Uncertainty-aware First-principles Exploration of Chemical Reaction Networks
arXiv:2312.15477 · doi:10.1021/acs.jpca.3c08386
Abstract
Exploring large chemical reaction networks with automated exploration approaches and accurate quantum chemical methods can require prohibitively large computational resources. Here, we present an automated exploration approach that focuses on the kinetically relevant part of the reaction network by interweaving (i) large-scale exploration of chemical reactions, (ii) identification of kinetically relevant parts of the reaction network through microkinetic modeling, (iii) quantification and propagation of uncertainties, and (iv) reaction network refinement. Such an uncertainty-aware exploration of kinetically relevant parts of a reaction network with automated accuracy improvement has not been demonstrated before in a fully quantum mechanical approach. Uncertainties are identified by local or global sensitivity analysis. The network is refined in a rolling fashion during the exploration. Moreover, the uncertainties are considered during kinetically steering of a rolling reaction network exploration. We demonstrate our approach for Eschenmoser-Claisen rearrangement reactions. The sensitivity analysis identifies that only a small number of reactions and compounds are essential for describing the kinetics reliably, resulting in efficient explorations without sacrificing accuracy and without requiring prior knowledge about the chemistry unfolding.
arXiv comment33 pages, 7 figures, 3 tables
References in corpus (14)
- Exploration of Reaction Pathways and Chemical Transformation Networks
- The Exploration of Chemical Reaction Networks
- Heuristics-Guided Exploration of Reaction Mechanisms
- Examination of the concept of degree of rate control by first-principles kinetic Monte Carlo simulations
- Error-Controlled Exploration of Chemical Reaction Networks with Gaussian Processes
- Systematic Error Estimation for Chemical Reaction Energies
- Autonomous Reaction Network Exploration in Homogeneous and Heterogeneous Catalysis
- Molassembler: Molecular graph construction, modification and conformer generation for inorganic and organic molecules
- Mechanism Deduction from Noisy Chemical Reaction Networks
- Minimum Energy Paths and Transition States by Curve Optimization
- Expansive Quantum Mechanical Exploration of Chemical Reaction Paths
- Pathfinder -- Navigating and Analyzing Chemical Reaction Networks with an Efficient Graph-based Approach
- On the Predictive Power of Chemical Concepts
- Concentration-Flux-Steered Mechanism Exploration with an Organocatalysis Application