Superconducting Phases of Phosphorus Hydride Under Pressure: Stabilization by Mobile Molecular Hydrogen

At 80 GPa, phases with the PH₂ stoichiometry, which are composed of simple cubic like phosphorus layers capped with hydrogen atoms and layers of H₂ molecules, are predicted to be important species contributing to the recently observed superconductivity in compressed phosphine. The electron–phonon coupling in these phases results from the motions of the phosphorus atoms and the hydrogen atoms bound to them. The role of the mobile H₂ layers is to decrease the Coulomb repulsion between the negatively charged hydrogen atoms capping the phosphorus layers. An insulating PH₅ phase, the structure and bonding of which is reminiscent of diborane, is also predicted to be metastable at this pressure.