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On the adequacy of the Redfield equation and related approaches to the study of quantum dynamics in electronic energy transfer
Abstract
The observation of long-lived electronic coherence in photosynthetic excitation energy transfer (EET) by Engel et al. [Nature (London) 446, 782 (2007)] raises questions about the role of the protein environment in protecting this coherence and the significance of the quantum coherence in light harvesting efficiency. In this paper we explore the applicability of the Redfield equation in its full form, in the secular approximation and with neglect of the imaginary part of the relaxation terms for the study of these phenomena. We find that none of the methods can give a reliable picture of the role of the environment in photosynthetic EET. In particular the popular secular approximation (or the corresponding Lindblad equation) produces anomalous behavior in the incoherent transfer region leading to overestimation of the contribution of environment-assisted transfer. The full Redfield expression on the other hand produces environment-independent dynamics in the large reorganization energy region. A companion paper presents an improved approach, which corrects these deficiencies [A. Ishizaki and G. R. Fleming, J. Chem. Phys. 130, 234111 (2009)].
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“This is particularly the case when considering interacting many-body systems, where the subsystem's coupling strength may be comparable to the coupling to the bath [4].”
From Entanglement and Non-Markovianity of Quantum Evolutions (2010) · cites this paper as [4]
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Metadata
- Authors
- Ishizaki, A., & Fleming, G. R.
- Affiliations
- Lawrence Berkeley National Laboratory (US)
- Venue
- The Journal of Chemical Physics
- Publisher
- AIP Publishing
- Published
- 2009-06-18
- Volume
- 130
- Issue
- 23
- Pages
- 234110-234110
- ISSN
- 0021-9606 (ISSN-L)
- 1089-7690
- OpenAlex
- W2009237413
- Cited by
- 430
- References
- 60
- Citations by year
- 2026: 15 · 2025: 19 · 2024: 18 · 2023: 9 · 2022: 21 · 2021: 17 · 2020: 21 · 2019: 32 · 2018: 19 · 2017: 23 · 2016: 22 · 2015: 31 · 2014: 36 · 2013: 25 · 2012: 39
- FWCI
- 22.64
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Chemical Physics (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Strong Light-Matter Interactions
- Keywords
- Redfield equation, excitation energy transfer, photosynthetic light harvesting, quantum coherence, secular approximation, Lindblad master equation, reorganization energy, protein environment, quantum dynamics
- MeSH terms
- Computer Simulation, Electrons, Energy Transfer, Models, Chemical, Quantum Theory
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