On couplings and excimers: lessons from studies of singlet fission in covalently linked tetracene dimers

Literature Information

Publication Date 2016-02-19
DOI 10.1039/C6CP00177G
Impact Factor 3.676
Authors

Xintian Feng, Anna I. Krylov


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Abstract

Electronic factors controlling singlet fission (SF) rates are investigated in covalently linked dimers of tetracene. Using covalent linkers, relative orientation of the individual chromophores can be controlled, maximizing the rates of SF. Structures with coplanar and staggered arrangements of tetracene moieties are considered. The electronic structure calculations and three-state kinetic model for SF rates provide explanations for experimentally observed low SF yields in coplanar dimers and efficient SF in staggered dimers. The calculations illuminate the role of the excimer formation in SF process. The structural relaxation in the S1 state leads to the increased rate of the multi-exciton (ME) state formation, but impedes the second step, separation of the ME state into independent triplets. The slower second step reduces SF yield by allowing other processes, such as radiationless relaxation, to compete with triplet generation. The calculations of electronic couplings also suggest an increased rate of radiationless relaxation at the excimer geometries. Thus, the excimer serves as a trap of the ME state. The effect of covalent linkers on the electronic factors and SF rates is investigated. In all considered structures, the presence of the linker leads to larger couplings, however, the effect on the overall rate is less straightforward, since the linkers generally result in less favorable energetics. This complex behavior once again illustrates the importance of integrative approaches that evaluate the overall rate, rather than focusing on specific electronic factors such as energies or couplings.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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