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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 ∼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 (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.United States. Department of Energy (DE-AC02-05CH11231

Water Exchange at a Hydrated Platinum Electrode is Rare and Collective