Pushing and pulling on OH- and H3O+ with electric fields across water’s surface

We use second harmonic generation (SHG) spectroscopy, molecular dynamics simulation, and theoretical modeling to study the response of the neat liquid water-air interface to changes in the potential of an external electrode positioned above the liquid. We observe a parabolic dependence of second harmonic intensity on applied potential. This dependence is reminiscent of bulk-phase electric field induced second harmonic (EFISH) but more complicated because it combines the second-order response of the topmost water layer and the potential dependent response of the interfacial electrical double-layer. Based on the literature values for these contributions, we derive a physical interpretation of our measurements that reveals new insight into the response of the neat water interface to external electric fields. Specifically, we find that the net dipolar orientation of water molecules within the double-layer is primarily responsive to the internal fields generated by the excess surface concentrations of OH- and H3O+ that arise to screen the external potential. Notably, this interpretation implies that the orientational response of water dipoles at the interface can actually oppose the direction of the external field, a subtle effect that is not captured by traditional models.