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Atomic-Scale Mechanistic Insights into the Ring-Opening Polymerization of Elemental Sulfur (publisher proof PDF)

Summary

This wiki entry registers a publisher proof / galley PDF (papers/Wang_Sulfur_Angewandte_galley_2025.pdf) for the same Angewandte Chemie International Edition article as paper:2025wang-angew-atomic-scale (DOI 10.1002/anie.202511640). The science targets ring-opening polymerization (ROP) in molten elemental sulfur near the λ-transition, where viscosity changes sharply and experimental characterization of transient polymeric sulfur species is difficult. The authors introduce a ReaxFF parameterization specialized for sulfur polymerization, trained against extensive quantum mechanical datasets, and apply it to large-scale reactive molecular dynamics with more than 10,000 atoms to sample melt composition and mechanism at relevant temperatures. The work contrasts simulation outcomes with classical narratives emphasizing S₈ rings and linear chains, reporting that very large macrocyclic sulfur rings can appear at polymerization onset.

Methods

1 — MD application (atomistic dynamics). The reactive model is a ReaxFF reparameterization for elemental sulfur and its polymerization chemistry, with parameters fit to QM reference data spanning bonding environments and reaction energetics in the article and Supporting Information. Simulations use classical reactive MD in the melt near the λ-transition (reported as ~159 °C, or approximately 432 K in the main text for MD targeting of the λ transition) with >10,000 atom composition; the VOR’s NVT (melt) production plan specifies thermostat type (commonly Berendsen or Nose–Hoover in such LAMMPS-class runs) and K-resolved ramps—N/A to quote those fs time step, full PBC slab/supercell description, and ps/ns stages from this galley file alone. N/A on this page: full NPT/NVE (branch) (if any). N/A — NPT barostat/bar (hydrostatic (GPa)) not restated here. N/A — static electric field; N/A — no replica/metadynamics; N/A — no umbrella sampling in the ROP production plan as cited on the canonical page. The galley may show author-query banners; confirm all numbers in the VOR.

2 — Force-field training. ReaxFF re-fit for S ROP with DFT/QM-based training and parameter optimization; structures and reaction targets in the main text and SI. N/A — this registrant file does not replace the version-of-record for table-level QM settings.

3 — Static QM only — N/A (supporting QM for the ReaxFF only).

4 — Review — N/A.

Findings

  • Melt reaction pathways, kinetics, and mechanism-level composition are interpreted in reactive MD, compared to classical models that cannot make/break bonds.
  • macrocycle-rich pictures at ROP onset and sensitivity to temperature (near the λ transition) follow the VOR; N/A on this page for exact reaction rates—treat 2025wang-angew-atomic-scale as the narrative benchmark.
  • Corpus honesty: galley layout may differ; author may have revised conclusions; proof page numbers are not canonical.

Limitations

Galley PDFs can differ in layout, pagination, and figure resolution from the VOR; pdf_sha256 differs from the canonical papers/Wang_Angewandte_Sulfur_2025.pdf path on [[2025wang-angew-atomic-scale]].

Reproducibility notes

Sulfur ROP simulations should record λ-transition targeting temperatures, thermostat coupling, and whether long-range corrections are applied, because molten sulfur’s ring–polymer equilibrium is sensitive to both thermodynamics and kinetic accessibility. When comparing to experiment, distinguish equilibrium composition metrics from transient macrocycle populations sampled in finite MD. If the galley and VOR disagree on Supporting Information filenames, prefer the journal’s final SI package for QM training tables.

Relevance to group

Duplicate ingest of the Angewandte sulfur ROP manuscript under a galley filename; modeling led by van Duin group collaborators.

Citations and evidence anchors

Reader notes (navigation)

  • Canonical article note: papers/Wang_Angewandte_Sulfur_2025.pdf → 2025wang-angew-atomic-scale; this slug tracks papers/Wang_Sulfur_Angewandte_galley_2025.pdf.