Stress effect on segregation and ordering in Pt-Ag nanoalloys

We performed a theoretical study of the chemical ordering and surface segregation of Pt-Ag nanoalloys in the range of size from 976 to 9879 atoms (3.12 to 6.76 nm). We used an original many-body potential able to stabilize the L1₁ordered phase at equiconcentration leading to a strong silver surface segregation. Based on a recent experimental study where nanoparticles up to 2.5 nm have been characterized by high transmission electron microscopy with the L1₁ordered phase in the core and a silver surface shell, we predict in our model via Monte Carlo simulations that the lower energy configuration is more complicated with a three-shell alternance of Ag/Pt/Ag from the surface surrounding the L1₁ordered phase in the core. The stress analysis demonstrates that this structure softens the local stress distribution inside the nanoparticle which contributes to reduce the internal energy.