H migration in peroxy radicals under atmospheric conditions
<p>A large data set of rate coefficients for H migration in peroxy radicals is presented and supplemented with literature data to derive a structure–activity relationship (SAR) for the title reaction class. The SAR supports aliphatic RO<sub>2</sub> radicals; unsaturated bonds a...
| Main Authors: | , |
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| Format: | Article |
| Language: | English |
| Published: |
Copernicus Publications
2020-06-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://www.atmos-chem-phys.net/20/7429/2020/acp-20-7429-2020.pdf |
| _version_ | 1828832282615480320 |
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| author | L. Vereecken L. Vereecken L. Vereecken B. Nozière |
| author_facet | L. Vereecken L. Vereecken L. Vereecken B. Nozière |
| author_sort | L. Vereecken |
| collection | DOAJ |
| description | <p>A large data set of rate coefficients for H migration in
peroxy radicals is presented and supplemented with literature data to
derive a structure–activity relationship (SAR) for the title reaction
class. The SAR supports aliphatic RO<sub>2</sub> radicals; unsaturated
bonds and <i>β</i>-oxo substitutions both endocyclic and exocyclic to the
transition state ring; and <i>α</i>-oxo (aldehyde), –OH, –OOH, and
–ONO<sub>2</sub> substitutions, including migration of O-based hydrogen atoms.
Also discussed are –C( = O)OH and –OR substitutions. The SAR allows
predictions of rate coefficients <i>k</i>(<i>T</i>) for a temperature range of 200 to 450 K,
with migrations spans ranging from 1,4 to 1,9-H shifts depending on the
functionalities. The performance of the SAR reflects the uncertainty of the
underlying data, reproducing the scarce experimental data on average to a
factor of 2 and the wide range of theoretical data to a factor of 10 to 100,
depending also on the quality of the data. The SAR evaluation discusses the
performance in multi-functionalized species. For aliphatic RO<sub>2</sub>, we also
present some experimental product identification that validates the expected
mechanisms. The proposed SAR is a valuable tool for mechanism development and
experimental design and guides future theoretical work, which should allow for
rapid improvements of the SAR in the future. Relative
multi-conformer transition state theory (rel-MC-TST) kinetic theory is introduced as an aid for
systematic kinetic studies.</p> |
| first_indexed | 2024-12-12T16:51:09Z |
| format | Article |
| id | doaj.art-d7c3a1a23cd046a897f70480c9bb4b8a |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-12T16:51:09Z |
| publishDate | 2020-06-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-d7c3a1a23cd046a897f70480c9bb4b8a2022-12-22T00:18:23ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242020-06-01207429745810.5194/acp-20-7429-2020H migration in peroxy radicals under atmospheric conditionsL. Vereecken0L. Vereecken1L. Vereecken2B. Nozière3Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, 3000 Leuven, BelgiumMax Planck Institute for Chemistry, Hahn-Meitner-Weg 1, 55128 Mainz, GermanyInstitute for Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich GmbH, 52428 Jülich, GermanyIRCELYON, CNRS and Université Claude Bernard Lyon, Avenue Albert Einstein 2, 69626 Villeurbanne, France<p>A large data set of rate coefficients for H migration in peroxy radicals is presented and supplemented with literature data to derive a structure–activity relationship (SAR) for the title reaction class. The SAR supports aliphatic RO<sub>2</sub> radicals; unsaturated bonds and <i>β</i>-oxo substitutions both endocyclic and exocyclic to the transition state ring; and <i>α</i>-oxo (aldehyde), –OH, –OOH, and –ONO<sub>2</sub> substitutions, including migration of O-based hydrogen atoms. Also discussed are –C( = O)OH and –OR substitutions. The SAR allows predictions of rate coefficients <i>k</i>(<i>T</i>) for a temperature range of 200 to 450 K, with migrations spans ranging from 1,4 to 1,9-H shifts depending on the functionalities. The performance of the SAR reflects the uncertainty of the underlying data, reproducing the scarce experimental data on average to a factor of 2 and the wide range of theoretical data to a factor of 10 to 100, depending also on the quality of the data. The SAR evaluation discusses the performance in multi-functionalized species. For aliphatic RO<sub>2</sub>, we also present some experimental product identification that validates the expected mechanisms. The proposed SAR is a valuable tool for mechanism development and experimental design and guides future theoretical work, which should allow for rapid improvements of the SAR in the future. Relative multi-conformer transition state theory (rel-MC-TST) kinetic theory is introduced as an aid for systematic kinetic studies.</p>https://www.atmos-chem-phys.net/20/7429/2020/acp-20-7429-2020.pdf |
| spellingShingle | L. Vereecken L. Vereecken L. Vereecken B. Nozière H migration in peroxy radicals under atmospheric conditions Atmospheric Chemistry and Physics |
| title | H migration in peroxy radicals under atmospheric conditions |
| title_full | H migration in peroxy radicals under atmospheric conditions |
| title_fullStr | H migration in peroxy radicals under atmospheric conditions |
| title_full_unstemmed | H migration in peroxy radicals under atmospheric conditions |
| title_short | H migration in peroxy radicals under atmospheric conditions |
| title_sort | h migration in peroxy radicals under atmospheric conditions |
| url | https://www.atmos-chem-phys.net/20/7429/2020/acp-20-7429-2020.pdf |
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