Publications

Abstract Collisional energy transfer is an essential aspect of chemical reactivity and maintenance of thermal equilibrium. Here we report the shape (energy-dependence) of the collisional energy transfer probability function for collisions of vibrationally excited NO2 entrained in a molecular beam and photoexcited to within 40 cm-1 of its dissociation threshold. The internally excited molecules undergo collisions with Ar atoms in a crossed beam apparatus. Dissociative collisions rapidly produce the NO(J) fragment, which is observed by velocity-mapped ion imaging and REMPI techniques. The measured collisional energy transfer function is obtained via energy conservation and is compared with the results of classical trajectory calculations. Good agreement between the theory and experiment is found for collisions that transfer small amounts of energy, but the theory predicts a higher likelihood of energetic collisions than is observed experimentally. We explore possible explanations for this discrepancy in the dynamics of the collision excitation process.

This report summarizes initial studies into the chemical basis of the thermal insensitivity of INMX-104. The work follows upon similar efforts investigating this behavior for another DNAN-based insensitive explosive, IMX-101. The experiments described demonstrate a clear similarity between the ingredient interactions that were shown to lead to the thermal insensitivity observed in IMX-101 and those that are active in IMX-104 at elevated temperatures. Specifically, the onset of decomposition of RDX is shifted to a lower temperature based on the interaction of the RDX with liquid DNAN. This early onset of decomposition dissipates some stored energy that is then unavailable for a delayed, more violent release.

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This report summarizes our development of spectroscopic chemical analysis techniques and spectral modeling for trace-gas measurements of highly-regulated low-concentration species present in flue gas emissions from utility coal boilers such as HCl under conditions of high humidity. Detailed spectral modeling of the spectroscopy of HCl and other important combustion and atmospheric species such as H 2 O, CO 2 , N 2 O, NO 2 , SO 2 , and CH 4 demonstrates that IR-laser spectroscopy is a sensitive multi-component analysis strategy. Experimental measurements from techniques based on IR laser spectroscopy are presented that demonstrate sub-ppm sensitivity levels to these species. Photoacoustic infrared spectroscopy is used to detect and quantify HCl at ppm levels with extremely high signal-to-noise even under conditions of high relative humidity. Additionally, cavity ring-down IR spectroscopy is used to achieve an extremely high sensitivity to combustion trace gases in this spectral region; ppm level CH 4 is one demonstrated example. The importance of spectral resolution in the sensitivity of a trace-gas measurement is examined by spectral modeling in the mid- and near-IR, and efforts to improve measurement resolution through novel instrument development are described. While previous project reports focused on benefits and complexities of the dual-etalon cavity ring-down infrared spectrometer, here details on steps taken to implement this unique and potentially revolutionary instrument are described. This report also illustrates and critiques the general strategy of IR- laser photodetection of trace gases leading to the conclusion that mid-IR laser spectroscopy techniques provide a promising basis for further instrument development and implementation that will enable cost-effective sensitive detection of multiple key contaminant species simultaneously.

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