Molecular Dynamics Simulations of the Solution−Air Interface of Aqueous Sodium Nitrate

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 111; no. 16; pp. 3091 - 3098
• Main Authors: Thomas, Jennie L, Roeselová, Martina, Dang, Liem X, Tobias, Douglas J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 26.04.2007
• Subjects: Air; Anions - chemistry; Computer Simulation; Mathematics; Models, Molecular; Nitrates - chemistry; Reactive Oxygen Species - chemistry; Solutions - chemistry; Surface Properties; Water - chemistry
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp0683972

Molecular dynamics simulations have been used to investigate the behavior of aqueous sodium nitrate in interfacial environments. Polarizable potentials for the water molecules and the nitrate ion in solution were employed. Calculated surface tension data at several concentrations are in good agreement with measured surface tension data. The surface potential of NaNO3 solutions at two concentrations also compare favorably with experimental measurements. Density profiles suggest that NO3 - resides primarily below the surface of the solutions over a wide range of concentrations. When the nitrate anions approach the surface of the solution, they are significantly undercoordinated compared to in the bulk, and this may be important for reactions where solvent cage effects play a role such as photochemical processes. Surface water orientation is perturbed by the presence of nitrate ions, and this has implications for experimental studies that probe interfacial water orientation. Nitrate ions near the surface also have a preferred orientation that places the oxygen atoms in the plane of the interface.