We demonstrate that double ionisation of the Ag atoms, leading to the forma
tion of d-holes, takes place in the initial oxidation stage of Ag(001). The
complex formed by the Ag2+ ion, two oxygen adatoms and one oxygen atom in
the octahedral interstitial gives rise to a dipole active electron energy l
oss at 130 me V. Signature of the electronic origin of this loss is the inv
erse isotope shift and the peculiar temperature dependence of the energy lo
ss, which can be reproduced by a theoretical model.