How and Why Does Helium Permeate Nonporous Arsenolite Under High Pressure?

Investigations into the helium permeation of arsenolite, the cubic, molecular arsenic(III) oxide polymorph As₄ O₆ , were carried out to understand how and why arsenolite helium clathrate As₄ O₆ ⋅2 He is formed. High-pressure synchrotron X-ray diffraction experiments on arsenolite single crystals revealed that the permeation of helium into nonporous arsenolite depends on the time for which the crystal is subjected to high pressure and on the crystal history. The single crystal was totally transformed into As₄ O₆ ⋅2 He within 45 h under 5 GPa. After release of the pressure, arsenolite was recovered and a repeated increase in pressure up to 3 GPa led to practically instant As₄ O₆ ⋅2 He formation. However, when a pristine arsenolite single crystal was quickly subjected to a pressure of 13 GPa, no helium permeation was observed at all. No neon permeation was observed in analogous experiments. Quantum mechanical computations indicate that there are no specific attractive interactions between He atoms and As₄ O₆ molecules at the distances observed in the As₄ O₆ ⋅2 He crystal structure. Detailed analysis of As₄ O₆ molecular structure changes has shown that the introduction of He into the arsenolite crystal lattice significantly reduces molecular deformations by decreasing the anisotropy of stress exerted on the As₄ O₆ molecules. This effect and the pΔV term, rather than any specific As⋅⋅⋅He binding, are the driving forces for the formation As₄ O₆ ⋅2 He.