Theoretical and Computational Chemistry

OH binding energy as a universal descriptor of the potential of zero charge on transition metal surfaces



The potential of zero charge (U_PZC) is an important quantity of metal-water interfaces that are central in many electrochemical applications. In this work, we use ab initio molecular dynamics (AIMD) simulations to study a large number of (111), (100), (0001) and (211) and overlayers of transition metal-water interfaces in order to identify simple descriptors to predict their U_PZC. We find a good correlation between water coverage and the work function reduction Δφ which is defined by the difference of the work function in vacuum and in the presence of water. Furthermore, we determine the vacuum binding energies of H2O and *OH species as good descriptors for the prediction of water coverage and thereby of ∆φ. Our insights unify different facet geometries and mixed metal surfaces and thereby generalize recent observations. We further present a scheme to predict U_PZC based only on the *OH binding and the vacuum work function estimated from static DFT calculations. This formalism is applicable to all investigated metals and mixed metal surfaces including terrace and step geometries and does not require expensive AIMD simulations. To evaluate physical influences to U_PZC, we decompose ∆φ into its orientational (∆φ_orient) and electronic(∆φ_el) components. We find ∆φ_orient to be a facet dependent property and a major contributor to ∆φ on (211) surfaces, while ∆φ_sub strongly depends on the metal identity.


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Supplementary material

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Supplementary Information
Experimental values for work function and potential of zero charge; computed values for vacuum work function, water work function (AIMD and implicit solvent), orientational and electronic components of work function reduction, water coverage, and OH and water binding energy.