摘要：本文合成了3-(2, 6-二氯苄基)-5-甲基-N-硝基-1, 3, 5-噁二嗪-4-亚胺(DNOI)，通过X射线单晶衍射、FT-IR、FT-Raman 和UV-Vis对其进行表征。CCD分析显示，由于存在分子间氢键的缘故，DNOI是一维结构。苯环和噁二嗪环不在一个平面，呈扭曲状。利用密度泛函方法(B3LYP, B3P86, M062X)，6-311++G(d, p) 基组对化合物进行了几何结构的优化和振动频率的计算。分别利用TD-B3LYP/6-311++G(d, p) 和PCM-B3LYP/6-311++G(d, p) 方法计算标题化合物在气相和甲醇溶液中的吸收光谱，计算结果发现理论值与实验值吻合。确定了在100-1000K 的温度范围内热力学函数与温度的关系，并对成键轨道的占有率、自然键轨道的贡献和自然原子杂化的问题进行了计算和讨论。52289

毕业论文关键词：密度泛函理论，振动光谱，电子光谱，自然键轨道，3-(2, 6-二氯苄基)-5-甲基-N-硝基-1, 3, 5-噁二嗪-4-亚胺

Abstract: 3-(2, 6-dichlorobenzyl)-5-methyl-N-nitro-1, 3, 5-oxadiazinan-4-imine (DNOI) was synthesized and characterized by X-ray diffraction, FT-IR, FT-Raman and UV-Vis spectra. The X-ray diffraction study showed that DNOI has a one dimensional configuration, due to the intermolecular C9H···O1 and N4H···O2 hydrogen bonds. The benzene ring and the oxadiazine rings are tilted with respect to each other. Vibrational spectra and electronic spectra measurements were made for the compound. Optimized geometrical structure and harmonic vibrational frequencies were computed with DFT (B3LYP, B3P86 and M062X) methods using 6-311++G(d, p) basis set. Assignments of the observed spectra were proposed. The equilibrium geometries computed by all of the methods were compared with X-ray diffraction results. The absorption spectra of the title compound were computed both in gas phase and in CH3OH solution using TD-B3LYP/6-311++G(d, p) and PCM-B3LYP/6-311++G(d, p) approaches, respectively. The calculated results provide a good description of positions of the bands maxima in the observed electronic spectrum. Temperature dependence of thermodynamic parameters in the range of 100-1000K were determined. The bond orbital occupancies, contribution from parent natural bond orbital (NBO), the natural atomic hybrids were also calculated and discussed.

Keywords: density functional theory, vibrational spectra, electronic spectra, natural bond orbital, 3-(2, 6-dichlorobenzyl)-5-methyl-N-nitro-1, 3, 5-oxadiazinan-4-imine

目  录

1  引言 4

2  实验与计算 4

2.1  实验部分 4

2.1.1  DNOI的合成 4

2.1.2  DNOI的表征 4

2.2  计算方法 5

3  结果与讨论 5

3.1  DNOI的几何结构 5

3.2  振动归属 8

3.2.1  CH振动模式 16

3.2.2  环振动模式 17

3.2.3  CCl振动模式 17

3.2.4  NO2振动模式 17

3.3电子性质 18

3.4  分子静电势 19

3.5  热力学性质 20

3.6  自然键轨道分析 21

3.7  全局和局域反应性能指数 26

结  论 27

参考文献