Voltage-dependent ordering of water molecules at an electrode–electrolyte interface

THE arrangement of water molecules at charged, aqueous interfaces is an important question in electrochemistry, geochemistry and biology. Theoretical studies1–11 suggest that the molecules become arranged in several layers adjacent to a solid interface, with densities similar to that in the bulk, and that the molecules in the first layer are reoriented from oxygen-up to oxygen-down as the electrode charge changes from negative to positive. Few of these predictions have been verified experimentally12–16, however. Using X-ray scattering, we have measured the water density profile perpendicular to a silver (111) surface at two applied voltages. We find that the water molecules are ordered in layers extending about three molecular diameters from the electrode, and that the spacing between the electrode and first water layer indicates an oxygen-up (oxygen-down) average orientation for negative (positive) charge. Contrary to current models, however, we find that the first layer has a far greater density than that in bulk water. This implies that the hydrogen-bonding network is disrupted in this layer, and that the properties of the water in the layer are likely to be very different from those in the bulk.