Charge Induced Chi(3) Susceptibility in Interfacial Nonlinear Optical Spectroscopy Beyond the Bulk Aqueous Contributions: The Case for Silica/Water Interface

The electric field induced (EFI) bulk Chi(3) contribution to the second harmonic generation (SHG) signal from charged interfaces was discovered and applied to study the interfacial chemistry of various charged interfaces three decades ago. For both the buried fused silica/water interface and the exposed charged monolayer covered air/water interface, such bulk Chi(3) contribution was all attributed to the Chi(3) term of the polarized water molecules near the charged interfaces. The puzzling experimental observation of the more than one-order of magnitude difference of the EFISHG intensity between the fully charged silica/water interface and the charged molecular covered air/water interface was generally overlooked in the EFISHG literature. Nevertheless, this significant signal difference suggests additional source for the Chi(3) contribution at the fully charged silica/water interface other than the polarized water molecules as in the case of charged monolayer covered air/water interface. In this report, we re-examine the treatment of the Chi(3) mechanism at the charged silica/water interface by including the contributions from the bulk silica using proper boundary condition and image charge distributions for the change screening effects inside bulk silica phase. We show that the Chi(3) contribution from the bulk silica is in similar form as that of the aqueous bulk phase, and it is with more than one-order of magnitude and with opposite sign. The treatment reported here can be extended to other charged interfaces.

Applications of sum-frequency generation vibrational spectroscopy in friction interface

Sum-frequency generation (SFG) vibrational spectroscopy is a second-order nonlinear optical spectroscopy technique. Owing to its interfacial selectivity, SFG vibrational spectroscopy can provide interfacial molecular information, such as molecular orientations and order, which can be obtained directly, or molecular density, which can be acquired indirectly. Interfacial molecular behaviors are considered the basic factors for determining the tribological properties of surfaces. Therefore, owing to its ability to detect the molecular behavior in buried interfaces in situ and in real time, SFG vibrational spectroscopy has become one of the most appealing technologies for characterizing mechanisms at friction interfaces. This paper briefly introduces the development of SFG vibrational spectroscopy and the essential theoretical background, focusing on its application in friction and lubrication interfaces, including film-based, complex oil-based, and water-based lubricating systems. Real-time detection using SFG promotes the nondestructive investigation of molecular structures of friction interfaces in situ with submonolayer interface sensitivity, enabling the investigation of friction mechanisms. This review provides guidance on using SFG to conduct friction analysis, thereby widening the applicability of SFG vibrational spectroscopy.