Polymorphic transitions of diborane at sub- and near-megabar pressures

Recent theoretical investigations of high-pressure structures of diborane have yielded many intriguing predictions which have so far remained untested due to challenges of acquiring experimental data at extreme pressures. Here we report new pressure-induced polymorphic transformations of crystalline diborane observed between 36 and 88 GPa by in situ Raman spectroscopy and interpreted using electronic structure calculations. Two previously unknown phase transitions are identified near 42 and 57 GPa, as evidenced by significant changes in the Raman profiles. The corresponding new phases, labeled IV and V, consist of B(2)H(6) molecules and have triclinic unit cells (P[Image: see text]), as deduced through evolutionary structure search and comparison of experimental and simulated Raman spectra. Density-functional calculations suggest that, at pressures above 110 GPa, phase V will form new molecular structures consisting of one-dimensional (BH(3))(n) chains and will become metallic near 138 GPa. Our findings make a significant contribution to the elucidation of the structures and properties of diborane in the near-megabar pressure region.