Low-symmetry polymorph of GaP upends bonding paradigms of metallic high-pressure III-V compounds

The pressure-induced polymorphism of binary octect compounds has long been considered a settled problem although the possible atomic disordering of some phases remains a puzzling observation. Taking GaP as a case study, we conclude, through x-ray microdiffraction and first-principles calculations, that its high-pressure phase II (previously reported as being disordered) adopts in fact an ordered base-centered monoclinic structure previously unknown in this class of compounds. The formation of layered patterns with variable degrees of interlayer dimerization, as observed in GaP, marks a paradigm shift of our understanding of ordering in octect high-pressure phases which calls for a more extensive re-examination. A rich polymorphism with fine tuning of chemical and physical properties can be envisioned.