  Stable oxygen sites on a PdO film over a Pd(100) thin structures with a
(sqrt{5} times sqrt{5}) R27^circ surface-unit cell are determined using the
first-principles electronic structure calculations with the generalized
gradient approximation. The adsorbed monatomic oxygen goes to a site bridging
two 2-fold-coordinated Pd atoms or to a site bridging a 2-fold-coordinated Pd
atom and a 4-fold-coordinated Pd atom. Estimated reaction energies of CO
oxidation by reduction of the oxidized PdO film and N_2O reduction mediated by
oxidation of the PdO film are exothermic. Motion of the adsorbed oxygen atom
between the two stable sites is evaluated using the nudged elastic band method,
where an energy barrier for a translational motion of the adsorbed oxygen may
become sim 0.45 eV, which is low enough to allow fluxionality of the surface
oxygen at high temperatures. The oxygen fluxionality is allowed by existence of
2-fold-coordinated Pd atoms on the PdO film, whose local structure has
similarity to that of Pd catalysts for the Suzuki-Miyaura cross coupling.
Although NO_x (including NO_2 and NO) reduction is not always catalyzed only by
the PdO film, we conclude that there may happen continual redox reactions
mediated by oxygen-adsorbed PdO films over a Pd surface structure, when the
influx of NO_x and CO continues, and when the reaction cycle is kept on a
well-designed oxygen surface.
