基于含时密度泛函理论的对位卤代二苯醚电子跃迁机理

姜龙; 曾娅玲; 蔡啸宇; 李鱼

doi:10.3788/fgxb20143505.0627

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基于含时密度泛函理论的对位卤代二苯醚电子跃迁机理

发光学应用及交叉前沿 | 更新时间：2020-08-12

- 基于含时密度泛函理论的对位卤代二苯醚电子跃迁机理
- Electron Transition Mechanism of para-Halogenated Diphenyl Ethers Based on TD-DFT
- 发光学报 2014年35卷第5期页码：627-636
- 作者机构：
  
  1. 华北电力大学资源与环境研究院北京,102206
  2. 华北电力大学区域能源系统优化教育部重点实验室北京,102206
- 作者简介：
- 基金信息：
  
  &ldquo();十一五&rdquo();科技支撑项目（2008BAC43B01）();2013中央高校基本科研业务专项资金（JB2013146）资助项目()
- DOI：10.3788/fgxb20143505.0627
  中图分类号： X592;O657.3
- 收稿日期：2014-01-11，
  
  修回日期：2014-02-18，
  
  纸质出版日期：2014-05-03
- 稿件说明：
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姜龙, 曾娅玲, 蔡啸宇等. 基于含时密度泛函理论的对位卤代二苯醚电子跃迁机理[J]. 发光学报, 2014,35(5): 627-636

JIANG Long, ZENG Ya-ling, CAI Xiao-yu etc. Electron Transition Mechanism of <em>para</em>-Halogenated Diphenyl Ethers Based on TD-DFT[J]. Chinese Journal of Luminescence, 2014,35(5): 627-636
姜龙, 曾娅玲, 蔡啸宇等. 基于含时密度泛函理论的对位卤代二苯醚电子跃迁机理[J]. 发光学报, 2014,35(5): 627-636 DOI： 10.3788/fgxb20143505.0627.

JIANG Long, ZENG Ya-ling, CAI Xiao-yu etc. Electron Transition Mechanism of <em>para</em>-Halogenated Diphenyl Ethers Based on TD-DFT[J]. Chinese Journal of Luminescence, 2014,35(5): 627-636 DOI： 10.3788/fgxb20143505.0627.

摘要

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。

Abstract

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.

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references

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