高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (5): 965-972.doi: 10.7503/cjcu20180851

• 物理化学 • 上一篇    下一篇

卟啉-碳硼烷-硼亚甲基二吡咯三元化合物二阶非线性光学性质的理论研究

康慧敏, 王洪强, 王慧莹, 吴黎歆, 仇永清()   

  1. 东北师范大学化学学院, 功能材料化学研究所, 长春 130024
  • 收稿日期:2018-12-20 出版日期:2019-04-17 发布日期:2019-04-17
  • 作者简介:

    联系人简介: 仇永清, 男, 博士, 教授, 博士生导师, 主要从事应用量子化学研究. E-mail: qiuyq466@nenu.edu.cn

  • 基金资助:
    吉林省教育厅“十二五”科学技术研究规划项目(批准号: 吉教科合字[2016]第494号)资助.

Theoretical Study on the Second-order Nonlinear Optical Properties of a Porphyrin-o-Carborane-Boron-dipyrromethene Triad Compound

KANG Huimin, WANG Hongqiang, WANG Huiying, WU Lixin, QIU Yongqing*()   

  1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
  • Received:2018-12-20 Online:2019-04-17 Published:2019-04-17
  • Contact: QIU Yongqing E-mail:qiuyq466@nenu.edu.cn
  • Supported by:
    † Supported by the “12th Five-Year” Science and Technology Research Project of the Education Department of Jilin Province, China(No.[2016]494)

摘要:

采用密度泛函理论(DFT)方法对卟啉-碳硼烷-硼亚甲基二吡咯(BODIPY)三元化合物的几何结构、 吸收光谱及二阶非线性光学(NLO)特性进行计算分析. 结果表明, V型化合物的静态第一超极化率(βtot)大于相应直线型化合物, 且延长共轭链可提高体系的βtot. 分析体系的电子密度差分图得出, 化合物氧化还原态的电荷转移方式与本征态相比发生了改变, 从而使其二阶NLO性质发生明显变化. 含频第一超极化率计算结果表明, 在一定范围内频率对化合物有较小的色散效应. 因此, 通过延长二维化合物的共轭链及氧化还原反应, 可以有效调控其二阶NLO响应.

关键词: 硼亚甲基二吡咯三元化合物, 氧化还原, 二阶非线性光学性质, 密度泛函理论

Abstract:

The calculations of geometric structures, electronic absorption spectra, second-order nonlinear optical(NLO) properties of porphyrin-o-carborane-boron-dipyrromethene(BODIPY) triad were carried out by density functional theory(DFT). The results show that the static first hyperpolarizability(βtot) of the V-shaped compound is larger than that of the linear-shaped compound, and the βtot values can be enhanced by extending π-conjugate bridge. The analysis of electron density difference maps can be seen that the charge transfer pattern of the oxidized/reduced species have changed, which lead to the second-order NLO properties have significantly varied. The investigation of the frequency-dependent first hyperpolarizability shown that less dispersion effect at restrictive frequency region for all of the compounds. Therefore, second-order NLO properties can be effectively modulated by extending π-conjugate bridge and oxidized/reduced reactions.

Key words: Boron-dipyrromethene(BODIPY) triad compound, Redox, Nonlinear optical property, Density functional theory

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