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. © 2014 IOP Publishing Ltd.

We acknowledge financial support from Ministerio de Economia y Competitividad (MINECO MAT2011/23791) and Aragonese IMANA projects, partially funded by the Fondo Europeo de Desarollo Regional program and the European Social Fund.

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