【作者】 苗体方；

【导师】 张敬来；

【作者基本信息】 河南大学 ， 高分子化学与物理， 2003， 硕士

【摘要】 本论文包括三部分内容。第一部分是关于具有共轭π电子体系的化合物的从头算研究；第二部分是关于N-丙烯酰基吩噻嗪及其氧化物的从头算研究；第三部分是关于草酰胺桥联配合物的从头算研究。第一部分用量子化学从头算方法，采用不同的基组，对具有共轭(电子体系化合物进行了理论研究，优化了它们的几何构型，在此基础上，并作了振动频率分析；计算了其总能量、前沿轨道能量，分析了它们的热力学和动力学稳定性；在-180～180o的范围内，计算得到了它们的旋转势能曲线，找到了各化合物的稳定构型和过渡构型。用PM3/CIS方法，计算了各化合物的电子光谱，所有计算结果和实验值符合的较好。通过前四章的计算，可以看出，平面性的差异是光谱性质差别的主要原因。第五章是对N、N、-二苯基- N、N、-二（1-萘基）-1，5-萘二胺的研究，优化了其几何构型,分析了其热力学和动力学稳定性,最后,计算了其电离势和电子光谱.所有计算结果和实验值符合的较好。第二部分本部分用量子化学从头算方法，对N-丙烯酰基吩噻嗪及其氧化物进行了理论研究，优化了其平衡几何构型，计算了它们的谐振动频率、电子吸收光谱，分析了静电荷。这些结果对探讨N-丙烯酰吩噻嗪及其氧化合物引发丙烯腈聚合的引发机理是有益的。第三部分用密度泛函方法，对配合物C18H12CuN4O2、CuCo(TS)(H2O)和Cu(Ⅱ)-VO(Ⅱ)进行了理论研究，优化了平衡几何构型，计算了静电荷及电子自旋布居，分析了前线轨道的组成，探讨了磁偶合机理，从理论上预测了磁偶合常数。更多还原

【Abstract】 This paper includes three parts: Ab initio study on conjugating πelectron compounds in the first part; Ab initio study on N-acrylyl-phenothiazine and its oxide in second part; Ab initio study on the Oxalamide-bridged coplex in the third part.The first PartConjugating πelectron compounds have been carried out with Ab initio calculation at different levels. The equilibrium geometries have been optimized and the harmonic vibrational frequencies have been calculated, their total energies and frontier obital energies were obtained and their thermodynamic and dynamic stability were nanlysed. From -180.0o to 180.0o, their potential energy curves were obtained to find the ground states and transition geometries. At PM3/CIS level, their electronic spectrums were calculated and the vertical excitation energies and corresponding oscillator strengths from the ground states to the excited states were obtained. These results are in good agreement with the results obtained from experiment. By calculation of front four chapters we can know that the change of spectrum is mainly due to different plane. 1,5-bis[N-(1-naphthy)-N-phenyl]naphthalene diamine has been studied in the fifth chapter. The equilibrium geometries have been optimized, their<WP=4>thermodynamic and dynamic stability were nanlysed. In the end, their electronic spectrums and ionization potentials were calculated. These results are in good agreement with the results obtained from experiment.The second PartN-acrylyl-phenothiazine and its oxide have been studied on with Ab initio calculation in this part. The equilibrium geometries have been optimized, the harmonic vibrational frequencies, the vertical excitation spectras have been calculated and total atomic charges were nanlysed. These results will be help to explore the mechanism for the photopolymerization of propenenitrile sensitized by N-acrylyl-phenothiazine .The third PartComplexs C18H12CuN4O2 、CuCo(TS)(H2O) and Cu(Ⅱ)-VO(Ⅱ) have been studied on with density functional theory(DFT) calculations . The equilibrium geometries of the Complex were optimized. We calculated the total atomic charges and spin populations, nanlysed the constitution of the frontier orbitals and discussed the magnetic coupling mechanism. On base of theory we can forcast magnetic coupling contants.更多还原