  Using first-principles calculations, we have systematically studied the
quantum size effects of ultrathin Pb(111) films on the adsorption energies and
diffusion 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 to 2.62 eV. For the
diffusion and penetration of the adsorbed oxygen atoms, it is found that the
most energetically favored paths are the same on different Pb(111) films. And
because of the modulation of quantum size effects, the corresponding energy
barriers are all oscillating with a bilayer period on different Pb(111) films.
Our studies indicate that the quantum size effect in ultrathin metal films can
modulate a lot of processes during surface oxidation.
