Large orbital magnetic moment in Pt₁₃ clusters

We present an extensive study of Pt₁₃ clusters embedded in a Na-Y zeolite, by comparing calculations for isolated clusters to experimental data. We perform structural refinements for various geometries involving the isolated clusters and calculate the corresponding x-ray absorption and magnetic circular dichroism spectra, from the joint perspective of pseudopotential plane wave calculations and real space multiple scattering theory. Taking into account the spin-orbit coupling significantly improves the previous scalar relativistic predictions of magnetic properties. The ensemble of embedded Pt₁₃ is found to be dominated by a non-magnetic cuboctahedral geometry. One of the implications is that the ground state of Pt₁₃ clusters in the zeolite environment is different from that of isolated particles. We investigate several isomers that yield a magnetic signature. Furthermore, their abundance was estimated by direct comparison with experiment. We found that one third of the magnetic moment of Pt₁₃ comes from the orbital contribution, in agreement with the experimental value. We therefore provide theoretical proof of the extraordinary orbital magnetization in Pt13 clusters.