• density functional theory;
  • polarized continuum model;
  • benzyl nitrites;
  • bond dissociation energy;
  • solvent effect


A PCM continuum model, at the B3LYP, B3P86, and B3PW91 three-parameter hybrid DFT methods with 6-311G** basis set, is used to study the bond dissociation energies (BDEs) of benzyl nitrites. Compared the computed results with the experimental values, it is noted that B3PW91 functional is the best method to compute the BDEs of benzyl nitrites. The solvent and substituent effects on the BDEs of the O[BOND]NO bond are analyzed, and it is shown that the BDE of the O[BOND]NO bond decreases with the increment of the Hammett constants of substituent groups on benzene for benzyl nitrites except C6H5CH2O[BOND]NO. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012