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Title: Pressure-induced polymerization of P(CN) 3

Motivated to explore the formation of novel extended carbon-nitrogen solids via well-defined molecular precursor pathways, we studied the chemical reactivity of highly pure phosphorous tricyanide, P(CN) 3, under conditions of high pressure at room temperature. Raman and infrared (IR) spectroscopic measurements reveal a series of phase transformations below 10 GPa, and several low-frequency vibrational modes are reported for the first time. Synchrotron powder Xray diffraction (PXRD) measurements taken during compression show that molecular P(CN) 3 is highly compressible with a bulk modulus of 10.0±0.3 GPa and polymerizes into an amorphous solid above ~10.0 GPa. Raman and infrared (IR) spectra, together with first-principles molecular-dynamics simulations, show that the amorphization transition is associated with polymerization of the cyanide groups into CN bonds with predominantly sp 2 character, similar to known carbon nitrides, resulting in a novel PCN polymeric phase, which is recoverable to ambient pressure.
Authors:
ORCiD logo [1] ;  [2] ;  [2] ;  [1] ;  [1] ;  [1]
  1. Carnegie Inst. of Washington, Argonne, IL (United States). Geophysical Lab.
  2. Naval Research Lab. (NRL), Washington, DC (United States)
Publication Date:
Grant/Contract Number:
NA0002006; AC02-06CH11357; FG02-99ER45775; NA0001974
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Carnegie Inst. of Washington, Argonne, IL (United States). Geophysical Lab.
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1338321
Alternate Identifier(s):
OSTI ID: 1228173

Gou, Huiyang, Yonke, Brendan L., Epshteyn, Albert, Kim, Duck Young, Smith, Jesse S., and Strobel, Timothy A.. Pressure-induced polymerization of P(CN) 3. United States: N. p., Web. doi:10.1063/1.4919640.
Gou, Huiyang, Yonke, Brendan L., Epshteyn, Albert, Kim, Duck Young, Smith, Jesse S., & Strobel, Timothy A.. Pressure-induced polymerization of P(CN) 3. United States. doi:10.1063/1.4919640.
Gou, Huiyang, Yonke, Brendan L., Epshteyn, Albert, Kim, Duck Young, Smith, Jesse S., and Strobel, Timothy A.. 2015. "Pressure-induced polymerization of P(CN) 3". United States. doi:10.1063/1.4919640. https://www.osti.gov/servlets/purl/1338321.
@article{osti_1338321,
title = {Pressure-induced polymerization of P(CN) 3},
author = {Gou, Huiyang and Yonke, Brendan L. and Epshteyn, Albert and Kim, Duck Young and Smith, Jesse S. and Strobel, Timothy A.},
abstractNote = {Motivated to explore the formation of novel extended carbon-nitrogen solids via well-defined molecular precursor pathways, we studied the chemical reactivity of highly pure phosphorous tricyanide, P(CN)3, under conditions of high pressure at room temperature. Raman and infrared (IR) spectroscopic measurements reveal a series of phase transformations below 10 GPa, and several low-frequency vibrational modes are reported for the first time. Synchrotron powder Xray diffraction (PXRD) measurements taken during compression show that molecular P(CN)3 is highly compressible with a bulk modulus of 10.0±0.3 GPa and polymerizes into an amorphous solid above ~10.0 GPa. Raman and infrared (IR) spectra, together with first-principles molecular-dynamics simulations, show that the amorphization transition is associated with polymerization of the cyanide groups into CN bonds with predominantly sp2 character, similar to known carbon nitrides, resulting in a novel PCN polymeric phase, which is recoverable to ambient pressure.},
doi = {10.1063/1.4919640},
journal = {Journal of Chemical Physics},
number = 19,
volume = 142,
place = {United States},
year = {2015},
month = {5}
}