Experimental and theoretical study of a surface stabilized monolayer phase of nickel oxide on Pd(100)

A surface stabilized monolayer phase of nickel oxide, c(4 x 2)-Ni3O4, has been found to grow epitaxially under reactive deposition conditions on Pd(100), in the presence of other adsorbed phases and in competition with them. High-quality scanning tunneling microscopy data are reported and discussed, including a detailed analysis of the defects and of the border morphology of this new phase. The data are discussed in the light of ab initio simulations of the electronic, energetic, and geometric properties of such a phase. A hybrid-exchange density functional theory approach has been used, and a slab model is adopted where palladium is simulated by a thin film covered on both sides by regular epilayers. A growth model has been developed that explains both the unusual stoichiometry of the phase and the observed defects.