Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 3, Pages 1035-1048Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b11009
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Funding
- Air Force Office of Scientific Research [FA9550-16-1-0208]
- DOE BES, the Division of Chemical Sciences, Geosciences, and Biosciences
- U.S. Department of Energy's National Nuclear Security Administration [DE-NA0003525]
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
- European Regional Development Fund
- Republic of Cyprus through the Research Promotion Foundation [Cy-Tera NEA GammaPiODeltaOMH/SigmaTPATH/0308/31]
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Ketohydroperoxides are important in liquid-phase autoxidation and in gas-phase partial oxidation and pre-ignition chemistry, but because of their low concentration, instability, and various analytical chemistry limitations, it has been challenging to experimentally determine their reactivity, and only a few pathways are known. In the present work, 75 elementary-step unimolecular reactions of the simplest gamma-ketohydroperoxide, 3-hydroperoxypropanal, were discovered by a combination of density functional theory with several automated transition-state search algorithms: the Berny algorithm coupled with the freezing string method, single- and double-ended growing string methods, the heuristic KinBot algorithm, and the single-component artificial force induced reaction method (SC-AFIR). The present joint approach significantly outperforms previous manual and automated transition-state searches 68 of the reactions of gamma-ketohydroperoxide discovered here were previously unknown and completely unexpected. All of the methods found the lowest-energy transition state, which corresponds to the first step of the Korcek mechanism, but each algorithm except for SC-AFIR detected several reactions not found by any of the other methods. We show that the low-barrier chemical reactions involve promising new chemistry that may be relevant in atmospheric and combustion systems. Our study highlights the complexity of chemical space exploration and the advantage of combined application of several approaches. Overall, the present work demonstrates both the power and the weaknesses of existing fully automated approaches for reaction discovery which suggest possible directions for further method development and assessment in order to enable reliable discovery of all important reactions of any specified reactant(s).
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