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

Andrew M Turner; Joshua H Marks; Jasmin T Lechner; Thomas M Klapötke; Rui Sun; Ralf I Kaiser

doi:10.1021/acs.jpca.3c03215

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

J Phys Chem A. 2023 Sep 21;127(37):7707-7717. doi: 10.1021/acs.jpca.3c03215. Epub 2023 Sep 8.

Authors

Andrew M Turner^{1

2}, Joshua H Marks^{1

2}, Jasmin T Lechner³, Thomas M Klapötke³, Rui Sun¹, Ralf I Kaiser^{1

2}

Affiliations

¹ Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822, United States.
² W. M. Keck Research Laboratory in Astrochemistry, University of Hawaii, Honolulu, Hawaii 96822, United States.
³ Department of Chemistry, Ludwig-Maximilian University of Munich, München 81377, Germany.

PMID: 37682229
DOI: 10.1021/acs.jpca.3c03215

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.