Compressibility of cubic white, orthorhombic black, rhombohedral black, and simple cubic black phosphorus

The effect of pressure on the crystal structure of white phosphorus has been studied up to 22.4 GPa. The alpha phase was found to transform into the alpha' phase at 0.87 perpendicular to 0.04 GPa with a volume change in 0.1 perpendicular to 0.3 cc/mol. A fit of a second-order Birch-Murnaghan equation to the data gave V(o) = 16.94 +/- 0.08 cc/mol and K(o) = 6.7 +/- 0.5 GPa for the alpha phase and V(o) = 16.4 +/- 0.1 cc/mol and K(o) = 9.1 +/- 0.3 GPa for the alpha' phase. The alpha' phase was found to transform to the A17 phase of black phosphorus at 2.68 +/- 0.34 GPa and then with increasing pressure to the A7 and then simple cubic phase of black phosphorus. A fit of a second-order Birch-Murnaghan equation to our data combined with previous measurements gave V(o) = 11.43 +/- 0.05 cc/mol and K(o) = 34.7 +/- 0.5 GPa for the A17 phase, V(o) = 9.62 +/- 0.01 cc/mol and K(o) = 65.0 +/- 0.6 GPa for the A7 phase and, V(o) = 9.23 +/- 0.01 cc/mol and K(o) = 72.5 +/- 0.3 GPa for the simple cubic phase.