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dc.contributor.authorMonge Palacios, Manuel
dc.contributor.authorGrajales Gonzalez, Edwing
dc.contributor.authorSarathy, Mani
dc.date.accessioned2019-05-07T11:21:19Z
dc.date.available2019-05-07T11:21:19Z
dc.date.issued2019-04-09
dc.identifier.citationMonge-Palacios M, Grajales-González E, Sarathy SM (2019) Formic acid catalyzed keto-enol tautomerizations for C2 and C3 enols: Implications in atmospheric and combustion chemistry. International Journal of Quantum Chemistry: e25954. Available: http://dx.doi.org/10.1002/qua.25954.
dc.identifier.issn0020-7608
dc.identifier.issn1097-461X
dc.identifier.doi10.1002/qua.25954
dc.identifier.urihttp://hdl.handle.net/10754/652450
dc.description.abstractEnols are important species in atmospheric and combustion chemistry. However, their implications in these environments are not well established due to a lack of accurate rate constants and mechanisms to determine their fate. In this work, we investigate the formic acid catalyzed keto-enol tautomerizations converting vinyl alcohol, propen-2-ol and 1-propenol into acetaldehyde, acetone and propanal, respectively. High-level ab initio and multistructural torsional variational transition state theory calculations are performed with small-curvature tunneling corrections to obtain rate constants in the temperature range 200 K-3000 K. Tunneling is shown to be pronounced as a consequence of very narrow adiabatic potential energy curves, and indicates a need to revisit previous calculations. We show the implications of the studied reactions on the fate of enols under combustion relevant conditions by detailed kinetic modeling simulations. The yield of vinyl alcohol predicted by our calculated rate constants may be useful to lessen the underestimation of organic acids concentrations in current atmospheric models.
dc.description.sponsorshipWe acknowledge funding from King Abdullah University of Science and Technology (KAUST), Office of Sponsored Research (OSR), Award No. OSR-2016-CRG5-3022 and the resources of the Supercomputing Laboratory at KAUST. We are grateful to Maria Cecilia Alvarado Bernaldez for her assistance in designing and elaborating the TOC graphic.
dc.publisherWiley
dc.relation.urlhttps://onlinelibrary.wiley.com/doi/full/10.1002/qua.25954
dc.rightsArchived with thanks to International Journal of Quantum Chemistry
dc.subjectab initio
dc.subjectatmospheric chemistry
dc.subjectcombustion chemistry
dc.subjectketo-enol tautomerizations
dc.subjectrate constants
dc.titleFormic acid catalyzed keto-enol tautomerizations for C2 and C3 enols: Implications in atmospheric and combustion chemistry
dc.typeArticle
dc.contributor.departmentChemical Engineering Program
dc.contributor.departmentClean Combustion Research Center
dc.contributor.departmentCombustion and Pyrolysis Chemistry (CPC) Group
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalInternational Journal of Quantum Chemistry
dc.eprint.versionPost-print
kaust.personMonge Palacios, Manuel
kaust.personGrajales Gonzalez, Edwing
kaust.personSarathy, Mani
kaust.grant.numberOSR-2016-CRG5-3022
refterms.dateFOA2020-04-09T00:00:00Z


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