Abstract
Molecular dynamics simulation and enhanced free energy sampling are used to study hydrophobic solute transfer across the water-oil interface with explicit consideration of the effect of different electrolytes: hydronium cation (hydrated excess proton) and sodium cation, both with chloride counterions (i.e., dissociated acid and salt, HCl and NaCl). With the Multistate Empirical Valence Bond (MS-EVB) methodology, we find that, surprisingly, hydronium can to a certain degree stabilize the hydrophobic solute, neopentane, in the aqueous phase and including at the oil-water interface. At the same time, the sodium cation tends to "salt out" the hydrophobic solute in the expected fashion. When it comes to the solvation structure of the hydrophobic solute in the acidic conditions, hydronium shows an affinity to the hydrophobic solute, as suggested by the radial distribution functions (RDFs). Upon consideration of this interfacial effect, we find that the solvation structure of the hydrophobic solute varies at different distances from the oil-liquid interface due to a competition between the bulk oil phase and the hydrophobic solute phase. Together with an observed orientational preference of the hydroniums and the lifetime of water molecules in the first solvation shell of neopentane, we conclude that hydronium stabilizes to a certain degree the dispersal of neopentane in the aqueous phase and eliminates any salting out effect in the acid solution; i.e., the hydronium acts like a surfactant. The present molecular dynamics study provides new insight into the hydrophobic solute transfer across the water-oil interface process, including for acid and salt solutions.