Abstract
The lattice-gas model is used to analyze statistical aspects of the initial stages of oxidation of metal surfaces. Any oxygen atom is assumed to be located in positions 1 or 2 which correspond to the chemisorbed and oxide state respectively. At low coverages, position 1 is stable and position 2 is metastable. The metastable phase is assumed to be stabilized at high coverages by lateral interactions between nearest-neighbour oxygen atoms. The fraction of oxygen atoms in state 2 is calculated as a function of the energy difference between states 1 and 2 and various lateral interactions. The first-order phase transition from the chemisorbed state to the oxide state is shown to occur with increasing coverage directly or through the intermediate mixed state. In both cases, the model predicts that the critical coverage should not be too low (θ c ≳ 0.5).
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