Structure, Thermodynamics, and Dynamics of Thiocyanate Ion Adsorption and Transfer across the Water/Toluene Interface.

Molecular dynamics simulations are used to examine in detail the structure, thermodynamics, and dynamics involve in the adsorption and transfer of the thiocyanate ion (SCN - ) across the water/toluene interface. Free energy, hydration structure, and several dynamical properties as a function of the ion location along the interface normal are calculated and contrasted with recent experiments. The free energy profile exhibits a local minimum near the interface corresponding to adsorption free energy relative to bulk water of -6 kJ/mol, in reasonable agreement with experiments. The simulations provide insight into the water surface fluctuations that are coupled to the ion transfer, demonstrating formation of water finger-like structures assisting the transfer process.