Synthesis of molecular metallic barium superhydride: pseudocubic BaH12

Following the discovery of high-temperature superconductivity in the La–H system, we studied the formation of new chemical compounds in the barium-hydrogen system at pressures from 75 to 173 GPa. Using in situ generation of hydrogen from NH₃BH₃, we synthesized previously unknown superhydride BaH₁₂ with a pseudocubic (fcc) Ba sublattice in four independent experiments. Density functional theory calculations indicate close agreement between the theoretical and experimental equations of state. In addition, we identified previously known P6/mmm-BaH₂ and possibly BaH₁₀ and BaH₆ as impurities in the samples. Ab initio calculations show that newly discovered semimetallic BaH₁₂ contains H₂ and H₃^– molecular units and detached H₁₂ chains which are formed as a result of a Peierls-type distortion of the cubic cage structure. Barium dodecahydride is a unique molecular hydride with metallic conductivity that demonstrates the superconducting transition around 20 K at 140 GPa.