Differences of cations and anions: their hydration, surface adsorption, and impact on water dynamics

The higher tendency for anions to accumulate at the salt aqueous solution/air interface than that of cations has been observed experimentally and theoretically, suggesting that the size and polarizability of the ions play essential roles in this effect. Here, we investigate the influence of the nonsymmetrical positive-vs-negative charge distribution in water molecules to the hydration and surface/bulk partition of the solvated positively and negatively charged particles by using molecular dynamics simulations with hypothetical ions to validate our theoretical models. The results indicate that positive and negative charges (called cations and anions, respectively, although they may not really exist in experiments) with all other properties identical are hydrated differently and that the anions are more likely to populate at the surface. The simulation on a combination series of cations and anions in aqueous solution shows significant variations on water dynamics, likely due to the specific cooperativity between oppositely charged ions.