Phase-Sensitive Second-Harmonic Generation of Electrochemical Interfaces

The interaction between molecular species and charged interfaces plays an indispensable role in a multitude of electrochemical devices. Yet, very little is understood about the nature of this interaction, in particular, the interfacial electric field. Second-order nonlinear spectroscopy such as second-harmonic generation (SHG) can provide chemical information on these interfacial interactions; however, the phase information has received limited attention in electrochemical SHG studies. Here, we demonstrate that the phase of the SHG is essential to the measurement of the electric field at the electrode-electrolyte interface. Our in situ SHG experiment provides strong evidence in support of the parabolic model with complex nonlinear susceptibilities. We conclude that if the absolute phase of the total SHG signal with both chi((2)) and chi((3)) contributions can be obtained, it would be possible to measure the potential of zero charge of any electrochemical material.