Molecular Dynamics Studies on the Effect of Surface Roughness and Surface Tension on the Thermodynamics and Dynamics of Hydronium Ion Transfer Across the Liquid/Liquid Interface.

Molecular dynamics simulations are used to examine the effect of surface roughness and surface tension on the transfer of the classical hydronium ion (HO) across the water/1,2-dichloroethane interface. Free energy of transfer, hydration structure, and dynamics as a function of the ion location along the interface normal are calculated with six different values of a control parameter whose variation modifies the surface tension without impacting the bulk properties of the two solvents. Transfer of the classical hydronium ion across the water/1,2-dichloroethan interface involves the cotransfer of three hydration shell water molecules, independent of the surface tension. However, as the interaction between the two liquids weakens, a rise in interfacial tension and decrease in intrinsic water fingering and capillary fluctuations result in fewer water molecules cotransported with the ion in the second shell and a reduction in the length of the finger that the ion is attached to, consistent with the reduced size of the second hydration shell. First shell water residence time and lateral ion diffusion constants vary with the surface tension in a way that is consistent with the abovementioned structural insight.