Towards multistate multimode landscapes in singlet fission of pentacene: the dual role of charge-transfer states,Chemical Science

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Towards multistate multimode landscapes in singlet fission of pentacene: the dual role of charge-transfer states
Chemical Science ( IF 7.6 ) Pub Date : 2021-08-30 , DOI: 10.1039/d1sc01703a
Rajat Walia ₁ , Zexiang Deng ₁ , Jun Yang ₁

Affiliation

Singlet fission duplicates triplet excitons for improving light harvesting efficiency. The presence of the interaction between electronic and nuclear degrees of freedom complicates the interpretation of correlated triplet pairs. We report a quantum chemistry study on the significance and subtleties of multistate and multimode pathways in forming triplet pair states of the pentacene dimer through a six-state vibronic-coupling Hamiltonian derived from many-electron adiabatic wavefunctions of an ab initio density matrix renormalization group. The resulting spin values of the singlet manifolds on each pentacene center are computed, and the varying spin nature can be distinguished clearly with respect to dimer stacking and vibronic progression. Our monomer spin assignments reveal the coexistence of both lower-lying weak and higher-lying strong charge transfer states which interact vibronically with the triplet pair state, providing important implications for its generation and separation occurring in vibronic regions. This work conveys the importance of the many-electron process requiring close low-lying singlet manifolds to determine the subtle fission details, and represents an important step for understanding vibronically resolved spin states and conversions underlying efficient singlet fission.

中文翻译：

并五苯单线态裂变中的多态多模景观：电荷转移态的双重作用

单线态裂变复制三线态激子，以提高光捕获效率。电子和核自由度之间相互作用的存在使相关三重态对的解释变得复杂。我们报告了一项量子化学研究，研究了多态和多模式路径在通过从头算密度矩阵重正化群的多电子绝热波函数衍生的六态振动耦合哈密顿量形成并五苯二聚体的三重对态时的重要性和微妙性。计算每个并五苯中心上的单重态流形的自旋值，并且可以在二聚体堆积和电子振动级数方面清楚地区分不同的自旋性质。我们的单体自旋分配揭示了较低位置的弱电荷转移态和较高位置的强电荷转移态的共存，这些电荷转移态与三重态对态发生振动相互作用，为其在振动区域中发生的生成和分离提供了重要的启示。这项工作传达了多电子过程的重要性，需要紧密的低位单线态流形来确定微妙的裂变细节，并且代表了理解振动分辨自旋态和有效单线态裂变背后的转换的重要一步。

更新日期：2021-09-06

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