FIRST-PRINCIPLES SIMULATIONS OF THE ELECTRODE-VERTICAL-BAR-ELECTROLYTE INTERFACE

We review a direct dynamics method for the simulation of metal\water i nterfaces. The occupancy of on-top binding sites for water in this mod el as applied to a (100) surface of 'copper' is very sensitive to pote ntial. We suggest that this may account for some previously unexplaine d features of X-ray data on water structure and noble metal\water inte rfaces. We discuss the problem of statistical fluctuations on the occu pancy of such tightly bound water molecules in such simulations. Thoug h the problem is not too serious for charged interfaces, the problem o f accounting for fluctuations at zero charge can be quite formidable, as we illustrate for the (100) surface of copper. (C) 1998 Elsevier Sc ience S.A. All rights reserved.