高等学校化学学报

高等学校化学学报

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1,3-二氮杂薁类衍生物电子结构和光谱性质的理论研究

李满宇1,2, 朱耘玑2, 艾希成2, 孙萌涛3, 张建平2   

    1. 北京分子科学国家实验室, 分子动态与稳态结构国家重点实验室, 中国科学院化学研究所, 北京 100080;
    2. 中国人民大学理学院化学系, 北京 100872;
    3. 北京凝聚态物理国家实验室, 中国科学院物理研究所, 北京 100080
  • 收稿日期:2007-12-06 修回日期:1900-01-01 出版日期:2008-11-10 发布日期:2008-11-10
  • 通讯作者: 艾希成

Theoretical Studies on Electronic Structures and Spectroscopic Properties of 1,3-Diazaazulene Derivatives

LI Man-Yu1,2, ZHU Yun-Ji2, AI Xi-Cheng2*, SUN Meng-Tao3, ZHANG Jian-Ping2   

    1. Beijing National Laboratory for Molecular Science(BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China;
    2. Department of Chemistry, Collegc of Sciences, Renmin University of China, Beijing 100872, China;
    3. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100080, China
  • Received:2007-12-06 Revised:1900-01-01 Online:2008-11-10 Published:2008-11-10
  • Contact: AI Xi-Cheng

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被引次数

2

摘要： 对1,3-二氮杂薁类衍生物采用密度泛函理论(DFT)在B3LYP/6-31G(d)的水平上进行了几何构型的全优化, 在此基础上探讨了分子结构和前线分子轨道能量等性质的变化规律, 采用含时密度泛函理论(TD-DFT)计算了分子的电子跃迁性质, 采用二维平面图和三维立体图来直观表示激发态的性质, 研究分子内电子转移特性. 跃迁密度矩阵的二维等高线图反映了电子-空穴相干性, 三维跃迁密度图反映了跃迁偶极矩的方向和强度, 三维电荷差异密度图说明了激发过程中分子内电子转移性质.

关键词: 1,3-二氮杂薁, 分子内电子转移, 跃迁密度, 电荷差异密度, 电子-空穴相干性

Abstract: The geometries of four different kinds of 1,3-diazaazulene derivatives were fully optimized with Density Function Theory(DFT) at B3LYP/6-31G(d) level, on basis of which the energies of frontier molecular orbitals and the energy gap were investigated and the electronic transition properties were calculated with time-dependent DFT(TD-DFT) at the same level. The excited-state properties and the intra-molecular charge transfer(ICT) character were investigated with the two-dimensional(2D) and three-dimensional(3D) real space analysis methods. The electron-hole coherence is investigated with 2D contour plots of transition density matrix. The orientation and strengths of absorptive transition dipole moment are obtained by 3D transition density(TD). The ICT orientations are obtained with 3D charge difference density(CDD).

Key words: 1,3-Diazaazulene derivative, Intra-molecular charge transfer, Transition density(TD), Charge difference density(CDD), Electron-hole coherence

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