Bonding between CO and the MgO(001) surface: A modified picture

The interaction energy and equilibrium distance for adsorption of CO on a perfect MgO(001) surface has been calculated, using a cluster approach for representing the surface. The cluster size has been varied from one single Mg2+ ion up to Mg14O5. Ab initio model potentials (AIMP) were used to embed the explicitly described cluster while the rest of the crystal was taken to be point charges. The AIMP model potentials are shown to be a necessary and reliable improvement, compared with using only point charges as a model for the surrounding crystal. It is found that the electrostatic attraction and Pauli repulsion almost cancel each other and the small binding energy obtained is ascribed to dispersive forces. The interaction energy is calculated to be 0.07–0.09 eV (depending on which approach to basis set superposition errors corrections is taken); this is rather low in comparison with the experimental value of 0.3–0.4 eV.