Abstract
We have investigated the core excited σ∗ resonance region in 1 monolayer of O 2, physisorbed on several substrates. Comparisons with the paramagnetic splitting obtained in X-ray photoelectron spectroscopy (XPS) and in ultraviolet photoelectron spectroscopy (UPS) are made. The paramagnetic splitting in XPS and UPS remains the same for the different systems studied, whereas the lineshape of the σ∗ resonance changes considerably. There is a strong indication that the 3 eV double structure seen in the NEXAFS spectrum of O 2 is not due to the splitting of the σ∗ resonance, but rather due to Rydberg states of different symmetry. We also present ab initio calculations which support this interpretation. The calculations give a value of the (1 s → 3σ u ) 3Σ exchange splitting of 0.73 eV.
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