Gu Zhihui, Bo Mengjie, Gao Zikai, Ma Congming, Ma Peng
College of Safety Science and Engineering, Nanjing Tech University, Nanjing, 210009, China.
J Mol Model. 2025 Feb 3;31(3):74. doi: 10.1007/s00894-025-06289-9.
Considering the excellent properties of 1,2,3,4-tetrazine-1,3-dinitroxides, several types of energetic derivatives have been synthesized from them. Among them, [1,2,5] oxadiazolo [3,4-e] [1,2,3,4]-tetrazine-4,6-Di-N-dioxide (FTDO), 5,7-dinitrobenzo-1,2,3,4-tetrazine-1,3-nitrogen dioxide (DTND), and [1,2,3,4] tetrazino [5,6-e] [1,2,3,4] tetrazine-1,3,8-tetraoxide (TTTO) are considered excellent energetic materials. However, there is limited research on their behavior under electric fields. The effect of electric fields was studied using density functional theory to calculate trigger bond changes, strain energy, chemical reactivity, and surface electrostatic potential. The results indicate that the planar structure of FTDO is more unique than that of DTND and TTTO, and its trigger bond is located at special position. Increased electric field strength can lengthen the trigger bond, increase sensitivity, and reduce strain energy of FTDO. Under a positive electric field, DTND and TTTO have longer trigger bond lengths, increased sensitivity, and increased strain energy, while exhibiting the opposite behavior under a negative electric field. Electric fields can affect the chemical reactivity of the all three derivatives. FTDO is less active under positive electric fields, DTND is more active under both electric fields, and TTTO becomes more active under negative electric fields. Finally, the electric field can expand their absorption spectrum range, affecting electron transfer between fragments.
All calculations in this article were completed on Gaussian 16 software. The calculation levels are B3LYP/6-311G**, B3LYP/Def2-TZVPP, and PBE1PBE/6-311G**. Multiwfn and VMD were used for wave function analysis. Electric fields have a strength range of - 0.02 to 0.02 a.u., with a growth gradient of 0.01 a.u.
鉴于1,2,3,4 - 四嗪 - 1,3 - 二氧化物具有优异的性能，已由它们合成了几种类型的含能衍生物。其中，[1,2,5]恶二唑并[3,4 - e][1,2,3,4] - 四嗪 - 4,6 - 二 - N - 二氧化物（FTDO）、5,7 - 二硝基苯并 - 1,2,3,4 - 四嗪 - 1,3 - 二氧化氮（DTND）和[1,2,3,4]四嗪并[5,6 - e][1,2,3,4]四嗪 - 1,3,8 - 四氧化物（TTTO）被认为是优异的含能材料。然而，关于它们在电场作用下行为的研究有限。利用密度泛函理论研究电场对引发键变化、应变能、化学反应活性和表面静电势的影响。结果表明，FTDO的平面结构比DTND和TTTO更独特，其引发键位于特殊位置。电场强度增加可使FTDO的引发键变长、敏感性增加并降低应变能。在正电场下，DTND和TTTO的引发键长度更长、敏感性增加且应变能增加，而在负电场下表现出相反的行为。电场会影响这三种衍生物的化学反应活性。FTDO在正电场下活性较低，DTND在两种电场下活性较高，TTTO在负电场下活性增加。最后，电场可扩展它们的吸收光谱范围，影响片段间的电子转移。
本文所有计算均在高斯16软件上完成。计算水平为B3LYP/6 - 311G**、B3LYP/Def2 - TZVPP和PBE1PBE/6 - 311G**。使用Multiwfn和VMD进行波函数分析。电场强度范围为 - 0.02至0.02 a.u.，增长梯度为0.01 a.u.
