We have utilized density-functional theory (DFT) calculations to develop a simple and physically transparent model for the analysis of the interactions between adsorbates on metal surfaces. We have applied this model to investigate underlying mechanisms that govern the interaction between Cs promoters and oxygen adsorbates on Ag(111).
We have also employed an atomistic thermodynamics approach and ab initio Monte Carlo simulations to extend the results of DFT calculations to realistic temperature and pressure. We found that the underlying mechanisms of chemical promotion by alkali promoters change significantly as a function of external conditions.