Comparative Study\nof <i>n</i>‑C<sub>5</sub> Bond Dissociation Energies\nand H‑Atom Abstraction\nvia H for Alkane, Alcohol, Methyl Ether, Nitroso, Nitro, Nitrite,\nand Nitrate

Energetic materials have a wide range of applications,\nfor many\nof which new materials are constantly developed. For understanding\nhow energetic materials are chemically converted, it is essential\nto systematically understand how relevant functional groups affect\nthe stability and properties of such materials. Here, the impact of\nnitroso, nitro, nitrite, and nitrate functional groups on a pentyl\nmoiety is studied theoretically, focusing on bond dissociation energies\nand H atom abstraction via Ḣ. The nitroso group is found to\nimply the strongest effects, while the nitro group appears to exert\na stabilizing effect on the pentyl moiety. Importantly, the nitrogenated\nfunctional groups generally stabilize the pentyl moiety, in contrast\nto alcohol and methyl ether functional groups. Therefore, it is concluded\nthat using analogies to the chemistries of the latter two functional\ngroups for chemical kinetic modeling of nitrogenated functional groups\nis not adequate. Based on the presented bond dissociation energies\nand rate coefficients, it is to be expected that unimolecular bond\nfissions at the nitrogenated functional groups will dominate over\na wide temperature range. Building on the provided data, future detailed\nchemical kinetic modeling efforts for nitroso, nitro, nitrite, and\nnitrate compounds can be aided or initiated.