Resolving the Controversy over Dipole versus Quadrupole Mechanism of Bend Vibration of Water in Vibrational Sum Frequency Generation Spectra

Recently, there has been controversy over whether the HOH bend signal of water in the vibrational sum frequency generation (VSFG) spectrum arises from the conventional dipole mechanism or the quadrupole mechanism. Here, we show that the Im chi((2)) (the imaginary part of the second-order nonlinear susceptibility) spectra of the HOH bend mode of water at oppositely charged monolayer/water interfaces all exhibit positive bands, irrespective of the difference in the sign of the charge at the interface. Furthermore, it is found that the peak frequency of the HOH bend band substantially changes depending on the chemical structure of the charged headgroup located at the interface. These results demonstrate that the VSFG signal of the HOH bend vibration is generated from interfacial water with the interfacial quadrupole mechanism that is associated with the large field gradient of incident lights localized in a very thin region at the interface.