Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Phys Rev Lett. 2014 Apr 4;112(13):136101. doi: 10.1103/PhysRevLett.112.136101. Epub 2014 Apr 2.
By treating both the short-range (solvation) and long-range (image force) electrostatic forces as well as charge polarization induced by these forces in a consistent manner, we obtain a simple theory for the self-energy of an ion that is continuous across the interface. Along with nonelectrostatic contributions, our theory enables a unified description of ions on both sides of the interface. Using intrinsic parameters of the ions, we predict the specific ion effect on the interfacial affinity of halogen anions at the water-air interface, and the strong adsorption of hydrophobic ions at the water-oil interface, in agreement with experiments and atomistic simulations.
通过一致地处理短程（溶剂化）和长程（映像力）静电作用力以及这些力引起的电荷极化，我们得到了一个离子自能的简单理论，该理论在界面处是连续的。除了非静电贡献外，我们的理论还使我们能够统一描述界面两侧的离子。使用离子的固有参数，我们预测了特定离子对卤阴离子在水-空气界面上的界面亲和力的影响，以及疏水分子在水-油界面上的强吸附作用，这与实验和原子模拟结果一致。
