  We use molecular dynamics simulations to study the exchange kinetics of water
molecules at a model metal electrode surface -- exchange between water
molecules in the bulk liquid and water molecules bound to the metal. This
process is a rare event, with a mean residence time of a bound water of about
40 ns for the model we consider. With analysis borrowed from the techniques of
rare-event sampling, we show how this exchange or desorption is controlled by
(1) reorganization of the hydrogen bond network within the adlayer of bound
water molecules, and by (2) interfacial density fluctuations of the bulk liquid
adjacent to the adlayer. We define collective coordinates that describe the
desorption mechanism. Spatial and temporal correlations associated with a
single event extend over nanometers and tens of picoseconds.
