HREELS study of O2 molecular chemisorption on Ag(001)

O-2 adsorption on Ag(001) at 100 K has been investigated by HREELS. Contrary to previous reports we could resolve 4 oxygen related peaks, 3 of which are due to the internal stretching vibration as confirmed by isotope labelling. The lowest frequency mode at 63 meV is assigned to molecular oxygen chemisorbed at defect sites. The further two features are very close to each other in frequency, at 79 and 84 meV. We assign them to molecules chemisorbed in a peroxidic state in two different adsorption sites. Initially both sites are filled simultaneously while at higher coverage adsorption in the higher frequency site is favoured