We present surface hopping simulations of singlet fission in 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene (ThBF). In particular, we performed simulations based on quantum mechanics/molecular mechanics (QM/MM) schemes in which either two or three ThBF molecules are inserted in the QM region and embedded in their MM crystal environment. Our aim was to investigate the changes in the photodynamics that are brought about by extending the delocalization of the excited states beyond the minimal model of a dimer. In the simulations based on the trimer model, compared to the dimer-based ones, we observed a faster time evolution of the state populations, with the largest differences associated with both the rise and decay times for the intermediate charge transfer states. Moreover, for the trimer, we predicted a singlet fission quantum yield of ∼204%, which is larger than both the one extracted for the dimer (∼179%) and the theoretical upper limit of 200% for the dimer-based model of singlet fission. Although our study cannot account for the effects of extending the delocalization beyond three molecules, our findings clearly indicate how and why the singlet fission dynamics can be affected.
REFERENCES
1.
M. B.
Smith
and J.
Michl
, “Singlet fission
,” Chem. Rev.
110
, 6891
–6936
(2010
).2.
M. B.
Smith
and J.
Michl
, “Recent advances in singlet fission
,” Annu. Rev. Phys. Chem.
64
, 361
–386
(2013
).3.
A.
Japahuge
and T.
Zeng
, “Theoretical studies of singlet fission: Searching for materials and exploring mechanisms
,” ChemPlusChem
83
, 146
–182
(2018
).4.
D.
Casanova
, “Theoretical modeling of singlet fission
,” Chem. Rev.
118
, 7164
–7207
(2018
).5.
V. K.
Thorsmølle
, R. D.
Averitt
, J.
Demsar
, D. L.
Smith
, S.
Tretiak
, R. L.
Martin
, X.
Chi
, B. K.
Crone
, A. P.
Ramirez
, and A. J.
Taylor
, “Morphology effectively controls singlet-triplet exciton relaxation and charge transport in organic semiconductors
,” Phys. Rev. Lett.
102
, 017401
–017404
(2009
).6.
J. J.
Burdett
, A. M.
Müller
, D.
Gosztola
, and C. J.
Bardeen
, “Excited state dynamics in solid and monomeric tetracene: The roles of superradiance and exciton fission
,” J. Chem. Phys.
133
, 144506
(2010
).7.
M. W. B.
Wilson
, A.
Rao
, J.
Clark
, R. S. S.
Kumar
, D.
Brida
, G.
Cerullo
, and R. H.
Friend
, “Ultrafast dynamics of exciton fission in polycrystalline pentacene
,” J. Am. Chem. Soc.
133
, 11830
–11833
(2011
).8.
J.
Lee
, P.
Jadhav
, P. D.
Reusswig
, S. R.
Yost
, N. J.
Thompson
, D. N.
Congreve
, E.
Hontz
, T.
Van Voorhis
, and M. A.
Baldo
, “Singlet exciton fission photovoltaics
,” Acc. Chem. Res.
46
, 1300
–1311
(2013
).9.
W.
Shockley
and H. J.
Queisser
, “Detailed balance limit of efficiency of p-n junction solar cells
,” J. Appl. Phys.
32
, 510
–519
(1961
).10.
M. C.
Hanna
and A. J.
Nozik
, “Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers
,” J. Appl. Phys.
100
, 1
–8
(2006
).11.
R.
Nagata
, H.
Nakanotani
, W. J.
Potscavage
, Jr., and C.
Adachi
, “Exploiting singlet fission in organic light-emitting diodes
,” Adv. Mater.
30
, 1801484
(2018
).12.
L. R.
Weiss
, S. L.
Bayliss
, F.
Kraffert
, K. J.
Thorley
, J. E.
Anthony
, R.
Bittl
, R. H.
Friend
, A.
Rao
, N. C.
Greenham
, and J.
Behrends
, “Strongly exchange-coupled triplet pairs in an organic semiconductor
,” Nat. Phys.
13
, 176
–181
(2017
).13.
N.
Monahan
and X.-Y.
Zhu
, “Charge transfer-mediated singlet fission
,” Annu. Rev. Phys. Chem.
66
, 601
–618
(2015
).14.
W.-L.
Chan
, T. C.
Berkelbach
, M. R.
Provorse
, N. R.
Monahan
, J. R.
Tritsch
, M. S.
Hybertsen
, D. R.
Reichman
, J.
Gao
, and X.-Y.
Zhu
, “The quantum coherent mechanism for singlet fission: Experiment and theory
,” Acc. Chem. Res.
46
, 1321
–1329
(2013
).15.
T. C.
Berkelbach
, M. S.
Hybertsen
, and D. R.
Reichman
, “Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange
,” J. Chem. Phys.
138
, 114103
(2013
).16.
T.
Zeng
, R.
Hoffmann
, and N.
Ananth
, “The low-lying electronic states of pentacene and their roles in singlet fission
,” J. Am. Chem. Soc.
136
, 5755
–5764
(2014
).17.
X.
Feng
, A. B.
Kolomeisky
, and A. I.
Krylov
, “Dissecting the effect of morphology on the rates of singlet fission: Insights from theory
,” J. Phys. Chem. C
118
, 19608
–19617
(2014
).18.
L.
Wang
, Y.
Olivier
, O. V.
Prezhdo
, and D.
Beljonne
, “Maximizing singlet fission by intermolecular packing
,” J. Phys. Chem. Lett.
5
, 3345
–3353
(2014
).19.
E. A.
Buchanan
, Z.
Havlas
, and J.
Michl
, “Singlet fission: Optimization of chromophore dimer geometry
,” Adv. Quantum Chem.
75
, 175
–227
(2017
).20.
M. H.
Farag
and A. I.
Krylov
, “Singlet fission in perylenediimide dimers
,” J. Phys. Chem. C
122
, 25753
–25763
(2018
).21.
E. A.
Buchanan
and J.
Michl
, “Optimal arrangements of 1,3-diphenylisobenzofuran molecule pairs for fast singlet fission
,” Photochem. Photobiol. Sci.
18
, 2112
–2124
(2019
).22.
N. J.
Hestand
, H.
Yamagata
, B.
Xu
, D.
Sun
, Y.
Zhong
, A. R.
Harutyunyan
, G.
Chen
, H.-L.
Dai
, Y.
Rao
, and F. C.
Spano
, “Polarized absorption in crystalline pentacene: Theory vs experiment
,” J. Phys. Chem. C
119
, 22137
–22147
(2015
).23.
S.
Sharifzadeh
, C. Y.
Wong
, H.
Wu
, B. L.
Cotts
, L.
Kronik
, N. S.
Ginsberg
, and J. B.
Neaton
, “Relating the physical structure and optoelectronic function of crystalline tips-pentacene
,” Phys. Rev. B
25
, 2038
–2046
(2015
).24.
T. C.
Berkelbach
, M. S.
Hybertsen
, and D. R.
Reichman
, “Microscopic theory of singlet exciton fission. III. Crystalline pentacene
,” J. Chem. Phys.
141
, 074705
(2014
).25.
H.
Tamura
, M.
Huix-Rotllant
, I.
Burghardt
, Y.
Olivier
, and D.
Beljonne
, “First-principles quantum dynamics of singlet fission: Coherent versus thermally activated mechanisms governed by molecular π stacking
,” Phys. Rev. Lett.
115
, 107401
(2015
).26.
P. E.
Teichen
and J. D.
Eaves
, “Collective aspects of singlet fission in molecular crystals
,” J. Chem. Phys.
143
, 044118
(2015
).27.
M.
Nakano
, T.
Nagami
, T.
Tonami
, K.
Okada
, S.
Ito
, R.
Kishi
, Y.
Kitagawa
, and T.
Kubo
, “Quantum master equation approach to singlet fission dynamics in pentacene linear aggregate models: Size dependences of excitonic coupling effects
,” J. Comput. Chem.
40
, 89
–104
(2019
).28.
R. D.
Pensack
, A. J.
Tilley
, S. R.
Parkin
, T. S.
Lee
, M. M.
Payne
, D.
Gao
, A. A.
Jahnke
, D. G.
Oblinsky
, P.-F.
Li
, J. E.
Anthony
, D. S.
Seferos
, and G. D.
Scholes
, “Exciton delocalization drives rapid singlet fission in nanoparticles of acene derivatives
,” J. Am. Chem. Soc.
137
, 6790
–6803
(2015
).29.
S. T.
Roberts
, R. E.
McAnally
, J. N.
Mastron
, D. H.
Webber
, M. T.
Whited
, R. L.
Brutchey
, M. E.
Thompson
, and S. E.
Bradforth
, “Efficient singlet fission discovered in a disordered acene film
,” J. Am. Chem. Soc.
134
, 6388
–6400
(2012
).30.
S.
Kawata
, Y.-J.
Pu
, A.
Saito
, Y.
Kurashige
, T.
Beppu
, H.
Katagiri
, M.
Hada
, and J.
Kido
, “Singlet fission of non-polycyclic aromatic molecules in organic photovoltaics
,” Adv. Mater.
28
, 1585
–1590
(2016
).31.
M.
Wibowo
, M.
Persico
, and G.
Granucci
, “Nonadiabatic dynamics simulations of singlet fission in 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene crystals
,” Phys. Chem. Chem. Phys.
21
, 692
–701
(2019
).32.
D.
Accomasso
, G.
Granucci
, R. W. A.
Havenith
, and M.
Persico
, “Testing new chromophores for singlet fission: A computational protocol applied to 2,3-diamino-1,4-benzoquinone
,” Chem. Phys.
515
, 635
–642
(2018
).33.
H. J. C.
Berendsen
, J. P. M.
Postma
, W. F.
van Gunsteren
, A.
DiNola
, and J. R.
Haak
, “Molecular dynamics with coupling to an external bath
,” J. Chem. Phys.
81
, 3684
–3690
(1984
).34.
J. W.
Ponder
, TINKER—Software tools for molecular design, Version 6.3, Copyright (c), 2014
.35.
G.
Granucci
, M.
Persico
, and A.
Toniolo
, “Direct semiclassical simulation of photochemical processes with semiempirical wave functions
,” J. Chem. Phys.
114
, 10608
–10615
(2001
).36.
J. J. P.
Stewart
, “Optimization of parameters for semiempirical methods II. Applications
,” J. Comput. Chem.
10
, 221
–264
(1989
).37.
G.
Bussi
and M.
Parrinello
, “Stochastic thermostats: Comparison of local and global schemes
,” Comput. Phys. Commun.
179
, 26
–29
(2008
).38.
L.
Creatini
, T.
Cusati
, G.
Granucci
, and M.
Persico
, “Photodynamics of azobenzene in a hindering environment
,” Chem. Phys.
347
, 492
–502
(2008
).39.
M.
Persico
and G.
Granucci
, “An overview of nonadiabatic dynamics simulations methods, with focus on the direct approach versus the fitting of potential energy surfaces
,” Theor. Chem. Acc.
133
, 1526-1
–1526-28
(2014
).40.
M.
Persico
, G.
Granucci
, S.
Inglese
, T.
Laino
, and A.
Toniolo
, “Semiclassical simulation of photochemical reactions in condensed phase
,” J. Mol. Struct. THEOCHEM
621
, 119
–126
(2003
).41.
G.
Granucci
, M.
Persico
, and A.
Zoccante
, “Including quantum decoherence in surface hopping
,” J. Chem. Phys.
133
, 134111-1
–134111-9
(2010
).42.
D.
Accomasso
, M.
Persico
, and G.
Granucci
, “Diabatization by localization in the framework of configuration interaction based on floating occupation molecular orbitals (FOMO-CI)
,” ChemPhotoChem.
3
, 933
–944
(2019
).43.
F. C.
Spano
, “The spectral signatures of Frenkel polarons in h- and j-aggregates
,” Acc. Chem. Res.
43
, 429
–439
(2010
).44.
P. B.
Coto
, S.
Sharifzadeh
, J. B.
Neaton
, and M.
Thoss
, “Low-lying electronic excited states of pentacene oligomers: A comparative electronic structure study in the context of singlet fission
,” J. Chem. Theory Comput.
11
, 147
–156
(2010
).© 2020 Author(s).
2020
Author(s)
You do not currently have access to this content.
