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Abstract

Ultraviolet irradiation of NO₂ adsorbed on top of a NO saturated Pd(111) surface causes the photodissociation of NO₂/N₂O₄ and results in the desorption of NO molecules. This process has been studied using excitation energies between 3.5 and 6.4 eV. At a photon energy of 6.4 eV, a cross section of 3×10⁻¹⁸ cm² is found. Using laser‐induced fluorescence to detect the desorbed NO molecules, fully state‐resolved data detailing the energy channeling into different degrees of freedom has been obtained. Two desorption channels are found, one characterized by nonthermal state populations, and one showing accommodation to the surface. The yield of the fast channel shows a marked increase above 4 eV photon energy. The slow channel is interpreted as being due to NO molecules which, after formation, undergo a trapping–desorption process. A polarization experiment indicates that the photodissociation is initiated by excitation of metal electrons rather than direct absorption by the adsorbate.