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Title: Pressure-Induced Polymerization of LiN(CN) 2

Abstract

The high-pressure behavior of lithium dicyanamide (LiN(CN) 2) was studied with in situ Raman and infrared (IR) spectroscopies, and synchrotron angle-dispersive powder X-ray diffraction (PXRD) in a diamond anvil cell (DAC) to 22 GPa. The fundamental vibrational modes associated with molecular units were assigned using a combination of experimental data and density functional perturbation theory. Some low-frequency modes were observed for the first time. On the basis of spectroscopic and diffraction data, we suggest a polymorphic phase transformation at ~8 GPa, wherein dicyanamide ions remain as discrete molecular species. Above ca. 18 GPa, dicyanamide units polymerize, forming a largely disordered network, and the extent of polymerization may be increased by annealing at elevated temperature. The polymerized product consists of tricyanomelaminate-like groups containing sp 2-hybidized carbon–nitrogen bonds and exhibits a visible absorption edge near 540 nm. Lastly, the product is recoverable to ambient conditions but is not stable in air/moisture.

Authors:
 [1];  [2];  [3];  [3];  [2];  [1];  [4]
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Carnegie Inst. of Washington, Washington, DC (United States); Center for High Pressure Science and Technology Advanced Research, Shanghai (China)
  3. Naval Research Lab., Washington, DC (United States)
  4. Carnegie Inst. of Washington, Washington, DC (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); Defense Advanced Research Projects Agency (DARPA)
OSTI Identifier:
1338990
Grant/Contract Number:  
AC02-06CH11357; U1530402; FG02-99ER45775; NA0001974; 31P4Q- 3-I-0005
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 47; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; polymerization; lattices; physical and chemical processes; lithium; materials

Citation Formats

Keefer, Derek W., Gou, Huiyang, Purdy, Andrew P., Epshteyn, Albert, Kim, Duck Young, Badding, John V., and Strobel, Timothy A. Pressure-Induced Polymerization of LiN(CN)2. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b06780.
Keefer, Derek W., Gou, Huiyang, Purdy, Andrew P., Epshteyn, Albert, Kim, Duck Young, Badding, John V., & Strobel, Timothy A. Pressure-Induced Polymerization of LiN(CN)2. United States. https://doi.org/10.1021/acs.jpca.6b06780
Keefer, Derek W., Gou, Huiyang, Purdy, Andrew P., Epshteyn, Albert, Kim, Duck Young, Badding, John V., and Strobel, Timothy A. Fri . "Pressure-Induced Polymerization of LiN(CN)2". United States. https://doi.org/10.1021/acs.jpca.6b06780. https://www.osti.gov/servlets/purl/1338990.
@article{osti_1338990,
title = {Pressure-Induced Polymerization of LiN(CN)2},
author = {Keefer, Derek W. and Gou, Huiyang and Purdy, Andrew P. and Epshteyn, Albert and Kim, Duck Young and Badding, John V. and Strobel, Timothy A.},
abstractNote = {The high-pressure behavior of lithium dicyanamide (LiN(CN)2) was studied with in situ Raman and infrared (IR) spectroscopies, and synchrotron angle-dispersive powder X-ray diffraction (PXRD) in a diamond anvil cell (DAC) to 22 GPa. The fundamental vibrational modes associated with molecular units were assigned using a combination of experimental data and density functional perturbation theory. Some low-frequency modes were observed for the first time. On the basis of spectroscopic and diffraction data, we suggest a polymorphic phase transformation at ~8 GPa, wherein dicyanamide ions remain as discrete molecular species. Above ca. 18 GPa, dicyanamide units polymerize, forming a largely disordered network, and the extent of polymerization may be increased by annealing at elevated temperature. The polymerized product consists of tricyanomelaminate-like groups containing sp2-hybidized carbon–nitrogen bonds and exhibits a visible absorption edge near 540 nm. Lastly, the product is recoverable to ambient conditions but is not stable in air/moisture.},
doi = {10.1021/acs.jpca.6b06780},
url = {https://www.osti.gov/biblio/1338990}, journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 47,
volume = 120,
place = {United States},
year = {2016},
month = {10}
}

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