Second-Order Vibrational Lineshapes from the Air/Water Interface

We explore by means of modeling how absorptive-dispersive mixing between the second- and third-order terms modifies the imaginary χ_total⁽²⁾ responses from air/water interfaces under conditions of varying charge densities and ionic strength. To do so, we use published Im(χ⁽²⁾) and χ⁽³⁾ spectra of the neat air/water interface that were obtained either from computations or experiments. We find that the χ_total⁽²⁾ spectral lineshapes corresponding to experimentally measured spectra contain significant contributions from both interfacial χ⁽²⁾ and bulk χ⁽³⁾ terms at interfacial charge densities equivalent to less than 0.005% of a monolayer of water molecules, especially in the 3100 to 3300 cm^-1 frequency region. Additionally, the role of short-range static dipole potentials is examined under conditions mimicking brine. Our results indicate that surface potentials, if indeed present at the air/water interface, manifest themselves spectroscopically in the tightly bonded H-bond network observable in the 3200 cm^-1 frequency range.