The UV photolysis of solid FOX-7 at 5 K with 355 and 532 nm photons was investigated to unravel initial isomerization and decomposition pathways. Isomer-selective single photon ionization coupled with reflectron time-of-flight mass spectrometry (ReTOF-MS) documented the nitric oxide (NO) loss channel at 355 nm along with a nitro-to-nitrite isomerization, which was observed by using infrared spectroscopy, representing the initial reaction pathway followed by O�NO bond rupture of the nitrite moiety. A residual gas analyzer detected molecular oxygen for the 355 and 532 nm photolysis at a ratio of 4.3 ± 0.3:1, which signifies FOX-7 as an energetic material that provides its own oxidant once the decomposition starts. Overall branching ratios for molecular oxygen versus nitric oxide were derived to be 700 ± 100:1 at 355 nm. It is notable that this is the first time that molecular oxygen was detected as a decomposition product of FOX-7. Computations show that atomic oxygen, which later combines to form molecular oxygen, is likely released from a nitro group involving conical intersections. The condensed phase potential energy profile computed at the CCSD(T) and CASPT2 level correlates well with the experiments and highlights the critical roles of conical intersections, nonadiabatic dynamics, and the encapsulated environment that dictate the mechanism of the reaction through intermolecular hydrogen bonds.

The bioactivity-guided examination of a Leptolyngbya sp. led to the isolation of leptazolines A–D (1–4), from the culture media, along with two degradation products (5 and 6). Density functional theory nuclear magnetic resonance calculations established the relative configurations of 1 and 2 and revealed that the calculated shifts depended on the operating system when using the “Willoughby–Hoye” Python scripts to streamline the processing of the output files, a previously unrecognized flaw that could lead to incorrect conclusions.

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The dynamics of the HBr + + CO 2 → HOCO + + Br reaction was recently investigated with guided ion beam experiments under various excitations (collision energy of the reactants, rotational and spin−orbital states of HBr + , etc.), and their impacts were probed through the change of the cross section of the reaction. The potential energy profile of this reaction has also been accurately characterized by high-level ab initio methods such as CCSD(T)/CBS, and the UMP2/cc-pVDZ/lanl08d has been identified as an ideal method to study its dynamics. This manuscript reports the first ab initio molecular dynamics simulations of this reaction at two different collision energies, 8.1 kcal/mol and 19.6 kcal/mol. The cross sections measured from the simulations agree very well with the experiments measured with HBr + in the 2 ∏ 1/2 state. The simulations reveal three distinct mechanisms at both collision energies: direct rebound (DR), direct stripping (DS), and indirect (Ind) mechanisms. DS and Ind make up 97% of the total reaction. The dynamics of this reaction is also compared with nucleophilic substitution (S N 2) reactions of X − + CH 3 Y → CH 3 X + Y − type. In summary, this research has revealed interesting dynamics of the HBr + + CO 2 → HOCO + + Br reaction at different collision energies and has laid a solid foundation for using this reaction to probe the impact of rotational excitation of ion−molecule reactions in general.

1,1-Diamino-2,2-dinitroethene (FOX-7) is an energetic material with low sensitivity and high detonation performance, thus it has been considered as a potential replacement for traditional nitro-based energetic materials. In a recent...