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Title: Pressure-induced polymerization of P(CN){sub 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){sub 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 X-ray diffraction measurements taken during compression show that molecular P(CN){sub 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 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{sup 2} character, similar to known carbon nitrides, resulting in a novel phosphorous carbon nitride (PCN) polymeric phase, which is recoverable to ambient pressure.
Authors:
; ;  [1] ;  [2] ;  [3] ;  [4]
  1. Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Road, NW, Washington, DC 20015 (United States)
  2. NRC Postdoctoral Associate, Naval Research Laboratory, 4555 Overlook Ave., SW, Washington, DC 20375 (United States)
  3. Naval Research Laboratory, 4555 Overlook Ave., SW, Washington, DC 20375 (United States)
  4. High Pressure Collaborative Access Team, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439 (United States)
Publication Date:
OSTI Identifier:
22415804
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 19; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMORPHOUS STATE; CARBON; CARBON NITRIDES; COMPRESSION; CYANIDES; INFRARED SPECTRA; MOLECULAR DYNAMICS METHOD; NITROGEN; PHASE TRANSFORMATIONS; POLYMERIZATION; POLYMERS; POWDERS; PRESSURE DEPENDENCE; PRESSURE RANGE GIGA PA; REACTIVITY; SOLIDS; TEMPERATURE RANGE 0273-0400 K; X-RAY DIFFRACTION