Bayesian unsupervised learning reveals hidden structure in concentrated electrolytes

• Published in: The Journal of chemical physics Vol. 154; no. 13; pp. 134902 - 134908
• Main Authors: Jones, Penelope, Coupette, Fabian, Härtel, Andreas, Lee, Alpha A.
• Format: Journal Article
• Language: English
• Published: United States 07.04.2021
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0039617

Electrolytes play an important role in a plethora of applications ranging from energy storage to biomaterials. Notwithstanding this, the structure of concentrated electrolytes remains enigmatic. Many theoretical approaches attempt to model the concentrated electrolyte by introducing the idea of ion pairs, with ions either being tightly “paired” with a counter-ion or “free” to screen charge. In this study, we reframe the problem into the language of computational statistics and test the null hypothesis that all ions share the same local environment. Applying the framework to molecular dynamics simulations, we find that this null hypothesis is not supported by data. Our statistical technique suggests the presence of two distinct local ionic environments at intermediate concentrations, whose differences surprisingly originate in like charge correlations rather than unlike charge attraction. Through considering the effect of these “aggregated” and “non-aggregated” states on bulk properties including effective ion concentration and dielectric constant, we identify a scaling relation between the effective screening length and theoretical Debye length, which applies across different dielectric constants and ion concentrations.