Adsorbate Resonance Induces Water‐Metal Bonds in Electrochemical Interfaces

Abstract This study delves into the intricate interactions between surface‐near species, OH and H 2 O, on electrodes in electrochemical interfaces. These species are an inevitable part of many electrocatalytic energy conversion reactions such as the oxygen reduction reaction. In our modeling, we utilize high statistics on a dataset of complex solid solutions with high atomic variability to show the emergence of H 2 O‐metal covalent bonds under specific conditions. Based on density functional theory (DFT) calculations of adsorption energies on many thousands of different surface compositions, we provide a quantifiable physical understanding of this induced water covalency, which is rooted in simple quantum mechanics. Directional hydrogen bonding between surface‐near H 2 O and OH, enables surface bonding electrons to delocalize, mediated by near‐symmetrical adsorbate resonance structures. The different adsorbate resonance structures differ by surface coordination explaining the induced H 2 O‐metal bonding.