Reddy S Rajagopala, Coto Pedro B, Thoss Michael
Institute of Theoretical Physics and Interdisciplinary Center for Molecular Materials , Friedrich-Alexander University Erlangen-Nürnberg , 91058 Erlangen , Germany.
Institute of Theoretical Physics , Friedrich-Alexander-University Erlangen-Nürnberg , 91058 Erlangen , Germany.
J Phys Chem Lett. 2018 Oct 18;9(20):5979-5986. doi: 10.1021/acs.jpclett.8b02674. Epub 2018 Oct 3.
We investigate the dynamics of intramolecular singlet fission in a dimer consisting of two pentacene-based chromophores covalently bonded to a phenylene spacer using an approach that combines high-level ab initio multireference perturbation theory methods and quantum dynamical simulations. The results show that the population of the multiexcitonic state, corresponding to the first step of singlet fission, is facilitated by the existence of higher-lying doubly excited and charge transfer states that participate in a superexchange-like way. The important role played by high-frequency ring-breathing molecular vibrations in the process is also discussed.
我们采用一种结合了高水平从头算多参考微扰理论方法和量子动力学模拟的方法，研究了由两个与亚苯基间隔基共价键合的并五苯类发色团组成的二聚体中的分子内单线态裂变动力学。结果表明，单线态裂变第一步对应的多激子态的布居，因存在以类似超交换方式参与的较高能级双激发态和电荷转移态而得到促进。还讨论了高频环呼吸分子振动在此过程中所起的重要作用。
