Anomalous Underscreening in the Restricted Primitive Model

Authors:
  • AHAndreas Härtel
    Andreas Härtel
  • MBMoritz Bültmann
    Moritz Bültmann
  • FCFabian Coupette
    Fabian Coupette
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Abstract
Underscreening is a collective term for charge correlations in electrolytes decaying slower than the Debye length. Anomalous underscreening refers to phenomenology that cannot be attributed alone to steric interactions. Experiments with concentrated electrolytes and ionic fluids report anomalous underscreening which so far has not been observed in simulation. We present Molecular Dynamics simulation results exhibiting anomalous underscreening that can be connected to cluster formation. A theory which accounts for ion pairing confirms the trend. Our results challenge the classic understanding of dense electrolytes impacting the design of technologies for energy storage and conversion.