Exotic stable cesium polynitrides at high pressure
Abstract
New polynitrides containing metastable forms of nitrogen are actively investigated as potential high energy-density materials. Using a structure search method based on the CALYPSO methodology, we investigated the stable stoichiometries and structures of cesium polynitrides at high pressures. Along with the CsN3, we identified five new stoichiometric compounds (Cs3N, Cs2N, CsN, CsN2, and CsN5) with interesting structures that may be experimentally synthesizable at modest pressures (i.e., less than 50 GPa). Nitrogen species in the predicted structures have various structural forms ranging from single atom (N) to highly endothermic molecules (N2, N3 , N4, N5, N6) and chains (N∞). Polymeric chains of nitrogen were found in the high-pressure C2/c phase of CsN2. This structure contains a substantially high content of single N-N bonds that exceeds the previously known nitrogen chains in pure forms, and also exhibit metastability at ambient conditions. We also identified a very interesting CsN crystal that contains novel N44- anion. In conclusion, to our best knowledge, this is the first time a charged N4 species being reported. Results of the present study suggest that it is possible to obtain energetic polynitrogens in main-group nitrides under high pressure.
- Authors:
-
- Luoyang Normal University, Luoyang (China). College of Physics and Electronic Information,; Beijing Computational Science Research Center, Beijing (China)
- Luoyang Normal University, Luoyang (China). College of Physics and Electronic Information
- Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
- Univ. of Saskatchewan, Saskatoon, SK (Canada). Department of Physics and Engineering Physics; Canadian Light Sources, Inc., Saskatoon, SK (Canada)
- Publication Date:
- Research Org.:
- Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.; Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research in Extreme Environments (EFree)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1241100
- Grant/Contract Number:
- SC-0001057; NA-0002006
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 5; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Peng, Feng, Han, Yunxia, Liu, Hanyu, and Yao, Yansun. Exotic stable cesium polynitrides at high pressure. United States: N. p., 2015.
Web. doi:10.1038/srep16902.
Peng, Feng, Han, Yunxia, Liu, Hanyu, & Yao, Yansun. Exotic stable cesium polynitrides at high pressure. United States. https://doi.org/10.1038/srep16902
Peng, Feng, Han, Yunxia, Liu, Hanyu, and Yao, Yansun. 2015.
"Exotic stable cesium polynitrides at high pressure". United States. https://doi.org/10.1038/srep16902. https://www.osti.gov/servlets/purl/1241100.
@article{osti_1241100,
title = {Exotic stable cesium polynitrides at high pressure},
author = {Peng, Feng and Han, Yunxia and Liu, Hanyu and Yao, Yansun},
abstractNote = {New polynitrides containing metastable forms of nitrogen are actively investigated as potential high energy-density materials. Using a structure search method based on the CALYPSO methodology, we investigated the stable stoichiometries and structures of cesium polynitrides at high pressures. Along with the CsN3, we identified five new stoichiometric compounds (Cs3N, Cs2N, CsN, CsN2, and CsN5) with interesting structures that may be experimentally synthesizable at modest pressures (i.e., less than 50 GPa). Nitrogen species in the predicted structures have various structural forms ranging from single atom (N) to highly endothermic molecules (N2, N3 , N4, N5, N6) and chains (N∞). Polymeric chains of nitrogen were found in the high-pressure C2/c phase of CsN2. This structure contains a substantially high content of single N-N bonds that exceeds the previously known nitrogen chains in pure forms, and also exhibit metastability at ambient conditions. We also identified a very interesting CsN crystal that contains novel N44- anion. In conclusion, to our best knowledge, this is the first time a charged N4 species being reported. Results of the present study suggest that it is possible to obtain energetic polynitrogens in main-group nitrides under high pressure.},
doi = {10.1038/srep16902},
url = {https://www.osti.gov/biblio/1241100},
journal = {Scientific Reports},
issn = {2045-2322},
number = ,
volume = 5,
place = {United States},
year = {Thu Nov 19 00:00:00 EST 2015},
month = {Thu Nov 19 00:00:00 EST 2015}
}
Web of Science
Works referenced in this record:
Synthesis and characterization of a binary noble metal nitride
journal, April 2004
- Gregoryanz, Eugene; Sanloup, Chrystele; Somayazulu, M.
- Nature Materials, Vol. 3, Issue 5
CALYPSO: A method for crystal structure prediction
journal, October 2012
- Wang, Yanchao; Lv, Jian; Zhu, Li
- Computer Physics Communications, Vol. 183, Issue 10
Charge, bond order and valence in the AB initio SCF theory
journal, May 1983
- Mayer, I.
- Chemical Physics Letters, Vol. 97, Issue 3
Cs-N (Cesium-Nitrogen)
journal, December 2004
- Sangster, James
- Journal of Phase Equilibria & Diffusion, Vol. 25, Issue 6
Synthesis and characterization of a binary noble metal nitride
journal, April 2004
- Gregoryanz, Eugene; Sanloup, Chrystele; Somayazulu, M.
- Nature Materials, Vol. 3, Issue 5
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Cagelike Diamondoid Nitrogen at High Pressures
journal, October 2012
- Wang, Xiaoli; Wang, Yanchao; Miao, Maosheng
- Physical Review Letters, Vol. 109, Issue 17
Ab initio studies of bonding trends
journal, September 1991
- Pyykkö, Pekka; Runeberg, Nino
- Journal of Molecular Structure: THEOCHEM, Vol. 234
Polynitrogen Chemistry. Synthesis, Characterization, and Crystal Structure of Surprisingly Stable Fluoroantimonate Salts of N 5 +
journal, July 2001
- Vij, Ashwani; Wilson, William W.; Vij, Vandana
- Journal of the American Chemical Society, Vol. 123, Issue 26
Polymerization of nitrogen in lithium azide
journal, October 2013
- Wang, Xiaoli; Li, Jianfu; Botana, Jorge
- The Journal of Chemical Physics, Vol. 139, Issue 16
Crystalline LiN 5 Predicted from First-Principles as a Possible High-Energy Material
journal, June 2015
- Peng, Feng; Yao, Yansun; Liu, Hanyu
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 12
Pressure-Induced Polymerization of Carbon Monoxide: Disproportionation and Synthesis of an Energetic Lactonic Polymer
journal, May 2006
- Evans, W. J.; Lipp, M. J.; Yoo, C. -S.
- Chemistry of Materials, Vol. 18, Issue 10
Evolving Structural Diversity and Metallicity in Compressed Lithium Azide
journal, September 2013
- Prasad, Dasari L. V. K.; Ashcroft, N. W.; Hoffmann, Roald
- The Journal of Physical Chemistry C, Vol. 117, Issue 40
Crystal structure prediction via particle-swarm optimization
journal, September 2010
- Wang, Yanchao; Lv, Jian; Zhu, Li
- Physical Review B, Vol. 82, Issue 9
N 6 2+ and N 4 2+ Dications and Their N 12 and N 10 Azido Derivatives: DFT/GIAO-MP2 Theoretical Studies 1
journal, April 2001
- Olah, George. A.; Surya Prakash, G. K.; Rasul, Golam
- Journal of the American Chemical Society, Vol. 123, Issue 14
Crystalline LiN 5 Predicted from First-Principles as a Possible High-Energy Material
journal, June 2015
- Peng, Feng; Yao, Yansun; Liu, Hanyu
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 12
Preparation, Crystal Structure, and Properties of Barium Pernitride, BaN2
journal, August 2001
- Vajenine, Grigori V.; Auffermann, Gudrun; Prots, Yurii
- Inorganic Chemistry, Vol. 40, Issue 19
The 28-Electron Tetraatomic Molecules: N 4 , CN 2 O, BFN 2 , C 2 O 2 , B 2 F 2 , CBFO, C 2 FN, and BNO 2 . Challenges for Computational and Experimental Chemistry
journal, January 1996
- Korkin, Anatoli A.; Balkova, Anna; Bartlett, Rodney J.
- The Journal of Physical Chemistry, Vol. 100, Issue 14
Ab initio studies of bonding trends
journal, September 1991
- Pyykkö, Pekka; Runeberg, Nino
- Journal of Molecular Structure: THEOCHEM, Vol. 234
Perdew, Burke, and Ernzerhof Reply:
journal, January 1998
- Perdew, J. P.; Burke, K.; Ernzerhof, M.
- Physical Review Letters, Vol. 80, Issue 4
Layered single-bonded nonmolecular phase of nitrogen from first-principles simulation
journal, December 2005
- Zahariev, F.; Hu, A.; Hooper, J.
- Physical Review B, Vol. 72, Issue 21
Spiral chain O4 form of dense oxygen
journal, January 2012
- Zhu, L.; Wang, Z.; Wang, Y.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 3
Pressure-induced planar N6 rings in potassium azide
journal, March 2014
- Zhang, Jie; Zeng, Zhi; Lin, Hai-Qing
- Scientific Reports, Vol. 4, Issue 1
Polynitrogen Chemistry. Synthesis, Characterization, and Crystal Structure of Surprisingly Stable Fluoroantimonate Salts of N 5 +
journal, July 2001
- Vij, Ashwani; Wilson, William W.; Vij, Vandana
- Journal of the American Chemical Society, Vol. 123, Issue 26
Energy storage capacity of polymeric nitrogen
journal, March 2006
- Uddin, Jamal; Barone, Verónica; Scuseria, Gustavo E.
- Molecular Physics, Vol. 104, Issue 5-7
Polymeric nitrogen
journal, December 1992
- Mailhiot, C.; Yang, L. H.; McMahan, A. K.
- Physical Review B, Vol. 46, Issue 22
Metastable high-pressure single-bonded phases of nitrogen predicted via genetic algorithm
journal, February 2008
- Yao, Yansun; Tse, John S.; Tanaka, Kaori
- Physical Review B, Vol. 77, Issue 5
Experimental Detection of the Pentaazacyclopentadienide (Pentazolate) Anion, cyclo-N5â This work was funded predominantly by the Defense Advanced Research Projects Agency, with additional support from the Air Force Office of Scientific Research and the National Science Foundation. The mass spectrometer instrumentation at UCSB was supported under the Army Research Office Award no. DAAD19-00-1-0026. We thank Dr. Robert Corley, Dr. Arthur Morrish, Dr. Don Woodbury, Dr. Michael Berman, and Prof. W. Kaska for their support, and Dr. Michael Gerken, Dr. Thorsten Schroer, Dr. Stefan Schneider, Dr. Ralf Haiges, Dr. Ross Wagner, and Dr. Suresh Suri for their collaboration and stimulating discussions.
journal, August 2002
- Vij, Ashwani; Pavlovich, James G.; Wilson, William W.
- Angewandte Chemie, Vol. 114, Issue 16
Decomposition mechanism of the polynitrogen N5 and N6 clusters and their ions
journal, February 2001
- Nguyen, Minh Tho; Ha, Tae-Kyu
- Chemical Physics Letters, Vol. 335, Issue 3-4
A simple measure of electron localization in atomic and molecular systems
journal, May 1990
- Becke, A. D.; Edgecombe, K. E.
- The Journal of Chemical Physics, Vol. 92, Issue 9
The crystal structures of lithium, sodium and strontium azides
journal, February 1968
- Pringle, G. E.; Noakes, D. E.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 24, Issue 2
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
Synthesis and Characterization of the Nitrides of Platinum and Iridium
journal, March 2006
- Crowhurst, J. C.
- Science, Vol. 311, Issue 5765
Toward new energy-rich molecular systems: from N10 to N60
journal, December 2000
- Manaa, M. Riad
- Chemical Physics Letters, Vol. 331, Issue 2-4
Series of phase transitions in cesium azide under high pressure studied by in situ x-ray diffraction
journal, August 2011
- Hou, Dongbin; Zhang, Fuxiang; Ji, Cheng
- Physical Review B, Vol. 84, Issue 6
A simple measure of electron localization in atomic and molecular systems
journal, May 1990
- Becke, A. D.; Edgecombe, K. E.
- The Journal of Chemical Physics, Vol. 92, Issue 9
SrN and SrN2: Diazenides by Synthesis under High N2-Pressure
journal, January 2001
- Auffermann, Gudrun; Prots, Yurii; Kniep, Rüdiger
- Angewandte Chemie International Edition, Vol. 40, Issue 3
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
Stationary points on the lowest doublet and quartet hypersurfaces of the N 3 radical: A comparison of molecular orbital and density functional approaches
journal, December 1996
- Wasilewski, J.
- The Journal of Chemical Physics, Vol. 105, Issue 24
Synthesis of Alkaline Earth Diazenides M AE N 2 (M AE = Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure
journal, January 2012
- Schneider, Sebastian B.; Frankovsky, Rainer; Schnick, Wolfgang
- Inorganic Chemistry, Vol. 51, Issue 4
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
Density-functional study of nonmolecular phases of nitrogen: Metastable phase at low pressure
journal, July 2003
- Alemany, M. M. G.; Martins, José Luís
- Physical Review B, Vol. 68, Issue 2
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
Hidden Thermodynamic Ground State of Calcium Diazenide
journal, December 2013
- Wang, Hui; Yao, Yansun; Si, Yanling
- The Journal of Physical Chemistry C, Vol. 118, Issue 1
Novel lithium-nitrogen compounds at ambient and high pressures
journal, September 2015
- Shen, Yanqing; Oganov, Artem R.; Qian, Guangri
- Scientific Reports, Vol. 5, Issue 1
Recent Advances in the Chemistry of N5+, N5− and High-Oxygen Compounds
journal, June 2007
- Christe, Karl O.
- Propellants, Explosives, Pyrotechnics, Vol. 32, Issue 3
Substitutional Alloy of Bi and Te at High Pressure
journal, April 2011
- Zhu, Li; Wang, Hui; Wang, Yanchao
- Physical Review Letters, Vol. 106, Issue 14
Polymerization of nitrogen in cesium azide under modest pressure
journal, July 2014
- Wang, Xiaoli; Li, Jianfu; Zhu, Hongyang
- The Journal of Chemical Physics, Vol. 141, Issue 4
Experimental Detection of Tetranitrogen
journal, January 2002
- Cacace, F.
- Science, Vol. 295, Issue 5554
N5+: A Novel Homoleptic Polynitrogen Ion as a High Energy Density Material
journal, July 1999
- Christe, Karl O.; Wilson, William W.; Sheehy, Jeffrey A.
- Angewandte Chemie International Edition, Vol. 38, Issue 13-14
Spiral chain O4 form of dense oxygen
journal, January 2012
- Zhu, L.; Wang, Z.; Wang, Y.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 3
Polymerization of nitrogen in lithium azide
journal, October 2013
- Wang, Xiaoli; Li, Jianfu; Botana, Jorge
- The Journal of Chemical Physics, Vol. 139, Issue 16
Novel lithium-nitrogen compounds at ambient and high pressures
journal, September 2015
- Shen, Yanqing; Oganov, Artem R.; Qian, Guangri
- Scientific Reports, Vol. 5, Issue 1
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
Crystal Structures of and Displacive Transitions in OsN2, IrN2, RuN2, and RhN2
journal, February 2007
- Yu, Rong; Zhan, Qian; De Jonghe, Lutgard C.
- Angewandte Chemie, Vol. 119, Issue 7
Novel high-pressure phase with pseudo-benzene “N 6 ” molecule of LiN 3
journal, January 2013
- Zhang, Meiguang; Yan, Haiyan; Wei, Qun
- EPL (Europhysics Letters), Vol. 101, Issue 2
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
Predicted Novel High-Pressure Phases of Lithium
journal, January 2011
- Lv, Jian; Wang, Yanchao; Zhu, Li
- Physical Review Letters, Vol. 106, Issue 1
Works referencing / citing this record:
High-pressure formation of antimony nitrides: a first-principles study
journal, January 2020
- Lian, Lili; Liu, Yan; Li, Da
- RSC Advances, Vol. 10, Issue 5
Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains
journal, July 2018
- Bykov, M.; Bykova, E.; Aprilis, G.
- Nature Communications, Vol. 9, Issue 1
The polymerization of nitrogen in Li2N2 at high pressures
journal, September 2018
- Zhang, Jie; Wang, Xianlong; Yang, Kaishuai
- Scientific Reports, Vol. 8, Issue 1
Stable zigzag and tripodal all-nitrogen anion N 4 4− in BeN 2
journal, May 2019
- Lin, Jiani; Zhu, Zuoqin; Jiang, Qiwen
- AIP Advances, Vol. 9, Issue 5
High energetic polymeric nitrogen sheet confined in a graphene matrix
journal, January 2018
- Niu, Shifeng; Liu, Shijie; Liu, Bo
- RSC Advances, Vol. 8, Issue 54
Metallic and anti-metallic properties of strongly covalently bonded energetic AlN 5 nitrides
journal, January 2019
- Liu, Zhao; Li, Da; Liu, Yan
- Physical Chemistry Chemical Physics, Vol. 21, Issue 22
Fe-N system at high pressure reveals a compound featuring polymeric nitrogen chains
text, January 2018
- Bykov, Maxim; Bykova, E.; Aprilis, G.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg