Direct Quantification of Water Surface Charge by Phase-Sensitive Second Harmonic Spectroscopy

We developed and verified a phase-sensitive second harmonic generation spectroscopic scheme that allows for direct determination of the absolute surface charge density and surface potential of a water interface without the need for prior interfacial information. The method relies on selective probing of surface-field-induced reorientation order of water molecules in the electrical double layer and is, hence, independent of the interfacial molecular bonding structure. Application of this technique to a mixed surfactant monolayer on water suggests the manifest effect of the chain–chain interactions among the monolayer on adsorption of soluble ionic surfactants. We also deduce the third-order nonlinear susceptibility of bulk water and prove its applicability to analysis of charges of various water interfaces. In addition, we show that Debye–Hückle theory should be avoided in the spectroscopic analysis for its potential significant error, as evidenced experimentally and theoretically.