Scaling Relations and Optimization of Excitonic Energy Transfer Rates between One-Dimensional Molecular Aggregates
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- 作者：Chern Chuang ; Jasper Knoester ; Jianshu Cao
- 刊名：Journal of Physical Chemistry B
- 出版年：2014
- 出版时间：July 17, 2014
- 年：2014
- 卷：118
- 期：28
- 页码：7827-7834
- 全文大小：332K
- ISSN：1520-5207
文摘
We theoretically study the distance, chain length, and temperature dependence of the electronic couplings as well as the excitonic energy transfer rates between one-dimensional (1D) chromophore aggregates. In addition to the well-known geometry dependent factor that leads to the deviation from F枚rster鈥檚 classic RDA鈥? scaling on the donor鈥揳cceptor separation, nonmonotonic dependence on aggregate size and the breakdown of far-field dipole selection rules are also investigated in detail and compared to prior calculations. Our analysis provides a simple, unifying framework to bridge the results of the ground state electronic couplings at low temperatures and those from the classical rate-summation at high temperatures. At low temperatures and in the near-field limit, the exciton transfer integral scales as RDA鈥?, in analogy to that of electric monopoles. For the case of aligned 1D J-aggregates, we predict a maximal excitonic energy transfer rate at temperatures on the order of the intra-aggregate coupling strength.