Ten Facets, One Force Field: The GAL19 Force Field for Water - Noble Metal Interfaces

Understanding the structure of the water/metal interfaces plays an important role in many are as ranging from surface chemistry to environmental processes. Due to their intrinsic complexity, the water/metal interfaces cannot yet be adequately described by quantum mechanical approaches and accurate force-fields are therefore needed. We develop and parametrize GAL19, a novel force-field to describe the interaction of water with two facets (111 and 100) of five metals (Pt, Pd, Au, Ag, Cu). To increase transferability compared to its predecessor GAL17, the water-metal interaction is described as a sum of pair-wise terms. The interaction energy has three contributions: (i) physisorption is described via a Tang and Toennies potential, (ii) chemisorption and surface corrugation relies on an attractive Gaussian term and (iii) the angular dependence is explicitly included as a truncated Fourier series. 13 parameters are used for each metal surface and were fitted on 250 water adsorption energies computed at the PBE+dDsC level.

The performance of GAL19 was evaluated on a set of more than 600 DFT adsorption energies for each surface, leading to an average root mean square deviation (RMSD) of only 1 kcal/mol, correctly reproducing the adsorption trends: strong on Pt and Pd but weaker on Ag, Au and Cu. This force-field was then used to simulate the water/metal interface for all ten surfaces for 1 ns. Structural analyses reveal similar tendencies for all surfaces: a first, dense water layer that is mostly adsorbed on the metal top sites, and a second layer up to around 6 Å, which is less structured. On Pt and Pd, the first layer is strongly organized with water lying flat on the surface. The pairwise additive functional form allows to simulate the water adsorption on alloys, which is demonstrated at the example of Ag/Cu and Au/Pt alloys. The water/Ag-Cu interface is predicted to be disordered with water mostly adsorbed on Cu which should exacerbate the Ag reactivity. On the contrary, incorporating Pt into Au materials leads to a structuring of the water interface. Our promising results make GAL19 an ideal candidate to get representative sampling of complex metal/water interfaces as a first step towards accurate estimation of free energies of reactions in solution at the metal interface.