Huang Jing, Du Likai, Hu Deping, Lan Zhenggang
Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266101, Shandong, People's Republic of China; University of Chinese Academy of Sciences, Beijing, 100049, People's Republic of China; The Qingdao Key Lab of Solar Energy Utilization and Energy Storage Technology, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266101, Shandong, People's Republic of China.
J Comput Chem. 2015 Jan 30;36(3):151-63. doi: 10.1002/jcc.23778. Epub 2014 Nov 21.
The excited states of the phenylene ethynylene dendrimer are investigated comprehensively by various electronic-structure methods. Several computational methods, including SCS-ADC(2), TDHF, TDDFT with different functionals (B3LYP, BH&HLYP, CAM-B3LYP), and DFT/MRCI, are applied in systematic calculations. The theoretical approach based on the one-electron transition density matrix is used to understand the electronic characters of excited states, particularly the contributions of local excitations and charge-transfer excitations within all interacting conjugated branches. Furthermore, the potential energy curves of low-lying electronic states as the functions of ethynylene bonds are constructed at different theoretical levels. This work provides us theoretical insights on the intramolecular excited-state energy transfer mechanism of the dendrimers at the state-of-the-art electronic-structure theories.
通过各种电子结构方法全面研究了亚苯基乙炔树枝状大分子的激发态。应用了几种计算方法，包括SCS-ADC(2)、TDHF、具有不同泛函（B3LYP、BH&HLYP、CAM-B3LYP）的TDDFT以及DFT/MRCI，进行了系统计算。基于单电子跃迁密度矩阵的理论方法用于理解激发态的电子特性，特别是所有相互作用共轭支链内局部激发和电荷转移激发的贡献。此外，在不同理论水平上构建了作为乙炔键函数的低电子态势能曲线。这项工作在最先进的电子结构理论下为我们提供了关于树枝状大分子分子内激发态能量转移机制的理论见解。
