Origin of the large differences in high-pressure stability and superconductivity between ThH9 and ThH18

Abstract

Recently, the thorium hydride ThH9 possessing an H-rich clathrate structure has been experimentally synthesized to exhibit a superconducting transition temperature Tc of 146 K at 170-175 GPa, while the more H-rich clathrate thorium hydride ThH18 was theoretically predicted to reach a Tc of 296 K at 400 GPa. Using first-principles calculations, we find that ThH9 has a more ionic character between Th atoms and H cages than ThH18 and that the latter has a more substantial hybridization of the Th 6p semicore and H 1s states than the former. These different bonding characteristics of ThH9 and ThH18 are associated with their stability at very different pressures. Furthermore, we reveal that (i) the H-derived density of states at the Fermi level Ef is about two times larger in ThH18 than in ThH9. (ii) the average squared phonon frequency of H atoms is about 29% higher in ThH18 than in ThH9, and (iii) the Fermi surface average squared electron-phonon matrix element is similar between the two hydrides. Consequently, the electron-phonon coupling constant of ThH18 becomes much greater than that of ThH9, leading to a significant Tc difference between the two thorium hydrides. Our findings not only provide an explanation for the very large differences in the stabilization pressure and superconducting transition temperature between ThH9 and ThH18 but also have important implications for the design of H-rich, high-Tc clathrate metal hydrides.