Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: An ab initio exciton model for singlet fission

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Knut and Alice Wallenberg Foundation
OSTI Identifier:
1768626
Alternate Identifier(s):
OSTI ID: 1712545
Grant/Contract Number:  
AC02-76SF00515; KAW-2014.0391
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 153; Journal Issue: 18; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; diabatic states; quantum chemical dynamics; molecular dynamics; excitons; polarization; HOMO and LUMO; potential energy surfaces; self consistent field methods; excitation energies

Citation Formats

Li, Xin, Parrish, Robert M., and Martínez, Todd J. An ab initio exciton model for singlet fission. United States: N. p., 2020. Web. doi:10.1063/5.0028605.
Copy to clipboard
Li, Xin, Parrish, Robert M., & Martínez, Todd J. An ab initio exciton model for singlet fission. United States. https://doi.org/10.1063/5.0028605
Copy to clipboard
Li, Xin, Parrish, Robert M., and Martínez, Todd J. Thu . "An ab initio exciton model for singlet fission". United States. https://doi.org/10.1063/5.0028605. https://www.osti.gov/servlets/purl/1768626.
Copy to clipboard
@article{osti_1768626,
title = {An ab initio exciton model for singlet fission},
author = {Li, Xin and Parrish, Robert M. and Martínez, Todd J.},
abstractNote = {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.},
doi = {10.1063/5.0028605},
journal = {Journal of Chemical Physics},
number = 18,
volume = 153,
place = {United States},
year = {Thu Nov 12 00:00:00 EST 2020},
month = {Thu Nov 12 00:00:00 EST 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/5.0028605
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers
journal, October 2006

  • Hanna, M. C.; Nozik, A. J.
  • Journal of Applied Physics, Vol. 100, Issue 7
  • DOI: 10.1063/1.2356795

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. II. Ab initio multiple spawning simulations
journal, April 2018

  • Glover, William J.; Mori, Toshifumi; Schuurman, Michael S.
  • The Journal of Chemical Physics, Vol. 148, Issue 16
  • DOI: 10.1063/1.5018130

An Ab Initio Exciton Model Including Charge-Transfer Excited States
journal, July 2017

  • Li, Xin; Parrish, Robert M.; Liu, Fang
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 8
  • DOI: 10.1021/acs.jctc.7b00171

Determination of the Crystal Structure of Substrate-Induced Pentacene Polymorphs in Fiber Structured Thin Films
journal, August 2007

  • Schiefer, Stefan; Huth, Martin; Dobrinevski, Alexander
  • Journal of the American Chemical Society, Vol. 129, Issue 34
  • DOI: 10.1021/ja0730516

Perspectives on Basis Sets Beautiful: Seasonal Plantings of Diffuse Basis Functions
journal, August 2011

  • Papajak, Ewa; Zheng, Jingjing; Xu, Xuefei
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 10
  • DOI: 10.1021/ct200106a

Wavefunction methods for noncovalent interactions: Noncovalent interactions
journal, July 2011

  • Hohenstein, Edward G.; Sherrill, C. David
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
  • DOI: 10.1002/wcms.84

Bimolecular radiationless transitions in crystalline tetracene
journal, September 1968

Recent Advances in Singlet Fission
journal, April 2013

Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy
journal, October 2015

  • Bakulin, Artem A.; Morgan, Sarah E.; Kehoe, Tom B.
  • Nature Chemistry, Vol. 8, Issue 1
  • DOI: 10.1038/nchem.2371

Exciton Fission and Charge Generation via Triplet Excitons in Pentacene/C 60 Bilayers
journal, September 2010

  • Rao, Akshay; Wilson, Mark W. B.; Hodgkiss, Justin M.
  • Journal of the American Chemical Society, Vol. 132, Issue 36
  • DOI: 10.1021/ja1042462

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

The Low-Lying Electronic States of Pentacene and Their Roles in Singlet Fission
journal, April 2014

  • Zeng, Tao; Hoffmann, Roald; Ananth, Nandini
  • Journal of the American Chemical Society, Vol. 136, Issue 15
  • DOI: 10.1021/ja500887a

TeraChem : A graphical processing unit ‐accelerated electronic structure package for large‐scale ab initio molecular dynamics
journal, July 2020

  • Seritan, Stefan; Bannwarth, Christoph; Fales, Bryan S.
  • WIREs Computational Molecular Science
  • DOI: 10.1002/wcms.1494

Levels of symmetry adapted perturbation theory (SAPT). I. Efficiency and performance for interaction energies
journal, March 2014

  • Parker, Trent M.; Burns, Lori A.; Parrish, Robert M.
  • The Journal of Chemical Physics, Vol. 140, Issue 9
  • DOI: 10.1063/1.4867135

Microscopic theory of singlet exciton fission. III. Crystalline pentacene
journal, August 2014

  • Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R.
  • The Journal of Chemical Physics, Vol. 141, Issue 7
  • DOI: 10.1063/1.4892793

Ultrafast Dynamics of Exciton Fission in Polycrystalline Pentacene
journal, August 2011

  • Wilson, Mark W. B.; Rao, Akshay; Clark, Jenny
  • Journal of the American Chemical Society, Vol. 133, Issue 31
  • DOI: 10.1021/ja201688h

TeraChem: Accelerating electronic structure and ab initio molecular dynamics with graphical processing units
journal, June 2020

  • Seritan, Stefan; Bannwarth, Christoph; Fales, B. Scott
  • The Journal of Chemical Physics, Vol. 152, Issue 22
  • DOI: 10.1063/5.0007615

Psi4: an open-source ab initio electronic structure program : Psi4: an electronic structure program
journal, October 2011

  • Turney, Justin M.; Simmonett, Andrew C.; Parrish, Robert M.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 4
  • DOI: 10.1002/wcms.93

Ab Initio Nonadiabatic Dynamics of Multichromophore Complexes: A Scalable Graphical-Processing-Unit-Accelerated Exciton Framework
journal, July 2014

  • Sisto, Aaron; Glowacki, David R.; Martinez, Todd J.
  • Accounts of Chemical Research, Vol. 47, Issue 9
  • DOI: 10.1021/ar500229p

Fully optimized contracted Gaussian basis sets for atoms Li to Kr
journal, August 1992

  • Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463096

Singlet Exciton Fission in Polycrystalline Pentacene: From Photophysics toward Devices
journal, May 2013

  • Wilson, Mark W. B.; Rao, Akshay; Ehrler, Bruno
  • Accounts of Chemical Research, Vol. 46, Issue 6
  • DOI: 10.1021/ar300345h

Exciton dynamics in pentacene thin films studied by pump-probe spectroscopy
journal, July 1995

Observing the Multiexciton State in Singlet Fission and Ensuing Ultrafast Multielectron Transfer
journal, December 2011

Ab Initio Molecular Dynamics of Excited-State Intramolecular Proton Transfer Using Multireference Perturbation Theory †
journal, November 2007

  • Coe, Joshua D.; Levine, Benjamin G.; Martínez, Todd J.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 44
  • DOI: 10.1021/jp072027b

Perturbation Theory Approach to Intermolecular Potential Energy Surfaces of van der Waals Complexes
journal, November 1994

  • Jeziorski, Bogumil; Moszynski, Robert; Szalewicz, Krzysztof
  • Chemical Reviews, Vol. 94, Issue 7
  • DOI: 10.1021/cr00031a008

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Direct diabatization of electronic states by the fourfold way. II. Dynamical correlation and rearrangement processes
journal, September 2002

  • Nakamura, Hisao; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 117, Issue 12
  • DOI: 10.1063/1.1500734

Singlet Fission in Crystalline Organic Materials: Recent Insights and Future Directions
journal, October 2019

  • Felter, Kevin M.; Grozema, Ferdinand C.
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 22
  • DOI: 10.1021/acs.jpclett.9b00754

A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers
journal, May 2016

Conical intersections and double excitations in time-dependent density functional theory
journal, March 2006

  • Levine, Benjamin G.; Ko, Chaehyuk; Quenneville, Jason
  • Molecular Physics, Vol. 104, Issue 5-7
  • DOI: 10.1080/00268970500417762

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

Mechanism for Singlet Fission in Pentacene and Tetracene: From Single Exciton to Two Triplets
journal, December 2011

  • Zimmerman, Paul M.; Bell, Franziska; Casanova, David
  • Journal of the American Chemical Society, Vol. 133, Issue 49
  • DOI: 10.1021/ja208431r

Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory
journal, June 2011

  • Granovsky, Alexander A.
  • The Journal of Chemical Physics, Vol. 134, Issue 21
  • DOI: 10.1063/1.3596699

Ultrafast internal conversion in ethylene. I. The excited state lifetime
journal, June 2011

  • Tao, H.; Allison, T. K.; Wright, T. W.
  • The Journal of Chemical Physics, Vol. 134, Issue 24
  • DOI: 10.1063/1.3604007

The nature of singlet excitons in oligoacene molecular crystals
journal, May 2011

  • Yamagata, H.; Norton, J.; Hontz, E.
  • The Journal of Chemical Physics, Vol. 134, Issue 20
  • DOI: 10.1063/1.3590871

Polarized Absorption in Crystalline Pentacene: Theory vs Experiment
journal, September 2015

  • Hestand, N. J.; Yamagata, H.; Xu, Bolei
  • The Journal of Physical Chemistry C, Vol. 119, Issue 38
  • DOI: 10.1021/acs.jpcc.5b07163

Singlet Fission
journal, November 2010

  • Smith, Millicent B.; Michl, Josef
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr1002613

Role of Rydberg States in the Photochemical Dynamics of Ethylene
journal, December 2011

  • Mori, Toshifumi; Glover, William J.; Schuurman, Michael S.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 11
  • DOI: 10.1021/jp2097185

Dynamical Correlation Effects on Photoisomerization: Ab Initio Multiple Spawning Dynamics with MS-CASPT2 for a Model trans -Protonated Schiff Base
journal, November 2015

  • Liu, Lihong; Liu, Jian; Martinez, Todd J.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 8
  • DOI: 10.1021/acs.jpcb.5b09838

Triplet Pair States in Singlet Fission
journal, January 2019

Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics
journal, August 2009

  • Ufimtsev, Ivan S.; Martinez, Todd J.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 10
  • DOI: 10.1021/ct9003004

Vibronic exciton theory of singlet fission. I. Linear absorption and the anatomy of the correlated triplet pair state
journal, May 2017

  • Tempelaar, Roel; Reichman, David R.
  • The Journal of Chemical Physics, Vol. 146, Issue 17
  • DOI: 10.1063/1.4982362

On-the-Fly CASPT2 Surface-Hopping Dynamics
journal, July 2017

  • Park, Jae Woo; Shiozaki, Toru
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 8
  • DOI: 10.1021/acs.jctc.7b00559

Assessment of the ΔSCF density functional theory approach for electronic excitations in organic dyes
journal, February 2011

  • Kowalczyk, Tim; Yost, Shane R.; Voorhis, Troy Van
  • The Journal of Chemical Physics, Vol. 134, Issue 5
  • DOI: 10.1063/1.3530801

Ab Initio Multiple Spawning Dynamics Using Multi-State Second-Order Perturbation Theory
journal, December 2009

  • Tao, Hongli; Levine, Benjamin G.; Martínez, Todd J.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 49
  • DOI: 10.1021/jp9063565

Ab Initio Implementation of the Frenkel–Davydov Exciton Model: A Naturally Parallelizable Approach to Computing Collective Excitations in Crystals and Aggregates
journal, November 2014

  • Morrison, Adrian F.; You, Zhi-Qiang; Herbert, John M.
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 12
  • DOI: 10.1021/ct500765m

Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene
journal, March 2017

Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells
journal, March 1961

  • Shockley, William; Queisser, Hans J.
  • Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519
  • DOI: 10.1063/1.1736034

Laser Generation of Excitons and Fluorescence in Anthracene Crystals
journal, January 1965

  • Singh, S.; Jones, W. J.; Siebrand, W.
  • The Journal of Chemical Physics, Vol. 42, Issue 1
  • DOI: 10.1063/1.1695695

Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange
journal, March 2013

  • Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R.
  • The Journal of Chemical Physics, Vol. 138, Issue 11
  • DOI: 10.1063/1.4794427

Effect of Magnetic Field on the Fluorescence of Tetracene Crystals: Exciton Fission
journal, March 1969

A transferable model for singlet-fission kinetics
journal, May 2014

  • Yost, Shane R.; Lee, Jiye; Wilson, Mark W. B.
  • Nature Chemistry, Vol. 6, Issue 6
  • DOI: 10.1038/nchem.1945

Evidence for conical intersection dynamics mediating ultrafast singlet exciton fission
journal, March 2015

  • Musser, Andrew J.; Liebel, Matz; Schnedermann, Christoph
  • Nature Physics, Vol. 11, Issue 4
  • DOI: 10.1038/nphys3241

The direct calculation of diabatic states based on configurational uniformity
journal, January 2001

  • Nakamura, Hisao; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 115, Issue 22
  • DOI: 10.1063/1.1412879
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: