Surface segregation in AuPd alloys: Ab initio analysis of the driving forces

In order to determine the energetic driving forces for surface segregation in AuPd alloys, we use a combined approach coupling ab initio calculations and an analysis via an effective Ising model. Previously, this approach has been used successfully in the framework of N-body interatomic potentials to study the surface segregation in both semi-infinite alloys and nanoparticles, allowing one to determine the relative contributions of the different elementary driving forces. Here, we go beyond the use of N-body interatomic potentials by using ab initio calculations to evaluate the segregation enthalpy and the effective pair interactions, the contribution due to the size difference between the constituants being still obtained by N-body interatomic potentials. We show that the decomposition of the segregation enthalpy into its different elementary contributions is still valid at this level of description. This allows us to analyze the segregation driving forces in the two infinite dilute limits of the Au–Pd system, for both (100) and (111) surfaces. Finally, between the two infinite dilute limits, we find that our results are consistent with existing experimental data. [Display omitted] •We analyze the surface segregation driving forces for AuPd alloys at the ab initio level.•We use a combined approach coupling ab initio calculations and an effective Ising Mode.l•Gold segregation is predicted for all surfaces.•A very satisfying agreement is obtained with available experimental data.