Insight into H2O-ice adsorption and dissociation on metal surfaces from first-principles simulations -: art. no. 113404

Density-functional theory has been used to perform a systematic study of (intact) H2O bilayer and (dissociated) H2O-OH-H overlayer adsorption on hexagonal 3d, 4d, and 5d transition- and noble-metal surfaces. Through careful decompositions of the H2O adsorption energies, we find that variations in the relative stability of intact bilayers and dissociated overlayers depend mainly on variations in adsorbate-substrate bonding, and not on variations in H bonding as previously assumed. Further, we show that the H2O dissociation energy in the bilayers is controlled by the OH-metal bond strength in the dissociated overlayers.