Structure of barium in three phases under pressure

A first-principles calculation of the structure of barium under pressure was done with a procedure which finds the equilibrium structure by minimizing the Gibbs free energy at zero temperature with respect to structure at each pressure. The calculated structures agree with measurements at the 1% level in three phases, Ba I (body-centered cubic), Ba II and V (hexagonal close-packed), over a range of pressure from 0 to 900 kbar. The fit to experiment is closer than that of two previous calculations, one of which used molecular dynamics under an applied stress to find equilibrium structure, and the other minimized the energy at constant volume. Hexagonal close-packed barium is shown to be metastable in the pressure range of the incommensurate Ba IV phase