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1.	Ceppatelli, Matteo, et al. (författare) High-Pressure and High-Temperature Chemistry of Phosphorus and Nitrogen: Synthesis and Characterization of α- and γ-P3N5 2022 Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 61:31, s. 12165-12180 Tidskriftsartikel (refereegranskat)abstract The direct chemical reactivity between phosphorus and nitrogen was induced under high-pressure and high-temperature conditions (9.1 GPa and 2000-2500 K), generated by a laser-heated diamond anvil cell and studied by synchrotron X-ray diffraction, Raman spectroscopy, and DFT calculations. alpha-P3N5 and gamma-P3N5 were identified as reaction products. The structural parameters and vibrational frequencies of gamma-P3N5 were characterized as a function of pressure during room-temperature compression and decompression to ambient conditions, determining the equation of state of the material up to 32.6 GPa and providing insight about the lattice dynamics of the unit cell during compression, which essentially proceeds through the rotation of the PN5 square pyramids and the distortion of the PN4 tetrahedra. Although the identification of alpha-P3N5 demonstrates for the first time the direct synthesis of this compound from the elements, its detection in the outer regions of the laser-heated area suggests alpha-P3N5 as an intermediate step in the progressive nitridation of phosphorus toward the formation of gamma-P3N5 with increasing coordination number of P by N from 4 to 5. No evidence of a higher-pressure phase transition was observed, excluding the existence of predicted structures containing octahedrally hexacoordinated P atoms in the investigated pressure range.

Ceppatelli, Matteo, et al. (författare)
High-Pressure and High-Temperature Chemistry of Phosphorus and Nitrogen: Synthesis and Characterization of α- and γ-P3N5
2022
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 61:31, s. 12165-12180
Tidskriftsartikel (refereegranskat)abstract
- The direct chemical reactivity between phosphorus and nitrogen was induced under high-pressure and high-temperature conditions (9.1 GPa and 2000-2500 K), generated by a laser-heated diamond anvil cell and studied by synchrotron X-ray diffraction, Raman spectroscopy, and DFT calculations. alpha-P3N5 and gamma-P3N5 were identified as reaction products. The structural parameters and vibrational frequencies of gamma-P3N5 were characterized as a function of pressure during room-temperature compression and decompression to ambient conditions, determining the equation of state of the material up to 32.6 GPa and providing insight about the lattice dynamics of the unit cell during compression, which essentially proceeds through the rotation of the PN5 square pyramids and the distortion of the PN4 tetrahedra. Although the identification of alpha-P3N5 demonstrates for the first time the direct synthesis of this compound from the elements, its detection in the outer regions of the laser-heated area suggests alpha-P3N5 as an intermediate step in the progressive nitridation of phosphorus toward the formation of gamma-P3N5 with increasing coordination number of P by N from 4 to 5. No evidence of a higher-pressure phase transition was observed, excluding the existence of predicted structures containing octahedrally hexacoordinated P atoms in the investigated pressure range.

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