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^*

^*Tämän työn vastaava kirjoittaja

Tutkimustuotos: Artikkeli › Tieteellinen › vertaisarvioitu

9 Sitaatiot (Scopus)

27 Lataukset (Pure)

Abstrakti

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.

Alkuperäiskieli	Englanti
Sivut	28205-28212
Sivumäärä	8
Julkaisu	Physical Chemistry Chemical Physics
Vuosikerta	25
Numero	41
DOI - pysyväislinkit	https://doi.org/10.1039/d3cp01833d
Tila	Julkaistu - 11 syysk. 2023
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

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.

Rahoittajat	Rahoittajan numero
European Research Council
Academy of Finland	353836, 336531, 331207, 346373
China Scholarship Council
Horizon 2020, EU	101002728

YK:n kestävän kehityksen tavoitteet

Tämä tuotos edistää seuraavia kestävän kehityksen tavoitteita:

SDG 11 – Kestävät kaupungit ja yhteisöt

Julkaisufoorumi-taso

Jufo-taso 3

!!ASJC Scopus subject areas

Yleinen fysiikka ja tähtitiede
Physical and Theoretical Chemistry

Pääsy asiakirjaan

10.1039/d3cp01833dLisenssi: CC BY

d3cp01833dFinal published version, 837 KBLisenssi: CC BY

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

Siteeraa tätä

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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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year = "2023",

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T1 - A systematic study on the kinetics of H-shift reactions in pristine acyl peroxy radicals

AU - Seal, Prasenjit

AU - Barua, Shawon

AU - Iyer, Siddharth

AU - Kumar, Avinash

AU - Rissanen, Matti

PY - 2023/9/11

Y1 - 2023/9/11

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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SN - 1463-9076

VL - 25

SP - 28205

EP - 28212

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 41

ER -

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

Abstrakti

Rahoitus

YK:n kestävän kehityksen tavoitteet

Julkaisufoorumi-taso

!!ASJC Scopus subject areas

Pääsy asiakirjaan

Sormenjälki

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