Thermodynamic and electronic properties of ReN2 polymorphs at high pressure

The high-pressure synthesis of rhenium nitride pernitride with a crystal structure that is unusual for transition metal dinitrides and high values of hardness and bulk modulus attracted significant attention to this system. We investigate the thermodynamic and electronic properties of the P2(1)/c phase of ReN2 and compare them with two other polytypes, the C2/m and P4/mbm phases, suggested in the literature. Our calculations of the formation enthalpy at zero temperature show that the former phase is the most stable of the three up to a pressure p = 170 GPa, followed by the stabilization of the P4/mbm phase at higher pressure. The theoretical prediction is confirmed by diamond anvil cell synthesis of the P4/mbm ReN2 at approximate to 175 GPa. Considering the effects of finite temperature in the quasiharmonic approximation at p = 100 GPa we demonstrate that the P2(1)/c phase has the lowest free energy of formation at least up to 1000 K. Our analysis of the pressure dependence of the electronic structure of rhenium nitride pernitride shows the presence of two electronic topological transitions around 18 GPa, when the Fermi surface changes its topology due to the appearance of an electron pocket at the high-symmetry Y-2 point of the Brillouin zone while the disruption of the neck takes place slightly off from the Gamma-A line.Funding Agencies|Knut and Alice Wallenberg Foundation (Wallenberg Scholar Grant) [KAW-2018.0194]; Swedish Government Strategic Research Areas in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; SeRC, the Swedish Research Council (VR) [2019-05600]; VINN Excellence Center Functional Nanoscale Materials (FunMat-2) [201605156]; Russian Science FoundationRussian Science Foundation (RSF) [18-12-00492]; Swedish Research CouncilSwedish Research CouncilEuropean Commission [2016-07213]