Structure determination of ζ-N2 from single-crystal X-ray diffraction and theoretical suggestion for the formation of amorphous nitrogen

Laniel, Dominique; Trybel, Florian; Aslandukov, Andrey; Spender, James; Ranieri, Umbertoluca; Fedotenko, Timofey; Glazyrin, Konstantin; Bright, Eleanor Lawrence; Chariton, Stella; Prakapenka, Vitali B.; Abrikosov, Igor A.; Dubrovinsky, Leonid; Dubrovinskaia, Natalia

doi:10.1038/s41467-023-41968-2

Title: Structure determination of ζ-N₂ from single-crystal X-ray diffraction and theoretical suggestion for the formation of amorphous nitrogen

Journal Article · Thu Oct 05 00:00:00 UTC 2023 · Nature Communications

DOI: https://doi.org/10.1038/s41467-023-41968-2 · OSTI ID:2470116

^[1];

^[2];

^[3]; Spender, James ^[1];

^[1]; Fedotenko, Timofey ^[4];

^[4]; Bright, Eleanor Lawrence ^[5];

^[6]; Prakapenka, Vitali B. ^[6];

^[2];

^[3];

^[7]

Univ. of Edinburgh, Scotland (United Kingdom)
Linköping University (United Kingdom)
Univ. of Bayreuth (Germany)
Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
European Synchrotron Radiation Facility (ESRF), Grenoble (France)
Univ. of Chicago, IL (United States)
Linköping University (United Kingdom); Univ. of Bayreuth (Germany)

The allotropy of solid molecular nitrogen is the consequence of a complex interplay between fundamental intermolecular as well as intramolecular interactions. Understanding the underlying physical mechanisms hinges on knowledge of the crystal structures of these molecular phases. That is especially true for ζ-N₂, key to shed light on nitrogen’s polymerization. Here, we perform single-crystal X-ray diffraction on laser-heated N₂ samples at 54, 63, 70 and 86 GPa and solve and refine the hitherto unknown structure of ζ-N₂. In its monoclinic unit cell (space group C2/c), 16 N₂ molecules are arranged in a configuration similar to that of ε-N₂. The structure model provides an explanation for the previously identified Raman and infrared lattice and vibrational modes of ζ-N₂. Density functional theory calculations give an insight into the gradual delocalization of electronic density from intramolecular bonds to intermolecular space and suggest a possible pathway towards nitrogen’s polymerization.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2470116

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemical physics
structure of solids and liquids

CCDC 2237807: Experimental Crystal Structure Determination Dominique, Laniel,; Florian, Trybel,; Andrey, Aslandukov, https://doi.org/10.5517/ccdc.csd.cc2f3mbj The current record is supplemented by this dataset	dataset	January 2023
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CCDC 2261391: Experimental Crystal Structure Determination Dominique, Laniel,; Florian, Trybel,; Andrey, Aslandukov, https://doi.org/10.5517/ccdc.csd.cc2fx53n The current record is supplemented by this dataset	dataset	January 2023
CCDC 2280044: Experimental Crystal Structure Determination Dominique, Laniel,; Florian, Trybel,; Andrey, Aslandukov, https://doi.org/10.5517/ccdc.csd.cc2gjktd The current record is supplemented by this dataset	dataset	January 2023

Title: Structure determination of ζ-N2 from single-crystal X-ray diffraction and theoretical suggestion for the formation of amorphous nitrogen

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Title: Structure determination of ζ-N₂ from single-crystal X-ray diffraction and theoretical suggestion for the formation of amorphous nitrogen