Pyridine-induced formation of 17O–2 adsorbed on thermally activated CaO

Abstract
Whatever the pretreatment of CaO (thermal activation or γ-irradiation in the presence of H2), the molecular ion O 2 could not be observed by direct oxygen adsorption. It was necessary to adsorb pyridine before oxygen to stabilize the molecular ion O 2 characterised by gzz= 2.169, gzz= 2.093 (major site), gyy= 2.0059 and gxx= 2.0004. Using oxygen isotopically enriched in 17O, it was possible to show that the oxygen nuclei were equivalent with a hyperfine constant Axx= 76 G, while the Ayy and Azz values of the tensor were too small to be resolved. The molecular ion O 2 was adsorbed with its internuclear axis (z) parallel to the surface plane and was shown to exchange readily with gas phase oxygen. O 2 could be eliminated by further pyridine adsorption and restored again by a consecutive oxygen adsorption. Several such cycles could be produced easily. For the O 2 molecular ions, the electron donor sites are thought to be the surface coordinatively unsaturated O2– ions and the adsorption sites the Ca2+ surface cations.

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