A systematic study on the kinetics of H-shift reactions in pristine acyl peroxy radicals

Prasenjit Seal; Shawon Barua; Siddharth Iyer; Avinash Kumar; Matti Rissanen

doi:10.1039/d3cp01833d

A systematic study on the kinetics of H-shift reactions in pristine acyl peroxy radicals

Prasenjit Seal^*
, Shawon Barua
, Siddharth Iyer
, Avinash Kumar
, Matti Rissanen^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

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Abstract

A series of acyl peroxy radical H-shifts were systematically studied using computational approaches. Acyl peroxy radicals were categorized into small- (ethanal-pentanal), medium- (hexanal and heptanal) and large-sized (octanal and nonanal) molecules. The H-shifts spanning from 1,4 to 1,9 were inspected for each studied system. For all acyl peroxy radicals, it is the combination of barrier heights and quantum mechanical tunneling that explains the yield of the peracid alkyl radical product. We used the ROHF-ROCCSD(T)-F12a/VDZ-F12//ωB97X-D/aug-cc-pVTZ level of theory to estimate the barrier heights and the subsequent rate coefficients with the exception of the smallest acyl peroxy radical ethanal, for which MN15 density functional was applied. The estimated multiconformer H-shift rate coefficients were found to be in the range of 10⁻² s⁻¹ to 10⁻¹ s⁻¹ for the fastest H-migrations. The determined rates imply that these H-shift reactions are often competitive with other RO₂ loss processes and should be considered as a path to functionalization in modelling not only rural but also urban air quality.

Original language	English
Pages (from-to)	28205-28212
Number of pages	8
Journal	Physical Chemistry Chemical Physics
Volume	25
Issue number	41
DOIs	https://doi.org/10.1039/d3cp01833d
Publication status	Published - 11 Sept 2023
Publication type	A1 Journal article-refereed

Funding

The authors would like to acknowledge the funding from the European Research Council under the European Union's Horizon 2020 research and innovation programme under Grant No. 101002728 (ERC Consolidator Grant Project ADAPT). The support from the Academy of Finland (331207, 336531, 353836 and 346373) and the Doctoral school of the Faculty of Engineering and Natural Sciences of Tampere University is greatly appreciated. We thank the CSC IT Center for Science in Espoo, Finland, for providing the computing resources. The authors would also like to acknowledge Prof. Theo Kurtén and Prof. Henrik Kjaergaard for fruitful discussions and suggestions in improving the manuscript.

Funders	Funder number
European Research Council
Academy of Finland	353836, 336531, 331207, 346373
China Scholarship Council
Horizon 2020, EU	101002728

UN SDGs

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SDG 11 Sustainable Cities and Communities

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ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1039/d3cp01833dLicence: CC BY

d3cp01833dFinal published version, 837 KBLicence: CC BY

https://urn.fi/URN:NBN:fi:tuni-2023111510013Licence: CC BY

Cite this

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title = "A systematic study on the kinetics of H-shift reactions in pristine acyl peroxy radicals",

abstract = "A series of acyl peroxy radical H-shifts were systematically studied using computational approaches. Acyl peroxy radicals were categorized into small- (ethanal-pentanal), medium- (hexanal and heptanal) and large-sized (octanal and nonanal) molecules. The H-shifts spanning from 1,4 to 1,9 were inspected for each studied system. For all acyl peroxy radicals, it is the combination of barrier heights and quantum mechanical tunneling that explains the yield of the peracid alkyl radical product. We used the ROHF-ROCCSD(T)-F12a/VDZ-F12//ωB97X-D/aug-cc-pVTZ level of theory to estimate the barrier heights and the subsequent rate coefficients with the exception of the smallest acyl peroxy radical ethanal, for which MN15 density functional was applied. The estimated multiconformer H-shift rate coefficients were found to be in the range of 10−2 s−1 to 10−1 s−1 for the fastest H-migrations. The determined rates imply that these H-shift reactions are often competitive with other RO2 loss processes and should be considered as a path to functionalization in modelling not only rural but also urban air quality.",

author = "Prasenjit Seal and Shawon Barua and Siddharth Iyer and Avinash Kumar and Matti Rissanen",

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AU - Seal, Prasenjit

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AU - Iyer, Siddharth

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AU - Rissanen, Matti

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N2 - A series of acyl peroxy radical H-shifts were systematically studied using computational approaches. Acyl peroxy radicals were categorized into small- (ethanal-pentanal), medium- (hexanal and heptanal) and large-sized (octanal and nonanal) molecules. The H-shifts spanning from 1,4 to 1,9 were inspected for each studied system. For all acyl peroxy radicals, it is the combination of barrier heights and quantum mechanical tunneling that explains the yield of the peracid alkyl radical product. We used the ROHF-ROCCSD(T)-F12a/VDZ-F12//ωB97X-D/aug-cc-pVTZ level of theory to estimate the barrier heights and the subsequent rate coefficients with the exception of the smallest acyl peroxy radical ethanal, for which MN15 density functional was applied. The estimated multiconformer H-shift rate coefficients were found to be in the range of 10−2 s−1 to 10−1 s−1 for the fastest H-migrations. The determined rates imply that these H-shift reactions are often competitive with other RO2 loss processes and should be considered as a path to functionalization in modelling not only rural but also urban air quality.

AB - A series of acyl peroxy radical H-shifts were systematically studied using computational approaches. Acyl peroxy radicals were categorized into small- (ethanal-pentanal), medium- (hexanal and heptanal) and large-sized (octanal and nonanal) molecules. The H-shifts spanning from 1,4 to 1,9 were inspected for each studied system. For all acyl peroxy radicals, it is the combination of barrier heights and quantum mechanical tunneling that explains the yield of the peracid alkyl radical product. We used the ROHF-ROCCSD(T)-F12a/VDZ-F12//ωB97X-D/aug-cc-pVTZ level of theory to estimate the barrier heights and the subsequent rate coefficients with the exception of the smallest acyl peroxy radical ethanal, for which MN15 density functional was applied. The estimated multiconformer H-shift rate coefficients were found to be in the range of 10−2 s−1 to 10−1 s−1 for the fastest H-migrations. The determined rates imply that these H-shift reactions are often competitive with other RO2 loss processes and should be considered as a path to functionalization in modelling not only rural but also urban air quality.

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A systematic study on the kinetics of H-shift reactions in pristine acyl peroxy radicals

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