AbstractWe present results from first-principles calculations on silane (SiH₄) under pressure. We find that a three dimensional P-3 structure becomes the most stable phase above 241 GPa. A prominent structural feature, which separates the P-3 structure from previously observed/predicted SiH₄ structures, is that a fraction of hydrogen leaves the Si-H bonding environment and forms segregated H₂ units. The H₂ units are sparsely populated in the system and intercalated with a polymeric Si-H framework. Calculations of enthalpy of formation suggest that the P-3 structure is against the decomposition into Si-H binaries and/or the elemental crystals. Structural stability of the P-3 structure is attributed to the electron-deficient multicenter Si-H-Si interactions when neighboring silicon atoms are linked together through a common hydrogen atom. Within the multicenter bonds, electrons are delocalized and this leads to a metallic state, possibly also a superconducting state, for SiH₄. An interesting outcome of the present study is that the enthalpy sum of SiH₄ (P-3 structure) and Si (fcc structure) appears to be lower than the enthalpy of disilane (Si₂H₆) between 200 and 300 GPa (for all previously predicted crystalline forms of Si₂H₆), which calls for a revisit of the stability of Si₂H₆ under high pressure.