DFT molecular orbital calculations of initial step in decomposition pathways of TNAZ and some of its derivatives with –F, –CN and –OCH3 groups

Abstract

1,3,3-Trinitroazetidine (TNAZ) and its derivatives are highly desirable energetic compounds, which can be used in explosive and/or propellant formulations. In this paper, the quantities of activation barriers, enthalpies, entropies and free energies of a few initial steps in the decomposition pathways of TNAZ and some of its derivatives with –F, –CN and –OCH3 groups have been computed by means of DFT with B3LYP/6–31G** model. The initial decomposition pathways including NO2 fission, HONO elimination and direct ring-opening reaction are investigated. For all of molecules, the results essentially confirm that the N–NO2 fission is the convenient pathway in the kinetics and thermodynamic properties of their decomposition.