含苯并五元环方酸衍生物的二阶非线性光学性质的理论研究有机化学.pdfVIP

2006 年第 26 卷 有 机 化 学 Vol. 26, 2006 第 6 期, 839～844 Chinese Journal of Organic Chemistry No. 6, 839～844 ·研究论文· 含苯并五元环方酸衍生物的二阶非线性光学性质的理论研究 a,b a *,a 李广学 彭新华 吕春绪 (a 南京理工大学精细化工系 南京 210094) (b 安徽理工大学化学工程系 淮南 232001) 摘要 利用从头算 HF/6-31G*方法对用苯并五元环取代的方酸衍生物体系 SQ1～SQ15 进行几何构型优化和电子结构 计算. 以优化后的构型为基础, 应用 ZINDO 方法计算电子光谱. 同时应用从头算 CPHF/6-31G*方法和半经验 FF/AM1, FF/PM3, FF/MNDO 等有限场方法计算了分子的二阶非线性光学系数 βµ . 研究几何结构、电子结构和前线分子轨道能与 βµ 之间的关系, 为设计性能优良的有机非线性光学材料提供理论指导, 并对这四种计算方法的结果进行了比较. 关键词 方酸; 苯并五元环; 二阶非线性光学系数; CPHF 方法; 有限场方法 Theoretical Studies of Second-Order Nonlinear Optical Properties of Benzo Five-Membered Heterocyclic Squaraine Derivatives LI, Guang-Xuea,b PENG, Xin-Huaa LÜ, Chun-Xu*,a a ( Department of Fine Chemicals , Nanjing University of Science and Technology, Nanjing 210094) (b Department of Chemical Engineering, Auhui University of Science and Technology, Huainan 232001) Abstract The geometry structures of squaraine derivatives substituted by benzo five-membered ring moi- ety were optimized and electronic structures were calculated with HF/6-31G* method. Based on the opti- mized structures, the electronic spectra were obtained by the ZINDO method. The second-order nonlinear optical coefficients βµ were calculated by ab initio method at CPHF/6-31G* level and finite field method at FF/AM1, FF/PM3, FF/MNDO and FF/MINDO3 levels, respectively. The relationship among geometry