Azole energetic materials: initial mechanisms for the energy release from electronical excited nitropyrazoles

Decomposition of energetic material 3,4-dinitropyrazole (DNP) and two model molecules 4-nitropyrazole and 1-nitropyrazole is investigated both theoretically and experimentally. The initial decomposition mechanisms for these three nitropyrazoles are explored with complete active space self-consistent field (CASSCF) level. The NO molecule is observed as an initial decomposition product from all three materials subsequent to UV excitation. Observed NO products are rotationally cold (<50 K) for all three systems. The vibrational temperature of the NO product from DNP is (3850 ± 50) K, 1350 K hotter than that of the two model species. Potential energy surface calculations at the CASSCF(12,8)/6-31+G(d) level illustrate that conical intersections plays an essential role in the decomposition mechanism. Electronically excited S2 nitropyraozles can nonradiatively relax to lower electronic states through (S2/S1)CI and (S1/S0)CI conical intersection and undergo a nitro-nitrite isomerization to generate NO product either in the S1 state or S0 state. In model systems, NO is generated in the S1 state, while in the energetic material DNP, NO is produced on the ground state surface, as the S1 decomposition pathway is energetically unavailable. The theoretically predicted mechanism is consistent with the experimental results, as DNP decomposes in a lower electronic state than do the model systems and thus the vibrational energy in the NO product from DNP should be hotter than from the model systems. The observed rotational energy distributions for NO are consistent with the final structures of the respective transition states for each molecule.