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Bond dissociation enthalpies in chlorinated benzenes and phenols and enthalpies of formation of their free radicals: A Gaussian-4 prediction

✍ Scribed by Liming Wang; Aili Tang

Publisher: John Wiley and Sons
Year: 2010
Tongue: English
Weight: 100 KB
Volume: 43
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.20528

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✦ Synopsis

The bond dissociation enthalpies (BDEs) in chlorinated benzenes and phenols and the standard gas-phase enthalpies of formation of chlorinated phenyl and phenoxy radicals are predicted by using Gaussian-4 (G4) and Gaussian-3X (G3X) model chemistries. The predicted G4 BDEs are systematically smaller than the G3X ones, with difference as much as ∼15 kJ/mol for the C 6 Cl 5 -Cl bond, and the G4 enthalpies of formation of the free radicals are systematically smaller than the G3X ones. The discrepancies increase gradually with the degree of chlorination; whereas for the closed-shell species, G4 and G3X enthalpies of formation agree closely within 2 kJ/mol. The difference between G4 and G3X arises mainly from the noncanceling high-level correction terms in G4.

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## Abstract Density functional theory was used to estimate the lifetime of fluorinated formates, which are primary products from the oxidation of hydrofluoroethers. First, the CH bond dissociation enthalpies (BDEs) of 10 fluorinated formates, C~__n__~F~2__n__ + 1~OC(O)H (__n__ = 1–4) and C~__n__~H