Adsorption of hydrated hydroxide and hydronium ions on Ag(111). A quantum mechanical investigation

In this paper we have studied comparatively the adsorption of hydroxide and hydronium ions, extending our previous study on hydronium adsorption [J. Phys. Chem. B. 105 (2001) 7227] and emphasizing the adsorption of hydroxide. The calculations were performed on the 111 surface of silver using ab initio quantum mechanical methods (Hartree-Fock + Molter-Plesset second order perturbation theory). The adsorption was investigated for the bare and the hydrated ions (up to three water molecules). Binding energies, equilibrium structures and charge transfer processes were investigated. While the successive hydration of hydronium detaches the ion from the surface, the hydrated hydroxide anion remains specifically adsorbed. Charge transfer processes between the adsorbates and the surface were studied using electron density difference plots and effective charges obtained from Mulliken populations and from surface-dipole moment curves. The energetics of the surface reactions leading to the formation of the hydrated hydronium and hydroxide ions from the bare adsorbed ions and water molecules was also investigated. Both reactions are exothermic mainly due to the formation of strong hydrogen bonds. The effect of an external homogeneous electric field perpendicular to the surface on different adsorbate properties was investigated for the bare and hydrated hydroxide ion in order to model the environment of the electrical double layer. The electric field affects the orientation of the water molecules on the surface and the hydroxide surface distance. (C) 2003 Elsevier Science B.V. All rights reserved.