The Surface Potential at the Air-water Interface Computed Using Density Functional Theory

Abstract: An accurate prediction of the surface potential at the air-water interface is critical to calculating ion hydration free energies and electrochemical half-cell potentials. Using Density Functional Theory (DFT), model interfacial configurations, and a theoretical definition of the surface potential, we report a value of +3.63~volt at 0.92~g/cc water density. A maximally localized Wannier function analysis confirms that the surface potential is dominated by molecular quadrupole (or "spherical second moment") contributions. We find that the predicted surface potential depends on computational details, and conclude that standard DFT codes may not yield surface potentials directly comparable to existing experiments.