DFT M06-2X investigation of alkaline hydrolysis of nitroaromatic compounds

► TNT hydrolysis reaction was modeled along with simulation of UV-VIS and NMR spectra. ► The most plausible initial intermediates are TNT anion and Meisenheimer complexes. ► Reaction proceeds toward polynegative complexes and Janovsky complexes. ► Polymeric compounds and cycle cleavage species are products of later stages. ► Alkaline hydrolysis of DNT and DNAN are energetically less favorable than the corresponding TNT reaction.