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Inorganic Polysulfides in Solution: Structural Properties and Conformational Isomerism.
Joaquín Gajst1, Jonathan A Semelak1, Damián Scherlis1
1Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, and INQUIMAE, Universidad de Buenos Aires - CONICET, Pabellón 2, Ciudad Universitaria, C1428EHA Ciudad Autónoma de Buenos Aires, Argentina.
We explored polysulfides and their radical anions in solution, revealing new stable structures and isomerizations influenced by solvents. These findings are key for improving metal-sulfur battery performance.
Area of Science:
- Computational chemistry
- Inorganic chemistry
- Electrochemistry
Background:
- Polysulfides are crucial components in metal-sulfur batteries.
- Understanding their structural dynamics in solution is vital for battery performance.
- Previous studies lacked detailed insights into polysulfide isomer stabilities and interconversions.
Purpose of the Study:
- To theoretically investigate the structural properties and conformational isomerism of dianionic polysulfides [Sn]2-, their conjugated monoacids [HSn]-, and radical anions [Sn]•-.
- To elucidate the influence of aqueous and dimethyl sulfoxide (DMSO) solvents on the stability and interconversion of these species.
- To identify previously unreported stable conformations and their potential significance in real systems.
Main Methods:
- Quantum Mechanics-Molecular Mechanics (QM-MM) Molecular Dynamics (MD) simulations were employed.
- Explicit solvent molecules were included to accurately model solution environments.
- Detailed analysis of conformational isomer stabilities and interconversion pathways was performed.
Main Results:
- Stable, previously unreported conformational isomers of polysulfides and their radical anions were identified in solution.
- Solvent effects significantly influence isomer stability and interconversion dynamics.
- Isomer interconversions occur on the picosecond timescale, comparable to cyclohexane derivatives.
Conclusions:
- Solvent choice critically impacts polysulfide speciation and structural dynamics.
- The findings provide fundamental insights into polysulfide behavior relevant to metal-sulfur battery electrolytes.
- Understanding these solvent-mediated isomerizations can guide strategies for enhancing battery efficiency and longevity.
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