Orbital interaction and local stability of Ni substituted Pd nanoalloys

We investigated the relationship between orbital interactions and binding energy in Pd13−xNix (x = 1–13) nanoalloys. We employed, DFT at DNP/(PW91, BLYP, PBE and VWN-BP) level of functionals. In spite of higher cohesive energy of Ni as compared to Pd the thermodynamic stability of ∼70–80% Ni substituted Pd13 cluster is higher than Ni13. Orbital interactions are analyzed using partial density of states to elucidate the underlying reasons. In the overall stability of these clusters, the interaction between Ni (4s, 3p) and Pd (4s, 4p) orbitals are crucial for the explanation of subtle changes in their stabilities. This study provides a new orbital picture for thermodynamic stability in transition metal nanoalloys.