A Computational Re-examination of the Criegee Intermediate-Sulfur Dioxide Reaction

Keith T. Kuwata, Emily J. Guinn, Matthew R. Hermes, Jenna A. Fernandez, Jon M. Mathison, Ke Huang

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Abstract

The atmospheric oxidation of sulfur dioxide by the parent and dimethyl Criegee intermediates (CIs) may be an important source of sulfuric acid aerosol, which has a large impact on radiative forcing and therefore upon climate. A number of computational studies have considered how the CH2OOS(O)O heteroozonide (HOZ) adduct formed in the CI + SO2 reaction converts SO2 to SO3. In this work we use the CBS-QB3 quantum chemical method along with equation-of-motion spin-flip CCSD(dT) and MCG3 theories to reveal new details regarding the formation and decomposition of the endo and exo conformers of the HOZ. Although 75% of the parent CI + SO2 reaction is initiated by formation of the exo HOZ, hyperconjugation preferentially stabilizes many of the endo intermediates and transition structures by 1-5 kcal mol-1. Our quantum chemical calculations, in conjunction with statistical rate theory models, predict a rate coefficient for the parent CI + SO2 reaction of 3.68 × 10-11 cm3 molecule-1 s-1, in good agreement with recent experimental measurements. RRKM/master equation simulations based on our quantum chemical data predict a prompt carbonyl + SO3 yield of >95% for the reaction of both the parent and dimethyl CI with SO2. The existence of concerted cycloreversion transition structures 10-15 kcal mol-1 higher in energy than the HOZ accounts for most of the predicted SO3 formation.

Original languageEnglish (US)
Pages (from-to)10316-10335
Number of pages20
JournalJournal of Physical Chemistry A
Volume119
Issue number41
DOIs
StatePublished - Oct 15 2015

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Sulfur Dioxide
Reaction intermediates
sulfur dioxides
reaction intermediates
examination
Aerosols
radiative forcing
Equations of motion
sulfuric acid
adducts
climate
Decomposition
Oxidation
aerosols
equations of motion
Molecules
decomposition
oxidation
coefficients
molecules

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A Computational Re-examination of the Criegee Intermediate-Sulfur Dioxide Reaction. / Kuwata, Keith T.; Guinn, Emily J.; Hermes, Matthew R.; Fernandez, Jenna A.; Mathison, Jon M.; Huang, Ke.

In: Journal of Physical Chemistry A, Vol. 119, No. 41, 15.10.2015, p. 10316-10335.

Research output: Contribution to journalArticle

Kuwata, Keith T. ; Guinn, Emily J. ; Hermes, Matthew R. ; Fernandez, Jenna A. ; Mathison, Jon M. ; Huang, Ke. / A Computational Re-examination of the Criegee Intermediate-Sulfur Dioxide Reaction. In: Journal of Physical Chemistry A. 2015 ; Vol. 119, No. 41. pp. 10316-10335.
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AB - The atmospheric oxidation of sulfur dioxide by the parent and dimethyl Criegee intermediates (CIs) may be an important source of sulfuric acid aerosol, which has a large impact on radiative forcing and therefore upon climate. A number of computational studies have considered how the CH2OOS(O)O heteroozonide (HOZ) adduct formed in the CI + SO2 reaction converts SO2 to SO3. In this work we use the CBS-QB3 quantum chemical method along with equation-of-motion spin-flip CCSD(dT) and MCG3 theories to reveal new details regarding the formation and decomposition of the endo and exo conformers of the HOZ. Although 75% of the parent CI + SO2 reaction is initiated by formation of the exo HOZ, hyperconjugation preferentially stabilizes many of the endo intermediates and transition structures by 1-5 kcal mol-1. Our quantum chemical calculations, in conjunction with statistical rate theory models, predict a rate coefficient for the parent CI + SO2 reaction of 3.68 × 10-11 cm3 molecule-1 s-1, in good agreement with recent experimental measurements. RRKM/master equation simulations based on our quantum chemical data predict a prompt carbonyl + SO3 yield of >95% for the reaction of both the parent and dimethyl CI with SO2. The existence of concerted cycloreversion transition structures 10-15 kcal mol-1 higher in energy than the HOZ accounts for most of the predicted SO3 formation.

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