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Experimental and theoretical chemical investigations of reactive materials and reactive intermediates
Bingham, Jacob Taylor
Bingham, Jacob Taylor
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2022
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Abstract
Reactive materials (RMs) and reactive intermediates (RIs) are frequently encountered across a broad diversity of chemical systems. Understanding their underlying chemical properties is paramount to numerous fundamental and applied scientific fields, as these species play critical roles in observable chemical properties such as reactivity, reaction mechanisms, thermodynamics, and kinetics. The studies conducted in this thesis have employed a combination of experimental and computational techniques to investigate the underlying chemistries of four different RM and RI chemical systems to advance the fundamental understanding of these high energy chemical species. The three diazidobenzene isomers were synthesized and a combination of density functional theory (DFT) calculations and spectroscopic studies were employed to gain insight into the photochemical mechanisms of RI nitrene formation from the RM diazide precursors. It was determined that aryl diazide photolysis followed a fundamentally different path for azide dissociation/nitrene formation than what is known for aryl monoazides. A comprehensive study on the photochemical reactivity of 1,3-diazidobenzene was performed, and a reaction scheme for the photolysis mechanisms of this RM in ambient solution was provided. Additionally, the presence of unique emission bands in the transient laser spectroscopy experiments were attributed to two different novel fluorescence events that had not been reported before. A detailed DFT computational analysis was conducted to determine characteristics that could predict post-ionization molecular fragmentation of four different organic RI dications that were formed after field ionization in atomic probe tomography experiments. A combination of spectroscopic and theoretical calculations helped clarify the adopted structure of the biologically important RM small molecule alloxan, as well as highlight underlying chemical explanations for the hydrolysis reactivity that was observed based on solvent conditions. Finally, a series of computational, synthetic, thermal, and spectral characterization experiments were performed for a new class of energetic RMs called high energy perovskites. The studies corroborated previous reports of the promising energetic properties for the materials, and models were developed that could help understand the perovskite formation process. This thesis presents the investigations and discoveries made for the four RM and RI systems in order to advance the overall chemical understanding of these important species.
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