Temperature Dependence and Energetics of Single Ions at the Aqueous Liquid–Vapor Interface

Abstract

We investigate temperature-dependence of free energetics with two single halide anions, I^– and Cl^–, crossing the aqueous liquid–vapor interface through molecular dynamics simulations. The result shows that I^– has a modest surface stability of 0.5 kcal/mol at 300 K and the stability decreases as the temperature increases, indicating the surface adsorption process for the anion is entropically disfavored. In contrast, Cl^– shows no such surface state at all temperatures. Decomposition of free energetics reveals that water–water interactions provide a favorable enthalpic contribution, while the desolvation of ion induces an increase in free energy. Calculations of surface fluctuations demonstrate that I^– generates significantly greater interfacial fluctuations compared to Cl^–. The fluctuation is attributed to the malleability of the solvation shells, which allows for more long-ranged perturbations and solvent density redistribution induced by I^– as the anion approaches the liquid–vapor interface. The increase in temperature of the solvent enhances the inherent thermally excited fluctuations and consequently reduces the relative contribution from anion to surface fluctuations, which is consistent with the decrease in surface stability of I^–. Our results indicate a strong correlation with induced interfacial fluctuations and anion surface stability; moreover, resulting temperature dependent behavior of induced fluctuations suggests the possibility of a critical level of induced fluctuations associated with surface stability