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We report two-dimensional electronic spectroscopy (2DES) experiments on the bacterial reaction center (BRC) from purple bacteria, revealing hidden vibronic and excitonic structure. Through analysis of the coherent dynamics of the BRC, we identify multiple quasi-resonances between pigment vibrations and excitonic energy gaps, and vibronic coherence transfer processes that are typically neglected in standard models of photosynthetic energy transfer and charge separation. We support our assignment with control experiments on bacteriochlorophyll and simulations of the coherent dynamics using a reduced excitonic model of the BRC. We find that specific vibronic coherence processes can readily reveal weak exciton transitions. While the functional relevance of such processes is unclear, they provide a spectroscopic tool that uses vibrations as a window for observing excited state structure and dynamics elsewhere in the BRC via vibronic coupling. Vibronic coherence transfer reveals the upper exciton of the “special pair” that was weakly visible in previous 2DES experiments.
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Photosynthetic Energy Transfer: Missing in Action (Detected Spectroscopy)?
In recent years, action-detected ultrafast spectroscopies have gained popularity offering distinct advantages over their coherently-detected counterparts, such as spatially-resolved and operando measurements with high sensitivity. However, there are also fundamental limitations connected to the process of signal generation in action-detected experiments. Here we perform fluorescence- detected two-dimensional electronic spectroscopy (F-2DES) of the light-harvesting II (LH2) complex from purple bacteria. We demonstrate that the B800-B850 energy transfer process in LH2 is weak but observable in F-2DES, unlike in coherently-detected 2DES where the energy transfer is visible with 100% contrast. We explain the weak signatures using a disordered excitonic model that accounts for experimental conditions. We further derive a general formula for the presence of excited-state signals in multichromophoric aggregates, dependent on the aggregate geometry, size, excitonic coupling and disorder. We find that the prominence of excited-state dynamics in action- detected spectroscopy offers a unique probe of excitonic delocalization in multichromophoric systems.
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- Award ID(s):
- 1914608
- PAR ID:
- 10635328
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry Letters
- Volume:
- 15
- Issue:
- 50
- ISSN:
- 1948-7185
- Page Range / eLocation ID:
- 12376 to 12386
- Subject(s) / Keyword(s):
- photosynthetic energy transfer multidimensional spectroscopy
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.jpclett.4c02665
