Orbital interaction and local stability of Ni substituted Pd nanoalloys

► Stability in Pd13−xNix (x = 1-13) nanoalloys. ► Subtle changes in stability at ∼70-80% Ni concentration. ► Ni (4s, 3p) and Pd (4s, 4p) orbital interactions are crucial. ► Pd 3d - Ni 4s orbital interactions are more favorable than Ni 3d - Pd 5s orbital.