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Formation of the –N(NO)N(NO)– polymer at high pressure and stabilization at ambient conditions

Xiao, Hai and An, Qi and Goddard, William A., III and Liu, Wei-Guang and Zybin, Sergey V. (2013) Formation of the –N(NO)N(NO)– polymer at high pressure and stabilization at ambient conditions. Proceedings of the National Academy of Sciences of the United States of America, 110 (14). pp. 5321-5325. ISSN 0027-8424. PMCID PMC3619361. doi:10.1073/pnas.1222890110.

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A number of exotic structures have been formed through high-pressure chemistry, but applications have been hindered by difficulties in recovering the high-pressure phase to ambient conditions (i.e., one atmosphere and 300 K). Here we use dispersion-corrected density functional theory [PBE-ulg (Perdew-Burke-Ernzerhof flavor of DFT with the universal low gradient correction for long range London dispersion)] to predict that above 60 gigapascal (GPa) the most stable form of N_(2)O (the laughing gas in its molecular form) is a one-dimensional polymer with an all-nitrogen backbone analogous to cis-polyacetylene in which alternate N are bonded (ionic covalent) to O. The analogous trans-polymer is only 0.03∼0.10 eV/molecular unit less stable. Upon relaxation to ambient conditions, both polymers relax below 14 GPa to the same stable nonplanar trans-polymer. The predicted phonon spectrum and dissociation kinetics validates the stability of this trans-poly-NNO at ambient conditions, which has potential applications as a type of conducting nonlinear optical polymer with all-nitrogen chains and as a high-energy oxidizer for rocket propulsion. This work illustrates in silico materials discovery particularly in the realm of extreme conditions (very high pressure or temperature).

Item Type:Article
Related URLs:
URLURL TypeDescription DOIArticle CentralArticle Information
Xiao, Hai0000-0001-9399-1584
An, Qi0000-0003-4838-6232
Goddard, William A., III0000-0003-0097-5716
Liu, Wei-Guang0000-0002-6633-7795
Additional Information:© 2013 National Academy of Sciences. Contributed by William A. Goddard III, December 31, 2012 (sent for review November 12, 2012). This work was supported by the Office of Naval Research (N00014-12-1-0538; program manager, Cliff Bedford) and the Defense Advanced Research Planning Agency (program manager, Judah Goldwasser). Author contributions: H.X., W.A.G., and S.V.Z. designed research; H.X., Q.A., W.A.G., and W.-G.L. performed research; H.X., Q.A., W.A.G., W.-G.L., and S.V.Z. analyzed data; and H.X., Q.A., W.A.G., W.-G.L., and S.V.Z. wrote the paper. The authors declare no conflict of interest. This article contains supporting information online at
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-12-1-0538
Defense Advanced Research Projects Agency (DARPA)UNSPECIFIED
Subject Keywords:DFT; high pressure physics and chemistry; prediction of novel materials
Issue or Number:14
PubMed Central ID:PMC3619361
Record Number:CaltechAUTHORS:20130530-133901125
Persistent URL:
Official Citation:Hai Xiao, Qi An, William A. Goddard III, Wei-Guang Liu, and Sergey V. Zybin Formation of the –N(NO)N(NO)– polymer at high pressure and stabilization at ambient conditions PNAS 2013 110 (14) 5321-5325; published ahead of print March 15, 2013, doi:10.1073/pnas.1222890110
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:38716
Deposited On:30 May 2013 21:10
Last Modified:09 Nov 2021 23:39

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