Coherent singlet fission activated by symmetry breaking

Kiyoshi Miyata, Yuki Kurashige, Kazuya Watanabe, Toshiki Sugimoto, Shota Takahashi, Shunsuke Tanaka, Jun Takeya, Takeshi Yanai, Yoshiyasu Matsumoto

Research output: Contribution to journalArticlepeer-review

148 Citations (Scopus)


Singlet fission, in which a singlet exciton is converted to two triplet excitons, is a process that could be beneficial in photovoltaic applications. A full understanding of the dynamics of singlet fission in molecular systems requires detailed knowledge of the relevant potential energy surfaces and their (conical) intersections. However, obtaining such information is a nontrivial task, particularly for molecular aggregates. Here we investigate singlet fission in rubrene crystals using transient absorption spectroscopy and state-of-the-art quantum chemical calculations. We observe a coherent and ultrafast singlet-fission channel as well as the well-known and conventional thermally assisted incoherent channel. This coherent channel is accessible because the conical intersection for singlet fission on the excited-state potential energy surface is located very close to the equilibrium position of the ground-state potential energy surface and also because of the excitation of an intermolecular symmetry-breaking mode, which activates the electronic coupling necessary for singlet fission.

Original languageEnglish
Pages (from-to)983-989
Number of pages7
JournalNature Chemistry
Issue number10
Publication statusPublished - Oct 1 2017
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General Chemical Engineering


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