Positive electrostatic potential over the central area of the molecular surface is one of the main characteristics of high energetic materials (HEMs) that determines their sensitivity towards detonation. The influence of halogen bonds on the values of the electrostatic potential of selected HEM molecules was studied in crystal structures extracted from the Cambridge Structural Database and by quantum chemical calculations. Analysis of halogen bonds in crystal structures containing halogen-substituted 2,4,6-trinitrophenyl fragments showed that these groups form halogen bonds (183 contacts). Analysis of electrostatic potential maps calculated for geometries of non-halogen bonded and halogen bonded HEM molecules extracted from crystal structures showed that halogen bonding modifies electrostatic potential in the centers of these compounds. Since in selected crystal structures other types of non-covalent interactions were also present, quantum chemical calculations on model systems were used to reveal and quantitatively describe the influence of halogen bonds on the electrostatic potential of selected HEM molecules. These results could be used for the design of new classes of halogen-containing high energetic molecules with reduced sensitivities towards detonation.

中文翻译：

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卤素键作为设计高能材料的工具：来自晶体结构和量子化学计算的证据

分子表面中心区域的正静电势是高能材料 (HEM) 的主要特征之一，决定了它们对爆炸的敏感性。在从剑桥结构数据库中提取的晶体结构中并通过量子化学计算研究了卤素键对所选 HEM 分子静电势值的影响。对包含卤素取代的 2,4,6-三硝基苯基片段的晶体结构中的卤素键的分析表明，这些基团形成卤素键（183 个触点）。对从晶体结构中提取的非卤素键合和卤素键合 HEM 分子的几何形状计算的静电势图的分析表明，卤素键合改变了这些化合物中心的静电势。由于在选定的晶体结构中还存在其他类型的非共价相互作用，因此使用模型系统的量子化学计算来揭示和定量描述卤素键对选定 HEM 分子静电势的影响。这些结果可用于设计新类别的含卤素高能分子，对爆炸的敏感性降低。