Molecular design and theoretical investigation of TNI based materials.

[Display omitted] • A series of bridged TNI based energetic materials were designed. • Density functional theory (DFT) method at B3LYP/6-311G (d,p) level was employed to calculate the detonation properties and electronic structures. • Some molecules were screened as candidates of high energy density materials which may shine lights on the synthesis of novel energetic materials. A series of highly symmetrical 2,4,5-trinitroimidazole (TNI) based energetic materials are designed. Based on the structures that optimized by density functional theory at the B3LYP/6-311G(d,p) level, their spectrum, heats of formation, detonation properties, thermal stability and thermodynamics are investigated. The results show that the −N N- bridge will be the most effective bridge to increase the heats of formation while the effect of –CH 2 CH 2 - bridge is on the opposite side. Compound G possesses the highest value of heat of detonation, detonation velocity and detonation pressure which reveals that heat of formation plays an important role in the detonation properties rather than the density. The calculated values of bond dissociation energy show that all the designed compounds (except for compound I) are more stable than those of RDX and HMX. Finally, their electronic structures and non-covalent interaction are simulated which may shine lights on the physicochemical properties of the designed compounds. [ABSTRACT FROM AUTHOR]