气相中苯基偶氮噻唑分子热致异构化机理及光学性质的理论研究  

Theoreticals study on thermoisomerization mechanism andoptical properties of phenylazothiazole in gas phase

作　　者：孙雕 肖洋 陈逸潇 花书贵 刘泽玉 陈立庄 SUN Diao;XIAO Yang;CHEN Yixiao;HUA Shugui;LIU Zeyu;CHEN Lizhuang(School of Environmental and Chemical Engineering,Jiangsu University of Science and Technology,Zhenjiang 212100,China;College of Life Science and Chemistry,Jiangsu Second Normal University,Nanjing 211200,China)

机构地区：[1]江苏科技大学环境与化学工程学院,镇江212100 [2]江苏第二师范学院生命科学与化学化工学院,南京211200

出　　处：《江苏科技大学学报(自然科学版)》2025年第2期101-106,共6页Journal of Jiangsu University of Science and Technology:Natural Science Edition

基　　金：国家自然科学基金面上项目(21671084)。

摘　　要：运用密度泛函理论方法(density functional theory,DFT),对不同构型的苯基偶氮噻唑分子的结构、电子吸收光谱和分子(超)极化率进行了系统地量子化学研究.计算结果表明,顺式和反式构型的苯基偶氮噻唑分子能够在温和条件下进行异构化反应,它们的电子吸收光谱具有明显差异,因此呈现出良好分离的吸收带;无论在零频极限和还是在含频外场条件下,反式构型分子都表现出更大的极化率和二阶超极化率,但是顺式构型分子的一阶超极化率却更显著,同时,含频外场下的分子(超)极化率均明显异于其零频极限值,且(超)极化率值随外场频率呈规律性变化.研究表明:苯基偶氮噻唑分子的光学性质可以通过调节分子构型和外场条件进行有效调控,相关结论可为实验设计合成高性能苯基偶氮噻唑类光电功能材料提供理论指导.In this paper,the structures,electronic absorption spectra,and molecular(hyper)polarizabilities of phenylazothiazole with different configurations have been systematically studied by density functional theory(DFT).The calculation results show that cis-and trans-phenylazothiazole can undergo isomerization reaction under mild conditions,and their electronic absorption spectra have very different characteristics,thus presenting well-separated absorption bands.The trans-configuration molecule exhibits larger polarizability and second hyperpolarizability under both zero-frequency limit and frequency-dependent fields,but the cis-configuration one displays more significant first hyperpolarizability.In addition,the molecular(hyper)polarizabilities under frequency-dependent field are significantly different from the values in zero-frequency limit,and the(hyper)polarizabilities vary regularly with the frequency of external field.The study shows that the optical properties of phenylazothiazole can be effectively controlled by adjusting the molecular configuration and external field,and the related conclusion can provide theoretical guidance for the experimental design and synthesis of high-performance phenylazothiazole-based photoelectric materials.

关 键 词：苯基偶氮噻唑 顺-反异构化 光学性质 电子吸收光谱 (超)极化率 

分 类 号：O641.121[理学—物理化学]