The absorption line shapes of model molecular aggregates are investigated using the recently developed Liouville space hierarchical equations of motion (HEOM) method. The exact results are further exploited for the assessment of several approximation schemes, including the high temperature approximation of HEOM, the stochastic Liouville equation approach, and the perturbative time-local and time-nonlocal quantum master equations (QMEs). The calculations on dimers, larger ring-shaped aggregates, and a model of the B850 ring in the LH2 of purple bacteria show that while the other approximate methods can give reasonable absorption line shapes over a wide range of parameter regimes, the second-order time-nonlocal QME is generally inaccurate and may give spurious peaks in the absorption spectra.

1.
S.
Mukamel
,
The Principles of Nonlinear Optical Spectroscopy
(
Oxford University Press
,
New York
,
1995
).
2.
Femtochemistry and Femtobiology: Ultrafast Dynamics in Molecular Science
, edited by
A.
Douhal
and
J.
Santamaria
(
World Scientific
,
Singapore
,
2002
).
3.
T.
Kobayashi
,
Aggregates
(
World Scientific
,
Singapore
,
1996
).
4.
H.
van Amerongen
,
L.
Valkunas
, and
R.
van Grondelle
,
Photosythetic Excitons
(
World Scientific
,
Singapore
,
2000
).
5.
T.
Renger
,
V.
May
, and
O.
Kühn
,
Phys. Rep.
343
,
137
(
2001
).
6.
R.
van Grondelle
and
V. I.
Novoderezhkin
,
Phys. Chem. Chem. Phys.
8
,
793
(
2006
).
7.
Y. -C.
Cheng
and
G. R.
Fleming
,
Annu. Rev. Phys. Chem.
60
,
241
(
2009
).
8.
O.
Kühn
and
V.
Sundström
,
J. Phys. Chem. B
101
,
3432
(
1997
).
9.
T.
Renger
and
V.
May
,
Phys. Rev. Lett.
84
,
5228
(
2000
).
10.
T.
Renger
and
R. A.
Marcus
,
J. Chem. Phys.
116
,
9997
(
2002
).
11.
S.
Jang
and
R. J.
Silbey
,
J. Chem. Phys.
118
,
9312
(
2003
).
12.
S.
Jang
and
R. J.
Silbey
,
J. Chem. Phys.
118
,
9324
(
2003
).
13.
M.
Schröder
,
U.
Kleinekathöfer
, and
M.
Schreiber
,
J. Chem. Phys.
124
,
084903
(
2006
).
14.
M. F.
Gelin
,
D.
Egorova
, and
W.
Domcke
,
J. Chem. Phys.
123
,
164112
(
2005
).
15.
D.
Egorova
,
M. F.
Gelin
, and
W.
Domcke
,
J. Chem. Phys.
126
,
074314
(
2007
).
16.
Y. -C.
Cheng
and
G. R.
Fleming
,
J. Phys. Chem. B
112
,
4254
(
2008
).
17.
M.
Yang
,
J. Chem. Phys.
123
,
124705
(
2005
).
18.
W. M.
Zhang
,
T.
Meier
,
V.
Chernyak
, and
S.
Mukamel
,
J. Chem. Phys.
108
,
7763
(
1998
).
19.
S.
Mukamel
and
D.
Abramavicius
,
Chem. Rev. (Washington, D.C.)
104
,
2073
(
2004
).
20.
K.
Ohta
,
M.
Yang
, and
G. R.
Fleming
,
J. Chem. Phys.
115
,
7609
(
2001
).
21.
M.
Yang
and
G. R.
Fleming
,
Chem. Phys.
282
,
163
(
2002
).
22.
M.
Cho
,
H. M.
Vaswani
,
T.
Brixner
,
J.
Stenger
, and
G. R.
Fleming
,
J. Phys. Chem. B
109
,
10542
(
2005
).
23.
V. I.
Novoderezhkin
,
M. A.
Palacios
,
H.
van Amerongen
, and
R.
van Grondelle
,
J. Phys. Chem. B
108
,
10363
(
2004
).
24.
K.
Hyeon-Deuk
,
Y.
Tanimura
, and
M.
Cho
,
J. Chem. Phys.
127
,
075101
(
2007
).
25.
M.
Schröder
,
M.
Schreiber
, and
U.
Kleinekathöfer
,
J. Lumin.
125
,
126
(
2007
).
26.
T.
Renger
,
I.
Trostmann
,
C.
Theiss
,
M. E.
Madjet
,
M.
Richter
,
H.
Paulsen
,
H. J.
Eichler
,
A.
Knorr
, and
G.
Renger
,
J. Phys. Chem. B
111
,
10487
(
2007
).
27.
I.
Barvik
,
C.
Warns
, and
P.
Reineker
,
J. Lumin.
76&77
,
331
(
1998
).
28.
M.
Wubs
and
J.
Knoester
,
Chem. Phys. Lett.
284
,
63
(
1998
).
29.
L. D.
Bakalis
,
M.
Coca
, and
J.
Knoester
,
J. Chem. Phys.
110
,
2208
(
1999
).
30.
Y.
Tanimura
and
R.
Kubo
,
J. Phys. Soc. Jpn.
58
,
101
(
1989
).
32.
Y.
Tanimura
and
P. G.
Wolynes
,
Phys. Rev. A
43
,
4131
(
1991
).
33.
A.
Ishizaki
and
Y.
Tanimura
,
J. Phys. Soc. Jpn.
74
,
3131
(
2005
).
34.
Y.
Tanimura
,
J. Phys. Soc. Jpn.
75
,
082001
(
2006
).
35.
R. X.
Xu
,
P.
Cui
,
X. Q.
Li
,
Y.
Mo
, and
Y. J.
Yan
,
J. Chem. Phys.
122
,
041103
(
2005
).
36.
R. X.
Xu
and
Y. J.
Yan
,
Phys. Rev. E
75
,
031107
(
2007
).
37.
Y. A.
Yan
,
F.
Yang
,
Y.
Liu
, and
J. S.
Shao
,
Chem. Phys. Lett.
395
,
216
(
2004
).
38.
J. S.
Jin
,
S.
Welack
,
J. Y.
Luo
,
X. Q.
Li
,
P.
Cui
,
R. X.
Xu
, and
Y. J.
Yan
,
J. Chem. Phys.
126
,
134113
(
2007
).
39.
J. S.
Jin
,
X.
Zheng
, and
Y. J.
Yan
,
J. Chem. Phys.
128
,
234703
(
2008
).
40.
P.
Han
,
R. X.
Xu
,
B. Q.
Li
,
J.
Xu
,
P.
Cui
,
Y.
Mo
, and
Y. J.
Yan
,
J. Phys. Chem. B
110
,
11438
(
2006
).
41.
R. X.
Xu
,
Y.
Chen
,
P.
Cui
,
H. W.
Ke
, and
Y. J.
Yan
,
J. Phys. Chem. A
111
,
9618
(
2007
).
42.
Q.
Shi
,
L. P.
Chen
,
G. J.
Nan
,
R. X.
Xu
, and
Y. J.
Yan
,
J. Chem. Phys.
130
,
164518
(
2009
).
43.
Y.
Tanimura
and
S.
Mukamel
,
J. Phys. Soc. Jpn.
63
,
66
(
1994
).
44.
Y.
Tanimura
and
Y.
Maruyama
,
J. Chem. Phys.
107
,
1779
(
1997
).
45.
A.
Ishizaki
and
Y.
Tanimura
,
J. Chem. Phys.
125
,
084501
(
2006
).
46.
A.
Ishizaki
and
Y.
Tanimura
,
J. Phys. Chem. A
111
,
9269
(
2007
).
47.
X.
Zheng
,
J. S.
Jin
, and
Y. J.
Yan
,
J. Chem. Phys.
129
,
184112
(
2008
).
48.
X.
Zheng
,
J. S.
Jin
, and
Y. J.
Yan
,
New J. Phys.
10
,
093016
(
2008
).
49.
X.
Zheng
,
J. Y.
Luo
,
J. S.
Jin
, and
Y. J.
Yan
,
J. Chem. Phys.
130
,
124508
(
2009
).
50.
X.
Zheng
,
J. S.
Jin
,
S.
Welack
,
M.
Luo
, and
Y. J.
Yan
,
J. Chem. Phys.
130
,
164708
(
2009
).
51.
L. P.
Chen
and
Q.
Shi
,
J. Chem. Phys.
130
,
134505
(
2009
).
52.
A.
Ishizaki
and
G. R.
Felming
,
J. Chem. Phys.
130
,
234110
(
2009
).
53.
A.
Ishizaki
and
G. R.
Felming
,
J. Chem. Phys.
130
,
234111
(
2009
).
54.
T.
Kato
and
Y.
Tanimura
,
J. Chem. Phys.
120
,
260
(
2004
).
55.
A.
Ishizaki
and
Y.
Tanimura
,
J. Chem. Phys.
123
,
014503
(
2005
).
56.
A.
Ishizaki
and
Y.
Tanimura
,
Chem. Phys.
347
,
185
(
2008
).
57.
Y.
Zhou
and
J. S.
Shao
,
J. Chem. Phys.
128
,
034106
(
2008
).
58.
A. G.
Redfield
,
IBM J. Res. Dev.
1
,
19
(
1957
).
59.
W. T.
Pollard
,
A. K.
Felts
, and
R. A.
Friesner
,
Adv. Chem. Phys.
93
,
77
(
1996
).
60.
K.
Blum
,
Density Matrix Theory and Applications
(
Plenum
,
New York
,
1996
).
61.
H. P.
Breuer
and
F.
Petruccione
,
The Theory of Open Quantum Systems
(
Oxford University Press
,
New York
,
2002
).
62.
Q.
Shi
,
L. P.
Chen
,
G. J.
Nan
,
R. X.
Xu
, and
Y. J.
Yan
,
J. Chem. Phys.
130
,
084105
(
2009
).
64.
A.
Garg
,
J. N.
Onuchic
, and
V.
Ambegaokar
,
J. Chem. Phys.
83
,
4491
(
1985
).
65.
P. A.
Frantsuzov
,
J. Chem. Phys.
111
,
2075
(
1999
).
66.
Y.
Jung
and
J. S.
Cao
,
J. Chem. Phys.
117
,
3822
(
2002
).
67.
T.
la Cour Jansen
,
W.
Zhuang
, and
S.
Mukamel
,
J. Chem. Phys.
121
,
10577
(
2004
).
68.
T.
la Cour Jansen
,
T.
Hayashi
,
W.
Zhuang
, and
S.
Mukamel
,
J. Chem. Phys.
123
,
114504
(
2005
).
69.
H.
Haken
and
P.
Reineker
,
Z. Phys.
249
,
253
(
1972
).
70.
H.
Haken
and
G.
Strobl
,
Z. Phys.
262
,
135
(
1973
).
71.
M.
Schröder
,
M.
Schreiber
, and
U.
Kleinekathöfer
,
J. Chem. Phys.
126
,
114102
(
2007
).
72.
C.
Meier
and
D. J.
Tannor
,
J. Chem. Phys.
111
,
3365
(
1999
).
73.
A.
Pomyalov
and
D. J.
Tannor
,
J. Chem. Phys.
123
,
204111
(
2005
).
74.
U.
Kleinekathöfer
,
J. Chem. Phys.
121
,
2505
(
2004
).
75.
M. -L.
Zhang
,
B. J.
Ka
, and
E.
Geva
,
J. Chem. Phys.
125
,
044106
(
2006
).
76.
G.
McDermott
,
S. M.
Prince
,
A. A.
Freer
,
A. M.
Hawthornthwaite-Lawless
,
M. Z.
Papiz
,
R. J.
Cogdell
, and
N. W.
Isaacs
,
Nature (London)
374
,
517
(
1995
).
77.
R. J.
Cogdell
and
H.
Scheer
,
Photochem. Photobiol.
42
,
669
(
1985
).
78.
K.
Sauer
,
R. J.
Cogdell
,
S. M.
Prince
,
A.
Freer
,
N. W.
Isaacs
, and
H.
Scheer
,
Photochem. Photobiol.
64
,
564
(
1996
).
79.
Y. J.
Ma
,
R. J.
Cogdell
, and
T.
Gillbro
,
J. Phys. Chem. B
101
,
1087
(
1997
).
80.
R.
Jimenez
,
F.
van Mourik
,
J. Y.
Yu
, and
G. R.
Felming
,
J. Phys. Chem. B
101
,
7350
(
1997
).
You do not currently have access to this content.