Computer simulation of hydrated ions near a mercury electrode

We present previously unpublished results and summarize recent computer simulation studies of the interfaces between water or aqueous solutions and liquid or solid mercury which serve as realistic molecular-level models of the electrochemical interface. Most simulations were performed employing a simple rigid crystal model of mercury. It is first shown that the water structure is not strongly affected by using a more realistic liquid model, thus justifying the simpler approach. Structural, dynamic and thermodynamic properties near the rigid mercury crystal are calculated for Li+, F- and I- ions dissolved in water. The differences between the ions are rationalized on the basis of solvation and steric interactions. (C) 1997 Elsevier Science Ltd.