Abstract:If the molecules in an energetic crystal are regarded as the bricks of the crystal building, the intermolecular interactions will be the adhesive among the bricks. Thus, the intermolecular interactions are one of directions and bases for understanding and designing energetic crystal. This article reviews the intermolecular hydrogen bonding, halogen bonding and π-π stacking in energetic crystals, and their influences on molecular stacking pattern, impact sensitivity and thermal stability. Some characteristics and enlightenment from the intermolecular interactions can be summarized as follows: (1) the hydrogen bonding in low impact sensitive crystals is stronger than that in highly sensitive ones; (2) the face-to-face π-π stacking is prone to low impact sensitivity; (3) it serves as one of the crystal engineering strategies to enhance intermolecular interactions and their anisotropy to reduce impact sensitivity; and (4) it will worsen thermal stability when the intermolecular hydrogen bonding is blindly strengthened. Besides, we should focus upon the accurate description of intermolecular interactions and their evolution rules against thermomechanical stimuli.