A REMPI study of the correlation of internal excitations and substrate-adsorbate coupling for CO molecules desorbed by electron impact

We compare vibrational, translational and rotational excitations of CO molecules desorbed by electron impact, and the yield of oxygen and carbon atoms from electron-induced fragmentation of CO molecules for: (1) CO monolayers on bare transition metals [Ru(001) and Pt(111)]; (2) CO monolayers coadsorbed with well-ordered oxygen atoms; (3) weakly bound CO monolayers on epitaxially grown silver films; and (4) CO monolayers decoupled from the metallic substrate by mono-atomic xenon spacer layers. For all but the last system, we find CO molecules which are vibrationally extremely hot. This is explained by the excitation of strongly antibonding multi-electron states which are quenched in the vicinity of the metal surface before enough translational energy is acquired by the nuclei to complete dissociation. For CO/Xe/Ag(111), vibrationally hot CO molecules are missing among the desorbing particles, whereas strong fragment signals persist. Because of the isolating Xe layer, the substrate-adsorbate coupling is too weak to terminate the dissociation reaction which is induced by the electron impact before the rupture of the molecular bond.