The EPR Observation of O2− Chemisorbed on a Metallic Silver Surface

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Abstract
The adsorption of oxygen on metallic silver surfaces has been studied using an EPR technique. The interaction of O2 with these surfaces at room temperature results in the rapid formation of a radical species having gxx = 2.0042, gyy = 2.0115, and gzz = 2.034. The stability of the radical to prolonged outgassing and thermal desorption is studied, and reactivity with moderate pressures of CO (∼20 Torr) at room temperature has been observed. Ageing of the silver surface under cyclic outgassing, adsorption, outgassing, and reduction with H2 at 110°C has been noted. On the basis of g values and molecular parameters λ/δ and λ/Δ calculated from theory, we postulate the radical to be the superoxide, O2−, in an adsorption site with a component of electric field perpendicular to the internuclear axis of the molecular ion.

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