Variation of Surface Propensity of Halides with Droplet Size and Temperature: The Planar Interface Limit.

The radial number density profiles of halide and alkali ions in aqueous clusters with equimolar radius ≲1.4 nm, which correspond to ≲255 HO molecules, have been extensively studied by computations. However, the surface abundance of Cl, Br, and I relative to the bulk interior in these smaller clusters may not be representative of the larger systems. Indeed, here we show that the larger the cluster is, the lower the relative surface abundance of chaotropic halides is. In droplets with an equimolar radius of ≈2.45 nm, which corresponds to ≈2000 HO molecules, the polarizable halides show a clear number density maximum in the droplet's bulk-like interior. A similar pattern is observed in simulations of the aqueous planar interface with halide salts at room temperature. At elevated temperature the surface propensity of Cl decreases gradually, while that of I is partially preserved. The change in the chaotropic halide location at higher temperatures than the room temperature may considerably affect photochemical reactivity in atmospheric aerosols, vapor-liquid nucleation and growth mechanisms, and salt crystallization via solvent evaporation. We argue that the commonly used approach of nullifying parameters in a force field in order to find the factors that determine the ion location does not provide transferable insight into other force fields.