Crystal structures and electronic properties of solid fluorine under high pressure

As the previously proposed structures of C2/m and C2/c possess similar enthalpies and x-ray diffraction patterns, the space group of fluorine at ambient pressure is in controversy. We successfully obtain its thermodynamically stable low-pressure phase, which shares the same structure as the earlier known C2/c. Further investigations on phonon spectra reveal the instability of the C2/m structure with imaginary frequency in the Brillouin zone and confirm the dynamically stable property of the C2/c structure at the same time. Compressing fluorine up to 8 GPa, the C2/c phase is found to undergo a phase transition to a new structure with a space group of Cmca. Electronic energy band structures indicate the insulating feature of C2/c and Cmca with no bands across the Fermi level. The infrared (IR) and Raman spectra of C2/c and Cmca at selected pressures are calculated to provide useful information to future experiments.