摘要
对三种二氨基二硝基乙烯同分异构体进行了HF/ 6- 3 1G 水平、DFT -B3LYP/ 6- 3 1G 水平的几何全优化以及MP2 / 6- 3 1G / /HF/ 6- 3 1G 水平的总能量计算 .结果表明 ,1,1-二氨基 - 2 ,2 -二硝基乙烯 (Ⅰ )总能量比顺式 (Ⅱ )和反式 (Ⅲ ) 1,2 -二氨基 - 1,2 -二硝基乙烯的总能量低 ,即热力学稳定性次序为Ⅰ >Ⅲ >Ⅱ .分子的共轭性和分子内氢键的强度次序为Ⅰ≈Ⅲ >Ⅱ ,前沿轨道能级差次序为Ⅰ >Ⅱ >Ⅲ ,也均表明 (Ⅰ )最稳定 .此外还计算研究了标题物的红外光谱 ;化合物Ⅰ的理论计算值与实验值良好相符 .
1,1 - Diamino - 2,2 - dinitroethylene recently synthesized is a new energetic compound, which may be an insensitive high explosive (ME). In this paper, the fully optimized molecular geometries and the total energies of diamino - dinitroethylene compomnds, 1,1 - diamino - 2,2 - dinitroethylene ( I), cis ( II) and trans (III) 1,2 - diamino - 1,2 - dinitroethylene, have been calculated using ab initio method at the HF/6 - 31G**, MP2/6 - 31G**//HF/6 - 31G** level and DFT method at B3LYP/6 - 31G** level, respectively. The result shows that the order of stability of the title compounds is I > III > II, thermodynamically. There exist strong intramolecular hydrogen bonds between nitro oxygen atoms and amino hydrogen atoms of the titled compounds and the hydrogen bond intensities of the title compounds are I > III > II. Their frontier orbital energy gaps (DeltaE) are I > II > III. Based on the analysis of molecular geometry and frontier orbital component, it is found that the pi - electron conjunction and delocalization of the title compounds are I approximate to III > II. The computed vibrational frequencies of 1,1 - diamino - 2,2 - dinitroethylene is in good agreement with the corresponding experiment results. The thermodynamic properties of DADNE were
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2001年第1期39-47,共9页
Acta Chimica Sinica
基金
中国工程物理研究院自然科学基金 ( 990 5 330 )资助项目
