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Abstract:
The ultraviolet photochemistry of dioxygen adsorbed on Pd(111) has been investigated by high-resolution electron energy-loss spectroscopy (HREELS). For excitation with 6.4 eV photons at normal incidence a dissociation cross section of 4 × 10-19 cm2 is found. The dependence of the cross section on polarization and angle of the incident laser light clearly demonstrates that photodissociation of the peroxo species is initiated by substrate excitations. Symmetry considerations show that direct excitations would give rise to dependences different from those characteristic of a substrate mediated process.
