Gregory K Schenter , John L Fulton , Thomas Huthwelker , Mahalingam Balasubramanian , Mirza Galib , Marcel D Baer , Jan Wilhelm , Jürg Hutter , Mauro Del Ben , X S Zhao , Christopher J Mundy

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由于钠离子和钾离子在广泛的重要现象中的重要性，因此能够重现钠离子和钾离子周围水的实验结构的能力，是对相互作用电位质量的关键测试。在这里，我们使用三种密度泛函理论函数来模拟散装水中的Na +和K +离子：（1）基于广义梯度近似（GGA）的色散校正修正的Perdew，Burke和Ernzerhof函数（revPBE-D3）（2）（3）钾的随机相近似（RPA）功能。我们将其与实验X射线衍射（XRD）和X射线吸收精细结构（EXAFS）的测量结果进行比较，以证明SCAN能够准确再现围绕钠和钾阳离子的水合结构的关键结构细节，而revPBE-D3无法做到这一点。但是，我们显示，与revPBE-D3相比，SCAN对纯净水的描述更差。RPA也显示了K +的改进，但是缓慢的收敛阻止了严格的比较。最后，我们分析了团簇能量学，表明与revPBE-D3相比，SCAN和RPA的离子水团簇结合能的平均误差波动较小。但是缓慢的收敛会阻止严格的比较。最后，我们分析了团簇能量学，表明与revPBE-D3相比，SCAN和RPA的离子水团簇结合能的平均误差波动较小。但是缓慢的收敛会阻止严格的比较。最后，我们分析了团簇能量学，表明与revPBE-D3相比，SCAN和RPA的离子水团簇结合能的平均误差波动较小。

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Quantifying the hydration structure of sodium and potassium ions: taking additional steps on Jacob's Ladder.

The ability to reproduce the experimental structure of water around the sodium and potassium ions is a key test of the quality of interaction potentials due to the central importance of these ions in a wide range of important phenomena. Here, we simulate the Na+ and K+ ions in bulk water using three density functional theory functionals: (1) the generalized gradient approximation (GGA) based dispersion corrected revised Perdew, Burke, and Ernzerhof functional (revPBE-D3) (2) the recently developed strongly constrained and appropriately normed (SCAN) functional (3) the random phase approximation (RPA) functional for potassium. We compare with experimental X-ray diffraction (XRD) and X-ray absorption fine structure (EXAFS) measurements to demonstrate that SCAN accurately reproduces key structural details of the hydration structure around the sodium and potassium cations, whereas revPBE-D3 fails to do so. However, we show that SCAN provides a worse description of pure water in comparison with revPBE-D3. RPA also shows an improvement for K+, but slow convergence prevents rigorous comparison. Finally, we analyse cluster energetics to show SCAN and RPA have smaller fluctuations of the mean error of ion-water cluster binding energies compared with revPBE-D3.

更新日期：2019-12-19

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