We investigate the oxidation of a wide range of metal surfaces by ab-initio calculations. We go through a wide range of metals (Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Cu, Ag, Au, Zn, Cd, Al) and surface oxygen coverages (Θ_O). Calculations of the adsorption energy per O atom (E_{ads_min}) are followed by characterizing the preferred distribution of O atoms on a partially oxidized surface (considering up to 329 distributions per metal). We find that individual metals exhibit qualitatively different E_{ads_min}(Θ_O) dependencies and thermodynamical preferences: (i) decreasing E_{ads_min}(Θ_O) and heterogeneous distribution of O atoms (stoichiometric oxide + metal; e.g. Al or La), (ii) increasing E_{ads_min}(Θ_O) and homogeneous distribution of O atoms (substoichiometric oxide; e.g. Ti or Zr), (iii) concave E_{ads_min}(Θ_O) and homogeneous distribution of O atoms at low Θ_O and heterogeneous at high Θ_O (e.g. Sc or Y), etc. This is of crucial importance for the quantities such as secondary electron emission yield, which are guaranteed to correspond to a weighted average of those of stoichiometric oxide and metal only in the case of heterogeneous O atom distribution. The results are correlated with formation enthalpies of oxides of various compositions, surface atomic densities of individual metals, and experimental results such as the time dependence of the magnetron voltage during sputter cleaning of oxidized metal targets. Furthermore, we demonstrate use of these results by presenting static and dynamic Monte Carlo simulations of sputtering.

我们通过从头算计算来研究各种金属表面的氧化。我们研究了多种金属（Sc，Y，La，Ti，Zr，Hf，V，Nb，Ta，Cr，Mo，W，Cu，Ag，Au，Zn，Cd，Al）和表面氧覆盖率（Θ _Ö）。计算每个O原子的吸附能（E _{ads_min}），然后表征部分氧化的表面上O原子的优选分布（考虑到每个金属最多329个分布）。我们发现，个别金属表现出质的不同Ë _{ads_min}（Θ _Ò）依赖关系和热力学的偏好：（一）降低Ë _{ads_min}（Θ _Ø）和O原子的不均匀分布（化学计量的氧化物+金属;例如，Al或La），（ⅱ）提高È _{ads_min}（Θ _ö）和均匀的O原子的分布（亚化学计量的氧化物;例如Ti或Zr），（ⅲ）凹È _{ads_min}（Θ _ö）和均匀的O原子的低分布Θ _ö和异构高Θ _Ô（例如Sc或Y）等。这对于诸如二次电子发射率之类的数量至关重要，只有在O原子分布不均匀的情况下，才能保证这些数量对应于化学计量的氧化物和金属的加权平均值。结果与各种组成的氧化物的形成焓，单个金属的表面原子密度以及实验结果（例如在溅射清洗氧化的金属靶期间磁控管电压的时间依赖性）相关。此外，我们通过提出溅射的静态和动态蒙特卡洛模拟来证明这些结果的使用。