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.
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7 September 2009
Research Article|
September 01 2009
Optical line shapes of molecular aggregates: Hierarchical equations of motion method
Liping Chen;
Liping Chen
1Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry,
Chinese Academy of Sciences
, Zhongguancun, Beijing 100190, China
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Renhui Zheng;
Renhui Zheng
1Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry,
Chinese Academy of Sciences
, Zhongguancun, Beijing 100190, China
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Qiang Shi;
Qiang Shi
a)
1Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry,
Chinese Academy of Sciences
, Zhongguancun, Beijing 100190, China
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YiJing Yan
YiJing Yan
2Department of Chemistry,
Hong Kong University of Science and Technology
, Kowloon, Hong Kong
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a)
Electronic mail: [email protected].
J. Chem. Phys. 131, 094502 (2009)
Article history
Received:
June 19 2009
Accepted:
August 07 2009
Citation
Liping Chen, Renhui Zheng, Qiang Shi, YiJing Yan; Optical line shapes of molecular aggregates: Hierarchical equations of motion method. J. Chem. Phys. 7 September 2009; 131 (9): 094502. https://doi.org/10.1063/1.3213013
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