Formation Mechanism of Chemically Precompressed Hydrogen Clathrates in Metal Superhydrides

Recently, the experimental discovery of high-T_c superconductivity in compressed hydrides H₃S and LaH₁₀ at megabar pressures has triggered searches for various superconducting superhydrides. It was experimentally observed that thorium superhydrides, ThH₁₀ and ThH₉, are stabilized at much lower pressures than LaH₁₀. Based on first-principles density functional theory calculations, we reveal that the isolated Th frameworks of ThH₁₀ and ThH₉ have relatively more excess electrons in interstitial regions than the La framework of LaH₁₀. Such interstitial excess electrons easily participate in the formation of the anionic H cage surrounding the metal atom. The resulting Coulomb attraction between cationic Th atoms and anionic H cages is estimated to be stronger than the corresponding one of LaH₁₀, thereby giving rise to larger chemical precompressions in ThH₁₀ and ThH₉. Such a formation mechanism of H clathrates can also be applied to other superhydrides such as CeH₉, PrH₉, and NdH₉. 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.