期刊
JOURNAL OF COMPUTATIONAL CHEMISTRY
卷 32, 期 9, 页码 1971-1981出版社
WILEY
DOI: 10.1002/jcc.21781
关键词
perylene bisimide; SCS-CC2; TD-HF; TD-DFT; charge-transfer state; neutral excited state; electronic-coupling matrix-element; exciton energy transfer; exciton trapping mechanism
资金
- Deutsche Forschungsgemeinschaft [GRK 1221]
- China Scholarship Council
- Volkswagen Stiftung
The reliability of linear response approaches such as time-dependent Hartree-Fock (TD-HF) and time-dependent density functional theory (TD-DFT) for the prediction of the excited state properties of 3,4; 9,10-tetracarboxylic-perylene-bisimide (PBI) aggregates is investigated. A dimer model of PBI is investigated as a function of a torsional motion of the monomers, which was shown before to be an important intermolecular coordinate in these aggregates. The potential energy curves of the ground state and the two energetically lowest neutral excited and charge-transfer (CT) states were obtained with the spin-component scaling modification of the approximate coupled-cluster singles-and-doubles (SCS-CC2) method as a benchmark for dispersion corrected TD-HF and a range of TD-DFT approaches. The highly accurate SCS-CC2 results are used to assess the other, computationally less demanding methods. TD-HF predicts similar potential energy curves and transition dipole moments as SCS-CC2, as well as the correct order of neutral and CT states. This supports an exciton trapping mechanism, which was found on the basis of TD-HF data. However, the investigated TD-DFT methods provide generally the opposite character for the excited states. As a consequence, these TD-DFT results have unacceptably large errors for optical properties of these dye aggregates. (C) 2011 Wiley Periodicals, Inc. J Comput Chem 32: 1971-1981, 2011
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据