The adsorption and dissociation of Cl2 on the MgO (001) surface with vacancies: embedded cluster model study

The adsorption of Cl(2) at a low-coordinated oxygen site (edge or corner site) and vacancy site (terrace, edge, corner F, F(+), or F(2+) center) has been studied by the density functional method, in conjunction with the embedded cluster models. First, we have studied the adsorption of Cl(2) at the edge and corner oxygen sites and the results show that Cl(2), energetically, is inclined to adsorb at the corner oxygen site. Moreover, similar to the most advantageous adsorption mode for Cl(2) on the MgO (001) perfect surface, the most favorable adsorption occurs when Cl(2) approaches the corner oxygen site along the normal direction. A small amount of electrons are transferred from the substrate to the antibonding orbital of the adsorbate, leading to the Cl-Cl bond strength weakened a little. Regarding Cl(2) adsorption at the oxygen vacancy site (F, F(+), or F(2+) center), both large adsorption energies and rather much elongation of the Cl-Cl bond length have been obtained, in particular at the corner oxygen vacancy site, with concurrently large amounts of electrons transferred from the substrate to the antibonding orbital of Cl(2). It suggests, at the oxygen vacancy site, that Cl(2) prefers to dissociate into Cl subspecies. And the potential energy surface indicates that the dissociation process of molecular Cl(2) to atomic Cl is virtually barrierless.