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:
-
- 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.
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
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.
@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}
}
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