物理化学学报 >> 2012, Vol. 28 >> Issue (06): 1329-1336.doi: 10.3866/PKU.WHXB201204193

理论与计算化学 上一篇    下一篇

态定(线性响应)-极化连续模型/含时密度泛函方法研究一种有机发光材料的吸收和发射光谱

刘小君1,2, 林涛1, 蔡新晨1, 高少伟1, 杨磊1, 马睿1, 张晋悦1   

  1. 1. 北京交通大学光电子技术研究所, 发光与光信息技术教育部重点实验室, 北京 100044;
    2. 中国科学院理化技术研究所, 光化学转换与功能材料重点实验室, 北京 100190
  • 收稿日期:2012-01-31 修回日期:2012-04-19 发布日期:2012-05-17
  • 通讯作者: 刘小君 E-mail:xjliu@bjtu.edu.cn
  • 基金资助:

    国家自然科学基金(21003009), 北京交通大学基金(2009JBZ019-4, 本科生创新实验项目)及中国科学院理化技术研究所光化学转换与功能材料重点实验室基金资助

State-Specific (Linear-Response)-Polarizable Continuum Models/ Time-Dependent Density Functional Theory Study on the Absorption and Emission Spectra of an Organic Fluorescent Emitter

LIU Xiao-Jun1,2, LIN Tao1, CAI Xin-Chen1, GAO Shao-Wei1, YANG Lei1, MA Rui1, ZHANG Jin-Yue1   

  1. 1. Key Laboratory of Luminescence and Optical Information, Ministry of Education, Institute of Optoelectronic Technology, Beijing Jiaotong University, Beijing 100044, P. R. China;
    2. Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
  • Received:2012-01-31 Revised:2012-04-19 Published:2012-05-17
  • Contact: LIU Xiao-Jun E-mail:xjliu@bjtu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21003009), Beijing Jiaotong University, China (2009JBZ019-4 and Undergraduates Innovating Experimentation Project), and the Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences.

摘要: 3-(二氰亚甲基)-5,5-二甲基-1-(3-[9-(2-乙基-己基)-咔唑基]-乙烯基)环己烷(DCDHCC)是一种用于光电器件中的有机染料, 它具有良好的发光特性. 我们使用含时密度泛函方法(TD-PBE0, TD-BMK和TD-M06)以及极化连续模型(PCM)计算了该材料在溶剂中的吸收和发射特性. 计算中使用了线性响应(LR)、态定(SS)两种溶剂模型和6-31G(d)、6-31+G(d,p)两种基组. 计算了DCDHCC在苯、四氢呋喃和丙酮溶剂中的吸收和发射光谱,并与实验观测进行了比较. 结果表明: 对于吸收光谱的计算, 杂化函数的影响大于基组和溶剂模型, 在三种函数中BMK更适于研究DCDHCC的吸收光谱; 而对于发射光谱, 基组的影响最大, 基组通过影响激发态构型从而影响发射光谱, 对于激发态构型的优化需要使用6-31+G(d,p)基组. 我们希望这些研究能对今后设计类似的发光分子有帮助.

关键词: 含时密度泛函理论, 态定极化连续模型, 紫外-可见光谱, 全局杂化, 线性响应极化连续模型

Abstract: 3-(dicyanomethylene)-5,5-dimethyl-1-(3-[9-(2-ethyl-hexyl)-carbazol]-vinyl) cyclohexene (DCDHCC) is one of a series of organic dyes with good emission performance in photoelectric devices. The absorption and emission spectra of DCDHCC were computed using PBE0, BMK, and M06 hybrids in the frame of time-dependent density functional theory (TDDFT) in combination with polarizable continuum models (PCMs). Linear-response (LR) and state-specific (SS) PCM approaches were used as well as 6-31G(d) and 6-31+G(d,p) basis sets. The absorption and emission spectra were calculated in benzene, tetrahydrofuran, and acetone and compared with experimental observations. On the one hand, choice of hybrids was found to have a greater effect on the absorption spectra than the basis sets or the solvent model and BMK was established to be a suitable functional for the calculation of the absorption spectra of DCDHCC, on the other hand, the basis set used had a significant impact on the geometries of the excited states and thus the emission spectra, and the 6-31+G(d,p) basis set was necessary for the optimization of the excited states. It is envisaged that our calculations may be of assistance in the design of analogous emitters.

Key words: Time-dependent density functional theory, State-specific polarizable continuum model, UV-Vis spectrum, Global hybrid, Linear-response polarizable continuum model

MSC2000: 

  • O644