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Title: Optimal Arrangements of Tetracene Molecule Pairs for Fast Singlet Fission

Abstract

In search for a qualitative understanding of the effects of molecular packing on singlet fission (SF) rate, a simplified version of the frontier orbital model is described and illustrated on a pair of tetracene molecules. To identify all favorable physically accessible pair geometries, all significant local maxima of the square of the electronic matrix element for SF have been located within the six-dimensional space of possible arrangements of two rigid bodies, using a grid of over 4.7 × 108 pair geometries. Those at which the molecules interpenetrate were excluded using a hard-sphere model. The effects of intermolecular interaction on the SF energy balance and thus its rate constant kSF were approximated using Marcus theory at each of the maxima using the same simplified version of the frontier orbital model. Starting at these local maxima, the pair geometries were optimized for maximum kSF and the 21 best are reported along with their computed Davydov splitting and triplet biexciton binding energies. The optimal pair structures at the resulting maxima follow qualitative rules published previously and further elaborated here.

Authors:
 [1];  [2];  [2]
+ Show Author Affiliations
  1. Univ. of Colorado, Boulder, CO (United States)
  2. Univ. of Colorado, Boulder, CO (United States); Czech Academy of Sciences, Prague (Czech Republic)
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1688406
Grant/Contract Number:  
SC0007004; 15- 19143S; 19-22806S
Resource Type:
Accepted Manuscript
Journal Name:
Bulletin of the Chemical Society of Japan
Additional Journal Information:
Journal Volume: 92; Journal Issue: 12; Journal ID: ISSN 0009-2673
Publisher:
Chemical Society of Japan
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; tetracene; singlet fission; molecular packing

Citation Formats

Buchanan, Eric A., Havlas, Zdeněk, and Michl, Josef. Optimal Arrangements of Tetracene Molecule Pairs for Fast Singlet Fission. United States: N. p., 2019. Web. doi:10.1246/bcsj.20190229.
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Buchanan, Eric A., Havlas, Zdeněk, & Michl, Josef. Optimal Arrangements of Tetracene Molecule Pairs for Fast Singlet Fission. United States. https://doi.org/10.1246/bcsj.20190229
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Buchanan, Eric A., Havlas, Zdeněk, and Michl, Josef. Sat . "Optimal Arrangements of Tetracene Molecule Pairs for Fast Singlet Fission". United States. https://doi.org/10.1246/bcsj.20190229. https://www.osti.gov/servlets/purl/1688406.
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@article{osti_1688406,
title = {Optimal Arrangements of Tetracene Molecule Pairs for Fast Singlet Fission},
author = {Buchanan, Eric A. and Havlas, Zdeněk and Michl, Josef},
abstractNote = {In search for a qualitative understanding of the effects of molecular packing on singlet fission (SF) rate, a simplified version of the frontier orbital model is described and illustrated on a pair of tetracene molecules. To identify all favorable physically accessible pair geometries, all significant local maxima of the square of the electronic matrix element for SF have been located within the six-dimensional space of possible arrangements of two rigid bodies, using a grid of over 4.7 × 108 pair geometries. Those at which the molecules interpenetrate were excluded using a hard-sphere model. The effects of intermolecular interaction on the SF energy balance and thus its rate constant kSF were approximated using Marcus theory at each of the maxima using the same simplified version of the frontier orbital model. Starting at these local maxima, the pair geometries were optimized for maximum kSF and the 21 best are reported along with their computed Davydov splitting and triplet biexciton binding energies. The optimal pair structures at the resulting maxima follow qualitative rules published previously and further elaborated here.},
doi = {10.1246/bcsj.20190229},
journal = {Bulletin of the Chemical Society of Japan},
number = 12,
volume = 92,
place = {United States},
year = {Sat Sep 14 00:00:00 EDT 2019},
month = {Sat Sep 14 00:00:00 EDT 2019}
}
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https://doi.org/10.1246/bcsj.20190229
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