Competitive Ion Pairing and the Role of Anions in the Behavior of Hydrated Electrons in Electrolytes

Experiments have shown that in the presence of electrolytes, the hydrated electron's absorption spectrum experiences a blue shift whose magnitude depends on both the salt concentration and chemical identity. Previous computer simulations have suggested that the spectral blue shift results from the formation of (cation, electron) contact pairs and that the concentration dependence arises because the number of cations simultaneously paired with the electron increases with increasing concentration. In this work, we perform new simulations to build an atomistic picture that explains the effect of salt identity on the observed hydrated electron spectral shifts. We simulate hydrated electrons in the presence of both monovalent (Na⁺) and divalent (Ca²⁺) cations paired with both Cl^- and a spherical species representing ClO₄^- anions. Our simulations reproduce the experimental observations that divalent ions produce larger blue shifts of the hydrated electron's spectrum than monovalent ions with the same anion and that perchlorate salts show enhanced blue shifts compared to chloride salts with the same cation. We find that these observations can be explained by competitive ion pairing. With small kosmotropic cations such as Na⁺ and Ca²⁺, aqueous chloride salts tend to form (cation, anion) contact pairs, whereas there is little ion pairing between these cations and chaotropic perchlorate anions. Hydrated electrons also strongly interact with these cations, but if the cations are also paired with anions, this affects the free energy of the electron-cation interaction. With chloride salts, hydrated electrons end up in complexes containing multiple cations plus a few anions as well as the electron. Repulsive interactions between the electron and the nearby Cl^- anions reduce the cation-induced spectral blue shift of the hydrated electron. With perchlorate salts, hydrated electrons pair with multiple cations without any associated anions, leading to the largest possible cation-induced spectral blue shift. We also see that the reason multivalent cations produce larger spectral blue shifts than monovalent cations is because hydrated electrons are able to simultaneously pair with a larger number of multivalent cations due to a larger free energy of interaction. Overall, the interaction of hydrated electrons with electrolytes fits well with the Hofmeister series, where the electron behaves as an anion that is slightly more able to break water's H-bond structure than chloride.