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 journalArticle

52 Citations (Scopus)

Abstract

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
Volume9
Issue number10
DOIs
Publication statusPublished - Oct 1 2017
Externally publishedYes

Fingerprint

Potential energy surfaces
Crystal symmetry
Excitons
Absorption spectroscopy
Excited states
Ground state
Crystals
LDS 751

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Miyata, K., Kurashige, Y., Watanabe, K., Sugimoto, T., Takahashi, S., Tanaka, S., ... Matsumoto, Y. (2017). Coherent singlet fission activated by symmetry breaking. Nature Chemistry, 9(10), 983-989. https://doi.org/10.1038/nchem.2784

Coherent singlet fission activated by symmetry breaking. / Miyata, Kiyoshi; Kurashige, Yuki; Watanabe, Kazuya; Sugimoto, Toshiki; Takahashi, Shota; Tanaka, Shunsuke; Takeya, Jun; Yanai, Takeshi; Matsumoto, Yoshiyasu.

In: Nature Chemistry, Vol. 9, No. 10, 01.10.2017, p. 983-989.

Research output: Contribution to journalArticle

Miyata, K, Kurashige, Y, Watanabe, K, Sugimoto, T, Takahashi, S, Tanaka, S, Takeya, J, Yanai, T & Matsumoto, Y 2017, 'Coherent singlet fission activated by symmetry breaking', Nature Chemistry, vol. 9, no. 10, pp. 983-989. https://doi.org/10.1038/nchem.2784
Miyata K, Kurashige Y, Watanabe K, Sugimoto T, Takahashi S, Tanaka S et al. Coherent singlet fission activated by symmetry breaking. Nature Chemistry. 2017 Oct 1;9(10):983-989. https://doi.org/10.1038/nchem.2784
Miyata, Kiyoshi ; Kurashige, Yuki ; Watanabe, Kazuya ; Sugimoto, Toshiki ; Takahashi, Shota ; Tanaka, Shunsuke ; Takeya, Jun ; Yanai, Takeshi ; Matsumoto, Yoshiyasu. / Coherent singlet fission activated by symmetry breaking. In: Nature Chemistry. 2017 ; Vol. 9, No. 10. pp. 983-989.
@article{3ad2f058f6804d5fbe41ccfbce6bf656,
title = "Coherent singlet fission activated by symmetry breaking",
abstract = "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.",
author = "Kiyoshi Miyata and Yuki Kurashige and Kazuya Watanabe and Toshiki Sugimoto and Shota Takahashi and Shunsuke Tanaka and Jun Takeya and Takeshi Yanai and Yoshiyasu Matsumoto",
year = "2017",
month = "10",
day = "1",
doi = "10.1038/nchem.2784",
language = "English",
volume = "9",
pages = "983--989",
journal = "Nature Chemistry",
issn = "1755-4330",
publisher = "Nature Publishing Group",
number = "10",

}

TY - JOUR

T1 - Coherent singlet fission activated by symmetry breaking

AU - Miyata, Kiyoshi

AU - Kurashige, Yuki

AU - Watanabe, Kazuya

AU - Sugimoto, Toshiki

AU - Takahashi, Shota

AU - Tanaka, Shunsuke

AU - Takeya, Jun

AU - Yanai, Takeshi

AU - Matsumoto, Yoshiyasu

PY - 2017/10/1

Y1 - 2017/10/1

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85029762307&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85029762307&partnerID=8YFLogxK

U2 - 10.1038/nchem.2784

DO - 10.1038/nchem.2784

M3 - Article

C2 - 28937675

AN - SCOPUS:85029762307

VL - 9

SP - 983

EP - 989

JO - Nature Chemistry

JF - Nature Chemistry

SN - 1755-4330

IS - 10

ER -