Structural rearrangement by coadsorption: a LEED IV determination of the Ru(001)-p(2 × 2)(2O + CO) structure

Abstract

This LEED IV analysis of the coadsorbate structure consisting of 0.5 monolayers (ML) of O and about half as much CO corroborates prior suggestions that the coadsorption of CO restructures the (2 × 1)O structure, with all O in hcp sites, into a honeycomb structure of the O atoms which now occupy both fcc and hcp sites; the CO molecule is adsorbed on top of the Ru atom in the center of the O hexagon. Any row structure for the O atoms in the coadsorbate layer can be clearly excluded, even though one starts from the (2 × 1)O row structure and adsorption of CO proceeds at low temperature. The intramolecular distance d(C-O) = 1.15 ± 0.04 Å is essentially unaltered by adsorption, and the bond length to the underlying Ru atom is d(C-Ru) = 1.98 ± 0.08 Å. The bond lengths found for the two different oxygen atoms in the unit cell are identical at d(O fcc-Ru) = d(O hcp-Ru) = 2.05 ± 0.16 Å; they are similar to the bond lengths of pure oxygen adsorbed on Ru(001). We find buckling of the first substrate layer, which leads to a partial expansion of the first layer distance of the substrate: All Ru atoms within this layer (with the exception of those underneath the CO molecules) are shifted outwards by 0.02 ± 0.02 Å with respect to their bulk positions; in contrast, a contraction of the first layer distance of − 2% has been found earlier for the clean surface. Additionally, the Ru atoms around the fcc site are shifted towards this site by an amount of 0.08 ± 0.08 Å; there is no change of the second layer. The structure analysis was performed by conventional search procedures and by Tensor LEED. A comparison of the time requirements of these two procedures yielded an advantage of factor 6 for Tensor LEED.