Sum Frequency Generation of O−H Vibrations on the Surface of H₂O/HNO₃Solutions and Liquid HNO₃

Abstract

The surfaces of aqueous HNO3 solutions and liquid HNO3 are examined using sum frequency generation (SFG). A molecular-level picture of these atmospherically relevant systems is developed. Consistent with previous interpretations, an electric double layer comprised of subsurface anions and cations develops in 0.005x and 0.01x HNO3 solutions, where x = mole fraction. Compared to pure water, these solutions generate more SFG signal in the hydrogen-bonded region as water molecules respond to the subsurface electric field by aligning with the surface normal. At higher concentrations, 0.05x and 0.4x HNO3, ionic complexes or molecules sufficiently approach the surface to disrupt the hydrogen-bonding network and perturb the first water layer. Neither liquid nitric acid nor its solutions show a clear O−H.