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 ―NO 2 , ―NHNO 2 , or ―NF 2 play a very important role in increasing the heats of formation of the derivatives. The calculated detonation velocities and pressures indicate that the group ―CF 2 NF 2 , ―NHNO 2 , ―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 ―NHNO 2 and ―NH 2 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.