Resist the Surface Field: The H-Bond Network Decides if Water Aligns at Metal Electrodes

At an electrode, water molecules align to the surface field upon voltage application. This initiates important electrochemical reactions, e.g., hydrogen and oxygen evolution reactions. Recently developed nonlinear optical techniques challenge the traditional picture by quantifying a lack of water alignment at metal electrodes. We here provide theoretical and experimental evidence for the existence of a driving force that opposes water alignment to the surface field. Such driving force originates from the ordering templated by the metal surface on the physisorbed water layer, and scales with surface hydrophilicity. We hence propose a physical model for water alignment at electrodes based on a balance of H-bond network and surface field driving forces, which reconciles the traditional picture with the new experimental observations.