A unique metallic phase of H3S at high-pressure: sulfur in three different local environments

Abstract

We propose a new metallic phase (Rm, Z = 24) for H₃S in a large pressure interval (∼108–166 GPa) using an evolutionary crystal structure search algorithm combined with first-principles calculations. This structure consists of SH₆, SH₃ and S units which are connected through strong S⋯H hydrogen-bonds. It supports four-types of S⋯H hydrogen-bonds that symmetrize at ∼166 GPa. This is the only phase in the H–S family where sulfur exists in three different local environments. Sulfur in SH₆ behaves as a cation, like in the SF₆ molecule, whereas other sulfurs behave as anions. Hydrogens in SH₆ behave like halogens (anions) whereas other hydrogens behave like alkalis (cations). The new structure has a substantially smaller DOS at the Fermi-level in comparison to earlier structures R3m and Imm. This implies a lower superconducting temperature (T_C) for the new phase and thus questions the validity of earlier high-T_C explanations. We also find that S–H covalent bonds are different from the B–B bonds of MgB₂.