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dc.contributor.authorAnglada Rull, Josep M.-
dc.contributor.authorDomingo, Víctor M.-
dc.identifier.citationJournal of Physical Chemistry A 109(47): 10786–10794 (2005)en_US
dc.description9 pages, 4 figures, 4 tables.-- PMID: 16863128 [PubMed].-- Printed version publidshed Dec 1, 2005.-- Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/jp054018den_US
dc.description.abstractWe present a high-level theoretical study on the gas-phase reaction between formaldehyde and hydroperoxyl radical carried out using the DFT-B3LYP, QCISD, and CCSD(T) theoretical approaches in connection with the 6-311+G(d,p), 6-311+G(2df,2p), and aug-cc-pVTZ basis sets. The most favorable reaction path begins with the formation of a pre-reactive complex and produces the peroxy radical CH2(OO)OH in a process that is computed to be exothermic by 16.8 kcal/mol. This reaction involves a process in which the oxygen terminal of the HO2 moiety adds to the carbon of formaldehyde, and, simultaneously, the hydrogen of the hydroperoxyl group is transferred to the oxygen of the carbonyl in a proton-coupled electron-transfer mechanism. Our calculations show that this transition state lies below the sum of the energy of the reactants, and we computed a rate constant at 300 K of 9.29 × 10-14 cm3 molecule-1 s-1, which is in good agreement with the experimental results. Also of interest in combustion chemistry, we studied the hydrogen abstraction process by HO2, the result of which is the formation of HCO + H2O2. We found two reaction paths with activation enthalpies close to 12 kcal/mol. For this process, we computed a rate constant of 1.48 × 10-16 cm3 molecule-1 s-1 at 700 K, which also agrees quite well with experimental results.en_US
dc.description.sponsorshipThe financial support for this research was provided by the Dirección General de Investigación Científica y Técnica (DGYCIT, Grant BQU2002-0485-C02-01) and by the Generalitat de Catalunya (Grant 2001SGR00048).en_US
dc.format.extent22195 bytes-
dc.publisherAmerican Chemical Societyen_US
dc.subjectGas-phase reactionen_US
dc.subjectHydroperoxyl radicalen_US
dc.subjectHydrogen abstractionen_US
dc.subjectPre-reactive complexesen_US
dc.titleMechanism for the gas-phase reaction between formaldehyde and hydroperoxyl radical. A theoretical studyen_US
dc.description.peerreviewedPeer revieweden_US
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