H₂ Chemical Bond in a High-Pressure Crystalline Environment

We show that the hydrogen in metal superhydride compounds can adopt two distinct states─atomic and molecular. At low pressures, the maximum number of atomic hydrogens is typically equal to the valency of the cation; additional hydrogens pair to form molecules with electronic states far below the Fermi energy causing low-symmetry structures with large unit cells. At high pressures, molecules become unstable, and all hydrogens become atomic. This study uses density functional theory, adopting BaH₄ as a reference compound, which is compared with other stoichiometries and other cations. Increased temperature and zero-point motion also favor high-symmetry atomic states, and picosecond-timescale breaking and remaking of the bond permutations via intermediate H₃^- units.