Optimal Arrangements of Tetracene Molecule Pairs for Fast Singlet Fission

Buchanan, Eric A.; Havlas, Zdeněk; Michl, Josef

doi:10.1246/bcsj.20190229

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

Journal Article · Sat Sep 14 00:00:00 EDT 2019 · Bulletin of the Chemical Society of Japan

DOI:https://doi.org/10.1246/bcsj.20190229· OSTI ID:1688406

Buchanan, Eric A. ^[1]; Havlas, Zdeněk ^[2]; Michl, Josef ^[2]

Univ. of Colorado, Boulder, CO (United States)
Univ. of Colorado, Boulder, CO (United States); Czech Academy of Sciences, Prague (Czech Republic)

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 k_SF 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 k_SF 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.

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Research Organization:: Univ. of Colorado, Boulder, CO (United States)

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

Grant/Contract Number:: SC0007004; 15- 19143S; 19-22806S

OSTI ID:: 1688406

Journal Information:: Bulletin of the Chemical Society of Japan, Vol. 92, Issue 12; ISSN 0009-2673

Publisher:: Chemical Society of JapanCopyright Statement

Country of Publication:: United States

Language:: English

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