Structural Investigation of Solid Methane at High Pressure

High pressure studies of solid methane are performed using both classical simulated annealing and first-principles methods. A series of simulated annealing and geometry optimization reveal a monoclinic P2₁/b structure with the unit cell containing four methane molecules. The phonon dispersion curves and vibrational density of states indicate that this structure is stable in the pressure range 10-90 GPa. The electronic band structure and density of states show that this structure has not metalized until 90 GPa.