Simulating the full spin manifold of triplet-pair states in a series of covalently linked TIPS-pentacenes,Journal of Computational Chemistry

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Simulating the full spin manifold of triplet-pair states in a series of covalently linked TIPS-pentacenes
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2024-08-14 , DOI: 10.1002/jcc.27475
Timo Schulz ₁ , Christel M Marian ₁

Affiliation

Combined density functional theory and multireference configuration interaction methods have been used to elucidate singlet fission (SF) pathways and mechanisms in three regioisomers of side-on linked pentacene dimers. In addition to the optically bright singlets (S

_{1}

and S

_{2}

) and singly excited triplets (T

_{1}

and T

_{2}

), the full spin manifold of multiexcitonic triplet-pair states (

^{1}

ME,

^{3}

ME,

^{5}

ME) has been considered. In the ortho- and para-regioisomers, the

^{1}

ME and S

_{1}

potentials intersect upon geometry relaxation of the S

_{1}

excitation. In the meta-regioisomer, the crossing occurs upon delocalization of the optically bright excitation. The energetic accessibility of these conical intersections and the absence of low-lying charge-transfer states suggests a direct SF mechanism, assisted by charge-resonance effects in the

^{1}

ME state. While the

^{5}

ME state does not appear to play a role in the SF mechanism of the ortho- and para-regioisomers, its participation in the disentanglement of the triplet pair is conceivable in the meta-regioisomer.

中文翻译：

模拟一系列共价连接的 TIPS-pentacenes 中三重态的全自旋流形

已使用联合密度泛函理论和多参比构型相互作用方法阐明了侧向连接的五苯二聚体的三种区域异构体中的单线态裂变（SF）途径和机制。除了光学明亮的单粒子（S 和 S）和单激发的三重粒子（T 和 T）之外，还考虑了多激子三重态态（