Unimolecular decomposition of tetrazine-N-oxide based high nitrogen content energetic materials from excited electronic states

Unimolecular excited electronic state decomposition of novel high nitrogen content energetic molecules, such as 3 , 3 ′ -azobis(6-amino-1,2,4,5-tetrazine)-mixed N-oxides ( DAATO 3.5 ) , 3-amino-6-chloro-1,2,4,5-tetrazine-2,4-dioxide (ACTO), and 3,6-diamino-1,2,4,5-tetrazine-1,4-dioxde (DATO), is investigated. Although these molecules are based on N-oxides of a tetrazine aromatic heterocyclic ring, their decomposition behavior distinctly differs from that of bare tetrazine, in which N 2 and HCN are produced as decomposition products through a concerted dissociation mechanism. NO is observed to be an initial decomposition product from all tetrazine-N-oxide based molecules from their low lying excited electronic states. The NO product from DAATO 3.5 and ACTO is rotationally cold (20 K) and vibrationally hot (1200 K), while the NO product from DATO is rotationally hot (50 K) and vibrationally cold [only the (0-0) vibronic transition of NO is observed]. DAATO 3.5 and ACTO primarily differ from DATO with regard to molecular structure, by the relative position of oxygen atom attachment to the tetrazine ring. Therefore, the relative position of oxygen in tetrazine-N-oxides is proposed to play an important role in their energetic behavior. N 2 O is ruled out as an intermediate precursor of the NO product observed from all three molecules. Theoretical calculations at CASMP2/CASSCF level of theory predict a ring contraction mechanism for generation of the initial NO product from these molecules. The ring contraction occurs through an ( S 1 / S 0 ) CI conical intersection.