Modeling Photolytic Decomposition of Energetically Functionalized Dodecanes

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 126; no. 40
• Main Authors: Nelson, Tammie Renee, Huestis, Patricia Leigh, Manner, Virginia Warren
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.10.2022
• Subjects: computational chemistry; degradation; energy; functional groups; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; molecules
• ISSN: 1089-5639; 1520-5215

The photolytic stability of explosives and energetic functional groups is of importance for those who regularly handle or are exposed to explosives in typical environmental conditions. This study models the photolytic degradation of dodecane substituted with various energetic functional groups: azide, nitro, nitrate ester, and nitramine. For the studied molecules, it was found that excitons localize on the energetic functional group, no matter where they were initially formed, and thus, the predominant degradation pathway involves the degradation of the energetic functional group. The relative trends for both 4 and 8 eV excitation energies followed with what is expected from the relative stability of the energetic functional groups to thermal and sub-shock degradation. The one notable exception was the azide functional group; more work should be done to further understand the photolytic effects on the azide functional group.