At an aqueous electrochemical interface the structure and dynamics of liquid water can differ substantially from that of the bulk liquid. These differences can significantly affect microscopic processes that are coupled to solvent fluctuations. Here we consider the process of aqueous charge seperation, comparing the bulk-phase dynamics to those within double layer environment. Specifically, using molecular dynamics simulations we consider the separation of classical ion pairs (such as Li+ and Cl-) as well as water ion pairs (i.e., H3O+ and OH-). It turns out that the dynamics of classical ion pairs are much more strongly affected in this environment than that of water ion pairs. This, as we demonstrate, is due to fundmental differences in the demands placed on the local hydration environment.

Microscopic dynamics of charge separation at the aqueous electrochemical double layer

251st National Meeting (2016)

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