Benchmarking water adsorption on metal surfaces with ab initio molecular dynamics

Solid-water interfaces are ubiquitous in nature and technology. In particular, technologies evolving in the green transition, such as electrocatalysis, heavily rely on the junction of an electrolyte and an electrode as a central part of the device. For the understanding of atomic-scale processes taking place at the electrolyte-electrode interface, density functional theory (DFT) has become the de facto standard. The validation of DFT’s ability to simulate the interfacial solid/water interaction is crucial, and ideal simulation setups need to be identified in order to prevent avoidable systematic errors. Here, we develop a rigorous sampling protocol for benchmarking the adsorption/desorption energetics of water on metallic surfaces against experimental temperature programmed desorption, single crystal adsorption calorimetry, and thermal energy atom scattering. We screened DFT’s quality on a series of transition metal surfaces, applying three of the most common exchange-correlation approximations: PBE-D3, RPBE-D3, and BEEF-vdW. We find that all three xc-functionals reflect the pseudo-zeroth order desorption of water rooted in the combination of attractive adsorbate-adsorbate interactions and their saturation at low and intermediate coverages, respectively. However, both RPBE-D3 and BEEF-vdW lead to more accurate water adsorption strengths, while PBE-D3 clearly overbinds near-surface water. We relate the variations in binding strength to specific variations in water-metal and water-water interactions, highlighting the structural consequences inherent in an uninformed choice of simulation parameters. Our study gives atomistic insight into water’s complex adsorption equilibrium. Furthermore, it represents a guideline for future DFT-based simulations of solvated solid interfaces by providing an assessment of systematic errors in specific setups.