The effect of electron correlation on the adsorption of hydrogen fluoride and water on magnesium fluoride surfaces

Abstract

We have performed periodic density functional and periodic local MP2 calculations for the adsorption of hydrogen fluoride and water on the four low index surfaces (001), (100), (101) and (110) of magnesium fluoride. While the adsorption of HF is described well using B3LYP, MP2 is required for a good description of the adsorption of H₂O. Post-optimization dispersion corrections of B3LYP are found to consistently overestimate the adsorption energy. The coordination of surface cations, the presence of hydroxyls on the surface, as well as the coverage appear to play an equally important role in the adsorption.