Bond Dissociation Enthalpies in Chlorinated Benzenes and Phenols and Enthalpies of Formation of Their Free Radicals: A Gaussian-4 Prediction

作者：Wang Liming^*; Tang Aili

来源：International Journal of Chemical Kinetics, 2011, 43(2): 62-69.

DOI：10.1002/kin.20528

• Bond dissociation enthalpies
• Chlorinated benzenes
• Closed shells
• Correction terms
• Degree of chlorination
• Enthalpies of formation
• Model chemistry
• Phenoxy radicals

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 similar to 15 kJ/mol for the C(6)Cl(5)-Cl bond, and the 04 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, 04 and G3X enthalpies of formation agree closely within 2 kJ/mol. The difference between 04 and G3X arises mainly from the noncanceling high-level correction terms in G4.

• 出版日期2011-2
• 单位华南理工大学