Correlated spectral fluctuations were suggested to coordinate excitation transport inside natural light harvesting complexes. We demonstrate the capacities of 2D line shapes from fifth-order coherent electronic signals (R5-2D) to report on such fluctuations in molecular aggregates and present a stochastic approach to fluctuations in correlated site and bi-exciton binding energies in the optical dynamics of Frenkel excitons. The model is applied to R5-2D line shapes of a homodimer, and we show that the peak tilt dynamics are a measure for site energy disorder, inter-site correlation, and the strength of bi-exciton binding energy fluctuations.
REFERENCES
1.
T.
Renger
, V.
May
, and O.
Kühn
, Phys. Rep.
343
, 137
(2001
).2.
S. F.
Huelga
and M. B.
Plenio
, Contemp. Phys.
54
, 181
(2013
).3.
V.
Perlík
, J.
Seibt
, L. J.
Cranston
, R. J.
Cogdell
, C. N.
Lincoln
, J.
Savolainen
, F.
Šanda
, T.
Mančal
, and J.
Hauer
, J. Chem. Phys.
142
, 212434
(2015
).4.
J. C.
Dean
, T.
Mirkovic
, Z. S. D.
Toa
, D. G.
Oblinsky
, and G. D.
Scholes
, Chem
1
, 858
(2016
).5.
B. S.
Rolczynski
, H.
Zheng
, V. P.
Singh
, P.
Navotnaya
, A. R.
Ginzburg
, J. R.
Caram
, K.
Ashraf
, A. T.
Gardiner
, S.-H.
Yeh
, S.
Kais
, R. J.
Cogdell
, and G. S.
Engel
, Chem
4
, 138
(2018
).6.
J.
Cao
, R. J.
Cogdell
, D. F.
Coker
, H.-G.
Duan
, J.
Hauer
, U.
Kleinekathöfer
, T. L. C.
Jansen
, T.
Mančal
, R. J. D.
Miller
, J. P.
Ogilvie
, V. I.
Prokhorenko
, T.
Renger
, H.-S.
Tan
, R.
Tempelaar
, M.
Thorwart
, E.
Thyrhaug
, S.
Westenhoff
, and D.
Zigmantas
, Sci. Adv.
6
, eaaz4888
(2020
).7.
L.
Wang
, M. A.
Allodi
, and G. S.
Engel
, Nat. Rev. Chem.
3
, 477
(2019
).8.
O.
Rancova
, R.
Jankowiak
, and D.
Abramavicius
, J. Phys. Chem. B
122
, 1348
(2018
).9.
B.
Brüggemann
and T.
Pullerits
, New J. Phys.
13
, 025024
(2011
).10.
J.
Dostál
, F.
Fennel
, F.
Koch
, S.
Herbst
, F.
Würthner
, and T.
Brixner
, Nat. Commun.
9
, 2466
(2018
).11.
V.
May
, J. Chem. Phys.
140
, 054103
(2014
).12.
C.
Heshmatpour
, J.
Hauer
, and F.
Šanda
, Chem. Phys.
528
, 110433
(2020
).13.
J.
Lüttig
, T.
Brixner
, and P.
Malý
, J. Chem. Phys.
154
, 154202
(2021
).14.
C.
Heshmatpour
, P.
Malevich
, F.
Plasser
, M.
Menger
, C.
Lambert
, F.
Šanda
, and J.
Hauer
, J. Phys. Chem. Lett.
11
, 7776
(2020
).15.
P.
Malý
, J.
Lüttig
, A.
Turkin
, J.
Dostál
, C.
Lambert
, and T.
Brixner
, Chem. Sci.
11
, 456
(2020
).16.
S. T.
Roberts
, J. J.
Loparo
, and A.
Tokmakoff
, J. Chem. Phys.
125
, 084502
(2006
).17.
K.
Kwak
, S.
Park
, I. J.
Finkelstein
, and M. D.
Fayer
, J. Chem. Phys.
127
, 124503
(2007
).18.
F.
Šanda
, V.
Perlík
, C. N.
Lincoln
, and J.
Hauer
, J. Phys. Chem. A
119
, 10893
(2015
).19.
F.
Šanda
and S.
Mukamel
, Phys. Rev. Lett.
98
, 080603
(2007
).20.
G. E.
Uhlenbeck
and L. S.
Ornstein
, Phys. Rev.
36
, 823
(1930
).21.
R.
Kubo
, J. Phys. Soc. Jpn.
9
, 935
(1954
).22.
J.
Frenkel
, Phys. Rev
37
, 1276
(1931
).23.
V.
Sláma
, V.
Perlík
, H.
Langhals
, A.
Walter
, T.
Mančal
, J.
Hauer
, and F.
Šanda
, Front. Chem.
8
, 579166
(2020
).24.
D.
Abramavicius
, B.
Palmieri
, D. V.
Voronine
, F.
Šanda
, and S.
Mukamel
, Chem. Rev.
109
, 2350
(2009
).25.
26.
N. J.
Higham
, Wiley Interdiscip. Rev.: Comput. Stat.
1
, 251
(2009
).27.
V.
May
and O.
Kuhn
, Charge and Energy Transfer Dynamics in Molecular Systems
(Wiley-VCH Verlag
, 2011
).28.
A. G.
Redfield
, IBM J. Res. Dev.
1
, 19
(1957
).29.
T.
Pullerits
, M.
Chachisvilis
, and V.
Sundström
, J. Phys. Chem.
100
, 10787
(1996
).30.
B.
Brüggemann
, J. L.
Herek
, V.
Sundström
, T.
Pullerits
, and V.
May
, J. Phys. Chem. B
105
, 11391
(2001
).31.
B.
Brüggemann
, N.
Christensson
, and T.
Pullerits
, Chem. Phys.
357
, 140
(2009
).32.
R.
Kubo
, J. Phys. Soc. Jpn.
12
, 570
(1957
).33.
S.
Mukamel
, Principles of Nonlinear Optical Spectroscopy
(Oxford University Press
, 1995
).34.
F.
Šanda
and S.
Mukamel
, J. Phys. Chem. B
112
, 14212
(2008
).35.
U.
Fano
, Rev. Mod. Phys.
29
, 74
(1957
).36.
R. W.
Zwanzig
, Lectures in Theoretical Physics
(Interscience
, New York, NY
, 1960
), Vol. 3, p. 106
.37.
V.
Perlík
and F.
Šanda
, J. Chem. Phys.
147
, 084104
(2017
).38.
P.
Malý
, S.
Mueller
, J.
Lüttig
, C.
Lambert
, and T.
Brixner
, J. Chem. Phys.
153
, 144204
(2020
).39.
Y.
Tanimura
, J. Chem. Phys.
153
, 020901
(2020
).40.
D.
Abramavicius
, L.
Valkunas
, and S.
Mukamel
, Europhys. Lett.
80
, 17005
(2007
).41.
F.
Domínguez-Adame
, Phys. Rev. B
51
, 12801
(1995
).42.
V. A.
Malyshev
, A.
Rodríguez
, and F.
Domínguez-Adame
, Phys. Rev. B
60
, 14140
(1999
).43.
E. W.
Knapp
, Chem. Phys.
85
, 73
(1984
).44.
M.
Bednarz
and P.
Reineker
, J. Lumin.
119–120
, 482
(2006
).45.
J.
Knoester
, J. Lumin.
58
, 107
(1994
).46.
J.
Knoester
, J. Chem. Phys.
99
, 8466
(1993
).47.
J. R.
Durrant
, J.
Knoester
, and D. A.
Wiersma
, Chem. Phys. Lett.
222
, 450
(1994
).48.
D.
Abramavicius
and S.
Mukamel
, J. Chem. Phys.
134
, 174504
(2011
).49.
J.
Lim
, D. J.
Ing
, J.
Rosskopf
, J.
Jeske
, J. H.
Cole
, S. F.
Huelga
, and M. B.
Plenio
, J. Chem. Phys.
146
, 024109
(2017
).50.
T. N.
Do
, L.
Chen
, A. K.
Belyaev
, H.-S.
Tan
, and M. F.
Gelin
, Chem. Phys.
515
, 119
(2018
).51.
A. O.
Caldeira
and A. J.
Leggett
, Physica A
121
, 587
(1983
).© 2022 Author(s). Published under an exclusive license by AIP Publishing.
2022
Author(s)
You do not currently have access to this content.
