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Theoretical study on intra-molecule interactions in TKX-50
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2023-09-14 , DOI: 10.1039/d3cp03564f
Chunhai Yang 1 , Xue Li 2 , Ning Zhou 2 , Huilong Dong 1 , Xiuli Hu 1 , Junxun Jin 1 , Tao Huang 1 , Jinhui Wang 3
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2023-09-14 , DOI: 10.1039/d3cp03564f
Chunhai Yang 1 , Xue Li 2 , Ning Zhou 2 , Huilong Dong 1 , Xiuli Hu 1 , Junxun Jin 1 , Tao Huang 1 , Jinhui Wang 3
Affiliation
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To fully and deeply understand the weak interactions in the gaseous structure of the TKX-50 molecule, two conformations I and II of the TKX-50 molecule confirmed in a crystal cell were optimized at the B3LYP/6-311g(d,p) level in the gas state, and the single point energy of the optimized structure was calculated at the M06-2X/ma-TZVPP level. Analyzing methods for weak interactions such as the interaction region indicator (IRI), topological basin analysis, and the extended transition state-natural orbitals for chemical valence (ETS-NOCV) theory with the help of Multiwfn code were employed to reveal the corresponding intramolecular weak interactions. The results showed that there were 5 kinds of intramolecular weak interaction in both conformations. They are two types of H bond, two types of intra-ring weak interaction, and one type of O–N bond within the molecular fragment containing the bis-tetrazole ring. The combined effect of all these weak interactions holds the bis-tetrazole ring of TKX-50 retaining an almost coplanar configuration. Meanwhile, the strength of these weak interactions is significantly different in conformation I and conformation II. The most obvious difference is that conformation II has a significant H transfer between intramolecular fragments due to the mirror rotation of almost 180° of cations (NH3OH)+ perpendicular to the N–O bond axis thereof as compared to the reference conformation I. This conformational difference not only makes the weak interaction between the two conformations very different but also forms a quasi-covalent bond in conformation II with much larger bonding energy than other H bonds, thus resulting in conformation II having lower electron energy and more stable geometry. In addition, the order of breaking various H bonds in the combustion decomposition process of TKX-50 is deduced by comparing various H bonds.
中文翻译：
TKX-50分子内相互作用的理论研究
为了全面深入地了解TKX-50分子气态结构中的弱相互作用，在B3LYP/6-311g(d,p)水平上对晶胞中确认的TKX-50分子的两种构象I和II进行了优化在气态下，计算了M06-2X/ma-TZVPP水平下优化结构的单点能量。借助Multiwfn代码，采用相互作用域指示符（IRI）、拓扑盆地分析、化学价扩展过渡态自然轨道（ETS-NOCV）理论等弱相互作用分析方法来揭示相应的分子内弱相互作用互动。结果表明，两种构象均存在5种分子内弱相互作用。它们是含有双四唑环的分子片段内的两种H键、两种环内弱相互作用和一种O-N键。所有这些弱相互作用的综合作用使 TKX-50 的双四唑环保持几乎共面的构型。同时，这些弱相互作用的强度在构象I和构象II中显着不同。最明显的区别是，与参考构象I相比，构象II由于几乎180°的阳离子（NH 3 OH）+垂直于其N-O键轴的镜像旋转而在分子内片段之间具有显着的H转移。这种构象差异不仅使两种构象之间的弱相互作用截然不同，而且在构象II中形成了比其他氢键键能大得多的准共价键，从而导致构象II具有更低的电子能量和更稳定的几何结构。另外，通过比较各种H键，推导出TKX-50燃烧分解过程中各种H键断裂的顺序。
更新日期：2023-09-14
中文翻译：
TKX-50分子内相互作用的理论研究
为了全面深入地了解TKX-50分子气态结构中的弱相互作用，在B3LYP/6-311g(d,p)水平上对晶胞中确认的TKX-50分子的两种构象I和II进行了优化在气态下，计算了M06-2X/ma-TZVPP水平下优化结构的单点能量。借助Multiwfn代码，采用相互作用域指示符（IRI）、拓扑盆地分析、化学价扩展过渡态自然轨道（ETS-NOCV）理论等弱相互作用分析方法来揭示相应的分子内弱相互作用互动。结果表明，两种构象均存在5种分子内弱相互作用。它们是含有双四唑环的分子片段内的两种H键、两种环内弱相互作用和一种O-N键。所有这些弱相互作用的综合作用使 TKX-50 的双四唑环保持几乎共面的构型。同时，这些弱相互作用的强度在构象I和构象II中显着不同。最明显的区别是，与参考构象I相比，构象II由于几乎180°的阳离子（NH 3 OH）+垂直于其N-O键轴的镜像旋转而在分子内片段之间具有显着的H转移。这种构象差异不仅使两种构象之间的弱相互作用截然不同，而且在构象II中形成了比其他氢键键能大得多的准共价键，从而导致构象II具有更低的电子能量和更稳定的几何结构。另外，通过比较各种H键，推导出TKX-50燃烧分解过程中各种H键断裂的顺序。
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