Structure and Electronic Properties of Transition-Metal/Mg Bimetallic Clusters at Realistic Temperatures and Oxygen Partial Pressures

  • Shikha Saini*
    Shikha Saini
    Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016, India
    *E-mail: [email protected]. (S.S.).
    More by Shikha Saini
  • Debalaya Sarker
    Debalaya Sarker
    Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016, India
  • Pooja Basera
    Pooja Basera
    Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016, India
    More by Pooja Basera
  • Sergey V. Levchenko
    Sergey V. Levchenko
    Theory Department, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany
    Materials Modeling and Development Laboratory, National University of Science and Technology “MISIS”, 119049 Moscow, Russia
  • Luca M. Ghiringhelli
    Luca M. Ghiringhelli
    Theory Department, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany
  • , and 
  • Saswata Bhattacharya*
    Saswata Bhattacharya
    Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016, India
    *E-mail: [email protected]. Phone: +91-2659 1359. Fax: +91-2658 2037 (S.B.).
Cite this: J. Phys. Chem. C 2018, 122, 29, 16788–16794
Publication Date (Web):June 27, 2018
https://doi.org/10.1021/acs.jpcc.8b03787
Copyright © 2018 American Chemical Society
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Abstract

Composition, atomic structure, and electronic properties of TMxMgyOz clusters [transition metal (TM) = Cr, Ni, Fe, and Co, x + y ≤ 3] under realistic temperature T and  oxygen partial pressure pO2 conditions are explored using the ab initio atomistic thermodynamics approach. The low-energy isomers of the different clusters are identified using a massively parallel cascade genetic algorithm on the hybrid density-functional theory level. On analyzing a large set of data, we find that the fundamental gap Eg of the thermodynamically stable clusters is strongly affected by the presence of Mg-coordinated O2 moieties. By contrast, the nature of the TM does not play a significant role in determining Eg. Using Eg of a cluster as a descriptor of its redox properties, our finding is against the conventional belief that the TM plays a key role in determining the electronic and therefore chemical properties of the clusters. High reactivity may be correlated more strongly with the oxygen content in the cluster than with any specific TM type.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.8b03787. All the structural details and output files can be downloaded from http://dx.doi.org/10.17172/NOMAD/2018.07.11-1.

  • Geometry coordinates and the fundamental gap for low-energy isomers of TMxMgyOz clusters (PDF)

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