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Designer magnetic superatoms

Nature Chemistry volume 1, pages 310–315 (2009)Cite this article

Abstract

The quantum states in metal clusters are grouped into bunches of close-lying eigenvalues, termed electronic shells, similar to those of atoms. Filling of the electronic shells with paired electrons results in local minima in energy to give stable species called magic clusters. This led to the realization that selected clusters mimic chemical properties of elemental atoms on the periodic table and can be classified as superatoms. So far the work on superatoms has focused on non-magnetic species. Here we propose a framework for magnetic superatoms by invoking systems that have both localized and delocalized electronic states, in which localized electrons stabilize magnetic moments and filled nearly-free electron shells lead to stable species. An isolated VCs8 and a ligated MnAu24(SH)18 are shown to be such magnetic superatoms. The magnetic superatoms' assemblies could be ideal for molecular electronic devices, as the coupling could be altered by charging or weak fields.

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Figure 1: Ground-state geometries of VNan and VCsn clusters.
Figure 2: Energetic and magnetic trends of VNan and VCsn clusters.
Figure 3: One-electron energy levels and molecular orbital charge density isosurfaces (isovalue 0.035 coulomb m−3) in the VNa8 cluster.
Figure 4: Lowest-energy structures of V2Na16 and the (VCs8)2 dimer, and total and net spin electron density of VCs8.
Figure 5: Total and net spin electron density and density of states (DOS) of the MnAu24(SH)18 cluster.

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Acknowledgements

We gratefully acknowledge support from the US Department of the Army through a MURI grant. Parts of the computations were performed at the cluster computing facility at the Harish-Chandra Research Institute, and on the computational equipment of La Dirección General de Servicios de Cómputo Académico de la Universidad Nacional Autónoma de México, particularly at the super computer KanBalam.

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Authors and Affiliations

  1. Department of Physics, Virginia Commonwealth University, Richmond, 23284, Virginia, USA

    J. Ulises Reveles, Peneé A. Clayborne, Arthur C. Reber & Shiv N. Khanna

  2. Harish-Chandra Research Institute, Chhatnag Road Jhunsi, 211019, Allahabad, India

    Kalpataru Pradhan & Prasenjit Sen

  3. Naval Research Laboratory, Center for Computational Materials Science, Washington, 20375, DC, USA

    Mark R. Pederson

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All the authors discussed the results and commented on the manuscript.

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Correspondence to Shiv N. Khanna.

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Reveles, J., Clayborne, P., Reber, A. et al. Designer magnetic superatoms. Nature Chem 1, 310–315 (2009). https://doi.org/10.1038/nchem.249

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