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Reaction Mechanism between Carbonyl Oxide and Hydroxyl Radical:  A Theoretical Study

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journal contribution
posted on 23.03.2006, 00:00 by Alex Mansergas, Josep M. Anglada
The reaction mechanism of carbonyl oxide with hydroxyl radical was investigated by using CASSCF, B3LYP, QCISD, CASPT2, and CCSD(T) theoretical approaches with the 6-311+G(d,p), 6-311+G(2df, 2p), and aug-cc-pVTZ basis sets. This reaction involves the formation of H2CO + HO2 radical in a process that is computed to be exothermic by 57 kcal/mol. However, the reaction mechanism is very complex and begins with the formation of a pre-reactive hydrogen-bonded complex and follows by the addition of HO radical to the carbon atom of H2COO, forming the intermediate peroxy-radical H2C(OO)OH before producing formaldehyde and hydroperoxy radical. Our calculations predict that both the pre-reactive hydrogen-bonded complex and the transition state of the addition process lie energetically below the enthalpy of the separate reactants (ΔH(298K) = −6.1 and −2.5 kcal/mol, respectively) and the formation of the H2C(OO)OH adduct is exothermic by about 74 kcal/mol. Beyond this addition process, further reaction mechanisms have also been investigated, which involve the abstraction of a hydrogen of carbonyl oxide by HO radical, but the computed activation barriers suggest that they will not contribute to the gas-phase reaction of H2COO + HO.

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