Electron stimulated desorption of O− and metastable CO* from physisorbed CO2

Abstract

We report electron stimulated desorption (ESD) measurements of O− yields produced by dissociative electron attachment (DEA) to physisorbed CO2. The molecules are condensed at about 17–20 K on polycrystalline Pt, either as pure multilayer films, or in submonolayer (ML) quantities onto thick rare gas substrates. For the pure disordered multilayer solids, we observe four peaks in the O− yield function at incident electron energies, E(e), of about 4.1, 8.5, 11.2, and 15 eV. The lowest two are assigned, respectively, to the 2Πu and 2Πg resonance states of CO−2, which dissociate into O−(2P)+CO(X 1Σ+), and are known to dominate the gas phase DEA O− production cross section for E(e)≤20 eV. Measurements of ESD CO* metastable yields from similar CO2 multilayer solids on Pt(111), also presented here, suggest that the 11.2 and 15 eV O− peaks are associated with the manifold of close-lying CO2*− states which dissociate into O−(2P)+CO* (a 3Π, a′ 3Σ+, or d 3Δ). For 0.15 ML of CO2 physisorbed on 20 ML thick rare gas substrate films significant sharp enhancements (fwhm ≤0.5 eV) are observed in the ESD O− yields at about 0.3–0.4 eV below the lowest substrate exciton energy. These enhancements are attributed to a coupling of the (electron plus exciton) core-excited anion resonances of the rare gas atoms to the dissociative Rydberg anion states of the coadsorbed CO2 at the solid’s surface. This is followed by a transfer of the charge and excitation energy to the coadsorbate.