Dynamic Ion Correlations and Ion-Pair Lifetimes in Aqueous Alkali Metal Chloride Electrolytes

• Published in: The journal of physical chemistry. B 2024-08, Vol.128 (30), p.7438-7444
• Main Authors: Elliott, Gareth R., Wanless, Erica J., Webber, Grant B., Andersson, Gunther G., Craig, Vincent S. J., Page, Alister J.
• Format: Article
• Language: English
• Subjects: B: Liquids; Chemical and Dynamical Processes in Solution
• ISSN: 1520-6106; 1520-5207; 1520-5207
• DOI: 10.1021/acs.jpcb.4c01992

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.