Unimolecular Reaction Pathways of a γ-Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods

Grambow, Colin A.; Jamal, Adeel; Li, Yi-Pei; Green, William H.; Zádor, Judit; Suleimanov, Yury V.

doi:10.1021/jacs.7b11009

Title: Unimolecular Reaction Pathways of a γ-Ketohydroperoxide from Combined Application of Automated Reaction Discovery Methods

Journal Article · Fri Dec 22 00:00:00 EST 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b11009· OSTI ID:1473944

^[1];

^[1]; Li, Yi-Pei ^[1];

^[1];

^[2]; Suleimanov, Yury V. ^[3]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Cyprus Inst., Nicosia (Cyprus)

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 γ-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 γ-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. Altogether, 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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Research Organization:: Sandia National Lab. (SNL-CA), Livermore, CA (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC04-94AL85000; AC02-05CH11231

OSTI ID:: 1473944

Alternate ID(s):: OSTI ID: 1421464

Report Number(s):: SAND-2018-9927J; 667762

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 3; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 60 works

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