The effect of pressure on the crystal structure of white phosphorus has been studied up to 22.4 GPa. The α phase was found to transform into the α' phase at 0.87 ± 0.04 GPa with a volume change of 0.1 ± 0.3 cc/mol. A fit of a second order BirchMurnaghan equation to the data gave Vo = 16.94 ± 0.08 cc/mol and K o = 6.7 ± 0.5 GPa for the α phase and Vo = 16.4 ± 0.1 cc/mol and K o = 9.1 ± 0.3 GPa for the α' phase. The α' 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 Vo = 11.43 ± 0.05 cc/mol and K o = 34.7 ± 0.5 GPa for the A17 phase, Vo = 9.62 ± 0.01 cc/mol and K o = 65.0 ± 0.6 GPa for the A7 phase and , Vo = 9.23 ± 0.01 cc/mol and K o = 72.5 ± 0.3 GPa for the simple cubic phase.
PACS numbers:Phase transitions, crystallographic aspects of, 61.50.KsHigh-pressure effects, structural properties of materials, 81.40.Vw X-ray diffraction in crystal structure, 61.05.cp