Polymorphism in Energetic Materials

Polymorphism often occurs in energetic materials. Differences in the forms range from conformational changes in the molecule from one system to another, to conformational equivalents packing in different manners. These differences, whether drastic or subtle, can lead to substantial alterations in stability and performance. The authors recently reported on the crystal structures of five polymorphs of picryl bromide (a common energetic precursor): the previously identified α and β forms, and three new forms, the γ, δ, and ε forms. A new type of interaction has been identified between the nitro groups and π-electrons of neighboring phenyl rings. Accurate estimation of the properties of new energetic materials can substantially reduce the development cost of new materials by focusing expensive scale-up and testing on only the most promising candidates. The characterization of this new force involved in crystal packing should greatly improve calculations of packing energy and thus improve predictions of explosive yield.