Pressure-induced polymerization of P(CN)3
Abstract
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 X-ray diffraction 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 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 phosphorous carbon nitride (PCN) polymeric phase, which is recoverable to ambient pressure.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- May 18, 2015
- Source ID
- 10.1063/1.4919640
Entities
People
- Albert Epshteyn
- Brendan L. Yonke
- Duck Young Kim
- Huiyang Gou
- Jesse S Smith
- Timothy A. Strobel
Organizations
- Carnegie Institution for Science
- Defense Advanced Research Projects Agency
- United States Department of Energy
- United States Naval Research Laboratory