Structure, energetic and phase transition of multi shell icosahedral bimetallic nanostructures: A molecular dynamics study of NimPdn (n + m = 55 and 147)

Abstract

Structure, energetic and thermodynamic properties of multi shell icosahedral bimetallic nickel–palladium nanostructures with the size of 55 and 147 atoms were studied by using the molecular dynamics simulations and the microcanonical ensemble version of multiple histogram method. In 55 atoms icosahedra, two core–shell motifs, Ni13Pd42 and Pd13Ni42 with their isomers Pd13(Pd29Ni13) and Ni13(Ni29Pd13) were considered. Similarly in 147 atoms icosahedra, all mutations corresponding to the occupations of either nickel atoms or palladium atoms in the core, inner shell or outer shell and their isomers generated by interchanging thirteen core atoms with thirteen atoms of the other type in the inner and outer shells were considered. It is found that the nickel-core clusters are more stable than the palladium-core clusters and cohesive energy increases with the nickel composition. Phase transition of each cluster was studied by means of constant volume heat capacity. The trend in variation of melting temperature is opposite to the energy trend and special increase in melting points was observed for nickel-core isomers compared to the palladium-core isomers. Helmholtz free energy change with temperature for shell to core interchange of thirteen atoms revealed the thermodynamic stability of the formation of NicorePdshell structures and the surface segregation of palladium.