Theoretical determination of the effects of various linkages between trinitrobenzenes on energetic properties and sensitivity.

Density functional theory (DFT) has been applied to understand the influence of various linkages on the energetic properties and stability of the polynitro-biphenyl compounds. Structures were optimized using the B3PW91/6-31G(d,p) level, and the heats of formation (HOFs) were computed by employing the selected isodesmic reactions. The results reveal that the -N=N- linkage helps to gain high HOF while the -O-, -NH-C(O)NH-, and -NH-C(O)-C(O)-NH- show a negative impact on energy content. Kamlet-Jacobs (K-J) equations were used to determine detonation properties based on the computed densities and HOFs, while stability and sensitivity were investigated by correlating with the bond dissociation energy (BDE), charge on the nitro group, and the balance parameter on surface potentials. Comparing the effect of different linkages on performance and stability of selected polynitro-biphenyl derivatives reveals that -NH-NH- and -N=N- are suitable for a connection between energetic moieties and these results are expected to demonstrate primary information for designing new energetic materials. Graphical abstract.