Pressure-induced polymerization of P(CN){sub 3}

Journal Article · Thu May 21 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4919640· OSTI ID:22415804

Gou, Huiyang; Kim, Duck Young; Yonke, Brendan L. ^[1]; Epshteyn, Albert ^[2]; Smith, Jesse S. ^[3]

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1. NRC Postdoctoral Associate, Naval Research Laboratory, 4555 Overlook Ave., SW, Washington, DC 20375 (United States)
2. Naval Research Laboratory, 4555 Overlook Ave., SW, Washington, DC 20375 (United States)
3. High Pressure Collaborative Access Team, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439 (United States)

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.

• OSTI ID: 22415804
• Journal Information: Journal of Chemical Physics, Vol. 142, Issue 19; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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