H-2 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 H-3- units.

Automated summary

We demonstrate that hydrogen in metal superhydride compounds can exist in two distinct states-atomic and molecular. At low pressures, additional hydrogen atoms form molecules with electronic states below the Fermi energy, resulting in low-symmetry structures with large unit cells. At high pressures, molecules become unstable and all hydrogens become atomic. This study uses density functional theory to compare BaH4 with other stoichiometries and cations, and shows that increased temperature and zero-point motion favor high-symmetry atomic states, with bond rearrangements occurring on a picosecond time scale.