六元环硼氮烷对称取代方酸的电子光谱和非线性光学性质的DFT研究  

DFT Studies on Electronic Spectra and Nonlinear Optical Properties of Symmetric Squaraine Derivatives Linked with Borazine

作　　者：岳淑美[1] 谭克[2] 张珉[3] 兰亚乾[3] 苏忠民[3] 

机构地区：[1]长春师范学院化学系,长春130032 [2]长春大学职业技术学院,长春130022 [3]东北师范大学化学学院功能材料化学研究所,长春130024

出　　处：《高等学校化学学报》2003年第12期2231-2234,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 0 2 43 0 0 3 ;2 0 160 0 2 5 );吉林省杰出青年基金 (批准号 :2 0 0 0 5 5 11)资助

摘　　要：用量子化学密度泛函理论 B3 LYP方法 ,在 6-3 1 G( d)水平上对环硼氮烷和苯基对称取代方酸进行几何构型优化 .以此为基础 ,利用 TD-DFT方法得到方酸衍生物的 UV-Vis吸收光谱 .进一步引入外电场 ,用有限场 ( FF/ DFT-B3 LYP)方法探讨了各体系的三阶非线性光学性质 ( NLO) .计算结果显示 ,对称环硼氮烷取代的方酸衍生物性质不同于苯环取代 ,取代位置对电荷分布、分子轨道特征和非线性光学性质的影响很大 .氮原子与方酸相连时对提高方酸体系的三阶非线性光学性质十分有效 ,其 NLO系数可达 2 .3 80 8×1 0 -2 4C·m.The geometrical structures of symmetric 2,4-squaraine compounds have been optimized by using DFT B3LYP/6-31G(d). On the basis of them, electronic absorption spectra of the compounds were investigated with TD-DFT and second-order hyperpolarizability γ were calculated by means of finite field (FF) method by introducing an external electronic filed. It is shown from the calculation that the borazine is a donor, different from benzene. Charge population, FMO and NLO properties change distinctly with change of the the atom linked to squaraine. To increase the γ value of a donor group, the atom linked to other group must be N atom. The best value of γ in the symmetric squaraine derivatives linked with borazine can reach 2.380 8×10 -24 C·m.

关 键 词：六元环硼氮烷 对称取代 方酸 电子光谱 非线性光学性质 DFT 密度泛函理论 

分 类 号：O625.5[理学—有机化学] O621.22[理学—化学]