A Computational Study of the Electronic Energy and Charge Transfer Rates and Pathways in the Tetraphenyldibenzoperiflanthene/Fullerene Interfacial Dyad
A Computational Study of the Electronic Energy and Charge Transfer Rates and Pathways in the Tetraphenyldibenzoperiflanthene/Fullerene Interfacial Dyad
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四苯基二苯并葘弗兰烯/富勒烯界面二元组中电子能量和电荷转移速率和路径的计算研究
DOI：
10.1021/acs.jpclett.3c01927
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Dunietz, Barry D.
中科院分区：
文献类型：
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作者：
Schubert, Alexander;Bhandari, Srijana;Geva, Eitan;Dunietz, Barry D.
计算研究了四苯基二苯并噻喃：富勒烯（DBP：C70）共混体系界面电荷分离的电子跃迁速率和途径。分析是基于一个极化一致的框架，采用屏蔽范围分离的混合功能在极化连续模型参数化费米的黄金法则率理论。该模型考虑了25个最低激发态的DBP：C70dyad，可通过光激发内的可能的过渡。已确定的有助于电荷载流子产生的不同途径包括电子和空穴转移和反向转移、激子转移和内部弛豫步骤。C70较大的态密度似乎解释了先前观察到的通过空穴转移机制进行电荷分离的较大效率。我们还分析了FGR理论的高温和短时半经典近似的有效性，其中高估和低估的Marcus理论常数都可能受到影响。
The electronic transition rates and pathways underlying interfacial charge separation in tetraphenyldibenzoperiflanthene:fullerene (DBP:C70) blends are investigated computationally. The analysis is based on a polarization-consistent framework employing screened range-separated hybrid functional in a polarizable continuum model to parametrize Fermi’s golden rule rate theory. The model considers the possible transitions within the 25 lowest excited states of a DBP:C70dyad that are accessible by photoexcitation. The different identified pathways contributing to charge carrier generation include electron and hole transfer and backtransfer, exciton transfer, and internal relaxation steps. The larger density of states of C70appears to explain the previously observed larger efficiency for charge separation through hole transfer mechanism. We also analyze the validity of the high-temperature and short-time semiclassical approximations of the FGR theory, where both overestimated and underestimated Marcus theory based constants can be affected.