Design strategy for TATB-like insensitive high explosives: rational design and high-throughput screening based on fused-ring frameworks

Abstract

The trade-off between safety and energy content has long been a central challenge in the design of energetic materials. Here we propose a TATB-inspired design strategy for high-energy, insensitive explosives: secure intrinsic safety at the electronic and molecular scales, and achieve synergistic optimization of safety and detonation performance at the crystal scale by enforcing planar packing motifs. Using fused five- and six-membered nitrogen-containing aromatic rings as the scaffold, and combining nitro, amino, and N-coordinated oxygen substituents, we constructed an initial molecular library of 1 00 413 compounds and applied five rounds of high-throughput virtual screening (oxygen balance, substituent counts, synthetic feasibility, planarity, predicted detonation velocity) to progressively down-select targets. Crystal structure prediction was then performed for 100 candidate molecules using USPEX coupled with GFN1-xTB, yielding ten compounds with planar, layered packing motifs. Theoretical evaluation indicates that mol-392 attains a calculated detonation velocity of 8541 m s⁻¹ and a predicted sensitivity at least comparable to TNT, demonstrating excellent overall performance. Furthermore, energy decomposition and correlation analyses identify van der Waals (dispersion) interactions as the dominant determinant of crystal density in these systems. This study validates the practicality of the TATB-like design strategy, provides a route for the rational discovery of insensitive high explosives, elucidates mechanisms governing crystal density in planar layered packings, and highlights the value of combining high-throughput virtual screening with crystal engineering in energetic-materials development.