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While the static structure of aqueous electrolytes has been studied for decades, their dynamic microscopic structure remains unresolved yet critical in many areas. We report a comparative study of dc and ac (1 Hz to 20 GHz) conductivity data of weak and strong electrolytes, highlighting previously missing differences and similarities. Based on these results, we introduce into consideration the intrinsic short-lived ions of water, namely, excess protons (H3O+) and proton holes (OH-). We show that the model accounting for the neutralization of these ions by the species of electrolyte explains the conductivity of aqueous solutions in the concentration range 10-7-10 M. Based on independent experimental data, we hypothesize that the aggregation of the species in weak electrolytes may determine the main difference between the conductivity of weak and strong electrolytes. Our results push forward the understanding of the dynamic structure of aqueous electrolyte solutions and are important to nanofluidic, biological, and electrochemical systems.
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Nicola Marzari, Matteo Cococcioni