OH frequency calculations for the hydroxylated MgO(001) surface

Abstract

We have performed periodic Hartree-Fock calculations for OH groups adsorbed on the MgO(001) surface considering different surface coverages. Six types of OH groups are discussed: OH m, OH . , H+, H . and hydrogen-bonded OH and H. It is found that when both OH and H are present on the surface, the two groups are best described as OH m . We suggest that the highest-frequency fundamental band (∼3750 cm m 1 in the experimental OH spectrum) is assigned to OH m groups adsorbed on top of Mg 2+ , while H + adsorbed on top of O 2 m give rise to the broader band at ∼3550 cm m 1 .