Theoretical investigations on N₂H₅N₅/PDO cocrystal via a first‐principles study

Abstract The exploration of cyclo ‐N 5 ˉ‐based energetic cocrystals represents a noteworthy avenue within pentazolate chemistry, focusing on leveraging cocrystallization to enhance stability. Recently, a novel cocrystal explosive, N 2 H 5 N 5 /PDO, was developed by combining N 2 H 5 N 5 with pyrazine 1,4‐dioxide (PDO), exhibiting promising detonation characteristics and reduced sensitivity. This study endeavors to elucidate how the structure and noncovalent interactions impact the performance of N 2 H 5 N 5 /PDO through a first‐principles investigation. The results indicate that the enhanced hydrogen bonding and wave‐like crystal packing structure within the cocrystal effectively bolster its stability compared to N 2 H 5 N 5 . The N···H and O···H interactions, in conjunction with π–π interactions, emerge as critical elements driving cocrystal formation. Compared to the pure N 2 H 5 N 5 , the detonation performance of the cocrystal exhibits a slight decline, albeit with a noticeable reduction in sensitivity.