Singlet Fission Driven by Anisotropic Vibronic Coupling in Single-Crystalline Pentacene

Deng, Gang-Hua; Qian, Yuqin; Li, Xia; Zhang, Tong; Jiang, Wei; Harutyunyan, Avetek R; Chen, Gugang; Chen, Hanning; Rao, Yi

doi:10.1021/acs.jpclett.1c00397

Singlet Fission Driven by Anisotropic Vibronic Coupling in Single-Crystalline Pentacene

Journal Article · Thu Apr 01 04:00:00 EDT 2021 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.1c00397· OSTI ID:1813945

Deng, Gang-Hua; Qian, Yuqin; Li, Xia; Zhang, Tong; Jiang, Wei; Harutyunyan, Avetek R; Chen, Gugang; Chen, Hanning; Rao, Yi

Vibronic coupling is believed to play an important role in siglet fission, wherein a photoexcited singlet exciton is converted into two triplet excitons. In the present study, we examine the role of vibronic coupling in singlet fission using polarized transient absorption microscopy and ab initio simulations on single-crystalline pentacene. It was found that singlet fission in pentacene is greatly facilitated by the vibrational coherence of a 35.0 cm(-1) phonon, where anisotropic coherence persists extensively for a few picoseconds. This coherence-preserving phonon that drives the anisotropic singlet fission is made possible by a unique cross-axial charge-transfer intermediate state. In the same fashion, this phonon was also found to predominantly drive the quantum decohence of a correlated triplet pair to form a decoupled triplet dimer. Moreover, our transient kinetic experimental data illustrates notable directional anisotropicity of the singlet fission rate in single-crystalline pentacene.

Research Organization:: Argonne National Laboratory (ANL)

Sponsoring Organization:: Utah State University; Honda R&D Americas Inc.

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1813945

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 12 Vol. 12; ISSN 1948-7185

Country of Publication:: United States

Language:: English

References (51)

Computer Simulation of Singlet Fission in Single Crystalline Pentacene by Functional Mode Vibronic Theory Elenewski, Justin E.; Cubeta, Ulyana S.; Ko, Edward The Journal of Physical Chemistry C, Vol. 121, Issue 21 https://doi.org/10.1021/acs.jpcc.7b03107	journal	May 2017
Observing the Multiexciton State in Singlet Fission and Ensuing Ultrafast Multielectron Transfer Chan, W. -L.; Ligges, M.; Jailaubekov, A. Science, Vol. 334, Issue 6062 https://doi.org/10.1126/science.1213986	journal	December 2011
Photovoltaic concepts inspired by coherence effects in photosynthetic systems Brédas, Jean-Luc; Sargent, Edward H.; Scholes, Gregory D. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4767	journal	December 2016
Vibrational coherence probes the mechanism of ultrafast electron transfer in polymer–fullerene blends Song, Yin; Clafton, Scott N.; Pensack, Ryan D. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5933	journal	September 2014
Vibronic coupling in organic semiconductors for photovoltaics De Sio, Antonietta; Lienau, Christoph Physical Chemistry Chemical Physics, Vol. 19, Issue 29 https://doi.org/10.1039/C7CP03007J	journal	January 2017
Long-lived quantum coherence in photosynthetic complexes at physiological temperature Panitchayangkoon, G.; Hayes, D.; Fransted, K. A. Proceedings of the National Academy of Sciences, Vol. 107, Issue 29 https://doi.org/10.1073/pnas.1005484107	journal	July 2010
Tracking the coherent generation of polaron pairs in conjugated polymers De Sio, Antonietta; Troiani, Filippo; Maiuri, Margherita Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13742	journal	December 2016
Polarized Absorption in Crystalline Pentacene: Theory vs Experiment Hestand, N. J.; Yamagata, H.; Xu, Bolei The Journal of Physical Chemistry C, Vol. 119, Issue 38 https://doi.org/10.1021/acs.jpcc.5b07163	journal	September 2015
Enhanced Triplet Formation in Polycrystalline Tetracene Films by Femtosecond Optical-Pulse Shaping Grumstrup, Erik M.; Johnson, Justin C.; Damrauer, Niels H. Physical Review Letters, Vol. 105, Issue 25 https://doi.org/10.1103/PhysRevLett.105.257403	journal	December 2010
Physical vapor growth of organic semiconductors Laudise, R. A.; Kloc, Ch; Simpkins, P. G. Journal of Crystal Growth, Vol. 187, Issue 3-4 https://doi.org/10.1016/S0022-0248(98)00034-7	journal	May 1998
Exploring Non-Condon Effects in a Covalent Tetracene Dimer: How Important Are Vibrations in Determining the Electronic Coupling for Singlet Fission? Alguire, Ethan C.; Subotnik, Joseph E.; Damrauer, Niels H. The Journal of Physical Chemistry A, Vol. 119, Issue 2 https://doi.org/10.1021/jp510777c	journal	December 2014
Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy Bakulin, Artem A.; Morgan, Sarah E.; Kehoe, Tom B. Nature Chemistry, Vol. 8, Issue 1 https://doi.org/10.1038/nchem.2371	journal	October 2015
Striking the right balance of intermolecular coupling for high-efficiency singlet fission Pensack, Ryan D.; Tilley, Andrew J.; Grieco, Christopher Chemical Science, Vol. 9, Issue 29 https://doi.org/10.1039/C8SC00293B	journal	January 2018
Ultrafast Dynamics of Exciton Fission in Polycrystalline Pentacene Wilson, Mark W. B.; Rao, Akshay; Clark, Jenny Journal of the American Chemical Society, Vol. 133, Issue 31 https://doi.org/10.1021/ja201688h	journal	August 2011
Quantum coherence as a witness of vibronically hot energy transfer in bacterial reaction center Paleček, David; Edlund, Petra; Westenhoff, Sebastian Science Advances, Vol. 3, Issue 9 https://doi.org/10.1126/sciadv.1603141	journal	September 2017
Robust singlet fission in pentacene thin films with tuned charge transfer interactions Broch, K.; Dieterle, J.; Branchi, F. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03300-1	journal	March 2018
Recent Advances in Singlet Fission Smith, Millicent B.; Michl, Josef Annual Review of Physical Chemistry, Vol. 64, Issue 1 https://doi.org/10.1146/annurev-physchem-040412-110130	journal	April 2013
Propagating and confined vibrational excitations in quasicrystals Hafner, J.; Krajci, M. Journal of Physics: Condensed Matter, Vol. 5, Issue 16 https://doi.org/10.1088/0953-8984/5/16/008	journal	April 1993
Intermolecular Vibrational Modes Speed Up Singlet Fission in Perylenediimide Crystals Renaud, Nicolas; Grozema, Ferdinand C. The Journal of Physical Chemistry Letters, Vol. 6, Issue 3 https://doi.org/10.1021/jz5023575	journal	January 2015
Does Coherence Enhance Transport in Photosynthesis? Kassal, Ivan; Yuen-Zhou, Joel; Rahimi-Keshari, Saleh The Journal of Physical Chemistry Letters, Vol. 4, Issue 3 https://doi.org/10.1021/jz301872b	journal	January 2013
Singlet Fission Smith, Millicent B.; Michl, Josef Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr1002613	journal	November 2010
Coherent ultrafast charge transfer in an organic photovoltaic blend Falke, S. M.; Rozzi, C. A.; Brida, D. Science, Vol. 344, Issue 6187 https://doi.org/10.1126/science.1249771	journal	May 2014
Functional Mode Singlet Fission Theory Elenewski, Justin E.; Cubeta, Ulyana S.; Ko, Edward The Journal of Physical Chemistry C, Vol. 121, Issue 8 https://doi.org/10.1021/acs.jpcc.6b11722	journal	February 2017
Quantum Photocell: Using Quantum Coherence to Reduce Radiative Recombination and Increase Efficiency Scully, Marlan O. Physical Review Letters, Vol. 104, Issue 20 https://doi.org/10.1103/PhysRevLett.104.207701	journal	May 2010
Intermolecular vibrations mediate ultrafast singlet fission Duan, Hong-Guang; Jha, Ajay; Li, Xin Science Advances, Vol. 6, Issue 38 https://doi.org/10.1126/sciadv.abb0052	journal	September 2020
Raman Identification of Polymorphs in Pentacene Films Girlando, Alberto; Masino, Matteo; Brillante, Aldo Crystals, Vol. 6, Issue 4 https://doi.org/10.3390/cryst6040041	journal	April 2016
Coherent singlet fission activated by symmetry breaking Miyata, Kiyoshi; Kurashige, Yuki; Watanabe, Kazuya Nature Chemistry, Vol. 9, Issue 10 https://doi.org/10.1038/nchem.2784	journal	May 2017
On the Interpretation of Quantum Coherent Beats Observed in Two-Dimensional Electronic Spectra of Photosynthetic Light Harvesting Complexes Ishizaki, Akihito; Fleming, Graham R. The Journal of Physical Chemistry B, Vol. 115, Issue 19 https://doi.org/10.1021/jp112406h	journal	May 2011
Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer Duan, Hong-Guang; Prokhorenko, Valentyn I.; Cogdell, Richard J. Proceedings of the National Academy of Sciences, Vol. 114, Issue 32 https://doi.org/10.1073/pnas.1702261114	journal	July 2017
Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission Hart, Stephanie M.; Silva, W. Ruchira; Frontiera, Renee R. Chemical Science, Vol. 9, Issue 5 https://doi.org/10.1039/C7SC03496B	journal	January 2018
Quantum Coherence in Photosynthetic Light Harvesting Ishizaki, Akihito; Fleming, Graham R. Annual Review of Condensed Matter Physics, Vol. 3, Issue 1 https://doi.org/10.1146/annurev-conmatphys-020911-125126	journal	March 2012
Anisotropic Singlet Fission in Single Crystalline Hexacene Sun, Dezheng; Deng, Gang-Hua; Xu, Bolei iScience, Vol. 19 https://doi.org/10.1016/j.isci.2019.08.053	journal	September 2019
Relaxation Dynamics of Photoexcited Excitons in Rubrene Single Crystals Using Femtosecond Absorption Spectroscopy Tao, S.; Ohtani, N.; Uchida, R. Physical Review Letters, Vol. 109, Issue 9 https://doi.org/10.1103/PhysRevLett.109.097403	journal	August 2012
Vibronic fingerprint of singlet fission in hexacene Deng, Gang-Hua; Wei, Qianshun; Han, Jian The Journal of Chemical Physics, Vol. 151, Issue 5 https://doi.org/10.1063/1.5110263	journal	August 2019
On the Nature of Nonplanarity in the [N]Phenylenes Holmes, Daniel; Kumaraswamy, Sriram; Matzger, Adam J. Chemistry - A European Journal, Vol. 5, Issue 11 https://doi.org/10.1002/(SICI)1521-3765(19991105)5:11<3399::AID-CHEM3399>3.0.CO;2-V	journal	November 1999
Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells Shockley, William; Queisser, Hans J. Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519 https://doi.org/10.1063/1.1736034	journal	March 1961
Mechanism for Singlet Fission in Pentacene and Tetracene: From Single Exciton to Two Triplets Zimmerman, Paul M.; Bell, Franziska; Casanova, David Journal of the American Chemical Society, Vol. 133, Issue 49 https://doi.org/10.1021/ja208431r	journal	December 2011
Intermolecular Charge Transfer Parameters, Electron–Phonon Couplings, and the Validity of Polaron Hopping Models in Organic Semiconducting Crystals: Rubrene, Pentacene, and C ₆₀ Yang, Hui; Gajdos, Fruzsina; Blumberger, Jochen The Journal of Physical Chemistry C, Vol. 121, Issue 14 https://doi.org/10.1021/acs.jpcc.7b00618	journal	March 2017
Quantum biology revisited Cao, Jianshu; Cogdell, Richard J.; Coker, David F. Science Advances, Vol. 6, Issue 14 https://doi.org/10.1126/sciadv.aaz4888	journal	April 2020
Using coherence to enhance function in chemical and biophysical systems Scholes, Gregory D.; Fleming, Graham R.; Chen, Lin X. Nature, Vol. 543, Issue 7647 https://doi.org/10.1038/nature21425	journal	March 2017
Evidence for conical intersection dynamics mediating ultrafast singlet exciton fission Musser, Andrew J.; Liebel, Matz; Schnedermann, Christoph Nature Physics, Vol. 11, Issue 4 https://doi.org/10.1038/nphys3241	journal	March 2015
Characterization of Phase Purity in Organic Semiconductors by Lattice-Phonon Confocal Raman Mapping: Application to Pentacene Brillante, A.; Bilotti, I.; Della Valle, R. G. Advanced Materials, Vol. 17, Issue 21 https://doi.org/10.1002/adma.200501350	journal	November 2005
Analysis of Femtosecond Dynamic Absorption Spectra of Nonstationary States Pollard, W. T.; Mathies, R. A. Annual Review of Physical Chemistry, Vol. 43, Issue 1 https://doi.org/10.1146/annurev.pc.43.100192.002433	journal	October 1992
Correlated Pair States Formed by Singlet Fission and Exciton–Exciton Annihilation Scholes, Gregory D. The Journal of Physical Chemistry A, Vol. 119, Issue 51 https://doi.org/10.1021/acs.jpca.5b09725	journal	December 2015
Theoretical studies of enzymic reactions: Dielectric, electrostatic and steric stabilization of the carbonium ion in the reaction of lysozyme Warshel, A.; Levitt, M. Journal of Molecular Biology, Vol. 103, Issue 2 https://doi.org/10.1016/0022-2836(76)90311-9	journal	May 1976
Dynamics of the Excitonic Coupling in Organic Crystals Aragó, Juan; Troisi, Alessandro Physical Review Letters, Vol. 114, Issue 2 https://doi.org/10.1103/PhysRevLett.114.026402	journal	January 2015
Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission Stern, Hannah L.; Cheminal, Alexandre; Yost, Shane R. Nature Chemistry, Vol. 9, Issue 12 https://doi.org/10.1038/nchem.2856	journal	September 2017
Maximizing Singlet Fission by Intermolecular Packing Wang, Linjun; Olivier, Yoann; Prezhdo, Oleg V. The Journal of Physical Chemistry Letters, Vol. 5, Issue 19 https://doi.org/10.1021/jz5015955	journal	September 2014
Interaction of charge carriers with lattice and molecular phonons in crystalline pentacene Girlando, Alberto; Grisanti, Luca; Masino, Matteo The Journal of Chemical Physics, Vol. 135, Issue 8 https://doi.org/10.1063/1.3625293	journal	August 2011
Raman phonon spectra of pentacene polymorphs Brillante, A.; Della Valle, R. G.; Farina, L. Chemical Physics Letters, Vol. 357, Issue 1-2 https://doi.org/10.1016/S0009-2614(02)00441-4	journal	May 2002
Optical properties of pentacene thin films and single crystals Faltermeier, Daniel; Gompf, Bruno; Dressel, Martin Physical Review B, Vol. 74, Issue 12 https://doi.org/10.1103/PhysRevB.74.125416	journal	September 2006

Similar Records

Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene

Journal Article · Wed Mar 08 19:00:00 EST 2017 · Journal of Physical Chemistry Letters · OSTI ID:1604466

Long-Lived Correlated Triplet Pairs in a π-Stacked Crystalline Pentacene Derivative

Journal Article · Thu Feb 01 19:00:00 EST 2018 · Journal of the American Chemical Society · OSTI ID:1543721

Vibronic fingerprint of singlet fission in hexacene

Journal Article · Sun Aug 04 20:00:00 EDT 2019 · Journal of Chemical Physics · OSTI ID:1546868

Singlet Fission Driven by Anisotropic Vibronic Coupling in Single-Crystalline Pentacene

Citation Formats

References (51)

Similar Records

Related Subjects