Insights into the high-pressure behaviour of solid bromine from hybrid DFT calculations

Abstract

Understanding the properties of molecular solids at high pressure is a key element in the development of new solid-state theories. However, the most commonly used generalized-gradient approximation (GGA) of the density functional theory (DFT) often fails to correctly describe the behavior of these systems at high pressure. Here we utilize the hybrid DFT approach to model the properties of elemental bromine at high pressure. The calculations reproduce in very good agreement with experiment the properties of the molecular phase I (Cmca symmetry) and its pressure-induced transition into the non-molecular phase II (Immm). The experimentally yet unobserved transition into phase III (I4/mmm) is predicted to occur at 128 GPa, followed by subsequent formation of an fcc lattice at 188 GPa. Analysis of the structure and electronic properties of the modelled phases indicates that the molecular Cmca phase becomes metallic just at the borderline of its stability, and that both Immm and I4/mmm phases are metallic and quasi-2D. Finally, we show that the incommensurate phases of bromine postulated from experiment are transient species which can be viewed as intermediates in the dissociation process occurring at the boundary of the transition from phase I to phase II.