Plasmonic Field Enhancement for Vibration Spectroscopy at Metal/Water Interfaces

Electrochemical (EC) reactions play vital roles in many disciplines, and its molecular-level understanding is highly desired, in particular under reactions. The vibration spectroscopy is a powerful in situ technique for chemical analysis, yet its application to EC reactions is hindered by the strong attenuation of infrared (IR) light in both electrodes and electrolytes. Here we demonstrate that by incorporating appropriate sub-wavelength plasmonic structures at the metal electrode, the IR field at the EC interface can be greatly enhanced via the excitation of surface plasmon. This scheme facilitates in situ vibrational spectroscopic studies, especially using the surface-specific sum-frequency generation technique.