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.

doi:10.1021/acs.jpca.6b06780

Pressure-Induced Polymerization of LiN(CN)₂

Journal Article · Fri Oct 28 00:00:00 EDT 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.6b06780· OSTI ID:1338990

Keefer, Derek W. ^[1]; Gou, Huiyang ^[2]; Purdy, Andrew P. ^[3]; Epshteyn, Albert ^[3]; Kim, Duck Young ^[2]; Badding, John V. ^[1]; Strobel, Timothy A. ^[4]

Pennsylvania State Univ., University Park, PA (United States)
Carnegie Inst. of Washington, Washington, DC (United States); Center for High Pressure Science and Technology Advanced Research, Shanghai (China)
Naval Research Lab., Washington, DC (United States)
Carnegie Inst. of Washington, Washington, DC (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: DARPA; National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; FG02-99ER45775; NA0001974

OSTI ID:: 1338990

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 47 Vol. 120; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
lattices
lithium
materials
physical and chemical processes
polymerization