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Published October 5, 2023 | Version v1
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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

Creators

  • 1. University of Edinburgh
  • 2. Linköping University
  • 3. University of Bayreuth
  • 4. Deutsches Elektronen-Synchrotron
  • 5. European Synchrotron Radiation Facility
  • 6. University of Chicago

Description

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.

Data availability

Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2237807-2237808, 2261391, and 2280044. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source data for Fig. 1 a, b; Fig. 3; Fig. 4; Supplementary Fig. 2a, b; Supplementary Fig. 7a, b, c, d, e; Supplementary Fig. 8; Supplementary Fig. 9, Supplementary Fig. 10, Supplementary Fig. 11, Supplementary Fig. 12 and Supplementary Fig. 13 are provided with this paper. The data for Fig. 4 b are provided as a zipped file containing the "cube" datatype. The Crystallographic Information Files (CIFs) for ε-N2 at 54 GPa as well as ζ-N2 at 63, 70, and 86 GPa can be found in Supplementary Data 1. Supplementary Data 2 contains the Electron Localization Functions (ELFs) of ζ-N2 at 110, 130, 140 and 150 GPa. The corresponding authors can be contacted for any requests. Source data are provided with this paper.

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Additional details

Identifiers

DOI
10.1038/s41467-023-41968-2
Other
oai:uchicago.tind.io:8442

Funding

UKRI
Future Leaders Fellowship
Federal Ministry of Education and Research, Germany
BMBF, 05K19WC1
Deutsche Forschungsgemeinschaft
DU 954–11/1
Deutsche Forschungsgemeinschaft
DU 393–13/1
Linköping University
Swedish Government Strategic Research Area in Materials Science on Functional Materials
Knut and Alice Wallenberg Foundation
Wallenberg Scholar grant
Swedish Research Council
2019-05600

UChicago Information

Division(s)
Physical Sciences Division
Center(s) or Institute(s)
Center for Advanced Radiation Sources