Ion-Size Dependent Adsorption Crossover on the Surface of a Water Droplet.

Abstract

The adsorption of ionic and neutral spherical solutes on the surface of a liquid water droplet are investigated using molecular dynamics simulations and theoretical analyses. The results reveal a crossover in the sign of the adsorption free energy as a function of ion size, with ions larger than iodide predicted to be increasingly surface active. Adsorption free energies are decomposed into competing energetic and entropic contributions arising from direct solute-water interaction energy and its fluctuations. The entropically driven surface activity of large ions is predicted to increase with ion size, while small ions are typically driven away from the interface by a more delicate balance of energetic and entropic contributions, with a nonmonotonic ion size dependence linked to the ion's hydration-shell structure and stability. The physical interpretation of the results is illuminated by comparisons with dielectric linear response and cavity formation predictions and implications to interfacial acidity and enhanced chemical reactivity are discussed.