### 四氢二嵌萘衍生物在不同环境中的电子结构及光谱特征的理论研究

1. (西南大学化学化工学院 重庆 400715)
• 收稿日期:2009-04-19 修回日期:2009-09-28 出版日期:2010-03-14 发布日期:2010-03-14
• 通讯作者: 何荣幸 E-mail:hrx77@yahoo.com.cn
• 基金资助:

国家自然科学基金（基金号：20803059）

### Theoretical Study on the Electronic Structures and Spectral Properties of the Tetrahydropyrene Derivatives in Different Environments

He Rongxing* Shen Wei Li Ming

1. (School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715)
• Received:2009-04-19 Revised:2009-09-28 Online:2010-03-14 Published:2010-03-14
• Contact: HE Rong-Xing E-mail:hrx77@yahoo.com.cn

The geometries of the ground and the first singlet excited states of the tetrahydropyrene derivatives were optimized respectively by the density functional theory (the used functional is B3LYP) and the single-excitation configuration interaction (CIS) method combining the 6-31＋G* basis set. According to the corresponding optimized structures, the absorption and emission spectra in different solvents are calculated using the time dependent density functional theory with the 6-311＋＋G** basis set. The solvent effect is considered by the polarizable continuum model. Inspection of the geometries reveals that, in acidic medium, the nitrogen atom located on the dimethylamino group of the THP can be protonated easily in the ground state. The calculated results indicate that the THP is not a dual fluorescence molecule, although its first excited state is a charge transfer (CT) state. In the presence of acidic solvents, the two emission bands of the THP are originated from two compounds, that is, the emission band at 2.71 eV is from the excited THP, and the fluorescence band at 3.69 eV from the protonated form of the THP. The absorption and decay pathways of the THP in acidic solvent are suggested based on the theoretical calculations. The calculated absorption and emission spectra are in good agreement with the experimental observations.