Theoretical and Computational Chemistry

Predictive stochastic analysis of massive filter-based electrochemical reaction networks

Authors

Abstract

Chemical reaction networks (CRNs) are powerful tools for obtaining mechanistic insight into complex reactive processes. However, they are limited in their applicability where reaction mechanisms are not well understood and products are unknown. Here we report new methods of CRN generation and analysis that overcome these limitations. By constructing CRNs using filters rather than templates, we can capture species and reactions that are unintuitive but fundamentally reasonable. The resulting massive CRNs can then be interrogated via stochastic methods, revealing thermodynamically bounded reaction pathways to species of interest and automatically identifying network products. We apply this methodology to study solid-electrolyte interphase (SEI) formation in Li-ion batteries, generating a CRN with ~86,000,000 reactions. Our methods automatically recover SEI products from the literature and predict previously unknown species. We validate their formation mechanisms using first-principles calculations, discovering novel kinetically accessible molecules. This methodology enables the de novo exploration of vast chemical spaces, with the potential for diverse applications across thermochemistry, electrochemistry, and photochemistry.

Version notes

Improved title and intro with other small updates throughout based on editor feedback.

Content

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Supplementary material

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Supplementary information
Supplementary information
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Reaction pathways
All data used to construct mechanisms (molecular structures, thermodynamics, vibrational frequencies, and frequency modes) provided in the Javascript Object Notation (JSON) format