Interplay of coulomb and exciton–phonon coupling controls singlet fission dynamics in two pentacene polymorphs

Arias, Dylan H.; Cohen, Galit; Damrauer, Niels H.; Refaely-Abramson, Sivan; Johnson, Justin C.

doi:10.1063/5.0222551

Interplay of coulomb and exciton–phonon coupling controls singlet fission dynamics in two pentacene polymorphs

Journal Article · Tue Sep 03 00:00:00 EDT 2024 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0222551· OSTI ID:2447473

Arias, Dylan H. ^[1]; ^[2]; ^[3]; ^[2]; ^[1]

National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Weizmann Institute of Science, Rehovot (Israel)
University of Colorado, Boulder, CO (United States)

Pentacene is an important model organic semiconductor in both the singlet exciton fission (SF) and organic electronics communities. We have investigated the effect of changing crystal structure on the SF process, generating multiple triplet excitons from an initial singlet exciton, and subsequent triplet recombination. Unlike for similar organic semiconductors that have strong SF sensitive to polymorphism, we find almost no quantitative difference between the kinetics of triplet pair (TT) formation in the two dominant polymorphs of pentacene. Both pairwise dimer coupling and momentum-space crystal models predict much faster TT formation from the bright singlet excited state of the Bulk vs ThinFilm polymorph, contrasting with the experiment. GW and Bethe–Salpeter equation calculations, including exciton–phonon coupling, reveal that ultrafast phonon-driven transitions in the ThinFilm polymorph compensate the intrinsically slower purely Coulomb-mediated TT formation channel, rationalizing the similarity in observed rates. Taking into account the influence of subtle structural distinctions on both the direct and phonon-mediated SF pathways reveals a predictive capability to these methods, expected to be applicable to a wide variety of molecular crystals.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: European Research Council (ERC); Israel Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 2447473

Report Number(s):: NREL/JA--5900-90283; MainId:92061; UUID:a0dcc77e-bbd2-4bde-bffa-911374abf444; MainAdminId:73790

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 161; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (37)

Charge transfer transitions in solid tetracene and pentacene studied by electroabsorption Sebastian, L.; Weiser, G.; Bässler, H. Chemical Physics, Vol. 61, Issue 1-2 https://doi.org/10.1016/0301-0104(81)85055-0	journal	October 1981
Molecular Control of Triplet-Pair Spin Polarization and Its Optoelectronic Magnetic Resonance Probes Reid, Obadiah G.; Johnson, Justin C.; Eaves, Joel D. Accounts of Chemical Research, Vol. 57, Issue 1 https://doi.org/10.1021/acs.accounts.3c00556	journal	December 2023
How Morphology Affects Singlet Fission in Crystalline Tetracene Piland, Geoffrey B.; Bardeen, Christopher J. The Journal of Physical Chemistry Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acs.jpclett.5b00569	journal	May 2015
Locally Broken Crystal Symmetry Facilitates Singlet Exciton Fission Petelenz, Piotr; Snamina, Mateusz The Journal of Physical Chemistry Letters, Vol. 7, Issue 10 https://doi.org/10.1021/acs.jpclett.6b00746	journal	May 2016
Observation of Two Triplet-Pair Intermediates in Singlet Exciton Fission Pensack, Ryan D.; Ostroumov, Evgeny E.; Tilley, Andrew J. The Journal of Physical Chemistry Letters, Vol. 7, Issue 13 https://doi.org/10.1021/acs.jpclett.6b00947	journal	June 2016
Signatures of Dimensionality and Symmetry in Exciton Band Structure: Consequences for Exciton Dynamics and Transport Qiu, Diana Y.; Cohen, Galit; Novichkova, Dana Nano Letters, Vol. 21, Issue 18 https://doi.org/10.1021/acs.nanolett.1c02352	journal	August 2021
The Dynamics of Singlet Fission in Crystalline Tetracene and Covalent Analogs Burdett, Jonathan J.; Bardeen, Christopher J. Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300191w	journal	January 2013
Controlling Polymorphic Transformations of Pentacene Crystal through Solvent Treatments: An Experimental and Theoretical Study Cheng, Horng-Long; Lin, Jr-Wei Crystal Growth & Design, Vol. 10, Issue 10 https://doi.org/10.1021/cg100760t	journal	October 2010
Singlet Fission for Dye-Sensitized Solar Cells: Can a Suitable Sensitizer Be Found? Paci, Irina; Johnson, Justin C.; Chen, Xudong Journal of the American Chemical Society, Vol. 128, Issue 51 https://doi.org/10.1021/ja063980h	journal	December 2006
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
Dynamic Exchange During Triplet Transport in Nanocrystalline TIPS-Pentacene Films Grieco, Christopher; Doucette, Grayson S.; Pensack, Ryan D. Journal of the American Chemical Society, Vol. 138, Issue 49 https://doi.org/10.1021/jacs.6b10010	journal	December 2016
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
A Road Map to Stable, Soluble, Easily Crystallized Pentacene Derivatives Anthony, John E.; Eaton, David L.; Parkin, Sean R. Organic Letters, Vol. 4, Issue 1 https://doi.org/10.1021/ol0167356	journal	January 2002
A transferable model for singlet-fission kinetics Yost, Shane R.; Lee, Jiye; Wilson, Mark W. B. Nature Chemistry, Vol. 6, Issue 6 https://doi.org/10.1038/nchem.1945	journal	May 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
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 Nature Chemistry, Vol. 9, Issue 4 https://doi.org/10.1038/nchem.2665	journal	December 2016
Ultra-flexible solution-processed organic field-effect transistors Yi, Hee Taek; Payne, Marcia M.; Anthony, John E. Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms2263	journal	January 2012
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
19.31% binary organic solar cell and low non-radiative recombination enabled by non-monotonic intermediate state transition Fu, Jiehao; Fong, Patrick W. K.; Liu, Heng Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-37526-5	journal	March 2023
Orbital-resolved observation of singlet fission Neef, Alexander; Beaulieu, Samuel; Hammer, Sebastian Nature, Vol. 616, Issue 7956 https://doi.org/10.1038/s41586-023-05814-1	journal	April 2023
Polymorphism influences singlet fission rates in tetracene thin films Arias, Dylan H.; Ryerson, Joseph L.; Cook, Jasper D. Chemical Science, Vol. 7, Issue 2 https://doi.org/10.1039/c5sc03535j	journal	January 2016
Efficient thin-film organic solar cells based on pentacene/C60 heterojunctions Yoo, S.; Domercq, B.; Kippelen, B. Applied Physics Letters, Vol. 85, Issue 22 https://doi.org/10.1063/1.1829777	journal	November 2004
Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers Hanna, M. C.; Nozik, A. J. Journal of Applied Physics, Vol. 100, Issue 7 https://doi.org/10.1063/1.2356795	journal	October 2006
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
Photophysics of pentacene thin films: The role of exciton fission and heating effects Rao, Akshay; Wilson, Mark W. B.; Albert-Seifried, Sebastian Physical Review B, Vol. 84, Issue 19 https://doi.org/10.1103/Physrevb.84.195411	journal	November 2011
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
Theory of exciton-phonon coupling Antonius, Gabriel; Louie, Steven G. Physical Review B, Vol. 105, Issue 8 https://doi.org/10.1103/physrevb.105.085111	journal	February 2022
Electron-hole excitations and optical spectra from first principles Rohlfing, Michael; Louie, Steven G. Physical Review B, Vol. 62, Issue 8 https://doi.org/10.1103/physrevb.62.4927	journal	August 2000
Electron-Phonon Coupling in Crystalline Pentacene Films Hatch, Richard C.; Huber, David L.; Höchst, Hartmut Physical Review Letters, Vol. 104, Issue 4 https://doi.org/10.1103/physrevlett.104.047601	journal	January 2010
Charge-Transfer Excitations Steer the Davydov Splitting and Mediate Singlet Exciton Fission in Pentacene Beljonne, D.; Yamagata, H.; Brédas, J. L. Physical Review Letters, Vol. 110, Issue 22 https://doi.org/10.1103/physrevlett.110.226402	journal	May 2013
Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach Refaely-Abramson, Sivan; da Jornada, Felipe H.; Louie, Steven G. Physical Review Letters, Vol. 119, Issue 26 https://doi.org/10.1103/physrevlett.119.267401	journal	December 2017
Exciton Delocalization and Superradiance in Tetracene Thin Films and Nanoaggregates Lim, Sang-Hyun; Bjorklund, Thomas G.; Spano, Frank C. Physical Review Letters, Vol. 92, Issue 10 https://doi.org/10.1103/physrevlett.92.107402	journal	March 2004
Electron-phonon interactions from first principles Giustino, Feliciano Reviews of Modern Physics, Vol. 89, Issue 1 https://doi.org/10.1103/revmodphys.89.015003	journal	February 2017
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
Nuclear dynamics of singlet exciton fission in pentacene single crystals Seiler, Hélène; Krynski, Marcin; Zahn, Daniela Science Advances, Vol. 7, Issue 26 https://doi.org/10.1126/sciadv.abg0869	journal	June 2021
Two temperature regimes of triplet transfer in the dissociation of the correlated triplet pair after singlet fission Lee, Tia S.; Lin, YunHui L.; Kim, Hwon Canadian Journal of Chemistry, Vol. 97, Issue 6 https://doi.org/10.1139/cjc-2018-0421	journal	June 2019
Toward high-mobility organic field-effect transistors: Control of molecular packing and large-area fabrication of single-crystal-based devices Li, Hanying; Giri, Gaurav; Tok, Jeffrey B. -H. MRS Bulletin, Vol. 38, Issue 1 https://doi.org/10.1557/mrs.2012.309	journal	January 2013

Similar Records

Phenylated Acene Derivatives as Candidates for Intermolecular Singlet Fission

Journal Article · Sun Feb 17 19:00:00 EST 2019 · Journal of Physical Chemistry. C · OSTI ID:1530410

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

Journal Article · Thu Apr 01 00:00:00 EDT 2021 · Journal of Physical Chemistry Letters · OSTI ID:1813945

Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
dark states
electronic coupling
excitons
organic semiconductors
phonons
polymorphism
potential energy surfaces
solar cell efficiency
thin films
triplet state

Interplay of coulomb and exciton–phonon coupling controls singlet fission dynamics in two pentacene polymorphs

Citation Formats

References (37)

Similar Records

Related Subjects