Interaction of NO and O2 with Pd(111) surfaces. I.

The adsorption of NO on Pd(111) was studied by means of LEED, UPS and thermal desorption measurements. Non-dissociative adsorption is characterized by additional maxima in the photomission spectra at 2.6, 9.2 and 14.6 eV below the Fermi level originating from chemisorption levels which are derived from the highest occupied molecular orbitais of NO. Thermal desorption takes place from three distinct states (α, β and γ) corresponding to binding energies of about 15, 17 and 31 kcal/mole, respectively, with about equal populations. The α-state is associated with a 2 × 2 LEED pattern and the β-state with a c4 × 2 structure, whereas the γ-state corresponds to disordered adsorption at low coverages. Plausible structure models are proposed for the ordered structures with θ = 0.75 for the α-state and θ = 0.5 for the β-state. The strong decrease of the adsorption energy is explained in terms of pronounced short-range repulsive interactions between neighbouring adsorbate molecules.