<p>We use second harmonic generation 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, indicating that water’s net
interfacial dipole responds linearly. We also observe a minimum intensity when
the potential is tuned to a specific positive value. Interpreting this minimum
based on the macroscopic electrostatic potential profile yields misleading
physical conclusions because it neglects the internal bias exerted on molecular
orientations by the excess surface concentrations of OH<sup>-</sup> or H<sub>3</sub>O<sup>+</sup>.
We thus find that water’s net interfacial dipole orientation is primarily
responsive to the effects of these ionic species rather than the external
electric field. </p>