Chemisorption of HCl to the MgO(001) surface: a DFT study

We use plane wave and embedded cluster ab initio density functional calculations to study adsorption, dissociation and diffusion of the HCl molecule on the MgO(001) surface. The two methods yield comparable results for adsorption of an isolated HCl molecule and complement each other when considering charged species and coverage effects. We find dissociative chemisorption at a coverage smaller than 0.5 monolayer with a Cl(-) ion electrostatically coupled to the OH(-) ion at the surface oxygen site. The adsorption energy of the Cl(-)[dot dot dot](OH)(-) complex is 1.5 eV and the activation energy of Cl(-) diffusion away from OH(-) is 0.6 eV. There is no significant activation energy for rotation of Cl(-) around the adsorption site. At rising coverage, an increase in dipole-dipole repulsion between HCl molecules leads to a lowering of the adsorption energy per HCl and a change of binding towards hydrogen-bridge type as well as a lowering of the activation energy for Cl(-) diffusion. OH(-) formed in the surface due to HCl adsorption has a stretch frequency of 3,083 cm(-1) with Cl(-) associated and 3,648 cm(-1) with Cl(-) removed.