碳硼烷桥连噻吩化合物结构和二阶非线性光学系数的DFT计算Density.PDF

2011 年第 69 卷 化 学 学 报 Vol. 69, 2011 第 5 期, 523～528 ACTA CHIMICA SINICA No. 5, 523～528 ·研究论文· 碳硼烷桥连噻吩化合物结构和二阶非线性光学系数的 DFT 计算 李 雪 孙世玲 麻娜娜 樊 敏 仇永清* 付 强* (东北师范大学化学学院 功能材料化学研究所 长春 130024) 摘要 采用密度泛函理论(DFT) B3LYP 方法, 计算分析了 7 个以碳硼烷和苯环为桥连基团化合物的非线性光学(NLO) 特征, 结果表明: 桥连基团的体积越大, 对提高极化率的值越有利; 分子桥连部分的电子离域性以及分子的几何构型 对二阶 NLO 系数有重要影响, 电子跃迁时的电荷转移程度对二阶 NLO 性质有较大贡献. 通过分析分子的电子光谱和 对应的分子轨道组成可知, 碳硼烷不仅可以作为传输电子的桥梁, 还可以作为吸电子基团. 关键词 碳硼烷; 电子光谱; NLO 性质; DFT Density Functional Theory Study on Structure and Second-order Nonlinear Optical Coefficients of Compounds Involving Carborane Bridges with Thiophen Li, Xue Sun, Shiling Ma, Nana Fan, Min Qiu, Yongqing* Fu, Qiang* (Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024) Abstract The nonlinear optical (NLO) properties of seven compounds using carborane and benzene rings as the bridging groups were investigated at the density functional theory (DFT) B3LYP method. The results indicate that a larger size bridging groups would be helpful in enhancing the polarizability. Electron delocal- ization of bridging group has an important influence on the second-order NLO coefficients as well as the molecular geometry, and the charge transfer has a greater contribution to the NLO properties. Moreover, from the analysis of electronic spectrum and the corresponding molecular orbit composition, it illustrates that the carborane can be not only the bridge for electron transmission, but also the electron withdrawi