New Implicit Solvation Scheme for Solid Surfaces

It is shown that the effect of water on the bonding characteristics of transition metal surfaces with adsorbates is short-ranged. As a result, adsorption energies in water can be evaluated by a combination of plane-wave density functional theory calculations in vacuum and properly chosen cluster model calculations with and without an implicit solvation model. The scheme is demonstrated for a model C–C cleavage reaction on Pt (111) and for predicting CO frequency shifts on Pd and Pt due to water. We conclude that these shifts originate from water–metal interactions and can be explained by changes in π back-donation. Overall, the results demonstrate that the proposed methodology represents a highly efficient computational approach for approximating the effect of solvents on elementary reaction steps occurring at solid–liquid interfaces of heterogeneous catalysts.