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Updated: Jun 20, 2025

Dynamic Electrochemical Measurement of Chloride Ions
Published on: February 5, 2016
Dynamic Ion Correlations and Ion-Pair Lifetimes in Aqueous Alkali Metal Chloride Electrolytes
Gareth R Elliott1, Erica J Wanless1, Grant B Webber2
1Discipline of Chemistry, The University of Newcastle, Callaghan, New South Wales 2308, Australia.
Abstract:
Electrolytes are central to many technological applications, as well as life itself. The behavior and properties of electrolytes are often described in terms of ion pairs, whereby ions associate as either contact ion pairs (in which ions are "touching") solvent-separated ion pairs (in which ions' solvent shells overlap) or solvent-solvent-separated ion pairs (in which ions' solvent shells are distinct). However, this paradigm is generally restricted to statistically averaged descriptions of solution structure and ignores temporal behavior. Here we elucidate the time-resolved dynamics of these ion-ion interactions in aqueous metal chloride electrolytes using the partial van Hove correlation function, based on polarizable molecular dynamics simulations. Our results show that the existence and persistence of ion pairs in aqueous metal chloride electrolytes should not be assumed a priori, but in fact are ion specific features of the solution with lifetimes on subpicosecond time scales.
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