噻唑衍生物电子光谱和二阶非线性光学性质的理论研究

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (2): 357.

噻唑衍生物电子光谱和二阶非线性光学性质的理论研究

谭回¹, 马小华², 梁然¹, 艾希成¹, 孙萌涛³, 张建平¹

1. 中国人民大学化学系, 北京 100872;
2. 北京大学化学与分子工程学院, 北京 100871;
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 100190

收稿日期:2009-04-02 出版日期:2010-02-10 发布日期:2010-02-10
通讯作者: 艾希成, 男, 教授, 博士生导师, 从事光谱学和结构化学研究. E-mail: xcai@chem.ruc.edu.cn; 孙萌涛, 男, 副研究员, 从事分子体系的电子态、振动态和转动态的电荷和能量转移研究. E-mail: mtsun@aphy.iphy.ac.cn
基金资助:
国家自然科学基金(批准号: 20703067)资助.

Theoretical Studies on Electronic Structures and Second-order Polarizabilities of Thiazole Derivatives

TAN Hui¹, MA Xiao-Hua², LIANG Ran¹, AI Xi-Cheng^1*, SUN Meng-Tao^3*, ZHANG Jian-Ping¹

1. Department of Chemistry, Renmin University of China, Beijing 100872, China;
2. College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China;
3. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

Received:2009-04-02 Online:2010-02-10 Published:2010-02-10
Contact: AI Xi-Cheng. E-mail: xcai@chem.ruc.edu.cn; SUN Meng-Tao. E-mail: mtsun@aphy.iphy.ac.cn
Supported by:
国家自然科学基金(批准号: 20703067)资助.

摘要/Abstract

摘要：

采用量子化学密度泛函方法(DFT)在B3LYP/6-31G(d)水平上对有机二阶非线性光学生色团(E)-2-(5-(4-(双(4-甲氧苯基)氨基)苯乙烯基)噻唑-5)三氰乙烯(TPA-Ti2-TCV)(1)和(E)-2-(5-(4-(双(4-甲氧苯基)氨基)苯乙烯基)噻唑-2)三氰乙烯(TPA-Ti5-TCV)(2)进行几何构型的完全优化, 在优化所得构型的基础上, 采用含时密度泛函方法(TDDFT)在6-31G(d)基组水平上计算了电子吸收光谱的跃迁性质. 再采用有限场法(FF)在B3LYP/6-31G(d)水平上计算了分子的一阶超极化率β. 计算结果表明, 三芳胺在噻唑环上取代C5比取代C2有更大的一阶超极化率, 这是由于噻唑的区域化学性导致ΔE_HOMO-LUMO(TPA-Ti2-TCV)比ΔE_HOMO-LUMO(TPA-Ti5-TCV)大很多造成的.

关键词: 噻唑; 电子吸收光谱; 一阶超极化率; 密度泛函理论

Abstract:

Two thiazole-based chromophores were fully optimized with density function theory at B3LYP/6-31G(d) level. Their calculated results are in accordance with the related experiments very well. The parameters which resulted in the difference of the two chromopheres were also calculated with TD-DFT method at the same calculation level. The result indicated that the chromophore(E)-2-(5-(4-(bis(4-methoxyphenyl)amino)styryl)thiazol-2-yl)ethene-1,1,2-tricarbonitrile(TPA-Ti5-TCV) had a larger hyperpolarizability, which was mainly due to its lower ground state to first excited state bandgap caused by the regiochemistry of thiazole.

Key words: Thiazole; Electron absorption spectrum; First-order hyperpolarizability; Density functional theory

TrendMD:

谭回, 马小华, 梁然, 艾希成, 孙萌涛, 张建平. 噻唑衍生物电子光谱和二阶非线性光学性质的理论研究. 高等学校化学学报, 2010, 31(2): 357.

TAN Hui, MA Xiao-Hua, LIANG Ran, AI Xi-Cheng*, SUN Meng-Tao*, ZHANG Jian-Ping. Theoretical Studies on Electronic Structures and Second-order Polarizabilities of Thiazole Derivatives. Chem. J. Chinese Universities, 2010, 31(2): 357.

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