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Abstract Understanding the solvation structures of OH − and H 3 O + at metal interfaces is crucial for developing efficient electrochemical devices. In this paper, we present a detailed investigation of the solvation structures of OH − and H 3 O + near gold electrodes under alkaline and acidic aqueous conditions, using ab initio molecular dynamics simulations at controlled surface charge density conditions. Our findings reveal that the adsorption tendencies of OH − and H 3 O + are strongly influenced by the oscillating net atomic charge of water normal to the electrified interface in concert with the distinct solvation patterns of these charge defects. While OH − preferentially adsorbs onto the gold surface within the first water layer, the positive net atomic charge restricts the closest approach of H 3 O + to beyond the first water layer. We unveil resting and active states that support charge transfer processes at the gold/water interface, which critically involve Au atoms in a unique Grotthuss-like mechanism.
Park et al. (Fri,) studied this question.