Quantum oscillations in adsorption energetics of atomic oxygen on Pb(111) ultrathin films: A density-functional theory study.

Using first-principles calculations, we have systematically studied the quantum size effects of ultrathin Pb(111) films on the adsorption energies and penetration energy barriers of oxygen atoms. For the on-surface adsorption of oxygen atoms at different coverages, all the adsorption energies are found to show bilayer oscillation behaviors. It is also found that the work function of Pb(111) films still keeps the bilayer-oscillation behavior after the adsorption of oxygen atoms, with the values being enlarged by 2.10-2.62 eV. For the penetration of the adsorbed oxygen atoms, it is found that the energy barriers are all oscillating with a bilayer period on different Pb(111) films because of the modulation of quantum size effects. Our studies indicate that the quantum size effect in ultrathin metal films can modulate a lot of processes during surface oxidation.