Bulklike Vibrational Coupling of Surface Water Revealed by Sum-Frequency Generation Spectroscopy

Phys Rev Lett. 2023 Dec 22;131(25):256202. doi: 10.1103/PhysRevLett.131.256202.

Abstract

Vibrational coupling between interfacial water molecules is important for energy dissipation after on-water chemistry, yet intensely debated. Here, we quantify the interfacial vibrational coupling strength through the linewidth of surface-specific vibrational spectra of the water's O─H (O─D) stretch region for neat H_{2}O/D_{2}O and their isotopic mixtures. The local-field-effect-corrected experimental SFG spectra reveal that the vibrational coupling between hydrogen-bonded interfacial water O─H groups is comparable to that in bulk water, despite the effective density reduction at the interface.