Ultrafast Energy Transfer in LHC-II Revealed by Three-Pulse Photon Echo Peak Shift Measurements
Abstract
We report the results of three-pulse photon echo peak shift (3PEPS) measurements on the light-harvesting complex II (LHC-II) of the green algae Chlamydomonas reinhardtii . Experiments were performed at two different excitation wavelengths, 670 and 650 nm, corresponding to Chl- a and Chl- b excitation, respectively. The 3PEPS data are analyzed using a new theory that incorporates the effect of energy transfer on third-order response functions. Our theoretical model separates energy transfer dynamics from the solvation dynamics arising from coupling of the electronic transitions to the protein environment. We suggest that the protein fluctuations can be described by an ultrafast solvation on a sub-100 fs time scale and a long time correlation (static disorder). Decay of the 670 nm peak shift reveals spectral equilibration time scales for Chl- a molecules that range from 300 fs to 6 ps and agree well with other experiments. 3PEPS data at 650 nm (Chl- b excitation) reveal rapid Chl- b to Chl- b energy transfer (<1 ps), which suggests excitation hopping between a pair of Chls- b, and slow energy transfer from these Chls- b to Chls- a . Also, a 60 cm -1 oscillatory mode is observed for Chl- b which we attribute to the first observation of coherent nuclear dynamics in LHC-II. Calculating the energy transfer dynamics based on recently proposed assignments of chromophores by solving the master equation reveals Chl- b intra- and interband energy transfer dynamics that are in qualitative agreement with the simulation model of the peak shift data.
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With the advent of femtosecond transient absorption spectroscopy in the early 1990s, long-lived vibrational coherences, lasting on the order of a picosecond, were detected for bacterial and plant light-harvesting complexes.
“With the advent of femtosecond transient absorption spectroscopy in the early 1990s, long-lived vibrational coherences, lasting on the order of a picosecond, were detected for bacterial and plant light-harvesting complexes [35 -40].”
From The future of quantum biology (2018) · cites this paper as [38]
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Third-order nonlinear optical response and energy transfer in static disordered systems
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Flexibility of an Antibody Binding Site Measured with Photon Echo Spectroscopy
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- Authors
- Agarwal, R., Krueger, B. P., Scholes, G. D., Yang, M., Yom, J., Mets, L., & Fleming, G. R.
- Affiliations
- Lawrence Berkeley National Laboratory (US)
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 2000-03-11
- Volume
- 104
- Issue
- 13
- Pages
- 2908-2918
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- OpenAlex
- W1989405442
- Cited by
- 114
- References
- 64
- Citations by year
- 2026: 1 · 2025: 1 · 2024: 2 · 2023: 2 · 2020: 5 · 2019: 6 · 2018: 4 · 2017: 4 · 2016: 3 · 2015: 5 · 2013: 2 · 2012: 2
- FWCI
- 10.40
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Physical Chemistry B (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
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Photosynthetic Processes and Mechanisms
- Keywords
- light-harvesting complex II, Chlamydomonas reinhardtii, ultrafast energy transfer, chlorophyll a, solvation dynamics, protein fluctuations, static disorder, master equation
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