Kinetics of decomposition pathways of an energetic GZT molecule

This investigation uses the Gaussian 98 program, density functional theory (DFT) B3LYP/6‐31G(d,p), and ab initio MP2/6‐31G(d,p) and HF/6‐31G(d) methods to model energetic diguanidinium 5,5′‐azotetrazolate (GZT) ionic species in order to determine their decomposition mechanisms. GZT was initially cracked into two guanidinium cations (G⁺) and a 5,5′‐azotetrazolate anion (ZT^2?). Three routes—the elimination of a hydronium ion (H⁺), the elimination of a hydrogen radical (H·), and the elimination of an amine radical (·NH₂)—are suggested for the decomposition of the G⁺ cation, and three routes—single ring opening, double ring opening and N? N bond cleavage outside the ring—are proposed for the further decomposition of the ZT^2? anion. Fourteen decomposition species were obtained on splitting both the cation and anion. This result reveals the reliability of the aforementioned decomposition mechanisms. The transition state species were also obtained using a two‐structure or three‐structure synchronous transit‐guided quasi‐Newton (STQN) between the Cartesian coordinates of related particles at specific decomposition stages in this research. The corresponding activation energies in all decomposition stages were considered to infer the most feasible pathways of GZT decomposition. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008