The Frenkel-Holstein model in the Born-Oppenheimer regime is used to interpret temperature-dependent photoluminescence spectra of solutions made with the poly(p-phenylene vinylene) derivative MEH-PPV. Using our recently developed structural optimization method and assuming only intrachain electronic coupling, we predict the structure of emissive MEH-PPV chromophores in terms of a mean torsional angle ϕ0 and its static fluctuations σϕ, assuming no cis-trans defects. This allows us to fully account for the observed changes in spectra, and the chromophore structures obtained are consistent with the known phase transition at 180 K between a “red” and “blue” phase.
REFERENCES
1.
W.
Barford
and M.
Marcus
, J. Chem. Phys.
146
, 130902
(2017
).2.
M.
Marcus
, J. D.
Milward
, A.
Köhler
, and W.
Barford
, J. Phys. Chem. A
122
, 3621
(2018
).3.
T.
Unger
, F.
Panzer
, C.
Consani
, F.
Koch
, T.
Brixner
, H.
Bässler
, and A.
Köhler
, ACS Macro Lett.
4
, 412
(2015
).4.
F.
Panzer
, H.
Bässler
, and A.
Köhler
, J. Phys. Chem. Lett.
8
, 114
(2017
).5.
A.
Köhler
, S. T.
Hoffmann
, and H.
Bässler
, J. Am. Chem. Soc.
134
, 11594
(2012
).6.
H.
Yamagata
, N. J.
Hestand
, F. C.
Spano
, A.
Köhler
, C.
Scharsich
, S.
Hoffmann
, and H.
Bässler
, J. Chem. Phys.
139
, 114903
(2013
).7.
H.
Yamagata
and F. C.
Spano
, J. Chem. Phys.
136
, 184901
(2012
).8.
N. J.
Hestand
and F. C.
Spano
, “Expanded Theory of H- and J-Molecular Aggregates: The Effects of Vibronic Coupling and Intermolecular Charge Transfer
,” Chem. Rev.
(published online).9.
Al.
Eisfeld
, C.
Marquardt
, A.
Paulheim
, and M.
Sokolowski
, Phys. Rev. Lett.
119
, 097402
(2017
).10.
C.
De Leener
, E.
Hennebicq
, J. C.
Sancho-Garcia
, and D. J.
Beljonne
, Phys. Chem. B
113
, 1311
(2009
).11.
L. A.
Peteanu
, G. A.
Sherwood
, J. H.
Werner
, A. P.
Shreve
, and T. M. J.
Smith
, Phys. Chem. C
115
, 15607
(2011
).12.
G. A.
Sherwood
, R.
Cheng
, R. M.
Smith
, J. H.
Werner
, A. P.
Shreve
, L. A.
Peteanu
, and J.
Wildeman
, J. Phys. Chem. C
113
, 18851
(2009
).13.
A. V.
Malyshev
and V. A.
Malyshev
, “Statistics of low energy levels of a one-dimensional weakly localized Frenkel exciton: A numerical study
,” Phys. Rev. B: Condens. Matter Mater. Phys.
63
, 195111
(2001
).14.
D. V.
Makhov
and W.
Barford
, “Local exciton ground states in disordered polymers
,” Phys. Rev. B: Condens. Matter Mater. Phys.
81
, 165201
(2010
).15.
W.
Barford
and M.
Marcus
, J. Chem. Phys.
141
, 164101
(2014
).16.
J. A.
Nelder
and R.
Mead
, Comput. J.
7
, 308
(1965
).17.
M.
Marcus
, O. R.
Tozer
, and W.
Barford
, J. Chem. Phys.
141
, 164102
(2014
).18.
K. H.
Dubay
, M. L.
Hall
, T. F.
Hughes
, C.
Wu
, D. R.
Reichman
, and R. A.
Friesner
, J. Chem. Theory Comput.
8
, 4556
(2012
).© 2018 Author(s).
2018
Author(s)
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