High Pressure and High Temperature Synthesis of the Iron Pernitride FeN₂

The high pressure chemistry of transition metals and nitrogen was recently discovered to be richer than previously thought, due to the synthesis of several transition metal pernitrides. Here, we explore the pressure-temperature domain of iron with an excess of nitrogen up to 91 GPa and 2200 K. Above 72 GPa and 2200 K, the iron pernitride FeN₂ is produced in a laser-heated diamond anvil cell. This iron-nitrogen compound is the first with a N/Fe ratio greater than 1. The FeN₂ samples were characterized from the maximum observed pressure down to ambient conditions by powder X-ray diffraction and Raman spectroscopy measurements. The crystal structure of FeN₂ is resolved to be a Pnnm marcasite structure, analogously to other transition metal pernitrides. On the basis of the lattice's axial ratios and the recorded N-N vibrational modes of FeN₂, a bond order of 1.5 for the nitrogen dimer is suggested. The bulk modulus of the iron pernitride is determined to be of K₀ = 344(13) GPa, corresponding to an astounding increase of about 208% from pure iron. Upon decompression to ambient conditions, a partial structural phase transition to the theoretically predicted R3̅ m FeN₂ is detected.