Oxygen adsorption on stepped Pd(100) surfaces

We use scanning tunneling microscopy (STM) and high-resolution core-level spectroscopy (XPS) measurements to study the initial oxidation of vicinal Pd(100) surfaces exhibiting close-packed (111) steps. The XPS data analysis is supported by detailed surface-core level shift calculations based on density-functional theory. Both STM images and the XPS spectra are found to be perfectly consistent with a characteristic zigzag O decoration of the Pd steps predicted by a preceding cluster-expansion based theoretical study [Y. Zhang and K. Reuter, Chem. Phys. Lett. 465,303 (2008)]. Continued oxygen uptake leads to the additional stabilization of a p(2 x 2)-O overlayer on the Pd(100) terraces, and ultimately to step bunching with the resulting large Pd(100) terraces covered by the PdO(101) surface oxide. (C) 2010 Elsevier B.V. All rights reserved.