Decomposition Products of Phosphine Under Pressure: PH2 Stable and Superconducting?

TL;DR

Using computational methods, this study predicts stable and superconducting phases of phosphine decomposition products under high pressure, suggesting these may explain recent experimental superconductivity observations.

Contribution

The paper introduces new stable and superconducting phases of PH2 under high pressure, identified through combined evolutionary algorithms and DFT calculations.

Findings

PH2 phases are stable and superconducting between 100-200 GPa.

Superconducting critical temperatures are 70-76 K for certain phases.

Decomposition products of phosphine may account for observed superconductivity at 207 GPa.

Abstract

Evolutionary algorithms (EA) coupled with Density Functional Theory (DFT) calculations have been used to predict the most stable hydrides of phosphorous (PHn, n = 1-6) at 100, 150 and 200 GPa. At these pressures phosphine is unstable with respect to decomposition into the elemental phases, as well as PH2 and H2. Three metallic PH2 phases were found to be dynamically stable and superconducting between 100-200 GPa. One of these contains five formula units in the primitive cell and has C2/m symmetry (5FU-C2/m). It is comprised of 1D periodic PH3-PH-PH2-PH-PH3 oligomers. Two structurally related phases consisting of phosphorous atoms that are octahedrally coordinated by four phosphorous atoms in the equatorial positions and two hydrogen atoms in the axial positions (I4/mmm and 2FU-C2/m) were the most stable phases between ~160-200 GPa. Their superconducting critical temperatures (Tc) were computed as being 70 and 76 K, respectively, via the Allen-Dynes modified McMillan formula and using a value of 0.1 for the Coulomb pseudopotential, u*. Our results suggest that the superconductivity recently observed by Drozdov, Eremets and Troyan when phosphine was subject to pressures of 207 GPa in a diamond anvil cell may result from these, and other, decomposition products of phosphine.