Neat Water–Vapor Interface: Proton Continuum and the Nonresonant Background

Whether the surface of neat water is “acidic” or “basic” remains an active and controversial field of research. Most of the experimental evidence supporting the preferential adsorption of H₃O⁺ ions stems from nonlinear optical spectroscopy methods typically carried out at extreme pH conditions (pH < 1). Here, we use vibrational sum frequency spectroscopy (VSFS) to target the “proton continuum”, an unexplored frequency range characteristic of hydrated protons and hydroxide ions. The VSFS spectra of neat water show a broad and nonzero signal intensity between 1700 and 3000 cm^–1 in the three different polarization combinations examined. By comparing the SF response of water with that from dilute HCl and NaOH aqueous solutions, we conclude the intensity does not originate from either adsorbed H₃O⁺ or OH^– ions. Contributions from the nonresonant background are then critically considered by comparing the experimental results with many-body molecular dynamics (MB-MD) simulated spectra.