Theoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implications

Handle URI:
http://hdl.handle.net/10754/627070
Title:
Theoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implications
Authors:
Monge Palacios, Manuel; Rissanen, Matti Petteri; Wang, Zhandong ( 0000-0003-1535-2319 ) ; Sarathy, Subram Mani
Abstract:
We performed a theoretical study on the double hydrogen shift isomerization reaction of a six carbon atom Criegee intermediate (C6-CI), catalyzed by formic acid (HCOOH), to produce vinylhydroperoxide (VHP), C6-CI+HCOOH→VHP+HCOOH. This Criegee intermediate can serve as a surrogate for larger CIs derived from important volatile organic compounds like monoterpenes, whose reactivity is not well understood and are difficult to handle computationally. The reactant HCOOH exerts a pronounced catalytic effect on the studied reaction by lowering the barrier height, but the kinetic enhancement is hindered by the multistructural anharmonicity. First, the rigid ring-structure adopted by the saddle point to facilitate simultaneous transfer of two atoms does not allow formation of as many conformers as those formed by the reactant C6-CI. And second, the flexible carbon chain of C6-CI facilitates the formation of stabilizing intramolecular C–H···O hydrogen bonds; this stabilizing effect is less pronounced in the saddle point structure due to its tightness and steric effects. Thus, the contribution of the reactant C6-CI conformers to the multistructural partition function is larger than that of the saddle point conformers. The resulting low multistructural anharmonicity factor partially cancels out the catalytic effect of the carboxylic acid, yielding in a moderately large rate coefficient, k(298 K) = 4.9·10-13 cm3 molecule-1 s-1. We show that carboxylic acids may promote the conversion of stabilized Criegee intermediates into vinylhydroperoxides in the atmosphere, which generates OH radicals and leads to secondary organic aerosol, thereby affecting the oxidative capacity of the atmosphere and ultimately the climate.
KAUST Department:
Clean Combustion Research Center; Physical Sciences and Engineering (PSE) Division
Citation:
Monge-Palacios M, Rissanen MP, Wang Z, Sarathy SM (2018) Theoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implications. Physical Chemistry Chemical Physics. Available: http://dx.doi.org/10.1039/c7cp08538a.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Physical Chemistry Chemical Physics
KAUST Grant Number:
OSR-2016-CRG5-3022
Issue Date:
29-Jan-2018
DOI:
10.1039/c7cp08538a
Type:
Article
ISSN:
1463-9076; 1463-9084
Sponsors:
This work was supported by King Abdullah University of Science and Technology (KAUST), Office of Sponsored Research (OSR) under Award No. OSR-2016-CRG5-3022. MPR is grateful for the support from the Academy of Finland (Project number 299574).
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2018/CP/C7CP08538A#!divAbstract
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorMonge Palacios, Manuelen
dc.contributor.authorRissanen, Matti Petterien
dc.contributor.authorWang, Zhandongen
dc.contributor.authorSarathy, Subram Manien
dc.date.accessioned2018-02-07T07:02:29Z-
dc.date.available2018-02-07T07:02:29Z-
dc.date.issued2018-01-29en
dc.identifier.citationMonge-Palacios M, Rissanen MP, Wang Z, Sarathy SM (2018) Theoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implications. Physical Chemistry Chemical Physics. Available: http://dx.doi.org/10.1039/c7cp08538a.en
dc.identifier.issn1463-9076en
dc.identifier.issn1463-9084en
dc.identifier.doi10.1039/c7cp08538aen
dc.identifier.urihttp://hdl.handle.net/10754/627070-
dc.description.abstractWe performed a theoretical study on the double hydrogen shift isomerization reaction of a six carbon atom Criegee intermediate (C6-CI), catalyzed by formic acid (HCOOH), to produce vinylhydroperoxide (VHP), C6-CI+HCOOH→VHP+HCOOH. This Criegee intermediate can serve as a surrogate for larger CIs derived from important volatile organic compounds like monoterpenes, whose reactivity is not well understood and are difficult to handle computationally. The reactant HCOOH exerts a pronounced catalytic effect on the studied reaction by lowering the barrier height, but the kinetic enhancement is hindered by the multistructural anharmonicity. First, the rigid ring-structure adopted by the saddle point to facilitate simultaneous transfer of two atoms does not allow formation of as many conformers as those formed by the reactant C6-CI. And second, the flexible carbon chain of C6-CI facilitates the formation of stabilizing intramolecular C–H···O hydrogen bonds; this stabilizing effect is less pronounced in the saddle point structure due to its tightness and steric effects. Thus, the contribution of the reactant C6-CI conformers to the multistructural partition function is larger than that of the saddle point conformers. The resulting low multistructural anharmonicity factor partially cancels out the catalytic effect of the carboxylic acid, yielding in a moderately large rate coefficient, k(298 K) = 4.9·10-13 cm3 molecule-1 s-1. We show that carboxylic acids may promote the conversion of stabilized Criegee intermediates into vinylhydroperoxides in the atmosphere, which generates OH radicals and leads to secondary organic aerosol, thereby affecting the oxidative capacity of the atmosphere and ultimately the climate.en
dc.description.sponsorshipThis work was supported by King Abdullah University of Science and Technology (KAUST), Office of Sponsored Research (OSR) under Award No. OSR-2016-CRG5-3022. MPR is grateful for the support from the Academy of Finland (Project number 299574).en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2018/CP/C7CP08538A#!divAbstracten
dc.rightsArchived with thanks to Physical Chemistry Chemical Physicsen
dc.titleTheoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implicationsen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalPhysical Chemistry Chemical Physicsen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Physics, University of Helsinki, P. O. Box 64, Helsinki, 00014, Finland.en
kaust.authorMonge Palacios, Manuelen
kaust.authorWang, Zhandongen
kaust.authorSarathy, Subram Manien
kaust.grant.numberOSR-2016-CRG5-3022en
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