物理化学学报 >> 2010, Vol. 26 >> Issue (04): 1051-1058.doi: 10.3866/PKU.WHXB20100420

量子化学及计算化学 上一篇    下一篇

14族杂环戊二烯分子(硅、锗、锡)的电子结构与光谱性质

邓春梅, 牛英利, 彭谦, 帅志刚   

  1. 中国科学院化学研究所, 北京分子科学国家实验室, 有机固体院重点实验室, 北京 100190; 清华大学化学系, 北京 100084
  • 收稿日期:2009-12-16 修回日期:2010-01-25 发布日期:2010-04-02
  • 通讯作者: 彭谦, 帅志刚 E-mail:qpeng@iccas.ac.cn; zgshuai@tsinghua.edu.cn

Electronic Structures and Spectroscopic Properties of Group-14 Metalloles MPh6 (M=Si, Ge, Sn)

DENG Chun-Mei, NIU Ying-Li, PENG Qian, SHUAI Zhi-Gang   

  1. Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China; Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China
  • Received:2009-12-16 Revised:2010-01-25 Published:2010-04-02
  • Contact: PENG Qian, SHUAI Zhi-Gang E-mail:qpeng@iccas.ac.cn; zgshuai@tsinghua.edu.cn

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摘要：

14族杂原子取代的杂环戊二烯分子具有独特的光谱性质, 成为发光材料的明星分子. 为了更深层次地理解硅、锗、锡杂环戊二烯分子的光谱性质, 本文从理论上计算了它们的电子结构及其吸收和发射光谱. 分别采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT), 优化了硅、锗、锡杂环戊二烯分子基态和第一激发态的平衡构型, 计算了电子结构和振动性质. 在此基础上, 运用振动关联函数公式计算了吸收光谱和发射光谱. 得到的吸收光谱和发射光谱, 特别是发射光谱的半峰宽与现有的实验值吻合很好. 通过分析结构和光谱性质的关系, 指出光谱的性质主要取决于苯环转动对应的低频振动模式和中心环C—C键的伸缩振动对应的高频振动模式.

关键词: 密度泛函理论, 14族杂环戊二烯, 振动关联函数, 光吸收, 光发射

Abstract:

Group-14 metalloles possess interesting optical properties and are promising molecules for light-emitting materials. We present a theoretical study of the electronic structures and the optical spectra from silole to stannole to gain insight into their optical properties. The optimized equilibrium geometries and the electronic and vibrational structures for the ground state (S0) and the first singlet excited state (S1) were calculated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively. The optical absorption and emission spectra were calculated using the thermal vibration correlation function formalism. The lineshapes of the calculated optical absorption and emission spectra, especially the full width at half maximum for all the compounds at room temperature, were found to be in good agreement with the available experimental data. Low-frequency modes that are assigned to the rotation motion of free aromatic rings and the high-frequency modes related to the stretching vibration of carbon-carbon bonds contribute greatly to the optical features such as the bandwidth of the optical line-shapes.

Key words: Density functional theory, Group-14 metalloles, Vibration correlation function, Optical absorption, Light emission

MSC2000: 

  • O641