journal article·2023-05-11

Dynamic Evolving Exothermicity Steers Ultrafast Formation of a Correlated Triplet Pair State

Yishi Wu, Lina Lu, Buyang Yu, San Zhang, Pengdong Luo, Mingxing Chen, Jingping He, Yongyao Li, Chunfeng Zhang, Jun Zhu, Jiannian Yao, Hongbing Fu

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Abstract

Singlet fission (SF) presents an attractive solution to overcome the Shockley–Queisser limit of single-junction solar cells. The conversion from an initial singlet state to final triplet is mediated by the correlated triplet pair state 1 (T 1 T 1 ). Despite significant advancement on 1 (T 1 T 1 ) properties and its role in SF, a comprehensive understanding of the energetic landscape during SF is still unclear. Here, we study an unconventional SF system with excited-state aromaticity, i.e., cyano-substituted dipyrrolonaphtheridinedione derivative (DPND-CN), using time-resolved spectroscopy as a function of the temperature. We demonstrate that the population transfer from S 1 to 1 (T 1 T 1 ) is driven by a time-dependent exothermicity resulting from the coherent coupling between electronic and spin degrees of freedom. This is followed by thermal-activated dissociation of 1 (T 1 T 1 ) to yield free triplets. Our results provide some new insight into the SF mechanism, which may guide the development of new efficient and stable SF materials for practical applications.
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Research context

OpenAlex topics: Spectroscopy and Quantum Chemical Studies · Advanced Chemical Physics Studies · Molecular Junctions and Nanostructures

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Beijing Key Laboratory for Optical Materials and Photonic Devices, Department of Chemistry, Capital Normal University, Beijing 100048, People’s Republic of China

National Laboratory of Solid State Microstructures, School of Physics, and Collaborative Innovation Center for Advanced Microstructures, Nanjing University, Nanjing, Jiangsu 210093, People’s Republic of China

Analytical Instrumentation Center, Peking University, Beijing 100871, People’s Republic of China

State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, People’s Republic of China

Beijing National Laboratory for Molecules Science (BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China

Funding

Ministry of Science and Technology of the People's Republic of China · Natural Science Foundation of Beijing Municipality · Jilin University · National Natural Science Foundation of China · Capital Normal University

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