A DFT study of bond dissociation energies of several alkyl nitrate and nitrite compounds

Quantum chemical calculations are used to estimate the bond dissociation energies (BDEs) for nine alkyl nitrate and nitrite compounds. These compounds are studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86) methods with 6-31G∗ and 6-311G∗ basis sets. It is demonstrated that the B3P86/6-31G∗ is the most accurate method to compute the reliable BDEs for the compounds studied. In order to test whether the non-local BLYP method suggested by Luo [Y.R. Luo, Handbook of Bond Dissociation Energies in Organic Compounds, CRC Press, Boca Raton, 2003] is general for our study and whether B3P86 method is sensitive to the basis set, the BDEs for nine alkyl nitrate and nitrite compounds are also calculated by using BLYP/6-31+G∗ and B3P86 method with 6-31+G∗, 6-31++G∗ and 6-31G∗∗ basis sets for comparison. The obtained results are compared with the available experimental results. It is noted that the use of diffuse functions cannot improve the results and the use of polarization functions is more computationally effective than diffuse functions in the BDEs calculation.