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Stability of xenon oxides at high pressures

Nature Chemistry volume 5, pages 61–65 (2013)Cite this article

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Abstract

Xenon, which is quite inert under ambient conditions, may become reactive under pressure. The possibility of the formation of stable xenon oxides and silicates in the interior of the Earth could explain the atmospheric missing xenon paradox. Using an ab initio evolutionary algorithm, we predict the existence of thermodynamically stable Xe–O compounds at high pressures (XeO, XeO2 and XeO3 become stable at pressures above 83, 102 and 114 GPa, respectively). Our calculations indicate large charge transfer in these oxides, suggesting that large electronegativity difference and high pressure are the key factors favouring the formation of xenon compounds. However, xenon compounds cannot exist in the Earth's mantle: xenon oxides are unstable in equilibrium with the metallic iron occurring in the lower mantle, and xenon silicates are predicted to decompose spontaneously at all mantle pressures (<136 GPa). However, it is possible that xenon atoms may be retained at defects in mantle silicates and oxides.

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Figure 1: Thermal stability of Xe–O compounds.
Figure 2: Crystal structures, chemical bonding and stability range of Xe–O compounds.
Figure 3: Electronic structures of selected Xe–O compounds.

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Acknowledgements

Calculations were performed on the CFN cluster and Blue Gene supercomputer (Brookhaven National Laboratory), Swiss Supercomputer Centre, Skif MSU supercomputer (Moscow State University) and at the Joint Supercomputer Center of the Russian Academy of Sciences (Moscow). A.R.O. thanks DARPA (grant no. W31P4Q1210008) and the National Science Foundation (grant no. EAR-1114313) for financial support.

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Authors and Affiliations

  1. Department of Geosciences, Department of Physics and Astronomy, Stony Brook University, Stony Brook, 11794-2100, New York, USA

    Qiang Zhu, Artem R. Oganov & Andriy O. Lyakhov

  2. Department of Materials, Laboratory of Crystallography, ETH Honggerberg, Zurich, Switzerland

    Daniel Y. Jung

  3. Geology Department, Moscow State University, Moscow, 119992, Russia

    Artem R. Oganov

  4. High Performance Computing Center, Universität Stuttgart, Stuttgart, 70550, Germany

    Colin W. Glass

  5. Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) e Dipartimento di Chimica, Universita' di Milano, via Golgi 19, Milan, 20133, Italy

    Carlo Gatti

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  1. Qiang Zhu
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Contributions

A.R.O. designed the research. Q.Z. and D.Y.J. performed the calculations. Q.Z., D.Y.J., A.R.O. and C.G. interpreted data. A.O.L. and C.W.G. wrote the structure prediction code. Q.Z., D.Y.J., A.R.O. and C.G. wrote the manuscript.

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Correspondence to Qiang Zhu or Artem R. Oganov.

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Zhu, Q., Jung, D., Oganov, A. et al. Stability of xenon oxides at high pressures. Nature Chem 5, 61–65 (2013). https://doi.org/10.1038/nchem.1497

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