The electronic structure of Cl2 adsorption on MgO(001) defective and irregular surfaces

Using the geometric configuration optimized from ab initio calculation, the electronic structures of Cl-2 adsorption on MgO(001) defective and irregular surfaces were studied by EHT crystal orbital method. The characteristics of bands have been discussed. The results of the optimization have proved that Cl-2 is preferable to bind over oxygen sites. Moreover, Cl-2 binds at Mg(3C) cations corner sites considerably stronger than at regular Mg(5C) and Mg(4C) sites. The charge re distributions in the Cl-2 molecule and in the substrate are considered. The magnesium vacancy of MgO(001) surface is more beneficial to Cl-2 adsorption and decompose on the surface than other configurations. It is proved that the interactions between the Cl-2/surface are weak physisorption.