Adsorptivity of atomic H and coadsorptivity of Mg and O ions on regular and irregular surfaces of MgO: DFT calculations

Abstract

An attempt has been made to clarify how the adsorptivity of atomic H and coadsorptivity of Mg and O ions depend on MgO surface irregularities (edge, Mg corner, O corner and dislocation) and electrostatic potentials using density functional theory calculations. Quantum clusters of moderate sizes were embedded in simulated Coulomb fields that closely approximate the Madelung potentials of the host surfaces. The results confirm the exclusive dependence of atomic H adsorption on the coordination numbers of irregular surfaces. Surface dislocation drastically enhances the adsorptivity of atomic H, but restricts its mobility. Coadsorptivity of Mg and O ion dimers plays a crucial role among adsorbates and is always greater than the adsorption energy of a single adsorbate. Stabilization due to Madelung potential increases on going from the flat to edge to corner surfaces and the three-coordinated corners are the most energetically preferred for nucleation of Mg and O ions.