Pentaerythritol tetranitrate (PETN) is a common secondary explosive and has been used extensively to study shock initiation and energy propagation in energetic materials. We report 2D IR measurements of PETN thin films that resolve vibrational energy transfer and relaxation mechanisms. Ultrafast anisotropy measurements reveal a sub-500 fs reorientation of transition dipoles in thin films of vapor-deposited PETN that is absent in solution measurements, consistent with intermolecular energy transfer. The anisotropy is frequency dependent, suggesting spectrally heterogeneous vibrational relaxation. Cross peaks are observed in 2D IR spectra that resolve a specific energy transfer pathway with a 2 ps time scale. Transition dipole coupling calculations of the nitrate ester groups in the crystal lattice predict that the intermolecular couplings are as large or larger than the intramolecular couplings. The calculations match well with the experimental frequencies and the anisotropy, leading us to conclude that the observed cross peak is measuring energy transfer between two eigenstates that are extended over multiple PETN molecules. Measurements of the transition dipole strength indicate that these vibrational modes are coherently delocalized over at least 15-30 molecules. We discuss the implications of vibrational relaxation between coherently delocalized eigenstates for mechanisms relevant to explosives.
Europa is a premier target for advancing both planetary science and astrobiology, as well as for opening a new window into the burgeoning field of comparative oceanography. The potentially habitable subsurface ocean of Europa may harbor life, and the globally young and comparatively thin ice shell of Europa may contain biosignatures that are readily accessible to a surface lander. Europa’s icy shell also offers the opportunity to study tectonics and geologic cycles across a range of mechanisms and compositions. Here we detail the goals and mission architecture of the Europa Lander mission concept, as developed from 2015 through 2020. The science was developed by the 2016 Europa Lander Science Definition Team (SDT), and the mission architecture was developed by the preproject engineering team, in close collaboration with the SDT. In 2017 and 2018, the mission concept passed its mission concept review and delta-mission concept review, respectively. Since that time, the preproject has been advancing the technologies, and developing the hardware and software, needed to retire risks associated with technology, science, cost, and schedule.
Vapor‐deposited hexanitroazobenzene (HNAB) films were observed to form a dense amorphous structure that crystallizes to a mixture of the HNAB‐II polymorph and an unidentified structure over a period ranging from hours to weeks depending on the ambient temperature. Films crystallized at various temperatures were characterized using scanning electron microscopy, atomic force microscopy, X‐ray diffraction, and Raman spectroscopy to measure the impact of crystallization temperature on resultant microstructure. Crystallization temperature was observed to have different effects on film microstructure over two temperature regimes. At temperatures below approximately 65 °C, increases in temperature led to a greater fraction of the film forming the HNAB‐II polymorph and caused subtle changes in morphology. However, at higher temperatures, a thin surface layer was observed to form prior to crystallization, which led to films composed primarily of the unknown crystal structure with conspicuous differences in morphology.
The initiation and detonation properties of explosives are often empirically correlated to density, surface area, and particle size. Although these correlations are sometimes used successfully to predict the performance of bulk samples, the data are spatially averaged, which unfortunately muddles information critical to understanding fundamental processes. Density and surface area are essentially an indirect measure of porosity, which is arguably a more appropriate metric in many applications. We report the direct characterization of porosity in polycrystalline molecular crystal explosives by focused ion beam nanotomography, a technique that is typically reserved for robust materials such as ceramics and metals. The resulting three-dimensional microstructural data are incredibly rich, promising a substantial advance in our ability to unravel the processes governing initiation and detonation of molecular crystal explosives. In a larger context, this work demonstrates that focused ion beam nanotomography may be successfully extended to the investigation of nanoscale porosity in other molecular crystal or polymer materials.
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