On the role of mechanical stress in the chemical ordering of nanoalloys

Abstract

Metallic alloy clusters at equilibrium display an inhomogeneous stress field which may contribute to the chemical ordering and segregation properties. We use the example of cuboctahedral and icosahedral Au-Pd clusters with the same size to compare these properties in systems displaying moderately and highly inhomogeneous stress fields. Metropolis Monte Carlo simulations in the semi-grand canonical ensemble are used with an empirical potential to predict equilibrium configurations. Pressure maps are used to estimate stress on each atom. It is found that when the stress field is moderately inhomogeneous, ordering is dominantly driven by thermodynamic forces. In icosahedral clusters, ordering is found to be the consequence of a balance where thermodynamic forces and mechanical stress may conflict or reinforce each other. Order-disorder transitions are smoother in the systems with higher stress inhomogeneity and it is conjectured that, in icosahedral clusters, disorder may nucleate in the central core.