Transition-density-fragment interaction combined with transfer integral approach for excitation-energy transfer via charge-transfer states
Transition-density-fragment interaction combined with transfer integral approach for excitation-energy transfer via charge-transfer states
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DOI：
10.1063/1.4733669
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发表时间：
2012-07-21
影响因子：
4.4
通讯作者：
Fujimoto, Kazuhiro J.
中科院分区：
文献类型：
--
作者：
Fujimoto, Kazuhiro J.
提出了一种结合转移积分（TI）的跃迁-密度-碎片相互作用（TDFI）方法。TDFI方法是为了描述电子库仑相互作用而发展起来的，它被应用于激发能量转移（EET）[K。J. Fujimoto和S. Hayashi，J. Am. 131，14152（2009）]和激子耦合圆二色光谱[K. J. Fujimoto，J. Chem. Phys. 133，124101（2010）]。在本研究中，TDFI方法扩展到交换相互作用，因此它是适用于通过电荷转移（CT）状态的EET与TI方法相结合。在该方案中，重叠校正也被考虑在内。为了检查TDFI-TI的准确性，对乙烯二聚体进行了几次测试计算。结果表明，TDFI-TI方法与TDFI方法相比，对电子耦合的描述有了很大的改进。在成功描述电子耦合的基础上，利用TDFI-TI方法进行了分解分析。目前的分析清楚地表明，在大多数情况下，库仑相互作用的贡献很大，并在小的分离的CT状态的显着影响。此外，交换相互作用被发现是小的，在这个系统中。该方法有助于分析和理解EET的机制。(C)2012年美国物理学会。[http：//dx.doi.org/10.1063/1.4733669]
A transition-density-fragment interaction (TDFI) combined with a transfer integral (TI) method is proposed. The TDFI method was previously developed for describing electronic Coulomb interaction, which was applied to excitation-energy transfer (EET) [K. J. Fujimoto and S. Hayashi, J. Am. Chem. Soc. 131, 14152 (2009)] and exciton-coupled circular dichroism spectra [K. J. Fujimoto, J. Chem. Phys. 133, 124101 (2010)]. In the present study, the TDFI method is extended to the exchange interaction, and hence it is combined with the TI method for applying to the EET via charge-transfer (CT) states. In this scheme, the overlap correction is also taken into account. To check the TDFI-TI accuracy, several test calculations are performed to an ethylene dimer. As a result, the TDFI-TI method gives a much improved description of the electronic coupling, compared with the previous TDFI method. Based on the successful description of the electronic coupling, the decomposition analysis is also performed with the TDFI-TI method. The present analysis clearly shows a large contribution from the Coulomb interaction in most of the cases, and a significant influence of the CT states at the small separation. In addition, the exchange interaction is found to be small in this system. The present approach is useful for analyzing and understanding the mechanism of EET. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4733669]