Issue 27, 2023

First principles reaction discovery: from the Schrodinger equation to experimental prediction for methane pyrolysis

Abstract

Our recent success in exploiting graphical processing units (GPUs) to accelerate quantum chemistry computations led to the development of the ab initio nanoreactor, a computational framework for automatic reaction discovery and kinetic model construction. In this work, we apply the ab initio nanoreactor to methane pyrolysis, from automatic reaction discovery to path refinement and kinetic modeling. Elementary reactions occurring during methane pyrolysis are revealed using GPU-accelerated ab initio molecular dynamics simulations. Subsequently, these reaction paths are refined at a higher level of theory with optimized reactant, product, and transition state geometries. Reaction rate coefficients are calculated by transition state theory based on the optimized reaction paths. The discovered reactions lead to a kinetic model with 53 species and 134 reactions, which is validated against experimental data and simulations using literature kinetic models. We highlight the advantage of leveraging local brute force and Monte Carlo sensitivity analysis approaches for efficient identification of important reactions. Both sensitivity approaches can further improve the accuracy of the methane pyrolysis kinetic model. The results in this work demonstrate the power of the ab initio nanoreactor framework for computationally affordable systematic reaction discovery and accurate kinetic modeling.

Graphical abstract: First principles reaction discovery: from the Schrodinger equation to experimental prediction for methane pyrolysis

Supplementary files

Article information

Article type
Edge Article
Submitted
06 3 2023
Accepted
02 6 2023
First published
09 6 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 7447-7464

First principles reaction discovery: from the Schrodinger equation to experimental prediction for methane pyrolysis

R. Xu, J. Meisner, A. M. Chang, K. C. Thompson and T. J. Martínez, Chem. Sci., 2023, 14, 7447 DOI: 10.1039/D3SC01202F

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