Density functional theory for N–NO2 bond dissociation energies of N-nitroacylamide compounds in acetonitrile — Theoretical method assessment and prediction

Abstract

The performance of various density functional theories (B3LYP, B3PW91, B3P86, B1LYP, BMK, MPWB1K, PBE0, and MPWB95) was examined for calculating N–NO2 bond dissociation energies (BDEs) of 10 N-nitroacylamide compounds. The CBS-4M method was also used. By comparing the calculated results with the experimental values, it was observed that B1LYP/6–31G** and B3LYP/6–31+G** provided accurate BDEs. Especially, B3LYP/6–31+G** was recommended because of its smaller maximum absolute deviation. Further, substituent effects based on the B3LYP/6–31+G** method were analyzed. The result shows that an electron-donating group increases the BDE of the parent C6H5–CON(CH3)NO2, while an electron-withdrawing group decreases the BDE of the parent C6H5–CON(CH3)NO2. Subsequently, the BDEs of the other N-nitroacylamindes were estimated.