LEED crystallographic studies for the chemisorption of oxygen on the (100) surface of copper

Abstract

Intensity analyses with low-energy electron diffraction (LEED) are reported for surface structures obtained by adsorbing submonolayer amounts of oxygen on the (100) surface of copper. It is found for chemisorption on the four-coordinate hollow sites that the correspondence between experimental and calculated intensity-versus-energy curves, for 10 diffracted beams, is slightly better for coplanar adsorption than for adsorption about 0.75 Å above the surface (the latter model is essentially as proposed previously by both SEXAFS and photoelectron diffraction). Nevertheless, in neither of these contrasting situations is the agreement sufficient to conclude that the structural analysis is complete. Evidence is presented that nearly coplanar chemisorption, in combination with a missing row model, can accommodate a number of structural features for this system, including the existence of the (2√2 × √2)45°−O phase, beam splittings resulting from antiphase domain boundaries, and the structural analogy noted in other studies between the (2√2 × √2)45°−O phase and the stepped nature of the (410) copper surface which can form by faceting in oxygen. Considerations of O–Cu surface bond lengths, guided by those in bulk Cu2O, suggest that additional lateral relaxations are likely in the topmost copper layer. This study provides no support for the O chemisorption occurring in tetrahedral-type sites.