Inorganic polysulfides: Quantum chemistry study and biological implications

[Display omitted] •wB97XD is most accurate compared with high-level ab initio theories.•Long-chain polysulfide can serve as reservoir of sulfane sulfur.•HS2− is the most nucleophilic and most easily oxidized.•Nucleophilic attacks on polysulfides involve low reaction barrier. The storage and exchange...

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Published in:Chemical physics letters 2020-12, Vol.761, p.138069, Article 138069
Main Authors: Song, Wei-Hao, Hu, Ching-Han
Format: Article
Language:English
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Summary:[Display omitted] •wB97XD is most accurate compared with high-level ab initio theories.•Long-chain polysulfide can serve as reservoir of sulfane sulfur.•HS2− is the most nucleophilic and most easily oxidized.•Nucleophilic attacks on polysulfides involve low reaction barrier. The storage and exchange of sulfane sulfur in inorganic polysulfides (HSnH, HSn− and Sn2−) are essential processes in cell signaling. We performed a benchmark study, in which wB97XD is most accurate among the investigated density functionals. Using wB97XD and a continuum model to account for the solvation effects of water, we studied polysulfides with n up to 30. Our computations suggest that long-chain polysulfides can serve as reservoirs of sulfane sulfur. Among the HSn− species, HS2− is the most nucleophilic, and is the most easily oxidized. For n > 4, the dianionic form of polysulfide is predominant.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2020.138069