Cl2 adsorption on MgO(001) surface supported sodium monolayers: a density functional theory study

The adsorption of Cl2 Na monolayers supported on the MgO(001) surface has been studied by the density functional method using cluster models embedded in a large array of point charges (PCs). The value of PCs was determined by charge self-consistent technique. The results indicate that Na-promoted MgO(001) surface is an efficient catalyst toward Cl2 adsorptive decomposition. Besides, it was found that the role of the MgO(001) surface is not passive, which is different from CO adsorption on MgO(001) surface supported Na metal monolayers. The analysis of band and projected density of states indicates that the electron transfer from the surface Mg 3s valence orbital and Na 3s valence orbital to the anti-bonding σ∗ orbital of Cl2 is the source of the Cl2 bond weakening. This is also different from the CO adsorption on MgO(001) surface supported Na metal monolayers, where only the electrons from the Na valence orbital are transferred to the anti-bonding π∗ orbital of adsorbed CO. Our study suggests that the essence of catalysis is different for CO and Cl2 adsorption on Na metal monolayers supported an MgO(001) surface.