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High-resolution measurements are reported of the surface core-level shift (SCLS) of the $3d$ level for the Rh(111) surface as a function of oxygen coverage $\ensuremath{\Theta}$ on the surface. These measurements are analyzed by density-functional theory calculations of the initial- and final-state contributions to the shifts. The calculations are found to reproduce well the trends and magnitudes of the experimental shifts. Adsorption of oxygen shifts the Rh $3d$ surface core levels to higher binding energies with the magnitude of the shift depending almost linearly on the coordination number of Rh surface atoms to O adatoms. The Rh $3d$ binding energy increases by about 0.3 eV per bond to an O adatom. This correlation is robust with respect to differences between initial- and transition-state theory calculations of the SCLS's. The results are discussed in a simple physical picture.

physical review. b, condensed matter

Oxygen-induced Rh<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mn>3</mml:mn><mml:mi>d</mml:mi></mml:mrow><mml:mrow><mml:mn>5</mml:mn><mml:mo>/</mml:mo><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>surface core-level shifts on Rh(111)

Oxygen-induced Rh3d5/2surface core-level shifts on Rh(111)