Two-dimensional energetic materials(2DEMs),characterized by their exceptional interlayer sliding properties,are recognized as exemplar of low-sensitivity energetic materials.However,the diversity of available 2DEMs is...Two-dimensional energetic materials(2DEMs),characterized by their exceptional interlayer sliding properties,are recognized as exemplar of low-sensitivity energetic materials.However,the diversity of available 2DEMs is severely constrained by the absence of efficient methods for rapidly predicting crystal packing modes from molecular structures,impeding the high-throughput rational design of such materials.In this study,we employed quantified indicators,such as hydrogen bond dimension and maximum planar separation,to quickly screen 172DEM and 16 non-2DEM crystal structures from a crystal database.They were subsequently compared and analyzed,focusing on hydrogen bond donor-acceptor combinations,skeleton features,and intermolecular interactions.Our findings suggest that theπ-πpacking interaction energy is a key determinant in the formation of layered packing modes by planar energetic molecules,with its magnitude primarily influenced by the strongest dimericπ-πinteraction(π-π2max).Consequently,we have delineated a critical threshold forπ-π2max to discern layered packing modes and formulated a theoretical model for predictingπ-π2max,grounded in molecular electrostatic potential and dipole moment analysis.The predictive efficacy of this model was substantiated through external validation on a test set comprising 31 planar energetic molecular crystals,achieving an accuracy of 84%and a recall of 75%.Furthermore,the proposed model shows superior classification predictive performance compared to typical machine learning methods,such as random forest,on the external validation samples.This contribution introduces a novel methodology for the identification of crystal packing modes in 2DEMs,potentially accelerating the design and synthesis of high-energy,low-sensitivity 2DEMs.展开更多
基金support from National Natural Science Foundation of China(Grant Nos.22275145,22305189and 21875184)Natural Science Foundation of Shaanxi Province(Grant Nos.2022JC-10 and 2024JC-YBQN-0112).
文摘Two-dimensional energetic materials(2DEMs),characterized by their exceptional interlayer sliding properties,are recognized as exemplar of low-sensitivity energetic materials.However,the diversity of available 2DEMs is severely constrained by the absence of efficient methods for rapidly predicting crystal packing modes from molecular structures,impeding the high-throughput rational design of such materials.In this study,we employed quantified indicators,such as hydrogen bond dimension and maximum planar separation,to quickly screen 172DEM and 16 non-2DEM crystal structures from a crystal database.They were subsequently compared and analyzed,focusing on hydrogen bond donor-acceptor combinations,skeleton features,and intermolecular interactions.Our findings suggest that theπ-πpacking interaction energy is a key determinant in the formation of layered packing modes by planar energetic molecules,with its magnitude primarily influenced by the strongest dimericπ-πinteraction(π-π2max).Consequently,we have delineated a critical threshold forπ-π2max to discern layered packing modes and formulated a theoretical model for predictingπ-π2max,grounded in molecular electrostatic potential and dipole moment analysis.The predictive efficacy of this model was substantiated through external validation on a test set comprising 31 planar energetic molecular crystals,achieving an accuracy of 84%and a recall of 75%.Furthermore,the proposed model shows superior classification predictive performance compared to typical machine learning methods,such as random forest,on the external validation samples.This contribution introduces a novel methodology for the identification of crystal packing modes in 2DEMs,potentially accelerating the design and synthesis of high-energy,low-sensitivity 2DEMs.
