When a slightly defective rutile TiO2(110) surface is exposed to O2 at elevated temperatures, the molecule dissociates at defects, filling O vacancies (VO) and creating O adatoms (Oad) on Ti5c rows. The adsorption of molecular O2 at low temperatures has remained controversial. Low-temperature scanning tunneling microscopy of O2, dosed on TiO2(110) at a sample temperature of ≈100 K and imaged at 17 K, shows a molecular precursor at Ov as a faint change in contrast. The adsorbed O2 easily dissociates during the STM measurements, and the formation of Oad's at both sides of the original VO is observed.
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