Photolysis of chemisorbed dioxygen on Pd(111): Dependence on photon energy

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Abstract
Photolysis of chemisorbed dioxygen bound in the peroxo and superoxo configurations to Pd(111) has been studied and cross section vs photon energy measurements have been made. Three photoprocesses occur: (1) photodesorption of O2(g); (2) photoconversion between different O2(a) species; and (3) photodissociation to produce O(a). The threshold photon energy for O2(a) photodesorption or photoconversion is 3.4±0.3 eV or lower; for photodissociation of O2(a) to produce O(a), the threshold photon energy is 3.7±0.3 eV. The cross sections for photodissociation and photodesorption of chemisorbed dioxygen on Pd(111) at a photon energy of 5.2 eV are (3.5±1.2)×10−20 and (1.3±0.1)×10−19 cm2 , respectively.