How Water–Ion Interactions Control the Formation of Hydrated Electron:Sodium Cation Contact Pairs

Although solvated electrons are a perennial subject of interest, relatively little attention has been paid to the way they behave in aqueous electrolytes. Experimentally, it is known that the hydrated electron’s (e_aq^–) absorption spectrum shifts to the blue in the presence of salts, and the magnitude of the shift depends on the ion concentration and the identities of both the cation and anion. Does the blue-shift result from some type of dielectric effect from the bulk electrolyte, or are there specific interactions between the hydrated electron and ions in solution? Previous work has suggested that e_aq^– forms contact pairs with aqueous ions such as Na⁺, leading to the question of what controls the stability of such contact pairs and their possible connection to the observed spectroscopy. In this work, we use mixed quantum/classical simulations to examine the nature of Na⁺:e^– contact pairs in water, using a novel method for quantum umbrella sampling to construct e_aq^––ion potentials of mean force (PMF). We find that the nature of the contact pair PMF depends sensitively on the choice of the classical interactions used to describe the Na⁺–water interactions. When the ion–water interactions are slightly stronger, the corresponding cation:e^– contact pairs form at longer distances and become free energetically less stable. We show that this is because there is a delicate balance between solvation of the cation, solvation of e_aq^– and the direct electronic interaction between the cation and the electron, so that small changes in this balance lead to large changes in the formation and stability of e^––ion contact pairs. In particular, strengthening the ion–water interactions helps to maintain a favorable local solvation environment around Na⁺, which in turn forces water molecules in the first solvation shell of the cation to be unfavorably oriented toward the electron in a contact pair; stronger solvation of the cation also reduces the electronic overlap of e_aq^– with Na⁺. We also find that the calculated spectra of different models of Na⁺:e^– contact pairs do not shift monotonically with cation–electron distance, and that the calculated spectral shifts are about an order of magnitude larger than experiment, suggesting that isolated contact pairs are not the sole explanation for the blue-shift of the hydrated electron’s spectrum in the presence of electrolytes.