Formation mechanism of chemically precompressed hydrogen clathrates in metal superhydrides

Abstract

Recently, the experimental discovery of high-$T_c$ superconductivity in compressed hydrides H${}_3$S and LaH${}_{10}$ at megabar pressures has triggered searches for various superconducting superhydrides. It was experimentally observed that thorium hydrides, ThH${}_{10}$ and ThH${}_9$, are stabilized at much lower pressures compared to LaH${}_{10}$. Based on first-principles density-functional theory calculations, we reveal that the isolated Th frameworks of ThH${}_{10}$ and ThH${}_9$ have relatively more excess electrons in interstitial regions than the La framework of LaH${}_{10}$. Such interstitial excess electrons easily participate in the formation of anionic H cage surrounding metal atom. The resulting Coulomb attraction between cationic Th atoms and anionic H cages is estimated to be stronger than the corresponding one of LaH${}_{10}$, thereby giving rise to larger chemical precompressions in ThH${}_{10}$ and ThH${}_9$. Such a formation mechanism of H clathrates can also be applied to another experimentally synthesized superhydride CeH${}_9$, confirming the experimental evidence that the chemical precompression in CeH${}_9$ is larger than that in LaH${}_{10}$. Our findings demonstrate that interstitial excess electrons in the isolated metal frameworks of high-pressure superhydrides play an important role in generating the chemical precompression of H clathrates.