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.2019 Oct 1;58(40):14260-14264.
doi: 10.1002/anie.201908327. Epub 2019 Aug 28.

Oganesson Is a Semiconductor: On the Relativistic Band-Gap Narrowing in the Heaviest Noble-Gas Solids

Affiliations

Oganesson Is a Semiconductor: On the Relativistic Band-Gap Narrowing in the Heaviest Noble-Gas Solids

Jan-Michael Mewes et al. Angew Chem Int Ed Engl..

Abstract

Oganesson (Og) is the most recent addition to Group 18. Investigations of its atomic electronic structure have unraveled a tremendous impact of relativistic effects, raising the question whether the heaviest noble gas lives up to its position in the periodic table. To address the issue, we explore the electronic structure of bulk Og by means of relativistic Kohn-Sham density functional theory and many-body perturbation theory in the form of the GW method. Calculating the band structure of the noble-gas solids from Ne to Og, we demonstrate excellent agreement for the band gaps of the experimentally known solids from Ne to Xe and provide values of 7.1 eV and 1.5 eV for the unknown solids of Rn and Og. While this is in line with periodic trends for Rn, the band gap of Og completely breaks with these trends. The surprisingly small band gap of Og moreover means that, in stark contrast to all other noble-gas solids, the solid form of Og is a semiconductor.

Keywords: band gap; noble gases; oganesson; radon; superheavy elements.

© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Radial densities and energy levels (in the inset) for the valence orbitals of Rn (top) and Og (bottom) from relativistic (and non‐relativistic) Dirac‐Hartree–Fock calculations for the excited p5s1 configuration (3P2 state) using the GRASP program.13
Figure 2
Figure 2
Transition energies (ΔE) of the four lowest excited states of the noble‐gas atoms (green: hole in p3/2, purple: hole in p1/2) compared to opticalOg (orange)17 and electronicEg (black) band gaps16 as well as cohesive energies (red, secondary axis)18, 19, 20 of the respective solids. Data for He–Rn from experiment, and for Og (Ecoh also Rn) from coupled‐cluster calculations. See the Supporting Information for details.
Figure 3
Figure 3
Experimental and calculated electronic band gapsEg of the noble‐gas solids. Calculations at the DFT (PBE, SCAN and HSE06, dark colors) andGW levels (GW/PBE, orange). Dotted lines show scalar‐relativisticGW results. Numerical values and experimental references are provided in the Supporting Information (Table SII).
Figure 4
Figure 4
DFT/SCAN band structures of Xe, Rn, and Og along the L‐Γ‐X symmetry‐path (42 points) at the spin‐orbit (SO) relativistic (darker solid lines) and scalar‐relativistic (SR, lighter dotted lines) levels of theory using the 8 (Xe) and 18 (Rn, Og) electron valence spaces. The (SO‐DFT) Fermi level is depicted by a black line. Its SO/SR values are Xe: −3.40/−3.72 eV, Rn: −1.09/−2.14 eV, Og: 3.30/1.50 eV). Arrows and lines depict the spin‐orbit splitting of the valence bands (DFT/SCAN) as well as experimental (exp) and theoretical best estimates (tbe) for the band gaps (at the Γ‐point) to scale.
See this image and copyright information in PMC

References

    1. Wang S.-G., Schwarz W., Angew. Chem. Int. Ed. 2009, 48, 3404–3415; - PubMed
    2. Angew. Chem. 2009, 121, 3456–3467.
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    1. Jerabek P., Schuetrumpf B., Schwerdtfeger P., Nazarewicz W., Phys. Rev. Lett. 2018, 120, 053001. - PubMed
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