LAUSR

Abstract To investigate the degree that efficient computational methods can be used for modelling adsorbates at solid/liquid interfaces, we have benchmarked gas phase and solvated energetics for H, O and OH adsorbates on the Pt(1 1 1) surface calculated from periodic slab and surface cluster models. We have found that absolute solvation energies using the VASPsol continuum solvation model under periodic boundary conditions are typically much smaller in magnitude compared to solvation energies computed using COSMO using a surface cluster model. Although the two models provide quite different absolute solvation energies, the relative energy contributions between the different models are generally similar with one notable exception being the OH adsorbate when bound at top sites on this surface. We provide recommendations for reliable computational quantum chemistry modelling of adsorption energies on solid/liquid interfaces.