基于含时密度泛函理论的对位卤代二苯醚电子跃迁机理

以二苯醚（DE）为参照物，借助Gaussian软件的量子化学计算并结合自然键理论与跃迁密度矩阵平面图对9种对位卤代二苯醚的基态分子活性、紫外光谱及基态-激发态电子跃迁机理进行了对比分析。研究结果表明：处于基态时的DE与4，4’-二氯二苯醚（CDE-15）分别最易发生亲电/核反应，对位卤代基的引入缩小了DE的能级差。随着取代基体积的增大，对位取代二苯醚紫外光谱的最大吸收波长变大，吸收增强。所研究的10种物质有着相似的跃迁机理。

Electron Transition Mechanism of para-Halogenated Diphenyl Ethers Based on TD-DFT

Taking diphenyl ether (DE) as the reference, the molecule activity on ground state, ultraviolet spectrum and ground-excited state electron transitions mechanism of other 9 para-halogenated diphenyl ethers were analyzed by the combination of Gaussian 09 software calculation, natural bond orbital theory, and transition density matrix. The results show that DE is most vulnerable to electrophilic substances in the ground state, meanswhile, CDE-15 is vulnerable to nucleophilic substances to lose electrons. The introduced para-halogen substituent can reduce the energy gap of DE, while the maximum absorption wavelength and absorption intensity of DE increase with the volume of substituents. Nine kinds of halogenated diphenyl ethers and DE have the similar ground-excited state electron transition mechanism.