164. Investigating the Photochemical Decomposition of Solid 1,3,5-Trinitro-1,3,5-triazinane (RDX)

Santosh K. Singh, Vasant Vuppuluri, Steven F. Son, and Ralf I. Kaiser; The Journal of Physical Chemistry A; (2020); DOI: 10.1021/acs.jpca.0c05726

Energetic materials such as 1,3,5-trinitro-1,3,5-triazinane (RDX) are known to photodissociate when exposed to UV light. However, the fundamental photochemical process(es) that initiate the decomposition of RDX is (are) still debatable. In this study we investigate the photodissociation of solid-phase RDX at four distinct UV wavelengths (254 nm (4.88 eV), 236 nm (5.25 eV), 222 nm (5.58 eV), 206 nm (6.02 eV)) exploiting a surface science machine at 5 K. We also conducted dose-dependent studies at the highest and lowest photon energy of 206 nm (6.02 eV) and 254 nm (4.88 eV). The products were monitored online and in situ via infrared spectroscopy. During the temperature-programmed desorption phase, the subliming products were detected with a reflectron time-of-flight mass spectrometer coupled with soft-photoionization at 10.49 eV (PI-ReTOF-MS). Infrared spectroscopy revealed the formation of small molecules including nitrogen monoxide (NO), nitrogen monoxide dimer ([NO]2), dinitrogen trioxide (N2O3), carbon dioxide (CO2), carbon monoxide (CO), dinitrogen monoxide (N2O), water (H2O), and nitrite group (−ONO) while ReTOF-MS identified 32 cyclic and acyclic products. Among these, 11 products such as nitryl isocyanate (CN2O3), 5-nitro-1,3,5-triazinan-2-one (C3H6N4O3) and 1,5-dinitro-1,3,5-triazinan-2-one (C3H5N5O5) were detected for the first time in photodecomposition of RDX. Dose-dependent in combination with wavelength-dependent photolysis experiments aid to identify key primary and secondary products as well as distinguished pathways that are more preferred at lower and higher photon energies. Our experiments reveled that N–NO2 bond fission and nitro–nitrite isomerization are the initial steps in the UV photolysis of RDX. Reaction mechanisms are derived by comparing the experimental findings with previous electronic structure calculations to rationalize the origin of the observed products. The present study can assist in understanding the complex chemistry behind the photodissociation of electronically excited RDX molecule, thus bringing us closer to unraveling the decomposition mechanisms of nitramine-based explosives.