Water exchange at a hydrated platinum electrode is rare and collective

TL;DR

This study uses molecular dynamics simulations to investigate the rare and collective water exchange process at a hydrated platinum electrode, revealing the underlying mechanisms involving hydrogen bond reorganization and density fluctuations.

Contribution

It introduces a detailed analysis of water exchange kinetics at metal interfaces, highlighting the collective nature and controlling factors of the process.

Findings

Water exchange is a rare event with ~40 ns residence time.

Desorption is controlled by hydrogen bond network reorganization.

Spatial and temporal correlations extend over nanometers and tens of picoseconds.

Abstract

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.