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Identifying barrierless mechanisms for benzene formation in the interstellar medium using permutationally invariant reaction discovery
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Robertson, Christopher, Hyland, Ross, Lacey, Andrew J. D., Havens, Sebastian and Habershon, Scott (2021) Identifying barrierless mechanisms for benzene formation in the interstellar medium using permutationally invariant reaction discovery. Journal of Chemical Theory and Computation, 17 (4). pp. 2307-2322. doi:10.1021/acs.jctc.1c00046 ISSN 1549-9618.
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WRAP-Identifying-barrierless-mechanisms-benzene-interstella-invariant-2021.pdf - Accepted Version - Requires a PDF viewer. Download (6Mb) | Preview |
Official URL: https://doi.org/10.1021/acs.jctc.1c00046
Abstract
Complex chemical reaction environments, such as those found in combustion engines, the upper atmosphere, or the interstellar medium, can contain large numbers of different reactive species participating in similarly large numbers of different chemical reactions. In such settings, identifying the most-likely multistep reaction mechanisms which lead to the production of a particular defined product species is an extremely challenging problem, requiring search and evaluation over a large number of different possible candidate mechanisms while also addressing the permutational challenges posed when considering a large number of reaction routes available to sets of identical molecular species. In this article, the problem of generating candidate reaction mechanisms which form a defined product from a diverse set of reactive molecules is cast as a discrete optimization of a permutationally invariant cost function describing similarity between the target product and the product generated by a trial reaction mechanism. This approach is demonstrated by generating 2230 candidate reaction mechanisms which form benzene from diverse sets of reactive molecules which have been experimentally identified in the interstellar medium. By screening this set of autogenerated mechanisms, using dispersion-corrected DFT to evaluate reaction energies and activation barriers, we identify several candidate barrierless reaction mechanisms (both previously proposed and new) for benzene formation which may operate in the low temperatures found in the interstellar medium and could be investigated further to supplement existing microkinetic models.
Item Type: | Journal Article | ||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Chemistry > Computational and Theoretical Chemistry Centre |
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Library of Congress Subject Headings (LCSH): | Benzene , Benzene -- Derivatives, Chemical reactions | ||||||||
Journal or Publication Title: | Journal of Chemical Theory and Computation | ||||||||
Publisher: | American Chemical Society | ||||||||
ISSN: | 1549-9618 | ||||||||
Official Date: | 13 April 2021 | ||||||||
Dates: |
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Volume: | 17 | ||||||||
Number: | 4 | ||||||||
Page Range: | pp. 2307-2322 | ||||||||
DOI: | 10.1021/acs.jctc.1c00046 | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Reuse Statement (publisher, data, author rights): | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jctc.1c00046 | ||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||
Date of first compliant deposit: | 25 March 2021 | ||||||||
Date of first compliant Open Access: | 9 June 2022 | ||||||||
RIOXX Funder/Project Grant: |
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