Ab initio atomistic thermodynamics study of the early stages of Cu(100) oxidation

Using an ab initio atomistic thermodynamics framework, we identify the stable surface structures during the early stages of Cu(100) oxidation at finite temperature and pressure conditions. We predict the clean surface, the 0.25 monolayer oxygen-covered surface, and the missing-row reconstruction as thermodynamically stable structures in range of 100–1000 K and 10−15–105atm, consistent with previous experimental and theoretical results. We also investigate the thermodynamic stabilities of possible precursors to Cu2O formation including missing-row reconstruction structures that include extra on- or subsurface oxygen atoms as well as boundary phases formed from two missing-row nanodomains. While these structures are not predicted to be thermodynamically stable for oxygen chemical potentials below the nucleation limit of Cu2O, they are likely to exist due to kinetic hindrance.