The evaluation of bond dissociation energies for NO 2 scission in nitro compounds using density functional and complete basis set methods

By using the density functional theory (B3LYP) and four highly accurate complete basis set (CBS-Q, CBS-QB3, CBS-Lq and CBS-4M) ab initio methods, the X (C, N, O)–NO 2 bond dissociation energies (BDEs) for CH 3 NO 2 , C 2 H 3 NO 2 , C 2 H 5 NO 2 , HONO 2 , CH 3 ONO 2 , C 2 H 5 ONO 2 , NH 2 NO 2 (CH 3 ) 2 NNO 2 are computed. By comparing the computed BDEs and experimental results, it is found that the B3LYP method is unable to predict satisfactorily the results of bond dissociation energy (BDE); however, all four CBS models are generally able to give reliable predication of the X (C, N, O)–NO 2 BDEs for these nitro compounds. Moreover, the CBS-4M calculation is the least computationally demanding among the four CBS methods considered. Therefore, we recommend CBS-4M method as a reliable method of computing the BDEs for this nitro compound system.