Modeling Vibrational Sum Frequency Generation Spectra of Interfacial Water on a Gold Surface: The Role of the Fermi Resonance.

Studying the hydrogen bonding structure of H 2 O at the metal-water interface is a highly complex yet fascinating endeavor. The intricate interactions and diverse orientations of water molecules on metal surfaces with varying potentials pose a significant challenge in elucidating the coupling between O-H stretching and H-O-H bending modes. In this study, we employed DFT-MD simulation to explore how the orientation of interfacial water molecules changes with the applied potential on the Au(111) surface. Based on the surface-specific velocity-velocity correlation function (ssVVCF) formula, we calculated vibrational sum frequency generation (VSFG) spectra for the O-H stretches. We found that three assigned peaks (∼3300, ∼3450, and 3650 cm -1 ) shifted toward lower frequencies as the potential moved toward more negative values. Our results align remarkably well with experimental Raman spectroscopy data. Notably, our VSFG analysis revealed a significant change in the VSFG spectra of the hydrogen-bonded O-H groups (∼3300 cm -1 ), switching from a negative to a positive sign with decreasing potential. This alteration suggests a substantial change in the orientation of these low-frequency O-H groups owing to their increased interactions with the Au surface. In contrast, the orientations of both the high-frequency O-H groups (∼3450 cm -1 ) and the dangling O-H groups (∼3650 cm -1 ) remained unaffected by the applied potentials. Furthermore, our analysis of the decomposed vibrational density of states (VDOS) for the H-O-H bending mode uncovered the coupling between the H-O-H bending and O-H stretching vibrations, known as the Fermi resonance. Our work suggests that the H-O-H bending vibration becomes restricted when water molecules transition from the ″one-H-down″ to the ″two-H-down″ conformation, leading to a redshift in the O-H stretching vibration through the Fermi resonance. By constructing the VSFG and decomposed VDOS spectra, we gained valuable insights into the structural changes that Raman spectra alone cannot fully interpret. Specifically, our analysis revealed the critical role of the Fermi resonance effect in shaping the spectroscopic signature of interfacial water molecules on the Au(111) surface.