摘要
在B3LYP/6 31++G 理论水平上优化了一系列多硝基吡啶的几何构型,计算了它们的电子结构、分子摩尔体积和标准摩尔热力学性质。结果表明,在吡啶的2、6位引入硝基,环上C—N键变短,而在吡啶的3、4位引入硝基和2、6位引入氨基都对环上C—N键影响很小。氨基的引入可使与C—NH2相邻的C—NO2键级增大。在B3LYP/6 31++G 水平上,Mulliken集居数分析方法不适合于吡啶类化合物原子净电荷的计算,而自然集居数分析方法是比较适用的。3,5 二氨基 2,4,6 三硝基吡啶的理论计算密度达到了2.2g·cm-3,并且它的C—NO2键级略小于DATB,预示着其为高密度低感高能炸药。
The geometries of polynitropyridines have been fully optimized at the level of B3LYP/6-31++G^(**). The electronic structures,the molar volumes,and the standard molar thermodynamic functions for these polynitropyridines have been calculated at the same level. Calculated results show that the C—N bonds in the pyridine ring shorten as —NO_2 groups are introduced into the 2 and 6 sites of pyridine ring and change slightly as the 3 and 4 positions are occupied by (—NO_2 ) groups and the 2 and 6 positions by —NH_2 groups. For polynitropyridines the introduction of —NH_2 group can increase the bond order of the neighboring C—NO_2 bond. At the B3LYP/6-31++G^(**) level,Mulliken population analysis is not suitable for the calculation of atomic charges of polynitropyridines,but natural population analysis can be applicable for it. For 3,5-diamino-2,4,6-trinitropyridine the predicted density reaches 2.2 g ·cm^(-3),and the smallest bonder order of C—NO_2 bonds is slightly smaller than that of DATB,implying that 3,5-diamino-2,4,6-trinitropyridine is a high density,low-sensitive explosive.
出处
《含能材料》
EI
CAS
CSCD
2003年第4期177-181,共5页
Chinese Journal of Energetic Materials
基金
中国工程物理研究院重大基金项目资助(2002Z0501)
关键词
多硝基吡啶
密度泛函理论
物理化学
低感炸药
热力学性质
键级
physical chemistry
polynitropyridine
density functional theory
bond order
thermodynamic property
