Nature of Excess Hydrated Proton at the Water–Air Interface

Understanding the interfacial molecular structure of acidic aqueous solutions is important in the context of, e.g., atmospheric chemistry, biophysics, and electrochemistry. The hydration of the interfacial proton is necessarily different from that in the bulk, given the lower effective density of water at the interface, but has not yet been elucidated. Here, using surface-specific vibrational spectroscopy, we probe the response of interfacial protons at the water–air interface and reveal the interfacial proton continuum. Combined with spectral calculations based on ab initio molecular dynamics simulations, the proton at the water–air interface is shown to be well-hydrated, despite the limited availability of hydration water, with both Eigen and Zundel structures coexisting at the interface. Notwithstanding the interfacial hydrated proton exhibiting bulk-like structures, a substantial interfacial stabilization by −1.3 ± 0.2 kcal/mol is observed experimentally, in good agreement with our free energy calculations. The surface propensity of the proton can be attributed to the interaction between the hydrated proton and its counterion.