Wavelength-scanning second-harmonic generation for determining absolute charge density at aqueous interfaces

We develop a new, to the best of our knowledge, optical scheme based on second-harmonic generation (SHG) at multiple wavelengths for unequivocal separation of the second-order and the electric-field-induced third-order nonlinear optical contributions from aqueous interfaces. The third-order SHG originating from the field-induced reorientation order of water molecules in the electrical double layer offers an optical label-free and inherent probe to the surface charge density and surface potential in the absolute scales. We verify this wavelength-scanning SHG scheme both theoretically and experimentally, and show that the approach is applicable to water interfaces with bulk ionic strength below 500 µM and can achieve a detection sensitivity for a surface charge density of ∼10^-4C/m².