Pressure-Induced polymerization of LiN(CN)2

Derek W. Keefer, Huiyang Gou, Andrew P. Purdy, Albert Epshteyn, Duck Young Kim, John V. Badding, Timothy A. Strobel

Research output: Contribution to journalArticle

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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 sp2-hybidized carbon−nitrogen bonds and exhibits a visible absorption edge near 540 nm. The product is recoverable to ambient conditions but is not stable in air/ moisture.

Original languageEnglish (US)
Pages (from-to)9370-9377
Number of pages8
JournalJournal of Physical Chemistry A
Volume120
Issue number47
DOIs
StatePublished - Jan 1 2016

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Diamond
Synchrotrons
Lithium
X ray powder diffraction
Raman spectroscopy
Infrared spectroscopy
Moisture
polymerization
Diffraction
Phase transitions
Polymerization
Annealing
Ions
products
anvils
Air
diffraction
moisture
phase transformations
vibration mode

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Keefer, D. W., Gou, H., Purdy, A. P., Epshteyn, A., Kim, D. Y., Badding, J. V., & Strobel, T. A. (2016). Pressure-Induced polymerization of LiN(CN)2. Journal of Physical Chemistry A, 120(47), 9370-9377. https://doi.org/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. In: Journal of Physical Chemistry A. 2016 ; Vol. 120, No. 47. pp. 9370-9377.
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Keefer, DW, Gou, H, Purdy, AP, Epshteyn, A, Kim, DY, Badding, JV & Strobel, TA 2016, 'Pressure-Induced polymerization of LiN(CN)2', Journal of Physical Chemistry A, vol. 120, no. 47, pp. 9370-9377. https://doi.org/10.1021/acs.jpca.6b06780

Pressure-Induced polymerization of LiN(CN)2. / Keefer, Derek W.; Gou, Huiyang; Purdy, Andrew P.; Epshteyn, Albert; Kim, Duck Young; Badding, John V.; Strobel, Timothy A.

In: Journal of Physical Chemistry A, Vol. 120, No. 47, 01.01.2016, p. 9370-9377.

Research output: Contribution to journalArticle

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Keefer DW, Gou H, Purdy AP, Epshteyn A, Kim DY, Badding JV et al. Pressure-Induced polymerization of LiN(CN)2. Journal of Physical Chemistry A. 2016 Jan 1;120(47):9370-9377. https://doi.org/10.1021/acs.jpca.6b06780