Work-function and structures of (100), (111) and (101) Au surfaces with/without oxygen (2411.16208v1)

Abstract: (100), (101), and (111) Au surfaces with chemisorbed oxygen of varying coverages are studied using density and hybrid functional theories and experiments. This clarifies the work function (f), surface structures, stability, and density of states. f of the (100), (101), and (111) Au surfaces calculated using the hybrid functional is 5.06-5.23 eV, and consistent with the reported experimental f of polycrystalline Au films (5.1 +- 0.1 eV). The hybrid functional calculations on f at (100) and (101) AuO surfaces agree with the experimental f. However, in the reported and present experiments, the difference in f between the Au and AuO surfaces (Df) is 0.8-0.9 eV. The reported theoretical Df at (111) surface (3 eV) completely contradicts this value, which has been unresolved. We find that when O atoms are at (111) surface and subsurface, the theoretical Df at (111) agrees with experimental Df (0.8-0.9 eV). This state is considered to correspond to the experiments, because the oxygen-chemisorption is more stable in this state than when O atoms are at (111) surface only. This property is unique to the (111) surface. The prediction of chemisorbed-oxygen-induced disorders that are experimentally observed provides more evidence for the veracity of these calculations.