Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 112, Issue 7, Pages 1587-1595Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp077266d
Keywords
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Funding
- Directorate For Geosciences
- Div Atmospheric & Geospace Sciences [0924146] Funding Source: National Science Foundation
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The existence of a series of organic peroxy radical-water complexes [CH3O2 center dot H2O (methyl peroxy); CH3CH2O2 center dot H2O (ethyl peroxy); CH3C(O)O-2 center dot H2O (acetyl peroxy); CH3C(O)CH2O2 center dot H2O (acetonyl peroxy); CH2-(OH)O-2 center dot H2O (hydroxyl methyl peroxy); CH2(OH)CH2O2 center dot H2O (2-hydroxy ethyl peroxy); CH2(F)O-2 center dot H2O (fluoro methyl peroxy); CH2(F)CH2O2 center dot H2O (2-fluoro ethyl peroxy)] is evaluated using high level ab initio calculations. A wide range of binding energies is predicted for these complexes, in which the difference in binding energies can be explained by examination of the composition of the R group attached to the peroxy moiety. The general trend in binding energies has been determined to be as follows: fluorine;approximate to alkyl < carbonyl < alcohol. The weakest bound complex, CH3O2 center dot H2O, is calculated to be bound by 2.3 kcal mol(-1), and the strongest, the CH2(OH)O-2 center dot H2O complex, is bound by 5.1 kcal mol(-1). The binding energy of the peroxy radical-water complexes which contain carbonyl and alcohol groups indicates that these complexes may perturb the kinetics and product branching ratios of reactions involving these complexes.
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