Intermolecular Vibrations Mediate Ultrafast Singlet Fission

Overview

Journal Sci Adv

Specialties Biology
Science

Date 2020 Sep 19

PMID 32948583

Citations 10

Authors

Hong-Guang Duan

Ajay Jha

Xin Li

Vandana Tiwari

Hanyang Ye

Pabitra K Nayak

Xiao-Lei Zhu

Zheng Li

Todd J Martinez

Michael Thorwart

R J Dwayne Miller

Affiliations

Soon will be listed here.

Abstract

Singlet fission is a spin-allowed exciton multiplication process in organic semiconductors that converts one spin-singlet exciton to two triplet excitons. It offers the potential to enhance solar energy conversion by circumventing the Shockley-Queisser limit on efficiency. We study the primary steps of singlet fission in a pentacene film by using a combination of TG and 2D electronic spectroscopy complemented by quantum chemical and nonadiabatic dynamics calculations. We show that the coherent vibrational dynamics induces the ultrafast transition from the singlet excited electronic state to the triplet-pair state via a degeneracy of potential energy surfaces, i.e., a multidimensional conical intersection. Significant vibronic coupling of the electronic wave packet to a few key intermolecular rocking modes in the low-frequency region connect the excited singlet and triplet-pair states. Along with high-frequency local vibrations acting as tuning modes, they open a new channel for the ultrafast exciton transfer through the resulting conical intersection.

Citing Articles

Machine learning photodynamics decode multiple singlet fission channels in pentacene crystal.

Li Z, Hernandez F, Salguero C, Lopez S, Crespo-Otero R, Li J Nat Commun. 2025; 16(1):1194.

PMID: 39885157 PMC: 11782655. DOI: 10.1038/s41467-025-56480-y.

Ultrafast Time-Domain Spectroscopy Reveals Coherent Vibronic Couplings upon Electronic Excitation in Crystalline Organic Thin Films.

Souri S, Timmer D, Lunemann D, Hadilou N, Winte K, De Sio A J Phys Chem Lett. 2024; 15(44):11170-11181.

PMID: 39480142 PMC: 11552073. DOI: 10.1021/acs.jpclett.4c02711.

Low- and high-frequency vibrations synergistically enhance singlet exciton fission through robust vibronic resonances.

Bhattacharyya A, Sahu A, Patra S, Tiwari V Proc Natl Acad Sci U S A. 2023; 120(49):e2310124120.

PMID: 38019862 PMC: 10710028. DOI: 10.1073/pnas.2310124120.

Theory predicts UV/vis-to-IR photonic down conversion mediated by excited state vibrational polaritons.

Terry Weatherly C, Provazza J, Weiss E, Tempelaar R Nat Commun. 2023; 14(1):4804.

PMID: 37558658 PMC: 10412565. DOI: 10.1038/s41467-023-40400-z.

Orbital-resolved observation of singlet fission.

Neef A, Beaulieu S, Hammer S, Dong S, Maklar J, Pincelli T Nature. 2023; 616(7956):275-279.

PMID: 37045918 PMC: 10097594. DOI: 10.1038/s41586-023-05814-1.

References

Monahan N, Sun D, Tamura H, Williams K, Xu B, Zhong Y . Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene. Nat Chem. 2017; 9(4):341-346. DOI: 10.1038/nchem.2665. View

Musser A, Maiuri M, Brida D, Cerullo G, Friend R, Clark J . The nature of singlet exciton fission in carotenoid aggregates. J Am Chem Soc. 2015; 137(15):5130-9. PMC: 4440407. DOI: 10.1021/jacs.5b01130. View

Rohrdanz M, Martins K, Herbert J . A long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states. J Chem Phys. 2009; 130(5):054112. DOI: 10.1063/1.3073302. View

Smith M, Michl J . Recent advances in singlet fission. Annu Rev Phys Chem. 2013; 64:361-86. DOI: 10.1146/annurev-physchem-040412-110130. View

Schiefer S, Huth M, Dobrinevski A, Nickel B . Determination of the crystal structure of substrate-induced pentacene polymorphs in fiber structured thin films. J Am Chem Soc. 2007; 129(34):10316-7. DOI: 10.1021/ja0730516. View

Duan H, Prokhorenko V, Cogdell R, Ashraf K, Stevens A, Thorwart M . Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer. Proc Natl Acad Sci U S A. 2017; 114(32):8493-8498. PMC: 5559008. DOI: 10.1073/pnas.1702261114. View

Grimme S, Antony J, Ehrlich S, Krieg H . A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. 2010; 132(15):154104. DOI: 10.1063/1.3382344. View

Harrop J, Taraskin S, Elliott S . Instantaneous frequency and amplitude identification using wavelets: application to glass structure. Phys Rev E Stat Nonlin Soft Matter Phys. 2002; 66(2 Pt 2):026703. DOI: 10.1103/PhysRevE.66.026703. View

Congreve D, Lee J, Thompson N, Hontz E, Yost S, Reusswig P . External quantum efficiency above 100% in a singlet-exciton-fission-based organic photovoltaic cell. Science. 2013; 340(6130):334-7. DOI: 10.1126/science.1232994. View

10.

Berkelbach T, Hybertsen M, Reichman D . Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange. J Chem Phys. 2013; 138(11):114103. DOI: 10.1063/1.4794427. View

11.

Xian R, Corthey G, Rogers D, Morrison C, Prokhorenko V, Hayes S . Coherent ultrafast lattice-directed reaction dynamics of triiodide anion photodissociation. Nat Chem. 2017; 9(6):516-522. DOI: 10.1038/nchem.2751. View

12.

Tsuchimoto M, Tanimura Y . Spins Dynamics in a Dissipative Environment: Hierarchal Equations of Motion Approach Using a Graphics Processing Unit (GPU). J Chem Theory Comput. 2015; 11(8):3859-65. DOI: 10.1021/acs.jctc.5b00488. View

13.

Wilson M, Rao A, Ehrler B, Friend R . Singlet exciton fission in polycrystalline pentacene: from photophysics toward devices. Acc Chem Res. 2013; 46(6):1330-8. DOI: 10.1021/ar300345h. View

14.

Wang J, Wolf R, Caldwell J, Kollman P, Case D . Development and testing of a general amber force field. J Comput Chem. 2004; 25(9):1157-74. DOI: 10.1002/jcc.20035. View

15.

Bakulin A, Morgan S, Kehoe T, Wilson M, Chin A, Zigmantas D . Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy. Nat Chem. 2015; 8(1):16-23. DOI: 10.1038/nchem.2371. View

16.

Hart S, Silva W, Frontiera R . Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission. Chem Sci. 2018; 9(5):1242-1250. PMC: 5885776. DOI: 10.1039/c7sc03496b. View

17.

Pensack R, Ostroumov E, Tilley A, Mazza S, Grieco C, Thorley K . Observation of Two Triplet-Pair Intermediates in Singlet Exciton Fission. J Phys Chem Lett. 2016; 7(13):2370-5. DOI: 10.1021/acs.jpclett.6b00947. View

18.

Zeng T, Hoffmann R, Ananth N . The low-lying electronic states of pentacene and their roles in singlet fission. J Am Chem Soc. 2014; 136(15):5755-64. DOI: 10.1021/ja500887a. View

19.

Folie B, Haber J, Refaely-Abramson S, Neaton J, Ginsberg N . Long-Lived Correlated Triplet Pairs in a π-Stacked Crystalline Pentacene Derivative. J Am Chem Soc. 2018; 140(6):2326-2335. DOI: 10.1021/jacs.7b12662. View

20.

Tayebjee M, McCamey D, Schmidt T . Beyond Shockley-Queisser: Molecular Approaches to High-Efficiency Photovoltaics. J Phys Chem Lett. 2015; 6(12):2367-78. DOI: 10.1021/acs.jpclett.5b00716. View