COMPUTER-SIMULATION OF HYDRATED IONS NEAR A MERCURY-ELECTRODE

We present previously unpublished results and summarize recent compute r simulation studies of the interfaces between water or aqueous soluti ons and liquid or solid mercury which serve as realistic molecular-lev el models of the electrochemical interface. Most simulations were perf ormed employing a simple rigid crystal model of mercury. It is first s hown that the water structure is not strongly affected by using a more realistic liquid model, thus justifying the simpler approach. Structu ral, dynamic and thermodynamic properties near the rigid mercury cryst al are calculated for Li+, F- and I- ions dissolved in water. The diff erences between the ions are rationalized on the basis of solvation an d steric interactions. (C) 1997 Elsevier Science Ltd.