Understanding and manipulating the sensitivity of nitrate ester explosives

Understanding the factors that influence sensitivity is critical for the design and screening of new energetic molecules and materials, but it is often difficult to isolate a single variable to analyze its effect. Pentaerythritol tetranitrate (PETN) is a very common nitrate ester explosive that has been widely studied due to its use in military and commercial explosives. We have developed PETN derivatives with modified sensitivity characteristics by substituting the -CCH2ONO2 moiety with other substituents, including -CH, -CNH2, -CNH3X, -CCH3, or -PO. We relate the handling sensitivity properties of each PETN derivative to its structure, and discuss the potential roles of the central atom, oxygen balance, thermal stability, heat capacity, crystal structure, and inter- and intramolecular hydrogen bonding on impact sensitivity. Reactive molecular dynamics (MD) simulations of the C, H, N, O-based PETN-derivatives have been performed under cook-off conditions that provide insights into how the substituents change the initial chemistry and decomposition paths.Understanding the factors that influence sensitivity is critical for the design and screening of new energetic molecules and materials, but it is often difficult to isolate a single variable to analyze its effect. Pentaerythritol tetranitrate (PETN) is a very common nitrate ester explosive that has been widely studied due to its use in military and commercial explosives. We have developed PETN derivatives with modified sensitivity characteristics by substituting the -CCH2ONO2 moiety with other substituents, including -CH, -CNH2, -CNH3X, -CCH3, or -PO. We relate the handling sensitivity properties of each PETN derivative to its structure, and discuss the potential roles of the central atom, oxygen balance, thermal stability, heat capacity, crystal structure, and inter- and intramolecular hydrogen bonding on impact sensitivity. Reactive molecular dynamics (MD) simulations of the C, H, N, O-based PETN-derivatives have been performed under cook-off conditions that provide insights into how the substituents ch...