蒽
化学
取代基
振荡器强度
激发态
光化学
密度泛函理论
荧光
跃迁偶极矩
发色团
吸收(声学)
偶极子
接受者
基准集
极性效应
激发
计算化学
立体化学
谱线
原子物理学
有机化学
材料科学
复合材料
工程类
物理
电气工程
量子力学
凝聚态物理
天文
作者
Salsabil Abou-Hatab,Vincent A. Spata,Spiridoula Matsika
标识
DOI:10.1021/acs.jpca.6b12031
摘要
Substitution can be used to efficiently tune the photophysical properties of chromophores. In this study, we examine the effect of substituents on the absorption and fluorescence properties of anthracene. The effects of mono-, di-, and tetrasubstitution of electron-donating and -withdrawing functional groups were explored. In addition, the influence of a donor–acceptor substituent pair and the position of substitution were investigated. Eleven functional groups were varied on positions 1, 2, and 9 of anthracene, and on position 6 of 2-methoxyanthracene and 2-carboxyanthracene. Moreover, the donor–acceptor pair NH2/CO2H was added on different positions of anthracene for additional studies of doubly substituted anthracenes. Finally, we looked into quadruple substitutions on positions 1,4,5,8 and 2,3,6,7. Vertical excitation energies and oscillator strengths were computed using density functional theory with the hybrid CAM-B3LYP functional and 6-311G(d) basis set. Correlations between the excitation energies or oscillator strengths of the low-lying bright La state and the Hammett sigma parameter, σp+, of the substituents were examined. The energy is red-shifted for all cases of substitution. Oscillator strengths increase when substituents are placed along the direction of the transition dipole moment of the bright La excited state. Substitution of long chain conjugated groups significantly increases the oscillator strength in comparison to the cases for other substituents. In addition, the results of quadruply substituted geometries reveal symmetric substitution at the 1,4,5,8 positions significantly increases the oscillator strength and can lower the band gap compared to that of the unsubstituted anthracene molecule by up to 0.5 eV.
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