Surface core-level shifts at an oxygen-rich Ru surface: O/Ru(0 0 0 1) vs. RuO2(1 1 0)

We present density-functional theory calculations of Ru 3d and O 1s surface core-level shifts (SCLSs) at an oxygen-rich Ru(0 0 0 1) surface, namely for the O(1×1)/Ru(0 0 0 1) chemisorption phase and for two surface terminations of fully oxidized RuO2(1 1 0). Including final-state effects, the computed SCLSs can be employed for the analysis of experimental X-ray photoelectron spectroscopy (XPS) data enabling a detailed study of the oxidation behaviour of the Ru(0 0 0 1) surface. We show that certain peaks can be used as a fingerprint for the existence of the various phases and propose that the long disputed satellite peak in RuO2(1 1 0) XPS data originates from a hitherto unaccounted surface termination.