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Synthesis and stability of xenon oxides Xe2O5 and Xe3O2 under pressure

Nature Chemistry volume 8, pages 784–790 (2016)Cite this article

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Abstract

The noble gases are the most inert group of the periodic table, but their reactivity increases with pressure. Diamond-anvil-cell experiments and ab initio modelling have been used to investigate a possible direct reaction between xenon and oxygen at high pressures. We have now synthesized two oxides below 100 GPa (Xe2O5 under oxygen-rich conditions, and Xe3O2 under oxygen-poor conditions), which shows that xenon is more reactive under pressure than predicted previously. Xe2O5 was observed using X-ray diffraction methods, its structure identified through ab initio random structure searching and confirmed using X-ray absorption and Raman spectroscopies. The experiments confirm the recent prediction of Xe3O2 as a stable xenon oxide under high pressure. Xenon atoms adopt mixed oxidation states of 0 and +4 in Xe3O2 and +4 and +6 in Xe2O5. Xe3O2 and Xe2O5 form extended networks that incorporate oxygen-sharing XeO4 squares, and Xe2O5 additionally incorporates oxygen-sharing XeO5 pyramids. Other xenon oxides (XeO2, XeO3) are expected to form at higher pressures.

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Figure 1: X-ray diffraction patterns of xenon and O2 mixtures under pressure.
Figure 2: Xe K-edge XAS of a 36% Xe–64% O2 mixture at about 82 GPa.
Figure 3: Raman spectra of Xe2O5 and Xe3O2.
Figure 4: Structures of the stable xenon oxides at 83 GPa.
Figure 5: Convex-hull diagram for xenon oxides that shows the calculated enthalpies of formation per atom from the elements for the predicted stable phases.
Figure 6: Band structure and electronic density of states of Xe2O5 at 83 GPa.

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Acknowledgements

The authors acknowledge the ESRF for the provision of beamtime under proposals HS-4067 and HC-767. Financial support was provided by the Engineering and Physical Sciences Research Council of the UK (EP/J017639/1). Computational resources were provided by the High Performance Computing Service at the University of Cambridge and the Archer facility of the UK's National High-Performance Computing Service, for which access was obtained via the UK Car–Parrinello Consortium (EP/K014560/1). C.J.P. is supported by the Royal Society through a Royal Society Wolfson Research Merit Award. Nanopolycrystalline diamond anvils were prepared based on Japan Society for the Promotion of Science grants (No. 25220712 and No. 15H05829) to T.I. We thank M. Hanfland for the use of his laser heating set-up, and P. Loubeyre, S. Mazevet, C. Sanloup and J. Trail for helpful discussions.

Author information

Authors and Affiliations

  1. CEA, DAM, DIF, Arpajon, F-91297, France

    Agnès Dewaele

  2. TCM Group, Cavendish Laboratory, University of Cambridge, J J Thomson Avenue, Cambridge, CB3 0HE, UK

    Nicholas Worth & Richard J. Needs

  3. Department of Physics and Astronomy, University College London, Gower Street, London, WC1E 6BT, UK

    Chris J. Pickard

  4. Department of Materials Science & Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge, CB3 0FS, UK

    Chris J. Pickard

  5. Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba, Sendai, 980-8577, Japan

    Chris J. Pickard

  6. European Synchrotron Radiation Facility, BP220, Grenoble Cedex, 38043, France

    Sakura Pascarelli, Olivier Mathon & Mohamed Mezouar

  7. Ehime University, 2–5 Bunkyo-cho, Matsuyama, 790-8577, Japan

    Tetsuo Irifune

  8. Earth-Life Science Institute, Tokyo Institute of Technology, Tokyo, 152-8500, Japan

    Tetsuo Irifune

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Contributions

A.D. proposed the research, and A.D. and R.J.N. coordinated the research. A.D. performed the experiments at the synchrotron source with the help of O.M. and M.M. T.I. provided the nanopolycrystalline diamond anvils. A.D. and S.P. analysed experimental data. N.W. and C.J.P. performed the theoretical and computational work. R.J.N., A.D. and N.W. wrote the paper. All the authors commented on the manuscript.

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Correspondence to Agnès Dewaele.

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Supplementary information

Supplementary information

Supplementary information (PDF 1629 kb)

Supplementary information

Theoretically derived crystallographic data for the Xe2O5 structure at 83GPa. (CIF 10 kb)

Supplementary information

Theoretically derived crystallographic data for the Xe2O structure at 83GPa. (CIF 16 kb)

Supplementary information

Theoretically derived crystallographic data for the Xe3O2 structure at 83GPa. (CIF 5 kb)

Supplementary information

Theoretically derived crystallographic data for the XeO2 structure at 200GPa. (CIF 9 kb)

Supplementary information

Theoretically derived crystallographic data for the XeO3 structure at 150GPa. (CIF 9 kb)

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Dewaele, A., Worth, N., Pickard, C. et al. Synthesis and stability of xenon oxides Xe2O5 and Xe3O2 under pressure. Nature Chem 8, 784–790 (2016). https://doi.org/10.1038/nchem.2528

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