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Reductive decomposition reactions of ethylene carbonate by explicit electron transfer from lithium: an eReaxFF molecular dynamics study

Summary

Solid-electrolyte interphase formation in lithium-ion batteries involves reduction of carbonate solvents at metal anodes, a process dominated by electron transfer, ring opening, and radical chemistry that is expensive to sample with ab initio molecular dynamics at electrode scales. This Journal of Physical Chemistry C article applies eReaxFF—an extension of ReaxFF that augments bond-order reactive dynamics with explicit pseudoclassical electron degrees of freedom—to ethylene carbonate reduction initiated by electron transfer from lithium metal. The model aims to capture SEI-relevant elementary events such as ring opening toward radical intermediates and subsequent termination reactions without prescribing a fixed reaction network beforehand. The authors argue that eReaxFF improves energetics for key reduction steps relative to standard ReaxFF and tracks literature quantum-chemistry trends for selected pathways. This wiki slug points at an ACS author-proof PDF; [[2016islam-venue-jp6b08688]] should be preferred for stable pagination and figure numbering when both files exist in the corpus.

Methods

Duplicate ACS author proof PDF for the same article as 2016islam-venue-jp6b08688 (DOI 10.1021/acs.jpcc.6b08688). Protocol matches that page: eReaxFF molecular dynamics in the NVT ensemble on 60 EC and 40 Li atoms (composition stated in the article) with three-dimensional periodic boundary conditions, 1 K relaxation, 300 K and 600 K production (gradual heating toward 600 K), Berendsen thermostat (100 fs damping), velocity Verlet at 0.10 fs, 1 amu fictitious mass per explicit electron carrier (Section 3.2), and multi‑ps segments discussed in Section 3 and figure captions. NPT barostats, N/A — applied electric field: not used in the primary workflow, and umbrella or replica metadynamics are likewise omitted. The paper applies published eReaxFF parameters and compares to literature quantum chemistry rather than reporting a new parametrization or standalone DFT campaign.

Findings

Same SEI-oriented picture as 2016islam-venue-jp6b08688: reduction and decomposition pathways begin with lithium-to-EC electron transfer, ring opening toward EC⁻/Li⁺-type radicals, and termination chemistry sampled without a fixed reaction network. eReaxFF tracks literature quantum-chemistry trends better than prior ReaxFF on EC electron affinity and dissociation kinetics—a direct versus-ReaxFF benchmark highlighted in the abstract. Temperature (300 K versus 600 K) changes which termination channels appear within the reported time windows, a key sensitivity lever for kinetics on multi‑ps trajectories. Limitations: the introduction stresses that salts, cosolvents, and additives at realistic interfaces remain beyond the EC + Li emphasis, an open modeling direction. Corpus honesty: this proof PDF defers figure and page locators to 2016islam-venue-jp6b08688 as the canonical slug for the same DOI.

Limitations

Proof PDFs can differ in line breaks and figure placement from the version of record; cite [[2016islam-venue-jp6b08688]] for authoritative locators. eReaxFF remains an approximate treatment of electronic structure; quantitative overpotentials and product distributions should be cross-checked against experiment and higher-level theory where decisions depend on fine energetics.

Relevance to group

The entry preserves manifest provenance for duplicate PDFs while routing readers to the canonical slug for DOI 10.1021/acs.jpcc.6b08688, a van Duin-coauthored eReaxFF battery-interface benchmark in the corpus.

Citations and evidence anchors

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