Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene

Morrison, Adrian F.; Herbert, John M.

doi:10.1021/acs.jpclett.7b00230

Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene

Journal Article · Thu Mar 09 00:00:00 EST 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b00230· OSTI ID:1604466

Morrison, Adrian F. ^[1]; ^[2]

The Ohio State Univ., Columbus, OH (United States); The Ohio State University
The Ohio State Univ., Columbus, OH (United States)

Singlet fission proceeds rapidly and with high quantum efficiency in both crystalline tetracene and pentacene, which poses a conundrum given that the process in tetracene is disfavored by the electronic energetics. In this work, we use an ab initio exciton model to compute nonadiabatic couplings in the unit cell of tetracene in order to identify the modes that promote this process. Four intramolecular modes in the range of 1400–1600 cm^–1, which are nearly resonant with the single-exciton/multiexciton energy gap, appear to play a key role. Ab initio calculations of the electron/phonon coupling constants for these modes reveal that they are almost entirely of “Holstein” type, modulating the site energies rather than the intersite couplings. The constants are used to parametrize a vibronic Hamiltonian, simulations with which suggest a vibronically coherent singlet fission mechanism that proceeds spontaneously despite unfavorable electronic energetics. In the absence of vibronic coupling, there is no significant fission according to our model.

View Accepted Manuscript (DOE)

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008850

OSTI ID:: 1604466

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 7 Vol. 8; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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