Electrostatic Complementarity as a Design Principle for Lamellar Packing in Nitro-Containing CHON Energetic Materials

Abstract The long-standing trade-off between energy density and mechanical safety has severely restricted the development of advanced energetic materials. 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB), the prototypical insensitive high-energy material (IHEM), owes its low sensitivity to a graphite-like lamellar structure, yet no quantitative model currently relates its intermolecular interactions to this lamellar assembly. Herein, we systematically decipher the hierarchical intermolecular interaction network of TATB through a multi-scale theoretical approach. We first identify a bimodal non-uniform interlamellar spacing (3.125 Å and 3.154 Å) in TATB and fully quantify the three-dimensional anisotropy of its intermolecular interactions in type, strength, and directionality. By combining electrostatic potential (ESP) and van der Waals analyses, we first elucidate the electronic origin of this anisotropy. Building on a gradient amino-substituted homologous series and nitro-containing CHON molecules, we further demonstrate that ESP complementarity decisively governs two-dimensional molecular expansion. Finally, we translate these findings into three actionable molecular screening criteria: backbone planarity, alternating donor−acceptor topology, and multidirectional in-plane ESP complementarity. This work provides a quantitative theoretical framework and practical guidance for the rational design of next-generation high-performance insensitive high-energy materials.