Abstract
Combining computer chemistry calculation with experimental verification is useful both in proving concepts and what is chemically possible. Computational predictions, using MOPAC quantum mechanical and classical force field mechanics, were used to investigate most likely first-tier intermediates of cyclic and cage cyclic nitramines—comparing bond lengths and angles, heats of formation, steric energy, dipole moments, solvent accessibility and electrostatic potential surfaces, partial charges, and Highest Occupied Molecular Orbitals/Lowest Unoccupied Molecular Orbitals (HOMO/LUMO) energies. Two competing modes of degradation are summarized: through addition of hydroxide ions and through addition of photo-induced free radicals. UV/VIS measured concentrations and followed the course of reactions. FTIR followed CL-20 degradation through alkali hydrolysis, where FTIR measurements verified theoretical predictions.
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Qasim, M.M., Fredrickson, H.L., McGrath, C. et al. Semiempirical Predictions of Chemical Degradation Reaction Mechanisms of CL-20 as Related to Molecular Structure. Structural Chemistry 15, 493–499 (2004). https://doi.org/10.1023/B:STUC.0000037907.27898.f5
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DOI: https://doi.org/10.1023/B:STUC.0000037907.27898.f5