Geometric and magnetic properties of Pt clusters supported on graphene: Relativistic density-functional calculations

The geometric and magnetic structures of small Pt-n clusters (n = 1 - 5) supported on a graphene layer have been investigated using ab initio density functional calculations including spin-orbit coupling. Pt-Pt interactions were found to be much stronger than the Pt-C interactions promoting the binding to the support. As a consequence, the equilibrium structure of the gas-phase clusters is preserved if they are deposited on graphene. However, the clusters bind to graphene only via at most two Pt-C bonds: A Pt-2 dumbbell prefers an upright position, the larger clusters are bound to graphene only via one edge of the planar cluster (Pt-3 and Pt-5) or via two terminal Pt atoms of a bent Pt-4 rhombus. Evidently, the strong buckling of the graphene layer induced by the Pt-C bonds prevents the formation of a larger number of cluster-support bonds. As the local spin and orbital magnetic moments are quenched on the Pt atoms forming Pt-C bonds, the magnetic structure of the supported clusters is much more inhomogeneous as in the gas-phase. This leads to noncollinear magnetic structures and a strongly reduced magnetic anisotropy energy. (C) 2011 American Institute of Physics. [doi:10.1063/1.3577517]