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dc.contributor.authorKumar, Manoj
dc.contributor.authorBusch, Daryle H.
dc.contributor.authorSubramaniam, Bala
dc.contributor.authorThompson, Ward H.
dc.date.accessioned2015-12-09T16:50:07Z
dc.date.available2015-12-09T16:50:07Z
dc.date.issued2014-09-18
dc.identifier.citationKumar, Manoj, Daryle H. Busch, Bala Subramaniam, and Ward H. Thompson. "Role of Tunable Acid Catalysis in Decomposition of α-Hydroxyalkyl Hydroperoxides and Mechanistic Implications for Tropospheric Chemistry." J. Phys. Chem. A The Journal of Physical Chemistry A 118.41 (2014): 9701-711. http://dx.doi.org/10.1021/jp505100xen_US
dc.identifier.urihttp://hdl.handle.net/1808/19151
dc.descriptionThis is the published version. Copyright 2014 Royal Society of Chemistryen_US
dc.description.abstractElectronic structure calculations have been used to investigate possible gas-phase decomposition pathways of α-hydroxyalkyl hydroperoxides (HHPs), an important source of tropospheric hydrogen peroxide and carbonyl compounds. The uncatalyzed as well as water- and acid-catalyzed decomposition of multiple HHPs have been examined at the M06-2X/aug-cc-pVTZ level of theory. The calculations indicate that, compared to an uncatalyzed or water-catalyzed reaction, the free-energy barrier of an acid-catalyzed decomposition leading to an aldehyde or ketone and hydrogen peroxide is dramatically lowered. The calculations also find a direct correlation between the catalytic effect of an acid and the distance separating its hydrogen acceptor and donor sites. Interestingly, the catalytic effect of an acid on the HHP decomposition resulting in the formation of carboxylic acid and water is relatively much smaller. Moreover, since the free-energy barrier of the acid-catalyzed aldehyde- or ketone-forming decomposition is ∼25% lower than that required to break the O–OH linkage of the HHP leading to the formation of hydroxyl radical, these results suggest that HHP decomposition is likely not an important source of tropospheric hydroxyl radical. Finally, transition state theory estimates indicate that the effective rate constants for the acid-catalyzed aldehyde- or ketone-forming HHP decomposition pathways are 2–3 orders of magnitude faster than those for the water-catalyzed reaction, indicating that an acid-catalyzed HHP decomposition is kinetically favored as well.en_US
dc.publisherRoyal Society of Chemistryen_US
dc.titleRole of Tunable Acid Catalysis in Decomposition of α-Hydroxyalkyl Hydroperoxides and Mechanistic Implications for Tropospheric Chemistryen_US
dc.typeArticle
kusw.kuauthorSubramaniam, Bala
kusw.kudepartmentChemical & Petroleum Engren_US
dc.identifier.doi10.1021/jp505100x
dc.identifier.orcidhttps://orcid.org/0000-0001-9650-5350
kusw.oaversionScholarly/refereed, publisher version
kusw.oapolicyThis item meets KU Open Access policy criteria.
dc.rights.accessrightsopenAccess


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