Surface photochemistry. II. Wavelength dependences of photoinduced dissociation, desorption, and rearrangement of O2 on Pt(111)

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Abstract
A Pt(111) surface saturated with molecular oxygen was irradiated by UV light from a mercury arc lamp with various cutoff filters. High‐resolution electron energy‐loss spectroscopy (HREELS) and temperature programmed desorption mass spectroscopy (TPD) were used to characterize the products retained on the surface. Upon UV irradiation at 95 K, chemisorbed O2 (peroxo) undergoes dissociation, desorption and rearrangement. Different wavelength dependences were observed for the three processes: dissociation was not observed at wavelengths longer than 295 nm, in agreement with gas phase photodissociation of the O–O bond in hydrogen peroxide; desorption and rearrangement became negligible at wavelengths longer than 420 nm, in agreement with the photolysis of an organometallic peroxoplatinum complex. For wavelengths between 230 and 315 nm, the average cross sections of dissociation and desorption were estimated to be 5.7×10−20 and 1.2×10−19 cm2 , respectively. The possible origins of the three processes are discussed.