Direct Evidence for a Surface and Bulk Specific Response in the Sum-Frequency Generation Spectrum of the Water Bend Vibration

We study the bending mode of pure water and charged aqueous surfaces using heterodyne-detected vibrational sum-frequency generation spectroscopy. We observe a low (1626  cm−1) and a high (1656  cm−1) frequency component that can be unambiguously assigned to an interfacial dipole and a bulk quadrupolar response, respectively. We thus demonstrate that probing the bending mode provides structural and quantitative information on both the surface and the bulk.