Underlying mechanism of charge transfer in Li-doped MgH16 at high pressure

A lithium-doped magnesium hydride ${\mathrm{Li}}₂{\mathrm{MgH}}₁₆$ was recently reported [Y. Sun et al., Phys. Rev. Lett. 123, 097001 (2019)] to exhibit the highest ever predicted superconducting transition temperature ${T}_{\mathrm{c}}$ under high pressure. Based on first-principles density-functional theory calculations, we reveal that the Li dopants locating in the pyroclore lattice sites give rise to the excess electrons distributed outside Li atoms. Such loosely bound anionic electrons are easily captured to stabilize a clathrate structure consisting of H cages. This addition of anionic electrons to H cages enhances the H-derived electronic density of states at the Fermi level, thereby leading to a high-${T}_{\mathrm{c}}$ superconductivity. We thus propose that the electride nature of Li dopants is an essential ingredient in the charge transfer between Li dopants and H atoms. Our findings offer a deeper understanding of the underlying mechanism of charge transfer in ${\mathrm{Li}}₂{\mathrm{MgH}}₁₆$ at high pressure.