Beyond single-crystal surfaces: The GAL21 water/metal force field

Abstract

Solvent effects are notoriously difficult to describe for metallic nano-particles (NPs). Here, we introduce GAL21 the first pair wise additive force field that is specifically designed to modulate the near chemisorption energy of water as a function of the coordination numbers of the metallic atoms. We find a quadratic dependence to be most suitable for capturing the dependence of the adsorption energy of water on the generalized coordination number (GCN) of the metal atoms. GAL21 has been fitted against DFT adsorption energies for Cu, Ag, Au, Ni, Pd, Pt, and Co on 500 configurations and validated on about 3000 configurations for each metal, constructed on five surfaces with GCNs varying from 2.5 to 11.25. Depending on the metals, the RMSD is found between 0.7 kcal·mol−1 (Au) to 1.6 kcal·mol−1 (Ni). Using GAL21, as implemented in the open-source code CP2K, we then evaluate the solvation energy of Au55 and Pt55 NPs in water using thermodynamic integration. The solvation free energy is found to be larger for Pt and Au, and systematically larger than 200 kcal·mol−1, demonstrating the large impact of solvent on the surface energetics of NPs. Still, given that the amorphous NPs are both, the most stable and the most solvated ones, we do not predict a change in preferred morphology between the gas-phase and in water.