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Photon-stimulated ion desorption from solid MoO3 following the Mo 2p3/2 resonant transition has been investigated. In the XANES spectrum, Mo 2p3/2 peak is split into two components corresponding to the excitations from Mo 2p3/2 into the t2g and eg orbitals. It was observed that the desorption yield of O+ ions at the Mo 2p3/2 ⇒ eg resonance is higher than that at the Mo 2p3/2 ⇒ t2g resonance. The Auger decay spectra reveal that there exist two kinds of spectator Auger decays. The high desorption yield at the 2p3/2 ⇒ eg resonance is interpreted by the fast breaking of the Mo-O bond due to the localization of the electrons in the highly antibonding eg.

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