Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene

Nicholas R. Monahan; Dezheng Sun; Hiroyuki Tamura; Kristopher W. Williams; Bolei Xu; Yu Zhong; Bharat Kumar; Colin Nuckolls; Avetik R. Harutyunyan; Gugang Chen; Hai Lung Dai; David Beljonne; Yi Rao; X. Y. Zhu

doi:10.1038/nchem.2665

Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene

Nicholas R. Monahan, Dezheng Sun, Hiroyuki Tamura, Kristopher W. Williams, Bolei Xu, Yu Zhong, Bharat Kumar, Colin Nuckolls, Avetik R. Harutyunyan, Gugang Chen, Hai Lung Dai, David Beljonne, Yi Rao, X. Y. Zhu

Research output: Contribution to journal › Article › peer-review

104 Citations (Scopus)

Abstract

The absorption of a photon usually creates a singlet exciton (S₁) in molecular systems, but in some cases S₁ may split into two triplets (2×T₁) in a process called singlet fission. Singlet fission is believed to proceed through the correlated triplet-pair ¹(TT) state. Here, we probe the ¹(TT) state in crystalline hexacene using time-resolved photoemission and transient absorption spectroscopies. We find a distinctive ¹(TT) state, which decays to 2×T₁ with a time constant of 270 fs. However, the decay of S₁ and the formation of ¹(TT) occur on different timescales of 180 fs and <50 fs, respectively. Theoretical analysis suggests that, in addition to an incoherent S₁ → ¹(TT) rate process responsible for the 180 fs timescale, S₁ may couple coherently to a vibronically excited ¹(TT) on ultrafast timescales (<50 fs). The coexistence of coherent and incoherent singlet fission may also reconcile different experimental observations in other acenes.

Original language	English
Pages (from-to)	341-346
Number of pages	6
Journal	Nature Chemistry
Volume	9
Issue number	4
DOIs	https://doi.org/10.1038/nchem.2665
Publication status	Published - 2017 Apr 1

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)

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Monahan, N. R., Sun, D., Tamura, H., Williams, K. W., Xu, B., Zhong, Y., Kumar, B., Nuckolls, C., Harutyunyan, A. R., Chen, G., Dai, H. L., Beljonne, D., Rao, Y., & Zhu, X. Y. (2017). Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene. Nature Chemistry, 9(4), 341-346. https://doi.org/10.1038/nchem.2665

Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene. / Monahan, Nicholas R.; Sun, Dezheng; Tamura, Hiroyuki; Williams, Kristopher W.; Xu, Bolei; Zhong, Yu; Kumar, Bharat; Nuckolls, Colin; Harutyunyan, Avetik R.; Chen, Gugang; Dai, Hai Lung; Beljonne, David; Rao, Yi; Zhu, X. Y.

In: Nature Chemistry, Vol. 9, No. 4, 01.04.2017, p. 341-346.

Research output: Contribution to journal › Article › peer-review

Monahan, NR, Sun, D, Tamura, H, Williams, KW, Xu, B, Zhong, Y, Kumar, B, Nuckolls, C, Harutyunyan, AR, Chen, G, Dai, HL, Beljonne, D, Rao, Y & Zhu, XY 2017, 'Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene', Nature Chemistry, vol. 9, no. 4, pp. 341-346. https://doi.org/10.1038/nchem.2665

Monahan, Nicholas R. ; Sun, Dezheng ; Tamura, Hiroyuki ; Williams, Kristopher W. ; Xu, Bolei ; Zhong, Yu ; Kumar, Bharat ; Nuckolls, Colin ; Harutyunyan, Avetik R. ; Chen, Gugang ; Dai, Hai Lung ; Beljonne, David ; Rao, Yi ; Zhu, X. Y. / Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene. In: Nature Chemistry. 2017 ; Vol. 9, No. 4. pp. 341-346.

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abstract = "The absorption of a photon usually creates a singlet exciton (S1) in molecular systems, but in some cases S1 may split into two triplets (2×T1) in a process called singlet fission. Singlet fission is believed to proceed through the correlated triplet-pair 1(TT) state. Here, we probe the 1(TT) state in crystalline hexacene using time-resolved photoemission and transient absorption spectroscopies. We find a distinctive 1(TT) state, which decays to 2×T1 with a time constant of 270 fs. However, the decay of S1 and the formation of 1(TT) occur on different timescales of 180 fs and <50 fs, respectively. Theoretical analysis suggests that, in addition to an incoherent S1 → 1(TT) rate process responsible for the 180 fs timescale, S1 may couple coherently to a vibronically excited 1(TT) on ultrafast timescales (<50 fs). The coexistence of coherent and incoherent singlet fission may also reconcile different experimental observations in other acenes.",

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AU - Xu, Bolei

AU - Zhong, Yu

AU - Kumar, Bharat

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AU - Harutyunyan, Avetik R.

AU - Chen, Gugang

AU - Dai, Hai Lung

AU - Beljonne, David

AU - Rao, Yi

AU - Zhu, X. Y.

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Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene

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