Theoretical study of energetic trinitromethyl‐substituted tetrazole and tetrazine derivatives

Density functional theory method was used to study the heats of formation, energetic properties, and thermal stability for a series of trinitromethyl‐substituted tetrazole and tetrazine derivatives with different substituents. It is found that the group ―NO₂, ―NHNO₂, or ―NF₂ play a very important role in increasing the heats of formation of the derivatives. The calculated detonation velocities and pressures indicate that the group ―CF₂NF₂, ―NHNO₂, ―1H‐tetrazolyl, ―2H‐tetrazolyl, or ―1,2,4,5‐tetrazinyl is an effective structural unit for enhancing their detonation performance. An analysis of the bond dissociation energies for several relatively weak bonds indicates that incorporating the group ―NHNO₂ and ―NH₂ into parent ring decreases their thermal stability. Considering the detonation performance and thermal stability, 37 compounds may be considered as the potential high‐energy compounds. Their oxygen balances are close to zero. These results provide basic information for the molecular design of novel high‐energy compounds. Copyright © 2013 John Wiley & Sons, Ltd.