摘要
用密度泛函理论的B3LYP方法,在6-31G*基组水平上,全优化计算了呋咱和氧化呋咱及其衍生物的几何构型,通过G3方法和设计等键反应计算出各物质的生成热(HOF),用Monte-Carlo方法,基于0.001 e·bohr3等电子密度面所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出各物质的爆热、爆速和爆压。结果表明:当呋咱环上配位氧原子成为氧化呋咱环后,与配位氧原子相邻的N-O键容易成为引发键,氧化呋咱环容易开环,而三唑环比氧化呋咱环更容易开环;9种化合物中呋咱并[3,4-e]-1,2,3,4-四嗪-1,3-二氧化物(FTDO)的生成热最大,爆轰性能最好,其次是四嗪并氧化呋咱和三唑并氧化呋咱,其生成热和爆轰性能优于呋咱类衍生物,且优于苯环并呋咱和苯环并氧化呋咱。说明化合物的含氮量和含氧量越高,氧平衡值越接近零,其爆轰性能越好。
The structures of fiJrazan, furoxan and their derivatives were studied with the density functional theory（DFT） method at B3LYP/ 6-31 G＊ level.The HOFs of the substances were calculated by the G3 method and isodesmic reactions. The theoretical density was estimated by Monte-Carlo method. The heats of explosion, detonation velocities and detonation pressure were calculated by Kamlet-Jacobs equation. It is found that the N-O bond adjacent to the coordinated oxygen atom is easier to break than in the ring of furazan. The ring of furoxan is easy to open and the ring of trizole is easier. The heat of formation （HOF） and the detonation properties of [1,2,5] oxadiazole[3,4-e] [1,2,3,4]-.tetrazine-4,6-di-N-dioxide（FTDO） is best in the nine substances. The next better are trizolefuroxan and tetrazanefuroxan. The HOFs and the detonation properties of trizolefuroxan and tetrazanefuroxan are better than the derivatives of furazan, and they are better than benzofurazan and benzofuroxan. This indicates that the HOF and detonation properties are better when the nitrogen content and oxygen content of the substance is higher and the oxygen balance is closer to zero.
出处
《计算机与应用化学》
CAS
2015年第9期1135-1139,共5页
Computers and Applied Chemistry
基金
江苏省自然科学基金(BK20140466)
关键词
呋咱和氧化呋咱
密度泛函理论
生成热
爆速
爆压
furazan and furoxan
density functional theory
heat of formation
detonation velocity
detonation pressure
