Electronic structure of bimetallic Ni–Rh nanowires

The electronic structure of a bare Rh(553) surface and of a Ni-decorated Rh(553) surface has been investigated by angle-resolved UV photoelectron spectroscopy and density functional theory calculations. The self-assembly of Ni adatoms leads to the decoration of the steps of the Rh(553) surface with monoatomic Ni rows under suitable kinetic conditions, thus forming a regular array of pseudomorphic bimetallic Ni–Rh nanowires. The electronic structure of the clean Rh(553) surface has been compared to the one of the flat Rh(111) surface, and additional surface states localized at the step edges due to the lower coordination of the step atoms have been detected. The Ni wires are weakly hybridized with the Rh substrate states and are characterized by only weakly dispersing states. This leads to a strong narrowing of the d-band, which is argued to be the origin of the observed high chemical reactivity of the Ni–Rh nanowires.