碳酰肼异构体及其晶体的密度泛函理论研究  

Study on the Isomers and Crystal of Carbohydrazide by Density Functional Theory

作　　者：黄辉胜[1] 张建国[1] 张同来[1] 王丽琼[1] 

机构地区：[1]北京理工大学爆炸科学与技术国家重点实验室,北京100081

出　　处：《含能材料》2009年第3期255-259,共5页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(No.20471008);北京理工大学爆炸科学与技术国家重点实验室开放基金(No.KFJJ08-06)

摘　　要：对碳酰肼(CHZ)异构体及其晶体进行了DFT-B3LYP/6-31G**理论水平的计算研究。讨论了各种异构体的优化几何构型、振动频率、NBO电荷、前线轨道能级以及晶体的能带结构和态密度分布。研究结果表明,异构体Ⅱ的总能量最低,前线轨道能级差最大,故其稳定性最好。同时该异构体的优化几何构型与碳酰肼的实测分子几何构型一致,这表明碳酰肼在晶体生长过程中优先选择稳定性最好的几何构型。由电荷分布得知碳酰肼的羰基氧原子和肼基的端位氮原子易于配位,这与实验事实相符。此外,晶体中存在较强的分子间相互作用,各类原子对其前线轨道的组成均有贡献,并且部分前沿能带曲线起伏较大,表明相应的分子轨道能态受晶体场的影响较大。The gaseous isomers and crystalline state of carbohydrazide （CHZ） were studied at the DFT-B3LYP/6-31G^＊＊ level. Three stable isomers were located. The strueture Ⅱ ,which is in agreement with the structure in the crystal,is the most stable. The vibrational frequencies were analyzed and they agree well with the experimental results. The terminal nitrogen atom of the hydrazine group and oxygen atom of the carbonyl group are preferable coordination sites for CHZ molecule and this was demonstrated by the experimental results. The intermoleeular interaction is strong in the crystal. Furthermore,all of the atoms have eontributions to the frontier bands. Some bands are very oscillatory,which show that the corresponding molecular orbitals are strongly perturbed by the crystalline environment.

关 键 词：物理化学 碳酰肼 电子结构 能带结构 态密度 密度泛函理论 

分 类 号：O621.1[理学—有机化学]