High-Pressure and High-Temperature Chemistry of Phosphorus and Nitrogen: Synthesis and Characterization of α- and γ-P 3 N 5 .

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. α-P 3 N 5 and γ-P 3 N 5 were identified as reaction products. The structural parameters and vibrational frequencies of γ-P 3 N 5 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 PN 5 square pyramids and the distortion of the PN 4 tetrahedra. Although the identification of α-P 3 N 5 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 α-P 3 N 5 as an intermediate step in the progressive nitridation of phosphorus toward the formation of γ-P 3 N 5 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.