Ultraviolet-Initiated Decomposition of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7).

ABSTRACT

FOX-7 (1,1-diamino-2,2-dinitroethylene) was photolyzed with 202 nm photons to probe reaction energies, leading to the decomposition of this energetic material and to compare results from irradiations using lower-energy 532 and 355 nm photons as well as higher-energy electrons. The photolysis occurred at 5 K to suppress thermal reactions, and the solid samples were monitored using Fourier transform infrared spectroscopy (FTIR), which observed carbon dioxide (CO2), carbon monoxide (CO), cyanide (CN-), and cyanate (OCN-) after irradiation. During warming to 300 K, subliming products were detected using electron-impact quadrupole mass spectrometry (EI-QMS) and photoionization time-of-flight mass spectrometry (PI-ReTOF-MS). Five products were observed in QMS water (H2O), carbon monoxide (CO), nitric oxide (NO), carbon dioxide (CO2), and cyanogen (NCCN). The ReTOF-MS results showed overlap with electron irradiation products but also included three intermediates for the oxidation of ammonia and nitric oxide hydroxylamine (NH2OH), nitrosamine (NH2NO), and the largest product at 76 amu with the proposed assignment of hydroxyurea (NH2C(O)NHOH). These results highlight the role of reactive oxygen intermediates and nitro-to-nitrite isomerization as key early reactions that lead to a diverse array of decomposition products.