Intermolecular vibrations mediate ultrafast singlet fission

Duan, Hong-Guang; Jha, Ajay; Li, Xin; Tiwari, Vandana; Ye, Hanyang; Nayak, Pabitra K.; Zhu, Xiao-Lei; Li, Zheng; Martinez, Todd J.; Thorwart, Michael; Miller, R. J.  Dwayne

doi:10.1126/sciadv.abb0052

Intermolecular vibrations mediate ultrafast singlet fission

Journal Article · Fri Sep 18 00:00:00 EDT 2020 · Science Advances

DOI:https://doi.org/10.1126/sciadv.abb0052· OSTI ID:1817119

^[1]; ^[2]; Li, Xin ^[3]; ^[4]; ^[5]; ^[6]; ^[7]; ^[8]; ^[9]; ^[10]; ^[11]

Max Planck Institute for the Structure and Dynamics of Matter, Hamburg (Germany); Universität Hamburg, (Germany). I. Institut für Theoretische Physik; The Hamburg Center for Ultrafast Imaging, Hamburg (Germany); OSTI
Max Planck Institute for the Structure and Dynamics of Matter, Hamburg (Germany)
Stanford Univ., CA (United States). Dept. of Chemistry. PULSE Inst.
Max Planck Institute for the Structure and Dynamics of Matter, Hamburg (Germany); Universität Hamburg, (Germany). Dept. of Chemistry
Univ. of Oxford (United Kingdom). Clarendon Lab. Dept. of Physics
TIFR Centre for Interdisciplinary Sciences, Hyderabad (India)
Stanford Univ., CA (United States). Dept. of Chemistry. PULSE Inst.
Max Planck Institute for the Structure and Dynamics of Matter, Hamburg (Germany); Peking Univ., Beijing (China). School of Physics. State Key Lab. for Mesoscopic Physics
Stanford Univ., CA (United States). Dept. of Chemistry. PULSE Inst.; SLAC National Accelerator Lab., Menlo Park, CA (United States)
Universität Hamburg, (Germany). I. Institut für Theoretische Physik; The Hamburg Center for Ultrafast Imaging, Hamburg (Germany)
Max Planck Institute for the Structure and Dynamics of Matter, Hamburg (Germany); The Hamburg Center for Ultrafast Imaging, Hamburg (Germany); Univ. of Toronto, ON (Canada). Depts. of Chemistry and Physics

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.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1817119

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 38 Vol. 6; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (59)

Research data supporting "Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission" Stern, H.; Cheminal, A.; Broch, K. Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.12611	dataset	January 2017
Development and testing of a general amber force field Wang, Junmei; Wolf, Romain M.; Caldwell, James W. Journal of Computational Chemistry, Vol. 25, Issue 9 https://doi.org/10.1002/jcc.20035	journal	January 2004
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
Exciton dynamics in pentacene thin films studied by pump-probe spectroscopy Jundt, C.; Klein, G.; Sipp, B. Chemical Physics Letters, Vol. 241, Issue 1-2 https://doi.org/10.1016/0009-2614(95)00603-2	journal	July 1995
Vibrational vs. electronic coherences in 2D spectrum of molecular systems Butkus, Vytautas; Zigmantas, Donatas; Valkunas, Leonas Chemical Physics Letters, Vol. 545 https://doi.org/10.1016/j.cplett.2012.07.014	journal	August 2012
Triplet Pair States in Singlet Fission Miyata, Kiyoshi; Conrad-Burton, Felisa S.; Geyer, Florian L. Chemical Reviews, Vol. 119, Issue 6 https://doi.org/10.1021/acs.chemrev.8b00572	journal	January 2019
Spins Dynamics in a Dissipative Environment: Hierarchal Equations of Motion Approach Using a Graphics Processing Unit (GPU) Tsuchimoto, Masashi; Tanimura, Yoshitaka Journal of Chemical Theory and Computation, Vol. 11, Issue 8 https://doi.org/10.1021/acs.jctc.5b00488	journal	July 2015
An Ab Initio Exciton Model Including Charge-Transfer Excited States Li, Xin; Parrish, Robert M.; Liu, Fang Journal of Chemical Theory and Computation, Vol. 13, Issue 8 https://doi.org/10.1021/acs.jctc.7b00171	journal	July 2017
Beyond Shockley–Queisser: Molecular Approaches to High-Efficiency Photovoltaics Tayebjee, Murad J. Y.; McCamey, Dane R.; Schmidt, Timothy W. The Journal of Physical Chemistry Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acs.jpclett.5b00716	journal	June 2015
Density Analysis of Intra- and Intermolecular Vibronic Couplings toward Bath Engineering for Singlet Fission Ito, Soichi; Nagami, Takanori; Nakano, Masayoshi The Journal of Physical Chemistry Letters, Vol. 6, Issue 24 https://doi.org/10.1021/acs.jpclett.5b02249	journal	December 2015
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
Ultrafast Energy Transfer in Excitonically Coupled Molecules Induced by a Nonlocal Peierls Phonon Duan, Hong-Guang; Nalbach, Peter; Miller, R. J. Dwayne The Journal of Physical Chemistry Letters, Vol. 10, Issue 6 https://doi.org/10.1021/acs.jpclett.9b00242	journal	February 2019
Direct Observation of Ultrafast Exciton Dissociation in Lead Iodide Perovskite by 2D Electronic Spectroscopy Jha, Ajay; Duan, Hong-Guang; Tiwari, Vandana ACS Photonics, Vol. 5, Issue 3 https://doi.org/10.1021/acsphotonics.7b01025	journal	December 2017
Singlet Exciton Fission in Polycrystalline Pentacene: From Photophysics toward Devices Wilson, Mark W. B.; Rao, Akshay; Ehrler, Bruno Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300345h	journal	May 2013
Ab Initio Nonadiabatic Dynamics of Multichromophore Complexes: A Scalable Graphical-Processing-Unit-Accelerated Exciton Framework Sisto, Aaron; Glowacki, David R.; Martinez, Todd J. Accounts of Chemical Research, Vol. 47, Issue 9 https://doi.org/10.1021/ar500229p	journal	July 2014
Singlet Fission Smith, Millicent B.; Michl, Josef Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr1002613	journal	November 2010
Quantum Chemistry on Graphical Processing Units. 2. Direct Self-Consistent-Field Implementation Ufimtsev, Ivan S.; Martinez, Todd J. Journal of Chemical Theory and Computation, Vol. 5, Issue 4 https://doi.org/10.1021/ct800526s	journal	March 2009
Determination of the Crystal Structure of Substrate-Induced Pentacene Polymorphs in Fiber Structured Thin Films Schiefer, Stefan; Huth, Martin; Dobrinevski, Alexander Journal of the American Chemical Society, Vol. 129, Issue 34 https://doi.org/10.1021/ja0730516	journal	August 2007
The Low-Lying Electronic States of Pentacene and Their Roles in Singlet Fission Zeng, Tao; Hoffmann, Roald; Ananth, Nandini Journal of the American Chemical Society, Vol. 136, Issue 15 https://doi.org/10.1021/ja500887a	journal	April 2014
The Nature of Singlet Exciton Fission in Carotenoid Aggregates Musser, Andrew J.; Maiuri, Margherita; Brida, Daniele Journal of the American Chemical Society, Vol. 137, Issue 15 https://doi.org/10.1021/jacs.5b01130	journal	April 2015
Quantitative Intramolecular Singlet Fission in Bipentacenes Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B. Journal of the American Chemical Society, Vol. 137, Issue 28 https://doi.org/10.1021/jacs.5b04986	journal	July 2015
Direct Observation of a Charge-Transfer State Preceding High-Yield Singlet Fission in Terrylenediimide Thin Films Margulies, Eric A.; Logsdon, Jenna L.; Miller, Claire E. Journal of the American Chemical Society, Vol. 139, Issue 2 https://doi.org/10.1021/jacs.6b07721	journal	December 2016
Triplet Separation Drives Singlet Fission after Femtosecond Correlated Triplet Pair Production in Rubrene Breen, Ilana; Tempelaar, Roel; Bizimana, Laurie A. Journal of the American Chemical Society, Vol. 139, Issue 34 https://doi.org/10.1021/jacs.7b02621	journal	August 2017
Long-Lived Correlated Triplet Pairs in a π-Stacked Crystalline Pentacene Derivative Folie, Brendan D.; Haber, Jonah B.; Refaely-Abramson, Sivan Journal of the American Chemical Society, Vol. 140, Issue 6 https://doi.org/10.1021/jacs.7b12662	journal	February 2018
Vibronic and Vibrational Coherences in Two-Dimensional Electronic Spectra of Supramolecular J-Aggregates Milota, Franz; Prokhorenko, Valentyn I.; Mancal, Tomas The Journal of Physical Chemistry A, Vol. 117, Issue 29 https://doi.org/10.1021/jp3119605	journal	March 2013
Long-Lived Electronic Coherence in Dissipative Exciton Dynamics of Light-Harvesting Complexes Kreisbeck, Christoph; Kramer, Tobias The Journal of Physical Chemistry Letters, Vol. 3, Issue 19 https://doi.org/10.1021/jz3012029	journal	September 2012
The energy barrier in singlet fission can be overcome through coherent coupling and entropic gain Chan, Wai-Lun; Ligges, Manuel; Zhu, X-Y. Nature Chemistry, Vol. 4, Issue 10 https://doi.org/10.1038/nchem.1436	journal	August 2012
Two-dimensional spectroscopy of a molecular dimer unveils the effects of vibronic coupling on exciton coherences Halpin, Alexei; Johnson, Philip J. M.; Tempelaar, Roel Nature Chemistry, Vol. 6, Issue 3 https://doi.org/10.1038/nchem.1834	journal	January 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
Local vibrational coherences drive the primary photochemistry of vision Johnson, Philip J. M.; Halpin, Alexei; Morizumi, Takefumi Nature Chemistry, Vol. 7, Issue 12 https://doi.org/10.1038/nchem.2398	journal	November 2015
Enabling singlet fission by controlling intramolecular charge transfer in π-stacked covalent terrylenediimide dimers Margulies, Eric A.; Miller, Claire E.; Wu, Yilei Nature Chemistry, Vol. 8, Issue 12 https://doi.org/10.1038/nchem.2589	journal	August 2016
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
Coherent ultrafast lattice-directed reaction dynamics of triiodide anion photodissociation Xian, Rui; Corthey, Gastón; Rogers, David M. Nature Chemistry, Vol. 9, Issue 6 https://doi.org/10.1038/nchem.2751	journal	March 2017
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
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
Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering Lukman, Steven; Chen, Kai; Hodgkiss, Justin M. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13622	journal	December 2016
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
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
Two-dimensional Fourier transform electronic spectroscopy Hybl, John D.; Albrecht Ferro, Allison; Jonas, David M. The Journal of Chemical Physics, Vol. 115, Issue 14, p. 6606-6622 https://doi.org/10.1063/1.1398579	journal	October 2001
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 Rohrdanz, Mary A.; Martins, Katie M.; Herbert, John M. The Journal of Chemical Physics, Vol. 130, Issue 5 https://doi.org/10.1063/1.3073302	journal	February 2009
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
New method for calculating wave packet dynamics: Strongly coupled surfaces and the adiabatic basis Manthe, U.; Köppel, H. The Journal of Chemical Physics, Vol. 93, Issue 1 https://doi.org/10.1063/1.459606	journal	July 1990
Microscopic theory of singlet exciton fission. I. General formulation Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R. The Journal of Chemical Physics, Vol. 138, Issue 11 https://doi.org/10.1063/1.4794425	journal	March 2013
Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R. The Journal of Chemical Physics, Vol. 138, Issue 11 https://doi.org/10.1063/1.4794427	journal	March 2013
Slow light enhanced singlet exciton fission solar cells with a 126% yield of electrons per photon Thompson, Nicholas J.; Congreve, Daniel N.; Goldberg, David Applied Physics Letters, Vol. 103, Issue 26 https://doi.org/10.1063/1.4858176	journal	December 2013
Microscopic theory of singlet exciton fission. III. Crystalline pentacene Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R. The Journal of Chemical Physics, Vol. 141, Issue 7 https://doi.org/10.1063/1.4892793	journal	August 2014
Tracking an electronic wave packet in the vicinity of a conical intersection Qi, Da-Long; Duan, Hong-Guang; Sun, Zhen-Rong The Journal of Chemical Physics, Vol. 147, Issue 7 https://doi.org/10.1063/1.4989462	journal	August 2017
Singlet fission in pentacene dimers Zirzlmeier, Johannes; Lehnherr, Dan; Coto, Pedro B. Proceedings of the National Academy of Sciences, Vol. 112, Issue 17 https://doi.org/10.1073/pnas.1422436112	journal	April 2015
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
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
Instantaneous frequency and amplitude identification using wavelets: Application to glass structure Harrop, J. D.; Taraskin, S. N.; Elliott, S. R. Physical Review E, Vol. 66, Issue 2 https://doi.org/10.1103/PhysRevE.66.026703	journal	August 2002
First-Principles Quantum Dynamics of Singlet Fission: Coherent versus Thermally Activated Mechanisms Governed by Molecular π Stacking Tamura, Hiroyuki; Huix-Rotllant, Miquel; Burghardt, Irene Physical Review Letters, Vol. 115, Issue 10 https://doi.org/10.1103/PhysRevLett.115.107401	journal	August 2015
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
Wavelets: the mathematical background Cohen, A.; Kovacevic, J. Proceedings of the IEEE, Vol. 84, Issue 4 https://doi.org/10.1109/5.488697	journal	April 1996
External Quantum Efficiency Above 100% in a Singlet-Exciton-Fission-Based Organic Photovoltaic Cell Congreve, D. N.; Lee, J.; Thompson, N. J. Science, Vol. 340, Issue 6130 https://doi.org/10.1126/science.1232994	journal	April 2013
Quantum Dynamics of System Strongly Coupled to Low-Temperature Colored Noise Bath: Reduced Hierarchy Equations Approach Ishizaki, Akihito; Tanimura, Yoshitaka Journal of the Physical Society of Japan, Vol. 74, Issue 12 https://doi.org/10.1143/JPSJ.74.3131	journal	December 2005
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
Vibrational and Nonadiabatic Coherence in 2D Electronic Spectroscopy, the Jahn–Teller Effect, and Energy Transfer Jonas, David M. Annual Review of Physical Chemistry, Vol. 69, Issue 1 https://doi.org/10.1146/annurev-physchem-052516-050602	journal	April 2018

Similar Records

Vibronic fingerprint of singlet fission in hexacene

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

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Intermolecular vibrations mediate ultrafast singlet fission

Citation Formats

References (59)

Similar Records

Related Subjects