An ab initio exciton model for singlet fission

Li, Xin; Parrish, Robert M.; Martínez, Todd J.

doi:10.1063/5.0028605

An ab initio exciton model for singlet fission

Journal Article · Thu Nov 12 00:00:00 EST 2020 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0028605· OSTI ID:1768626

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Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)

Here we present an ab initio exciton model that extends the Frenkel exciton model and includes valence, charge-transfer, and multiexcitonic excited states. It serves as a general, parameter-free, yet computationally efficient and scalable approach for simulation of singlet fission processes in multichromophoric systems. A comparison with multiconfigurational methods confirms that our exciton model predicts consistent energies and couplings for the pentacene dimer and captures the correct physics. Calculations of larger pentacene clusters demonstrate the computational scalability of the exciton model and suggest that the mixing between local and charge-transfer excitations narrows the gap between singlet and multiexcitonic states. Local vibrations of pentacene molecules are found to facilitate singlet–multiexcitonic state-crossing and hence are important for understanding singlet fission. The exciton model developed in this work also sets the stage for further implementation of the nuclear gradients and nonadiabatic couplings needed for first principles nonadiabatic quantum molecular dynamics simulations of singlet fission.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: Knut and Alice Wallenberg Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1768626

Alternate ID(s):: OSTI ID: 1712545

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 153; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

References (61)

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
TeraChem : A graphical processing unit ‐accelerated electronic structure package for large‐scale ab initio molecular dynamics Seritan, Stefan; Bannwarth, Christoph; Fales, Bryan S. WIREs Computational Molecular Science https://doi.org/10.1002/wcms.1494	journal	July 2020
Wavefunction methods for noncovalent interactions: Noncovalent interactions Hohenstein, Edward G.; Sherrill, C. David Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.84	journal	July 2011
Psi4: an open-source ab initio electronic structure program : Psi4: an electronic structure program Turney, Justin M.; Simmonett, Andrew C.; Parrish, Robert M. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 4 https://doi.org/10.1002/wcms.93	journal	October 2011
Bimolecular radiationless transitions in crystalline tetracene Swenberg, C. E.; Stacy, W. T. Chemical Physics Letters, Vol. 2, Issue 5 https://doi.org/10.1016/0009-2614(68)80087-9	journal	September 1968
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
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
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
On-the-Fly CASPT2 Surface-Hopping Dynamics Park, Jae Woo; Shiozaki, Toru Journal of Chemical Theory and Computation, Vol. 13, Issue 8 https://doi.org/10.1021/acs.jctc.7b00559	journal	July 2017
Dynamical Correlation Effects on Photoisomerization: Ab Initio Multiple Spawning Dynamics with MS-CASPT2 for a Model trans -Protonated Schiff Base Liu, Lihong; Liu, Jian; Martinez, Todd J. The Journal of Physical Chemistry B, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcb.5b09838	journal	November 2015
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
Low-Scaling Quantum Chemistry Approach to Excited-State Properties via an ab Initio Exciton Model: Application to Excitation Energy Transfer in a Self-Assembled Nanotube Morrison, Adrian F.; Herbert, John M. The Journal of Physical Chemistry Letters, Vol. 6, Issue 21 https://doi.org/10.1021/acs.jpclett.5b02109	journal	October 2015
Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene Morrison, Adrian F.; Herbert, John M. The Journal of Physical Chemistry Letters, Vol. 8, Issue 7 https://doi.org/10.1021/acs.jpclett.7b00230	journal	March 2017
Singlet Fission in Crystalline Organic Materials: Recent Insights and Future Directions Felter, Kevin M.; Grozema, Ferdinand C. The Journal of Physical Chemistry Letters, Vol. 10, Issue 22 https://doi.org/10.1021/acs.jpclett.9b00754	journal	October 2019
A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers Fuemmeler, Eric G.; Sanders, Samuel N.; Pun, Andrew B. ACS Central Science, Vol. 2, Issue 5 https://doi.org/10.1021/acscentsci.6b00063	journal	May 2016
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
Perturbation Theory Approach to Intermolecular Potential Energy Surfaces of van der Waals Complexes Jeziorski, Bogumil; Moszynski, Robert; Szalewicz, Krzysztof Chemical Reviews, Vol. 94, Issue 7 https://doi.org/10.1021/cr00031a008	journal	November 1994
Singlet Fission Smith, Millicent B.; Michl, Josef Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr1002613	journal	November 2010
Perspectives on Basis Sets Beautiful: Seasonal Plantings of Diffuse Basis Functions Papajak, Ewa; Zheng, Jingjing; Xu, Xuefei Journal of Chemical Theory and Computation, Vol. 7, Issue 10 https://doi.org/10.1021/ct200106a	journal	August 2011
Ab Initio Implementation of the Frenkel–Davydov Exciton Model: A Naturally Parallelizable Approach to Computing Collective Excitations in Crystals and Aggregates Morrison, Adrian F.; You, Zhi-Qiang; Herbert, John M. Journal of Chemical Theory and Computation, Vol. 10, Issue 12 https://doi.org/10.1021/ct500765m	journal	November 2014
Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics Ufimtsev, Ivan S.; Martinez, Todd J. Journal of Chemical Theory and Computation, Vol. 5, Issue 10 https://doi.org/10.1021/ct9003004	journal	August 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
Exciton Fission and Charge Generation via Triplet Excitons in Pentacene/C ₆₀ Bilayers Rao, Akshay; Wilson, Mark W. B.; Hodgkiss, Justin M. Journal of the American Chemical Society, Vol. 132, Issue 36 https://doi.org/10.1021/ja1042462	journal	September 2010
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
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
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
Ab Initio Molecular Dynamics of Excited-State Intramolecular Proton Transfer Using Multireference Perturbation Theory ^† Coe, Joshua D.; Levine, Benjamin G.; Martínez, Todd J. The Journal of Physical Chemistry A, Vol. 111, Issue 44 https://doi.org/10.1021/jp072027b	journal	November 2007
Role of Rydberg States in the Photochemical Dynamics of Ethylene Mori, Toshifumi; Glover, William J.; Schuurman, Michael S. The Journal of Physical Chemistry A, Vol. 116, Issue 11 https://doi.org/10.1021/jp2097185	journal	December 2011
Ab Initio Multiple Spawning Dynamics Using Multi-State Second-Order Perturbation Theory Tao, Hongli; Levine, Benjamin G.; Martínez, Todd J. The Journal of Physical Chemistry A, Vol. 113, Issue 49 https://doi.org/10.1021/jp9063565	journal	December 2009
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
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
Atomistic non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model Sisto, Aaron; Stross, Clem; van der Kamp, Marc W. Physical Chemistry Chemical Physics, Vol. 19, Issue 23 https://doi.org/10.1039/c7cp00492c	journal	January 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
The direct calculation of diabatic states based on configurational uniformity Nakamura, Hisao; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 115, Issue 22 https://doi.org/10.1063/1.1412879	journal	January 2001
Direct diabatization of electronic states by the fourfold way. II. Dynamical correlation and rearrangement processes Nakamura, Hisao; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 117, Issue 12 https://doi.org/10.1063/1.1500734	journal	September 2002
Laser Generation of Excitons and Fluorescence in Anthracene Crystals Singh, S.; Jones, W. J.; Siebrand, W. The Journal of Chemical Physics, Vol. 42, Issue 1 https://doi.org/10.1063/1.1695695	journal	January 1965
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
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
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
Assessment of the ΔSCF density functional theory approach for electronic excitations in organic dyes Kowalczyk, Tim; Yost, Shane R.; Voorhis, Troy Van The Journal of Chemical Physics, Vol. 134, Issue 5 https://doi.org/10.1063/1.3530801	journal	February 2011
The nature of singlet excitons in oligoacene molecular crystals Yamagata, H.; Norton, J.; Hontz, E. The Journal of Chemical Physics, Vol. 134, Issue 20 https://doi.org/10.1063/1.3590871	journal	May 2011
Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory Granovsky, Alexander A. The Journal of Chemical Physics, Vol. 134, Issue 21 https://doi.org/10.1063/1.3596699	journal	June 2011
Ultrafast internal conversion in ethylene. I. The excited state lifetime Tao, H.; Allison, T. K.; Wright, T. W. The Journal of Chemical Physics, Vol. 134, Issue 24 https://doi.org/10.1063/1.3604007	journal	June 2011
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
Fully optimized contracted Gaussian basis sets for atoms Li to Kr Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 97, Issue 4 https://doi.org/10.1063/1.463096	journal	August 1992
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
Levels of symmetry adapted perturbation theory (SAPT). I. Efficiency and performance for interaction energies Parker, Trent M.; Burns, Lori A.; Parrish, Robert M. The Journal of Chemical Physics, Vol. 140, Issue 9 https://doi.org/10.1063/1.4867135	journal	March 2014
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
Vibronic exciton theory of singlet fission. I. Linear absorption and the anatomy of the correlated triplet pair state Tempelaar, Roel; Reichman, David R. The Journal of Chemical Physics, Vol. 146, Issue 17 https://doi.org/10.1063/1.4982362	journal	May 2017
Analytic derivative couplings and first-principles exciton/phonon coupling constants for an ab initio Frenkel-Davydov exciton model: Theory, implementation, and application to compute triplet exciton mobility parameters for crystalline tetracene Morrison, Adrian F.; Herbert, John M. The Journal of Chemical Physics, Vol. 146, Issue 22 https://doi.org/10.1063/1.4985607	journal	June 2017
Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations Glover, William J.; Mori, Toshifumi; Schuurman, Michael S. The Journal of Chemical Physics, Vol. 148, Issue 16 https://doi.org/10.1063/1.5018130	journal	April 2018
TeraChem: Accelerating electronic structure and ab initio molecular dynamics with graphical processing units Seritan, Stefan; Bannwarth, Christoph; Fales, B. Scott The Journal of Chemical Physics, Vol. 152, Issue 22 https://doi.org/10.1063/5.0007615	journal	June 2020
Conical intersections and double excitations in time-dependent density functional theory Levine, Benjamin G.; Ko, Chaehyuk; Quenneville, Jason Molecular Physics, Vol. 104, Issue 5-7 https://doi.org/10.1080/00268970500417762	journal	March 2006
On the Quantum Correction For Thermodynamic Equilibrium Wigner, E. Physical Review, Vol. 40, Issue 5 https://doi.org/10.1103/physrev.40.749	journal	June 1932
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
Effect of Magnetic Field on the Fluorescence of Tetracene Crystals: Exciton Fission Geacintov, N.; Pope, M.; Vogel, F. Physical Review Letters, Vol. 22, Issue 12 https://doi.org/10.1103/physrevlett.22.593	journal	March 1969
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
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

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An ab initio exciton model for singlet fission

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