LDS751 激发态电荷转移和光致异构化的量子化学研究Quantum.PDF

2011 年第69 卷 化 学 学 报 Vol. 69, 2011 第2 期, 176～182 ACTA CHIMICA SINICA No. 2, 176～182 ·研究论文· LDS751 激发态电荷转移和光致异构化的量子化学研究 王素凡* 周 涛 黄玉成 叶世勇 沈伟丽 (安徽师范大学化学与材料科学学院 芜湖 241000) 摘要 利用密度泛函方法对激光染料分子 LDS751 的电子结构和激发态性质进行了一系列的量子化学计算, 在理论上 对其激发态下可能的构型变化和动力学过程进行了预测. 从计算结果得出 LDS751 分子可能存在两个分别通过 C—C 桥键和端基 C—N 键旋转而实现的影响其光谱性质的光致异构化通道. 利用分子内官能团在激发过程中的电荷布居变 化定量地分析了分子内电荷转移过程. 所得结论可以预测不同时间尺度下的光谱特征谱线和解释相关的光谱实验. 关键词 染料分子; 共轭; 电荷转移; 光致异构化 Quantum Chemical Investigation on the Charge Transfer and Photo-isomerization for the Excited State of LDS751 Wang, Sufan* Zhou, Tao Huang, Yucheng Ye, Shiyong Shen, Weili (College of Chemistry and Materials Science, Anhui Normal University , Wuhu 241000) Abstract A series of quantum calculation have been done to investigate the excited state property of laser dye molecule LDS751 by density function theory. The possible configuration and processes have been pre- dicted by the theoretical point of view. Two major isomization pathways which may have influence on the excitation spectral property have been analyzed, it is indicated that rotation corresponding to the bridge C— C bond and terminal C—N maybe the comparable reaction channels in the first excited state. The in- tramolecular charge transfer and the degree have been estimated by the comparison of the summary of the charge re-distribution during different function group in the excitation. The conclusion can give some evi- dence and support to the relative absorption and emission spectra in different time scale experimental inves- tigat