A unique metallic phase of H3S at high-pressure: sulfur in three different local environments
文献信息
Ashok K. Verma, P. Modak
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 (TC) for the new phase and thus questions the validity of earlier high-TC explanations. We also find that S–H covalent bonds are different from the B–B bonds of MgB2.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.


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