Unusually complex phase of dense nitrogen at extreme conditions
Abstract
Here, nitrogen exhibits an exceptional polymorphism under extreme conditions, making it unique amongst the elemental diatomics and a valuable testing system for experiment-theory comparison. Despite attracting considerable attention, the structures of many high-pressure nitrogen phases still require unambiguous determination. Here, we report the structure of the elusive high-pressure high-temperature polymorph ι–N2 at 56 GPa and ambient temperature, determined by single crystal X-ray diffraction, and investigate its properties using ab initio simulations. We find that ι–N2 is characterised by an extraordinarily large unit cell containing 48 N2 molecules. Geometry optimisation favours the experimentally determined structure and density functional theory calculations find ι–N2 to have the lowest enthalpy of the molecular nitrogen polymorphs that exist between 30 and 60 GPa. The results demonstrate that very complex structures, similar to those previously only observed in metallic elements, can become energetically favourable in molecular systems at extreme pressures and temperatures.
- Authors:
-
- Univ. of Edinburgh, Edinburgh (United Kingdom)
- European Synchrotron Radiation Facility, Grenoble (France)
- Center for High Pressure Science & Technology Advanced Research, Shanghai (China)
- Univ. of Edinburgh, Edinburgh (United Kingdom); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Chinese Academy of Sciences, Hefei (China)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1490646
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Turnbull, Robin, Hanfland, Michael, Binns, Jack, Martinez-Canales, Miguel, Frost, Mungo, Marqués, Miriam, Howie, Ross T., and Gregoryanz, Eugene. Unusually complex phase of dense nitrogen at extreme conditions. United States: N. p., 2018.
Web. doi:10.1038/s41467-018-07074-4.
Turnbull, Robin, Hanfland, Michael, Binns, Jack, Martinez-Canales, Miguel, Frost, Mungo, Marqués, Miriam, Howie, Ross T., & Gregoryanz, Eugene. Unusually complex phase of dense nitrogen at extreme conditions. United States. https://doi.org/10.1038/s41467-018-07074-4
Turnbull, Robin, Hanfland, Michael, Binns, Jack, Martinez-Canales, Miguel, Frost, Mungo, Marqués, Miriam, Howie, Ross T., and Gregoryanz, Eugene. Fri .
"Unusually complex phase of dense nitrogen at extreme conditions". United States. https://doi.org/10.1038/s41467-018-07074-4. https://www.osti.gov/servlets/purl/1490646.
@article{osti_1490646,
title = {Unusually complex phase of dense nitrogen at extreme conditions},
author = {Turnbull, Robin and Hanfland, Michael and Binns, Jack and Martinez-Canales, Miguel and Frost, Mungo and Marqués, Miriam and Howie, Ross T. and Gregoryanz, Eugene},
abstractNote = {Here, nitrogen exhibits an exceptional polymorphism under extreme conditions, making it unique amongst the elemental diatomics and a valuable testing system for experiment-theory comparison. Despite attracting considerable attention, the structures of many high-pressure nitrogen phases still require unambiguous determination. Here, we report the structure of the elusive high-pressure high-temperature polymorph ι–N2 at 56 GPa and ambient temperature, determined by single crystal X-ray diffraction, and investigate its properties using ab initio simulations. We find that ι–N2 is characterised by an extraordinarily large unit cell containing 48 N2 molecules. Geometry optimisation favours the experimentally determined structure and density functional theory calculations find ι–N2 to have the lowest enthalpy of the molecular nitrogen polymorphs that exist between 30 and 60 GPa. The results demonstrate that very complex structures, similar to those previously only observed in metallic elements, can become energetically favourable in molecular systems at extreme pressures and temperatures.},
doi = {10.1038/s41467-018-07074-4},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {Fri Nov 09 00:00:00 EST 2018},
month = {Fri Nov 09 00:00:00 EST 2018}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Pressure-Induced Symmetry-Lowering Transition in Dense Nitrogen to Layered Polymeric Nitrogen (LP-N) with Colossal Raman Intensity
journal, November 2014
- Tomasino, Dane; Kim, Minseob; Smith, Jesse
- Physical Review Letters, Vol. 113, Issue 20
Cagelike Diamondoid Nitrogen at High Pressures
journal, October 2012
- Wang, Xiaoli; Wang, Yanchao; Miao, Maosheng
- Physical Review Letters, Vol. 109, Issue 17
High P-T transformations of nitrogen to 170GPa
journal, May 2007
- Gregoryanz, Eugene; Goncharov, Alexander F.; Sanloup, Chrystele
- The Journal of Chemical Physics, Vol. 126, Issue 18
Ab initio random structure searching
journal, January 2011
- Pickard, Chris J.; Needs, R. J.
- Journal of Physics: Condensed Matter, Vol. 23, Issue 5
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Orientational behavior of solid nitrogen at high pressures investigated by vibrational Raman spectroscopy
journal, August 1996
- Scheerboom, M. I. M.; Schouten, J. A.
- The Journal of Chemical Physics, Vol. 105, Issue 7
Extraordinarily complex crystal structure with mesoscopic patterning in barium at high pressure
journal, June 2012
- Loa, I.; Nelmes, R. J.; Lundegaard, L. F.
- Nature Materials, Vol. 11, Issue 7
Measurement of temperature distributions across laser heated samples by multispectral imaging radiometry
journal, January 2008
- Campbell, Andrew J.
- Review of Scientific Instruments, Vol. 79, Issue 1
Single-bonded cubic form of nitrogen
journal, July 2004
- Eremets, Mikhail I.; Gavriliuk, Alexander G.; Trojan, Ivan A.
- Nature Materials, Vol. 3, Issue 8
High-pressure amorphous nitrogen
journal, July 2001
- Gregoryanz, Eugene; Goncharov, Alexander F.; Hemley, Russell J.
- Physical Review B, Vol. 64, Issue 5
The crystal structures of δ and δ[sup ∗] nitrogen
journal, January 2009
- Stinton, G. W.; Loa, I.; Lundegaard, L. F.
- The Journal of Chemical Physics, Vol. 131, Issue 10
SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
Pressure calibration of diamond anvil Raman gauge to 410 GPa
journal, March 2010
- Akahama, Yuichi; Kawamura, Haruki
- Journal of Physics: Conference Series, Vol. 215
Phase behavior of krypton and xenon to 50 GPa
journal, June 2002
- Errandonea, Daniel; Schwager, Beate; Boehler, Reinhard
- Physical Review B, Vol. 65, Issue 21
Crystal Structures of the Three Modifications of Nitrogen 14 and Nitrogen 15 at High Pressure
journal, June 1970
- Schuch, A. F.; Mills, R. L.
- The Journal of Chemical Physics, Vol. 52, Issue 12
Structures of Molecular Nitrogen at High Pressures.
journal, January 1998
- Hanfland, M.; Lorenzen, M.; Wassilew-Reul, C.
- THE REVIEW OF HIGH PRESSURE SCIENCE AND TECHNOLOGY, Vol. 7
Calculations predict a stable molecular crystal of N8
journal, December 2013
- Hirshberg, Barak; Gerber, R. Benny; Krylov, Anna I.
- Nature Chemistry, Vol. 6, Issue 1
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Structures and phase diagrams of N 2 and CO to 13 GPa by x‐ray diffraction
journal, March 1986
- Mills, R. L.; Olinger, Bart; Cromer, D. T.
- The Journal of Chemical Physics, Vol. 84, Issue 5
Crystal structure refinement with SHELXL
journal, January 2015
- Sheldrick, George M.
- Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
Melting and phase transitions of nitrogen under high pressures and temperatures
journal, June 2014
- Tomasino, Dane; Jenei, Zsolt; Evans, William
- The Journal of Chemical Physics, Vol. 140, Issue 24
Cold melting and solid structures of dense lithium
journal, January 2011
- Guillaume, Christophe L.; Gregoryanz, Eugene; Degtyareva, Olga
- Nature Physics, Vol. 7, Issue 3
Structural Diversity of Sodium
journal, May 2008
- Gregoryanz, E.; Lundegaard, L. F.; McMahon, M. I.
- Science, Vol. 320, Issue 5879
Crystal structure prediction using ab initio evolutionary techniques: Principles and applications
journal, June 2006
- Oganov, Artem R.; Glass, Colin W.
- The Journal of Chemical Physics, Vol. 124, Issue 24
Novel high-pressure nitrogen phase formed by compression at low temperature
journal, January 2016
- Frost, Mungo; Howie, Ross T.; Dalladay-Simpson, Philip
- Physical Review B, Vol. 93, Issue 2
Route to high-energy density polymeric nitrogen t-N via He−N compounds
journal, February 2018
- Li, Yinwei; Feng, Xiaolei; Liu, Hanyu
- Nature Communications, Vol. 9, Issue 1
Quantum dissipation driven by electron transfer within a single molecule investigated with atomic force microscopy
journal, March 2020
- Berger, Jan; Ondráček, Martin; Stetsovych, Oleksandr
- Nature Communications, Vol. 11, Issue 1
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
Polymeric nitrogen
conference, January 1994
- Mailhiot, C.; Yang, L. H.; McMahan, A. K.
- High-pressure science and technology—1993, AIP Conference Proceedings
Calculations predict a stable molecular crystal of N8
journal, December 2013
- Hirshberg, Barak; Gerber, R. Benny; Krylov, Anna I.
- Nature Chemistry, Vol. 6, Issue 1
Single-bonded cubic form of nitrogen
journal, July 2004
- Eremets, Mikhail I.; Gavriliuk, Alexander G.; Trojan, Ivan A.
- Nature Materials, Vol. 3, Issue 8
Extraordinarily complex crystal structure with mesoscopic patterning in barium at high pressure
journal, June 2012
- Loa, I.; Nelmes, R. J.; Lundegaard, L. F.
- Nature Materials, Vol. 11, Issue 7
Cold melting and solid structures of dense lithium
journal, January 2011
- Guillaume, Christophe L.; Gregoryanz, Eugene; Degtyareva, Olga
- Nature Physics, Vol. 7, Issue 3
Crystal Structures of the Three Modifications of Nitrogen 14 and Nitrogen 15 at High Pressure
journal, June 1970
- Schuch, A. F.; Mills, R. L.
- The Journal of Chemical Physics, Vol. 52, Issue 12
Crystal structure prediction using ab initio evolutionary techniques: Principles and applications
journal, June 2006
- Oganov, Artem R.; Glass, Colin W.
- The Journal of Chemical Physics, Vol. 124, Issue 24
Measurement of temperature distributions across laser heated samples by multispectral imaging radiometry
journal, January 2008
- Campbell, Andrew J.
- Review of Scientific Instruments, Vol. 79, Issue 1
Structures and phase diagrams of N 2 and CO to 13 GPa by x‐ray diffraction
journal, March 1986
- Mills, R. L.; Olinger, Bart; Cromer, D. T.
- The Journal of Chemical Physics, Vol. 84, Issue 5
Orientational behavior of solid nitrogen at high pressures investigated by vibrational Raman spectroscopy
journal, August 1996
- Scheerboom, M. I. M.; Schouten, J. A.
- The Journal of Chemical Physics, Vol. 105, Issue 7
Pressure calibration of diamond anvil Raman gauge to 410 GPa
journal, March 2010
- Akahama, Yuichi; Kawamura, Haruki
- Journal of Physics: Conference Series, Vol. 215
Crystal structure from one-electron theory
journal, February 1985
- Skriver, Hans L.
- Physical Review B, Vol. 31, Issue 4
Polymeric nitrogen
journal, December 1992
- Mailhiot, C.; Yang, L. H.; McMahan, A. K.
- Physical Review B, Vol. 46, Issue 22
Raman, infrared, and x-ray evidence for new phases of nitrogen at high pressures and temperatures
journal, December 2002
- Gregoryanz, Eugene; Goncharov, Alexander F.; Hemley, Russell J.
- Physical Review B, Vol. 66, Issue 22
Theoretical description of pressure- and temperature-induced structural phase transition mechanisms of nitrogen
journal, August 2008
- Katzke, Hannelore; Tolédano, Pierre
- Physical Review B, Vol. 78, Issue 6
Triple Point on the Melting Curve and Polymorphism of Nitrogen at High Pressure
journal, August 2008
- Goncharov, Alexander F.; Crowhurst, Jonathan C.; Struzhkin, Viktor V.
- Physical Review Letters, Vol. 101, Issue 9
Novel High Pressure Structures of Polymeric Nitrogen
journal, February 2009
- Ma, Yanming; Oganov, Artem R.; Li, Zhenwei
- Physical Review Letters, Vol. 102, Issue 6
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009
- Tkatchenko, Alexandre; Scheffler, Matthias
- Physical Review Letters, Vol. 102, Issue 7
High-Pressure Phases of Nitrogen
journal, March 2009
- Pickard, Chris J.; Needs, R. J.
- Physical Review Letters, Vol. 102, Issue 12
Melting Curve and Liquid Structure of Nitrogen Probed by X-ray Diffraction to 120 GPa
journal, December 2017
- Weck, Gunnar; Datchi, Frédéric; Garbarino, Gaston
- Physical Review Letters, Vol. 119, Issue 23
Optical Evidence for a Nonmolecular Phase of Nitrogen above 150 GPa
journal, August 2000
- Goncharov, Alexander F.; Gregoryanz, Eugene; Mao, Ho-kwang
- Physical Review Letters, Vol. 85, Issue 6
Prediction of New Phases of Nitrogen at High Pressure from First-Principles Simulations
journal, September 2004
- Mattson, William D.; Sanchez-Portal, Daniel; Chiesa, Simone
- Physical Review Letters, Vol. 93, Issue 12
Phase diagram of nitrogen at high pressures and temperatures
journal, August 2002
- Gregoryanz, E.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 58, Issue s1
A refinement of the positional parameter in α-nitrogen
journal, September 1961
- Donohue, J.
- Acta Crystallographica, Vol. 14, Issue 9
Structural Diversity of Sodium
journal, May 2008
- Gregoryanz, E.; Lundegaard, L. F.; McMahon, M. I.
- Science, Vol. 320, Issue 5879
Structures of Molecular Nitrogen at High Pressures.
journal, January 1998
- Hanfland, M.; Lorenzen, M.; Wassilew-Reul, C.
- THE REVIEW OF HIGH PRESSURE SCIENCE AND TECHNOLOGY, Vol. 7
High-Pressure Amorphous Nitrogen
text, January 2001
- Gregoryanz, Eugene; Goncharov, Alexander F.; Hemley, Russell J.
- arXiv
Unusually complex phase of dense nitrogen at extreme conditions
dataset, January 2018
- Martinez-Canales, Miguel
- University of Edinburgh. School of Physics and Astronomy
Works referencing / citing this record:
High-pressure polymorphism in l -threonine between ambient pressure and 22 GPa
journal, January 2019
- Giordano, Nico; Beavers, Christine M.; Kamenev, Konstantin V.
- CrystEngComm, Vol. 21, Issue 30
Theoretical assessment of the structure and stability of the phase of nitrogen
journal, September 2019
- Sontising, Watit; Beran, Gregory J. O.
- Physical Review Materials, Vol. 3, Issue 9
Figures / Tables found in this record: