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The vapor−liquid interface of aqueous inorganic acid and salt solutions are examined using sum frequency generation (SFG). The results show that the SFG intensity of hydrogen-bonded water on 0.01x acid (HCl, HNO3, and H2SO4) solutions, where x = mole fraction, is greatly enhanced compared to the 0.01x solution of the corresponding salts (NaCl, NaNO3, and KHSO4). This suggests that either surface water molecules on the acid solutions orient with the dipole in a more vertically aligned fashion than those on the salt solutions or that more layers of water are ordered. These results are interpreted with an electric double layer model, in which the double layer is composed of subsurface anions and cations. The weak association of protons, as opposed to Na+ or K+, with anions results in a greater electric field at the surface on acid solutions. The perturbation of surface water on ionic solutions is discussed in terms of electrostatic and displacement mechanisms.

The OH and CH regions of glycerol/water mixtures in the concentration range 0.0-1.0 mole fraction have been investigated with vibrational sum frequency generation. Glycerol is found to partition to the surface of these solutions in all concentrations. Neat glycerol surfaces contain no free OH groups projecting into the vapor. The surface orientation of glycerol is constant through most of the concentration range.

Sum frequency generation (SFG) vibrational spectroscopy is applied to study the surface characteristics of a film composed of nanoscale TiO2 particles, in which methanol is employed as a molecular probe. The SFG signal from methanol adsorbed on the TiO2 film surface in the CH region consists of four primary peaks located at 2828, 2855, 2935, and 2968 cm-1. The peaks at 2855 and 2968 cm-1 arise from molecular methanol; the other two are attributed to methoxy produced by dissociative chemisorption of methanol on TiO2. Changes in the SFG features with methanol pressure and with surface temperature provide the first direct proof of methoxy generation on nanoparticulate films. In comparison with molecular methanol, methoxy sits more perpendicularly on the surface. The chemisorption is barrierless, and a Langmuir constant of (2.13 ± 0.14) × 103 is derived from the adsorption isotherm. Moreover, UV pretreatment of the TiO2 film substantially increases the methoxy signal. Changes in SFG intensity are in good agreement with the current models for surface active sites and face specificities on TiO2.