苯并1,2,3,4-四嗪-1,3-二氧化物(BTDO)及其硝基衍生物爆轰性能的量子化学研究  

Quantum chemistry studies on the detonation property of the nitro derivations of benzo-1,2,3,4-tetrazine-1,3-dioxide

作　　者：褚玉婷[1,2] 魏文杰[2] 石文艳[1] 

机构地区：[1]化学化工学院盐城工学院,江苏盐城224000 [2]南京理工大学化工学院,江苏南京210094

出　　处：《计算机与应用化学》2015年第9期1117-1120,共4页Computers and Applied Chemistry

基　　金：江苏省自然科学基金(BK20140466)

摘　　要：用密度泛函理论的B3LYP方法,在6-31G*的基础上,全优化计算了苯并1,2,3,4-四嗪-1,3-二氧化物及其硝基衍生物的几何构型,包括其与5-硝基取代物,7-硝基取代物和5.7-二硝基取代物,分别用(1),(2),(3),(4)表示。通过PM6方法计算出物质的生成热,并研究了热力学参数和温度的关系式。用Monto-Carlo方法,基于0.001 e.born-3等电子密度面包围的空间求得分子平均摩尔体积和理论密度,用Kamlet-Jacobs方程基于理论密度和生成热计算各物质的爆热,爆速和爆压。结果表明:苯并1,2,3,4-四嗪-1,3-二氧化物上的苯环发生硝基取代后,5位取代比7位取代的C-NO2更容易发生断键,5,7-二硝基苯并1,2,3,4-四嗪-1,3-二氧化物的生成热和爆轰性能最好,其值接近于环三亚甲基三硝胺(RDX)。4种物质的生成热的大小顺序是(4)>(2)>(1)>(3),说明5位硝基取代后能有效地增大物质的生成热。爆轰性能的大小顺序是(4)>(2)>(3)>(1),说明硝基基团能有效地增大物质的爆轰性能,且对苯并1,2,3,4-四嗪-1,3-二氧化物来说,5位取代的效果要比7位取代好。Density functional theory （DFT） method was used to study the structure of benzo-l,2,3,4-tetrazine-l,3-dioxide（BTDO） and its derivatives on the B3LYP/6-31G＊ level, including it and 5-nitro substitute, 7-nitro substitute and 5.7-dinitro substitute. They are marked as （1）, （2）, （3） and （4）. The heats of formation （HOFs） of the substances was calculated by the PM6 method and the relationship of the thermodynamic properties and temperature were studied. The theoretical density was estimated by Monto-Carlo method. The heats of explosion, detonation velocity and detonation pressure were calculated by Kamlet-Jacobs equation. It is found that the bond of C-NO2 is easier to break when the nitro substituted on benzene ring at position 5 than at position 7 of benzo-1,2,3,4-tetrazine-l,3-dioxide. 5,7-binitro- benzo-l,2,3,4- tetrazine-l,3-dioxide has the best heat of formation and detonation properties, and the value is close to 1,3,5-trinitro-l,3,5-triaznane （RDX）. The HOFs of the four compounds is obey the order （4） 〉 （2） 〉 （1） 〉 （3）, this means the HOF can be enhanced when there is a nitro-group in 5-position. The detonation properties of the four compounds is obey the order （4） 〉 （2） 〉 （3） 〉 （1）, this means the nitro-group is propitious to enhance the detonation properties of the compounds. The 5-position nitro substitute is better than 7-position for BTDO.

关 键 词：密度泛函理论 爆速 爆压 

分 类 号：O641.12[理学—物理化学]